commit cf3f7a39e098c4279fb686d4a01ec4441874f5aa Author: linjie zheng Date: Fri Sep 13 15:20:56 2019 +0200 first try diff --git a/achemso.bst b/achemso.bst new file mode 100644 index 0000000..f76f3d2 --- /dev/null +++ b/achemso.bst @@ -0,0 +1,1709 @@ +%% +%% This is file `achemso.bst', +%% generated with the docstrip utility. +%% +%% The original source files were: +%% +%% achemso.dtx (with options: `bst') +%% ---------------------------------------------------------------- +%% achemso --- Support for submissions to American Chemical Society +%% journals +%% E-mail: joseph.wright@morningstar2.co.uk +%% Released under the LaTeX Project Public License v1.3c or later +%% See http://www.latex-project.org/lppl.txt +%% ---------------------------------------------------------------- +%% + + +ENTRY + { + address + author + booktitle + chapter + ctrl-article-title + ctrl-chapter-title + ctrl-etal-firstonly + ctrl-etal-number + ctrl-use-title + doi + edition + editor + howpublished + institution + journal + key + maintitle + note + number + organization + pages + publisher + school + series + title + type + url + version + volume + year + } + { } + { + label + short.names + } + + +FUNCTION { and } { + { } + { + pop$ + #0 + } + if$ +} + +FUNCTION { not } { + { #0 } + { #1 } + if$ +} + +FUNCTION { or } { + { + pop$ + #1 + } + { } + if$ +} + +FUNCTION { xor } { + { not } + { } + if$ +} + + +FUNCTION { chr.to.value.error } { + #48 + + int.to.chr$ + "'" swap$ * + "'" * + " is not a number: treated as zero." * + warning$ + #0 +} + +FUNCTION { chr.to.value } { + chr.to.int$ #48 - + duplicate$ + #0 < + { chr.to.value.error } + { + duplicate$ + #9 > + { chr.to.value.error } + { } + if$ + } + if$ +} + +STRINGS { + extract.input.str + extract.output.str +} + +FUNCTION { is.a.digit } { + duplicate$ + "" = + { + pop$ + #0 + } + { + chr.to.int$ + #48 - + duplicate$ + #0 < swap$ #9 > or not + } + if$ +} + +FUNCTION{ is.a.number } { + { + duplicate$ + #1 #1 substring$ + is.a.digit + } + { #2 global.max$ substring$ } + while$ + "" = +} + +FUNCTION { extract.number } { + duplicate$ + 'extract.input.str := + "" 'extract.output.str := + { extract.input.str empty$ not } + { + extract.input.str #1 #1 substring$ + extract.input.str #2 global.max$ substring$ 'extract.input.str := + duplicate$ + is.a.number + { extract.output.str swap$ * 'extract.output.str := } + { + pop$ + "" 'extract.input.str := + } + if$ + } + while$ + extract.output.str empty$ + { } + { + pop$ + extract.output.str + } + if$ +} + +FUNCTION { field.or.null } { + duplicate$ + empty$ + { + pop$ + "" + } + { } + if$ +} + +INTEGERS { + multiply.a.int + multiply.b.int +} + +FUNCTION { multiply } { + 'multiply.a.int := + 'multiply.b.int := + multiply.b.int #0 < + { + #-1 + #0 multiply.b.int - 'multiply.b.int := + } + { #1 } + if$ + #0 + { multiply.b.int #0 > } + { + multiply.a.int + + multiply.b.int #1 - 'multiply.b.int := + } + while$ + swap$ + { } + { #0 swap$ - } + if$ +} + +INTEGERS { str.conversion.int } + +FUNCTION { str.to.int.aux.ii } { + { + duplicate$ + empty$ not + } + { + swap$ + #10 multiply 'str.conversion.int := + duplicate$ + #1 #1 substring$ + chr.to.value + str.conversion.int + + swap$ + #2 global.max$ substring$ + } + while$ + pop$ +} + +FUNCTION { str.to.int.aux.i } { + duplicate$ + #1 #1 substring$ + "-" = + { + #1 swap$ + #2 global.max$ substring$ + } + { + #0 swap$ + } + if$ + #0 + swap$ + str.to.int.aux.ii + swap$ + { #0 swap$ - } + { } + if$ +} + +FUNCTION { str.to.int } { + duplicate$ + empty$ + { + pop$ + #0 + } + { str.to.int.aux.i } + if$ +} + +FUNCTION { tie.or.space.connect } { + duplicate$ + text.length$ #3 < + { "~" } + { " " } + if$ + swap$ * * +} + +FUNCTION { yes.no.to.bool } { + duplicate$ + empty$ + { + pop$ + #0 + } + { + "l" change.case$ + "yes" = + { #1 } + { #0 } + if$ + } + if$ +} + + +FUNCTION { bold } { + duplicate$ + empty$ + { + pop$ + "" + } + { "\textbf{" swap$ * "}" * } + if$ +} + +FUNCTION { emph } { + duplicate$ + empty$ + { + pop$ + "" + } + { "\emph{" swap$ * "}" * } + if$ +} + +FUNCTION { paren } { + duplicate$ + empty$ + { + pop$ + "" + } + { "(" swap$ * ")" * } + if$ +} + + +FUNCTION { add.comma } { ", " * } + +FUNCTION { add.colon } { ": " * } + +FUNCTION { add.period } { add.period$ " " * } + +FUNCTION { add.semicolon } { "; " * } + +FUNCTION { add.space } { " " * } + + +FUNCTION { bbl.and } { "and" } + +FUNCTION { bbl.chapter } { "Chapter" } + +FUNCTION { bbl.doi } { "DOI:" } + +FUNCTION { bbl.editor } { "Ed." } + +FUNCTION { bbl.editors } { "Eds." } + +FUNCTION { bbl.edition } { "ed." } + +FUNCTION { bbl.etal } { "\latin{et~al.}" } + +FUNCTION { bbl.in } { "In" } + +FUNCTION { bbl.inpress } { "in press" } + +FUNCTION { bbl.msc } { "M.Sc.\ thesis" } + +FUNCTION { bbl.page } { "p" } + +FUNCTION { bbl.pages } { "pp" } + +FUNCTION { bbl.phd } { "Ph.D.\ thesis" } + +FUNCTION { bbl.version } { "version" } + +FUNCTION { bbl.volume } { "Vol." } + + +STRINGS { pages.str } + +FUNCTION { hyphen.to.dash } { + 'pages.str := + "" + { pages.str empty$ not } + { + pages.str #1 #1 substring$ + "-" = + { + "--" * + { + pages.str #1 #1 substring$ + "-" = + } + { pages.str #2 global.max$ substring$ 'pages.str := } + while$ + } + { + pages.str #1 #1 substring$ + * + pages.str #2 global.max$ substring$ 'pages.str := + } + if$ + } + while$ +} + +INTEGERS { multiresult.bool } + +FUNCTION { multi.page.check } { + 'pages.str := + #0 'multiresult.bool := + { + multiresult.bool not + pages.str empty$ not + and + } + { + pages.str #1 #1 substring$ + duplicate$ + "-" = swap$ duplicate$ + "," = swap$ + "+" = + or or + { #1 'multiresult.bool := } + { pages.str #2 global.max$ substring$ 'pages.str := } + if$ + } + while$ + multiresult.bool +} + + +INTEGERS { + current.name.int + names.separate.comma + names.separate.semicolon + names.separate.comma.bool + remaining.names.int + total.names.int +} + +STRINGS { + current.name.str + names.str +} + +FUNCTION { full.format.names } { + 'names.str := + #1 'current.name.int := + names.str num.names$ 'remaining.names.int := + { remaining.names.int #0 > } + { + names.str current.name.int "{vv~}{ll}" format.name$ + current.name.int #1 > + { + swap$ add.comma swap$ + remaining.names.int #1 > + { } + { + duplicate$ + "others" = + { bbl.etal } + { bbl.and } + if$ + add.space swap$ * + } + if$ + * + } + { } + if$ + remaining.names.int #1 - 'remaining.names.int := + current.name.int #1 + 'current.name.int := + } + while$ +} + +FUNCTION { full.author } { + author empty$ + { "" } + { author full.format.names } + if$ +} + +FUNCTION { full.author.editor } { + author empty$ + { + editor empty$ + { "" } + { editor full.format.names } + if$ + } + { author full.format.names } + if$ +} + +FUNCTION { full.editor } { + editor empty$ + { "" } + { editor full.format.names } + if$ +} + +FUNCTION { short.format.names } { + 'names.str := + names.str #1 "{vv~}{ll}" format.name$ + names.str num.names$ + duplicate$ + #2 > + { + pop$ + add.space bbl.etal * + } + { + #2 < + { } + { + names.str #2 "{ff }{vv }{ll}{ jj}" format.name$ + "others" = + { add.space bbl.etal * } + { + add.space + bbl.and add.space + * + names.str #2 "{vv~}{ll}" format.name$ + * + } + if$ + } + if$ + } + if$ +} + +FUNCTION { short.author.key } { + author empty$ + { + key empty$ + { cite$ #1 #3 substring$ } + { key } + if$ + } + { author short.format.names } + if$ +} + +FUNCTION { short.author.editor.key } { + author empty$ + { + editor empty$ + { + key empty$ + { cite$ #1 #3 substring$ } + { key } + if$ + } + { editor short.format.names } + if$ + } + { author short.format.names } + if$ +} + +FUNCTION { short.author.key.organization } { + author empty$ + { + key empty$ + { + organization empty$ + { cite$ #1 #3 substring$ } + { + organization #1 #4 substring$ + "The " = + { organization } + { organization #5 global.max$ substring$ } + if$ + #3 text.prefix$ + } + if$ + } + { key } + if$ + } + { author short.format.names } + if$ +} + +FUNCTION { short.editor.key.organization } { + editor empty$ + { + key empty$ + { + organization empty$ + { cite$ #1 #3 substring$ } + { + organization #1 #4 substring$ + "The " = + { organization } + { organization #5 global.max$ substring$ } + if$ + #3 text.prefix$ + } + if$ + } + { key } + if$ + } + { editor short.format.names } + if$ +} + +FUNCTION { calculate.full.names } { + type$ "book" = + type$ "inbook" = + or + { full.author.editor } + { + type$ "proceedings" = + { full.editor } + { full.author } + if$ + } + if$ +} + +FUNCTION { calculate.short.names } { + type$ "book" = + type$ "inbook" = + or + { short.author.editor.key } + { + type$ "proceedings" = + { short.editor.key.organization } + { + type$ "manual" = + { short.author.key.organization } + { short.author.key } + if$ + } + if$ + } + if$ + 'short.names := +} + +FUNCTION { calculate.names } { + calculate.short.names + short.names + year empty$ + { "()" } + { "(" year * ")" * } + if$ + * + 'label := +} + + +INTEGERS { entries.int } + +FUNCTION { initialize.count.entries } { + #0 'entries.int := +} + +FUNCTION { count.entries } { + entries.int #1 + 'entries.int := +} + + +FUNCTION { begin.bib } { + preamble$ empty$ + { } + { + preamble$ write$ + newline$ + } + if$ + "\providecommand{\latin}[1]{#1}" write$ + newline$ + "\providecommand*\mcitethebibliography{\thebibliography}" write$ + newline$ + "\csname @ifundefined\endcsname{endmcitethebibliography}" write$ + " {\let\endmcitethebibliography\endthebibliography}{}" write$ + newline$ + "\begin{mcitethebibliography}{" + entries.int int.to.str$ * "}" * write$ + newline$ + "\providecommand*\natexlab[1]{#1}" write$ + newline$ + "\providecommand*\mciteSetBstSublistMode[1]{}" write$ + newline$ + "\providecommand*\mciteSetBstMaxWidthForm[2]{}" write$ + newline$ + "\providecommand*\mciteBstWouldAddEndPuncttrue" write$ + newline$ + " {\def\EndOfBibitem{\unskip.}}" write$ + newline$ + "\providecommand*\mciteBstWouldAddEndPunctfalse" write$ + newline$ + " {\let\EndOfBibitem\relax}" write$ + newline$ + "\providecommand*\mciteSetBstMidEndSepPunct[3]{}" write$ + newline$ + "\providecommand*\mciteSetBstSublistLabelBeginEnd[3]{}" write$ + newline$ + "\providecommand*\EndOfBibitem{}" write$ + newline$ + "\mciteSetBstSublistMode{f}" write$ + newline$ + "\mciteSetBstMaxWidthForm{subitem}{(\alph{mcitesubitemcount})}" write$ + newline$ + "\mciteSetBstSublistLabelBeginEnd" write$ + newline$ + " {\mcitemaxwidthsubitemform\space}" write$ + newline$ + " {\relax}" write$ + newline$ + " {\relax}" write$ + newline$ +} + +FUNCTION { end.bib } { + newline$ + "\end{mcitethebibliography}" write$ + newline$ +} + + +INTEGERS { + ctrl.article.title.bool + ctrl.chapter.title.bool + ctrl.etal.firstonly.bool + ctrl.etal.number.int +} + +FUNCTION { initialize.control.values } { + #0 'ctrl.article.title.bool := + #0 'ctrl.chapter.title.bool := + #1 'ctrl.etal.firstonly.bool := + #15 'ctrl.etal.number.int := +} + +FUNCTION { control } { + ctrl-article-title yes.no.to.bool 'ctrl.article.title.bool := + ctrl-chapter-title yes.no.to.bool 'ctrl.chapter.title.bool := + ctrl-etal-firstonly yes.no.to.bool 'ctrl.etal.firstonly.bool := + ctrl-etal-number str.to.int 'ctrl.etal.number.int := + ctrl-use-title empty$ + 'skip$ + { ctrl-use-title yes.no.to.bool 'ctrl.article.title.bool := } + if$ +} + + +INTEGERS { + next.punct.comma + next.punct.period + next.punct.semicolon + next.punct.space +} + +FUNCTION { initialize.tracker } { + #0 'next.punct.comma := + #1 'next.punct.period := + #2 'next.punct.semicolon := + #3 'next.punct.space := +} + +INTEGERS { next.punct.int } + +FUNCTION { output } { + swap$ + duplicate$ empty$ + { pop$ } + { + next.punct.int next.punct.space = + { add.space } + { + next.punct.int next.punct.comma = + { add.comma } + { + next.punct.int next.punct.semicolon = + { add.semicolon } + { add.period } + if$ + } + if$ + } + if$ + write$ + } + if$ + next.punct.comma 'next.punct.int := +} + + +FUNCTION { begin.bibitem } { + newline$ + "\bibitem" write$ + label + calculate.full.names + duplicate$ + short.names = + { pop$ } + { * } + if$ + "[" swap$ * "]" * write$ + "{" cite$ * "}" * write$ + newline$ + "" + next.punct.comma 'next.punct.int := +} + +INTEGERS { add.period.length.int } + +FUNCTION { would.add.period } { + duplicate$ + add.period$ + text.length$ 'add.period.length.int := + duplicate$ + text.length$ + add.period.length.int = + { #0 } + { #1 } + if$ +} + +FUNCTION { end.bibitem } { + would.add.period + { + "\relax" * write$ + newline$ + "\mciteBstWouldAddEndPuncttrue" write$ + newline$ + "\mciteSetBstMidEndSepPunct{\mcitedefaultmidpunct}" write$ + newline$ + "{\mcitedefaultendpunct}{\mcitedefaultseppunct}\relax" + } + { + "\relax" * write$ + newline$ + "\mciteBstWouldAddEndPunctfalse" write$ + newline$ + "\mciteSetBstMidEndSepPunct{\mcitedefaultmidpunct}" write$ + newline$ + "{}{\mcitedefaultseppunct}\relax" + } + if$ + write$ + newline$ + "\EndOfBibitem" write$ +} + + +FUNCTION { initialize.name.separator } { + #1 'names.separate.comma := + #0 'names.separate.semicolon := +} + +FUNCTION { format.names.loop } { + { remaining.names.int #0 > } + { + names.str current.name.int "{vv~}{ll,}{~f.}{,~jj}" format.name$ + duplicate$ + 'current.name.str := + current.name.int #1 > + { + duplicate$ + "others," = + { + bbl.etal + add.space + remaining.names.int #1 - 'remaining.names.int := + } + { + swap$ + names.separate.comma.bool + { add.comma } + { add.semicolon } + if$ + swap$ + * + } + if$ + } + { } + if$ + remaining.names.int #1 - 'remaining.names.int := + current.name.int #1 + 'current.name.int := + } + while$ +} + +FUNCTION { format.names.all } { + total.names.int 'remaining.names.int := + format.names.loop +} + +FUNCTION { format.names.etal } { + ctrl.etal.firstonly.bool + { #1 'remaining.names.int := } + { ctrl.etal.number.int 'remaining.names.int := } + if$ + format.names.loop + current.name.str "others," = + { } + { + add.space + bbl.etal + add.space + * + } + if$ +} + +FUNCTION { format.names } { + 'names.separate.comma.bool := + 'names.str := + #1 'current.name.int := + names.str num.names$ 'total.names.int := + total.names.int ctrl.etal.number.int > + { + ctrl.etal.number.int #0 = + { format.names.all } + { format.names.etal } + if$ + } + { format.names.all } + if$ +} + + +FUNCTION { bbl.first } { "1st" } + +FUNCTION { bbl.second } { "2nd" } + +FUNCTION { bbl.third } { "3rd" } + +FUNCTION { bbl.fourth } { "4th" } + +FUNCTION { bbl.fifth } { "5th" } + +FUNCTION { bbl.st } { "st" } + +FUNCTION { bbl.nd } { "nd" } + +FUNCTION { bbl.rd } { "rd" } + +FUNCTION { bbl.th } { "th" } + +STRINGS { + ord.input.str + ord.output.str +} + +FUNCTION { make.ordinal } { + duplicate$ + "1" swap$ + * + #-2 #1 substring$ + "1" = + { + bbl.th * + } + { + duplicate$ + #-1 #1 substring$ + duplicate$ + "1" = + { + pop$ + bbl.st * + } + { + duplicate$ + "2" = + { + pop$ + bbl.nd * + } + { + "3" = + { bbl.rd * } + { bbl.th * } + if$ + } + if$ + } + if$ + } + if$ +} + +FUNCTION { convert.to.ordinal } { + extract.number + "l" change.case$ 'ord.input.str := + ord.input.str "first" = ord.input.str "1" = or + { bbl.first 'ord.output.str := } + { + ord.input.str "second" = ord.input.str "2" = or + { bbl.second 'ord.output.str := } + { + ord.input.str "third" = ord.input.str "3" = or + { bbl.third 'ord.output.str := } + { + ord.input.str "fourth" = ord.input.str "4" = or + { bbl.fourth 'ord.output.str := } + { + ord.input.str "fifth" = ord.input.str "5" = or + { bbl.fifth 'ord.output.str := } + { + ord.input.str #1 #1 substring$ + is.a.number + { ord.input.str make.ordinal } + { ord.input.str } + if$ + 'ord.output.str := + } + if$ + } + if$ + } + if$ + } + if$ + } + if$ + ord.output.str +} + + +FUNCTION { format.address } { + address empty$ + { } + { + address + output + } + if$ +} + +FUNCTION { format.authors } { + author empty$ + { } + { + author names.separate.semicolon format.names + output + next.punct.space 'next.punct.int := + } + if$ +} + +FUNCTION { format.editors } { + editor empty$ + { } + { + editor names.separate.comma format.names + add.comma + editor num.names$ #1 > + { bbl.editors } + { bbl.editor } + if$ + * + output + next.punct.semicolon 'next.punct.int := + } + if$ +} + +FUNCTION { format.authors.or.editors } { + author empty$ + { format.editors } + { format.authors } + if$ + next.punct.space 'next.punct.int := +} + +FUNCTION { format.chapter } { + chapter empty$ + { } + { + bbl.chapter add.space + chapter + * + output + } + if$ +} + +FUNCTION { format.doi } { + next.punct.comma 'next.punct.int := + bbl.doi add.space + doi * + output +} + +FUNCTION { format.edition } { + edition empty$ + { } + { + edition convert.to.ordinal + add.space bbl.edition * + output + } + if$ + next.punct.semicolon 'next.punct.int := +} + +FUNCTION { format.group.address } { + duplicate$ + empty$ + { pop$ } + { + address empty$ + { } + { + add.colon + address + * + } + if$ + output + } + if$ +} + +FUNCTION { format.howpublished } { + howpublished empty$ + { } + { + howpublished + output + } + if$ +} + +FUNCTION { format.journal } { + journal emph + output + next.punct.space 'next.punct.int := +} + +FUNCTION { format.journal.unpub } { + journal emph + output +} + +FUNCTION { format.note } { + note empty$ + { } + { + note + output + } + if$ +} + +FUNCTION { format.number.series } { + series empty$ + { } + { + series + number empty$ + { } + { + add.space + number * + } + if$ + output + next.punct.semicolon 'next.punct.int := + } + if$ +} + +FUNCTION { format.organization } { + organization empty$ + { } + { + organization paren + output + next.punct.period 'next.punct.int := + } + if$ +} + +FUNCTION { format.organization.address } { + organization format.group.address +} + +FUNCTION { format.pages } { + pages empty$ + { } + { + pages multi.page.check + { + bbl.pages + pages hyphen.to.dash + } + { bbl.page pages } + if$ + tie.or.space.connect + output + } + if$ +} + +FUNCTION { format.pages.article } { + pages empty$ + { } + { + pages hyphen.to.dash + output + } + if$ +} + +FUNCTION { format.publisher.address } { + publisher format.group.address +} + +FUNCTION { format.school.address } { + school + duplicate$ + empty$ + { pop$ } + { + address empty$ + { } + { + add.comma + address + * + } + if$ + output + } + if$ +} + +FUNCTION { format.title } { + title empty$ + { } + { + title + output + next.punct.period 'next.punct.int := + } + if$ +} + +FUNCTION { format.title.article } { + ctrl.article.title.bool + { + title empty$ + { } + { + title + output + next.punct.period 'next.punct.int := + } + if$ + } + { } + if$ +} + +FUNCTION { format.title.techreport } { + title empty$ + { } + { + title emph + output + next.punct.semicolon 'next.punct.int := + } + if$ +} + +FUNCTION { format.title.booktitle } { + title empty$ + { } + { + title + output + next.punct.period 'next.punct.int := + } + if$ + booktitle empty$ + { } + { + booktitle + output + next.punct.period 'next.punct.int := + } + if$ +} + +FUNCTION { format.chapter.title } { +} + +STRINGS { + book.title + chapter.title +} + +FUNCTION { format.title.booktitle.book } { + "" 'chapter.title := + booktitle empty$ + { + "" 'chapter.title := + title 'book.title := + } + { + ctrl.chapter.title.bool + { + title empty$ + 'skip$ + { title 'chapter.title := } + if$ + } + 'skip$ + if$ + maintitle empty$ + { booktitle 'book.title := } + { maintitle add.period booktitle * 'book.title := } + if$ + } + if$ + chapter.title empty$ + { } + { + chapter.title + output + next.punct.period 'next.punct.int := + } + if$ + book.title emph + chapter.title empty$ + { + author empty$ + { } + { + editor empty$ + { } + { bbl.in add.space swap$ * } + if$ + } + if$ + } + { bbl.in add.space swap$ * } + if$ + output +} + +FUNCTION { format.type } { + type empty$ + { } + { + pop$ + type + } + if$ + output +} + +FUNCTION { format.type.number } { + type empty$ + { } + { + type + number empty$ + { } + { number tie.or.space.connect } + if$ + output + } + if$ +} + +FUNCTION { format.url } { + url empty$ + { } + { + "\url{" url * "}" * + output + } + if$ +} + +FUNCTION { format.year } { + year empty$ + { } + { + year + output + next.punct.semicolon 'next.punct.int := + } + if$ +} + +FUNCTION { format.year.article } { + year empty$ + { } + { + year bold + output + } + if$ +} + +FUNCTION { format.version } { + version empty$ + { } + { + bbl.version add.space + version + * + output + } + if$ +} + +FUNCTION { format.volume.article } { + volume emph + output +} + +FUNCTION { format.volume } { + volume empty$ + { } + { + bbl.volume + volume + tie.or.space.connect + output + next.punct.semicolon 'next.punct.int := + } + if$ +} + + +FUNCTION { article } { + begin.bibitem + format.authors + format.title.article + format.journal + format.year.article + format.volume.article + format.pages.article + format.note + end.bibitem +} + +FUNCTION { book } { + begin.bibitem + format.authors.or.editors + format.title.booktitle.book + format.edition + author empty$ + { } + { format.editors } + if$ + format.number.series + format.publisher.address + format.year + format.volume + format.chapter + format.pages + format.note + end.bibitem +} + +FUNCTION { inbook } { book } + +FUNCTION { booklet } { + begin.bibitem + format.authors + format.title + format.howpublished + format.address + format.year + format.note + end.bibitem +} + +FUNCTION { collection } { book } + +FUNCTION { incollection } { book } + +FUNCTION { inpress } { + begin.bibitem + format.authors + format.journal.unpub + doi empty$ + { + bbl.inpress + output + } + { + format.year.article + format.doi + } + if$ + format.note + end.bibitem +} + +FUNCTION { inproceedings } { + begin.bibitem + format.authors + format.title.booktitle + format.address + format.year + format.pages + format.note + end.bibitem +} + +FUNCTION { manual } { + begin.bibitem + format.authors + format.title + format.version + format.organization.address + format.year + format.note + end.bibitem +} + +FUNCTION { mastersthesis } { + begin.bibitem + format.authors + format.title + bbl.msc format.type + format.school.address + format.year + format.note + end.bibitem +} + +FUNCTION { misc } { + begin.bibitem + format.authors + format.title + format.howpublished + format.year + format.url + format.note + end.bibitem +} + +FUNCTION { patent } { + begin.bibitem + format.authors + format.organization + format.title + format.type.number + format.year + format.note + end.bibitem +} + +FUNCTION { phdthesis } { + begin.bibitem + format.authors + format.title + bbl.phd format.type + format.school.address + format.year + format.note + end.bibitem +} + +FUNCTION { proceeding } { + begin.bibitem + format.title + format.address + format.year + format.pages + format.note + end.bibitem +} + +FUNCTION { techreport } { + begin.bibitem + format.authors.or.editors + format.title.techreport + format.type.number + format.organization.address + format.year + format.volume + format.pages + format.note + end.bibitem +} + +FUNCTION { unpublished } { + begin.bibitem + format.authors + format.journal.unpub + doi empty$ + { format.howpublished } + { + format.year + format.doi + } + if$ + format.note + end.bibitem +} + +FUNCTION { default.type } { misc } + + +MACRO { jan } { "Jan." } +MACRO { feb } { "Feb." } +MACRO { mar } { "Mar." } +MACRO { apr } { "Apr." } +MACRO { may } { "May" } +MACRO { jun } { "June" } +MACRO { jul } { "July" } +MACRO { aug } { "Aug." } +MACRO { sep } { "Sept." } +MACRO { oct } { "Oct." } +MACRO { nov } { "Nov." } +MACRO { dec } { "Dec." } + +MACRO { acbcct } { "ACS Chem.\ Biol." } +MACRO { achre4 } { "Acc.\ Chem.\ Res." } +MACRO { acncdm } { "ACS Chem.\ Neurosci." } +MACRO { ancac3 } { "ACS Nano" } +MACRO { ancham } { "Anal.\ Chem." } +MACRO { bichaw } { "Biochemistry" } +MACRO { bcches } { "Bioconjugate Chem." } +MACRO { bomaf6 } { "Biomacromolecules" } +MACRO { bipret } { "Biotechnol.\ Prog." } +MACRO { crtoec } { "Chem.\ Res.\ Toxicol." } +MACRO { chreay } { "Chem.\ Rev." } +MACRO { cmatex } { "Chem.\ Mater." } +MACRO { cgdefu } { "Cryst.\ Growth Des." } +MACRO { enfuem } { "Energy Fuels" } +MACRO { esthag } { "Environ.\ Sci.\ Technol." } +MACRO { iechad } { "Ind.\ Eng.\ Chem.\ Res." } +MACRO { inoraj } { "Inorg.\ Chem." } +MACRO { jafcau } { "J.~Agric.\ Food Chem." } +MACRO { jceaax } { "J.~Chem.\ Eng.\ Data" } +MACRO { jceda8 } { "J.~Chem.\ Ed." } +MACRO { jcisd8 } { "J.~Chem.\ Inf.\ Model." } +MACRO { jctcce } { "J.~Chem.\ Theory Comput." } +MACRO { jcchff } { "J. Comb. Chem." } +MACRO { jmcmar } { "J. Med. Chem." } +MACRO { jnprdf } { "J. Nat. Prod." } +MACRO { joceah } { "J.~Org.\ Chem." } +MACRO { jpcafh } { "J.~Phys.\ Chem.~A" } +MACRO { jpcbfk } { "J.~Phys.\ Chem.~B" } +MACRO { jpccck } { "J.~Phys.\ Chem.~C" } +MACRO { jpclcd } { "J.~Phys.\ Chem.\ Lett." } +MACRO { jprobs } { "J.~Proteome Res." } +MACRO { jacsat } { "J.~Am.\ Chem.\ Soc." } +MACRO { langd5 } { "Langmuir" } +MACRO { mamobx } { "Macromolecules" } +MACRO { mpohbp } { "Mol.\ Pharm." } +MACRO { nalefd } { "Nano Lett." } +MACRO { orlef7 } { "Org.\ Lett." } +MACRO { oprdfk } { "Org.\ Proc.\ Res.\ Dev." } +MACRO { orgnd7 } { "Organometallics" } + + +READ + +EXECUTE { initialize.control.values } + +EXECUTE { initialize.count.entries } + +EXECUTE { initialize.name.separator } + +EXECUTE { initialize.tracker } + +ITERATE { calculate.names } + +ITERATE { count.entries } + +EXECUTE { begin.bib } + +ITERATE { call.type$ } + +EXECUTE { end.bib } +%% +%% Originally developed by Mats Dahlgren +%% Copyright (C) 1996-1998 by Mats Dahlgren +%% Copyright (C) 2008-2014 by +%% Joseph Wright +%% +%% Part of this bundle is derived from cite.sty, to which the +%% following license applies: +%% Copyright (C) 1989-2009 by Donald Arseneau +%% These macros may be freely transmitted, reproduced, or +%% modified provided that this notice is left intact. +%% +%% It may be distributed and/or modified under the conditions of +%% the LaTeX Project Public License (LPPL), either version 1.3c of +%% this license or (at your option) any later version. The latest +%% version of this license is in the file: +%% +%% http://www.latex-project.org/lppl.txt +%% +%% This work is "maintained" (as per LPPL maintenance status) by +%% Joseph Wright. +%% +%% This work consists of the file achemso.dtx +%% and the derived files achemso.cls, +%% achemso.ins, +%% achemso.pdf, +%% achemso.sty, +%% achemso-demo.bib, +%% achemso-demo.tex, +%% natmove.sty and +%% a number of configuration files. +%% +%% +%% End of file `achemso.bst'. diff --git a/achemso.cls b/achemso.cls new file mode 100644 index 0000000..cee1551 --- /dev/null +++ b/achemso.cls @@ -0,0 +1,1458 @@ +%% +%% This is file `achemso.cls', +%% generated with the docstrip utility. +%% +%% The original source files were: +%% +%% achemso.dtx (with options: `class') +%% ---------------------------------------------------------------- +%% achemso --- Support for submissions to American Chemical Society +%% journals +%% E-mail: joseph.wright@morningstar2.co.uk +%% Released under the LaTeX Project Public License v1.3c or later +%% See http://www.latex-project.org/lppl.txt +%% ---------------------------------------------------------------- +%% +\NeedsTeXFormat{LaTeX2e} + +\ProvidesClass{achemso} + [2014/08/18 v3.8k Submission to ACS journals] +\LoadClass[12pt,letter]{article} +\newcommand*\acs@warning{\ClassWarning{achemso}} +\newcommand*\acs@ifundefined[1]{% + \begingroup\expandafter\expandafter\expandafter\endgroup + \expandafter\ifx\csname #1\endcsname\relax + \expandafter\@firstoftwo + \else + \expandafter\@secondoftwo + \fi +} +\RequirePackage{xkeyval} +\newcommand*\acs@keyval@bool[2]{% + \acs@ifundefined{acs@#1#2}{% + \acs@warning{Unknown option `#2' for key #1}% + }{% + \@nameuse{acs@#1#2}% + }% +} +\newif\ifacs@abbreviations +\newif\ifacs@articletitle +\newif\ifacs@biochem +\newif\ifacs@chaptertitle +\newif\ifacs@email +\newif\ifacs@hyperref +\newif\ifacs@keywords +\newif\ifacs@super +\define@key{acs}{abbreviations}[true]{% + \acs@keyval@bool{abbreviations}{#1}% +} +\define@key{acs}{articletitle}[true]{% + \acs@keyval@bool{articletitle}{#1}% +} +\define@key{acs}{biochem}[true]{% + \acs@keyval@bool{biochem}{#1}% +} +\define@key{acs}{chaptertitle}[true]{% + \acs@keyval@bool{chaptertitle}{#1}% +} +\define@key{acs}{email}[true]{% + \acs@keyval@bool{email}{#1}% +} +\define@key{acs}{hyperref}[true]{% + \acs@keyval@bool{hyperref}{#1}% +} +\define@key{acs}{keywords}[true]{% + \acs@keyval@bool{keywords}{#1}% +} +\define@key{acs}{super}[true]{% + \acs@keyval@bool{super}{#1}% +} +\define@key{acs}{usetitle}[true]{% + \acs@keyval@bool{articletitle}{#1}% +} +\newcommand*\acs@journal{jacsat} +\newcommand*\acs@layout{traditional} +\newcommand*\acs@manuscript{article} +\newcommand*\acs@maxauthors{15} +\define@key{acs}{journal}{% + \def\acs@journal{#1}% +} +\define@key{acs}{layout}{% + \def\acs@layout{#1}% +} +\define@key{acs}{manuscript}{% + \def\acs@manuscript{#1}% +} +\define@key{acs}{maxauthors}{% + \def\acs@maxauthors{#1}% +} +\newif\ifacs@etal@truncate +\define@key{acs}{etalmode}{% + \acs@ifundefined{acs@etal@#1}{% + \acs@warning{% + Unknown value `#1' for\MessageBreak etalmode option% + }% + }{% + \@nameuse{acs@etal@#1}% + }% +} +\newcommand*\acs@etal@firstonly{\acs@etal@truncatefalse} +\newcommand*\acs@etal@truncate{\acs@etal@truncatetrue} +\define@key{acs}{biochemistry}{% + \setkeys{acs}{biochem = #1}% +} +\define@key{acs}{biblabel}{% + \acs@ifundefined{acs@biblabel@#1}{% + \acs@warning{% + Unknown value `#1' for\MessageBreak biblabel option% + }% + }{% + \acs@activate@biblabel{\@nameuse{acs@biblabel@#1}}% + }% +} +\newcommand*\acs@activate@biblabel{} +\let\acs@activate@biblabel\AtEndOfClass +\AtEndOfClass{\let\acs@activate@biblabel\@firstofone} +\newcommand*\acs@biblabel@brackets{\def\bibnumfmt##1{(##1)}} +\newcommand*\acs@biblabel@fullstop{\def\bibnumfmt##1{##1.}} +\newcommand*\acs@biblabel@period{\def\bibnumfmt##1{##1.}} +\newcommand*\acs@biblabel@plain{\def\bibnumfmt##1{##1}} +\setkeys{acs}{ + email = true, + super = true +} +\ProcessOptionsX* +\newcommand*\acs@manuscript@communication{communication} +\newcommand*\acs@manuscript@letter{letter} +\newcommand*\acs@manuscript@note{note} +\newcommand*\acs@manuscript@review{review} +\newcommand*\acs@manuscript@suppinfo{suppinfo} +\newcommand*\acs@niib@create{% + \@namedef{ver@notes2bib.sty}{% + 2009/04/20 v1.6a Integrating notes into the bibliography (achemso + version) + }% + \@ifundefined{c@bibnote}{\newcounter{bibnote}}{} + \def\thebibnote{% + Note-\the\value{bibnote}% + }% + \DeclareRobustCommand*{\bibnote}[1][\thebibnote]{% + \stepcounter{bibnote}% + \def\acs@niib@after@text{\cite{##1}}% + \acs@niib@text{##1}% + }% + \DeclareRobustCommand*{\bibnotemark}[1][\thebibnote]{% + \stepcounter{bibnote}% + \cite{##1}% + }% + \DeclareRobustCommand*{\bibnotetext}[1][\thebibnote]{% + \let\acs@niib@after@text\relax + \acs@niib@text{##1}% + }% + \newcommand*\printbibnotes{% + \ifnum\the\value{bibnote}>\z@\relax + \nocite{achemso-control}% + \acs@bibliography{acs-\jobname}% + \fi + }% +} +\newcommand*\acs@niib@after@text{} +\newcommand*\acs@niib@text{% + \@bsphack + \if@filesw + \expandafter\acs@niib@write + \else + \expandafter\acs@niib@no@write + \fi +} +\newcommand*\acs@niib@write[1]{% + \begingroup + \let\do\@makeother + \dospecials + \catcode`\{ 1\relax + \catcode`\} 2\relax + \acs@niib@write@aux@i{#1}% +} +\newcommand*\acs@niib@write@aux@i[1]{% + \long\def\@tempa##1{% + \def\@tempa{##1}% + \@onelevel@sanitize\@tempa + \expandafter\endgroup + \expandafter\def\expandafter\@tempa\expandafter{\@tempa}% + \acs@niib@write@aux@ii{#1}% + }% + \catcode`\^^M 10\relax + \@tempa +} +\newcommand*\acs@niib@write@aux@ii[1]{% + \immediate\write\acs@bib@file{% + @Misc\string{#1,^^J% + \space\space note = \string{\@tempa\string},^^J% + \string}^^J% + }% + \@esphack + \acs@niib@after@text +} +\newcommand\acs@niib@no@write[2]{% + \@esphack + \acs@niib@after@text +} +\AtBeginDocument{ + \def\nmv@natbib@detect{% + \ifNAT@super + \expandafter\acs@nmv@activate + \else + \expandafter\acs@autonote + \fi + } +} +\newcommand*\acs@nmv@activate{% + \let\nmv@citex@nat\@citex + \let\@citex\nmv@citex + \let\nmv@cite\cite + \renewcommand*{\cite}[2][]{% + \nmv@ifmtarg{##1}{% + \nmv@citetrue + \nmv@cite{##2}% + }{% + \nocite{##2}% + \bibnote{Ref.~\citenum{##2}, ##1}% + }% + }% +} +\newcommand*\acs@autonote{% + \let\nmv@cite\cite + \renewcommand*{\cite}[2][]{% + \nmv@ifmtarg{##1}{% + \nmv@cite{##2}% + }{% + \nocite{##2}% + \bibnote{Ref.~\citenum{##2}, ##1}% + }% + }% +} +\newwrite\acs@bib@file +\newcommand*\acs@bib@message{% + This is an auxiliary file used by the `achemso' bundle.^^J% + This file may safely be deleted. It will be recreated as required.^^J +} +\newcommand*\acs@bib@name{acs-\jobname.bib} +\newcommand*\acs@bib@write{% + \if@filesw + \expandafter\acs@bib@write@aux + \fi +} +\AtBeginDocument{\acs@bib@write} +\newcommand*\acs@bib@write@aux{% + \immediate\openout\acs@bib@file\acs@bib@name\relax + \immediate\write\acs@bib@file{\acs@bib@message}% + \edef\@tempa##1##2{% + \space\space##1\space = "##2",^^J% + }% + \immediate\write\acs@bib@file{% + @Control\string{% + achemso-control,^^J% + \@tempa{ctrl-article-title\space}{% + \ifacs@articletitle yes\else no\fi + }% + \@tempa{ctrl-chapter-title\space}{% + \ifacs@chaptertitle yes\else no\fi + }% + \@tempa{ctrl-etal-number\space\space\space}{\acs@maxauthors}% + \@tempa{ctrl-etal-firstonly}{% + \ifacs@etal@truncate no\else yes\fi + }% + \string}^^J% + }% + \immediate\write\@auxout{% + \string\citation\string{achemso-control\string}% + }% + \AtEndDocument{% + \immediate\closeout\acs@bib@file\relax + }% +} +\AtBeginDocument{% + \let\acs@bibliography\bibliography + \def\bibliography#1{% + \acs@bibliography{acs-\jobname,#1}% + }% +} +\AtBeginDocument{ + \providecommand{\latin}[1]{#1} +} +\setkeys{acs}{ + abbreviations = false, + articletitle = false, + biblabel = brackets, + biochem = false, + etalmode = firstonly, + keywords = false, + maxauthors = 15, + super = true +} +\acs@niib@create +\RequirePackage[margin=2.54cm]{geometry} +\RequirePackage{ + caption, + float, + graphicx, + setspace, + url +} +\ifacs@hyperref + \expandafter\RequirePackage +\else + \expandafter\@gobble +\fi + {hyperref} +\AtBeginDocument{\doublespacing} +\renewcommand*{\title}[2][]{% + \gdef\acs@title@short{#1}% + \gdef\@title{#2}% + \ifx\acs@title@short\@empty + \global\let\acs@title@short\@title + \fi +} +\@onlypreamble\title +\newcount\acs@author@cnt +\newcount\acs@affil@cnt +\newcount\acs@affil@alt@cnt +\newcount\acs@footnote@cnt +\newcount\acs@affil@marker@cnt +\def\author#1{% + \global\advance\acs@author@cnt\@ne\relax + \expandafter\gdef\csname @author@\@roman\acs@author@cnt\endcsname{#1}% + \begingroup + \advance\acs@affil@cnt\@ne + \expandafter\xdef\csname @author@affil@\@roman + \acs@author@cnt\endcsname + {\the\acs@affil@cnt}% + \endgroup +} +\@onlypreamble\author +\def\and{% + \acs@warning{% + \string\and\space not used by the achemso class: please see + the\MessageBreak package documentation for details% + }% +} +\def\thanks{% + \acs@warning{% + \string\thanks\space not used by the achemso class: please see + the\MessageBreak the package documentation for details% + }% +} +\newcommand*\affiliation[2][\relax]{% + \ifnum\acs@author@cnt>\z@\relax + \acs@affil@ifdup{#2}{% + \acs@affil@swap{#2}% + }{% + \global\advance\acs@affil@cnt\@ne\relax + \expandafter\gdef\csname @address@\@roman\acs@affil@cnt\endcsname + {#2}% + \ifx\relax#1\relax + \expandafter\gdef\csname @affil@\@roman\acs@affil@cnt\endcsname + {#2}% + \else + \expandafter\gdef\csname @affil@\@roman\acs@affil@cnt\endcsname + {#1}% + \fi + }% + \else + \acs@warning{Affiliation with no author}% + \fi +} +\@onlypreamble\affiliation +\newcommand*\acs@affil@ifdup[1]{% + \begingroup + \def\@tempa{#1}% + \@tempswafalse + \@tempcnta\z@\relax + \acs@affil@ifdup@aux + \if@tempswa + \aftergroup\@firstoftwo + \else + \aftergroup\@secondoftwo + \fi + \endgroup +} +\newcommand*\acs@affil@ifdup@aux{% + \advance\@tempcnta\@ne\relax + \expandafter\expandafter\expandafter\def\expandafter\expandafter + \expandafter\@tempb\expandafter\expandafter\expandafter + {\csname @address@\@roman\@tempcnta\endcsname}% + \ifx\@tempa\@tempb + \expandafter\@tempswatrue + \else + \ifnum\@tempcnta<\acs@affil@cnt\relax + \expandafter\expandafter\expandafter\acs@affil@ifdup@aux + \fi + \fi +} +\newcommand*\acs@affil@swap[1]{% + \begingroup + \def\@tempa{#1}% + \@tempcnta\z@\relax + \@tempcntb\z@\relax + \acs@affil@ifdup@aux + \advance\acs@affil@cnt\@ne\relax + \acs@affil@swap@aux + \endgroup +} +\newcommand*\acs@affil@swap@aux{% + \advance\@tempcntb\@ne\relax + \expandafter\ifnum\csname @author@affil@\@roman\@tempcntb\endcsname + = \acs@affil@cnt\relax + \expandafter\xdef\csname @author@affil@\@roman\@tempcntb\endcsname{% + \the\@tempcnta + }% + \fi + \ifnum\@tempcntb<\acs@author@cnt\relax + \expandafter\acs@affil@swap@aux + \fi +} +\newcommand*\alsoaffiliation[2][\relax]{% + \ifnum\acs@author@cnt>\z@\relax + \acs@affil@ifdup{#2}{% + \acs@alsoaffil@find{#2}% + }{% + \global\advance\acs@affil@cnt\@ne\relax + \@tempcnta\acs@affil@cnt\relax + \expandafter\gdef\csname @address@\@roman\acs@affil@cnt\endcsname + {#2}% + \ifx\relax#1\relax + \expandafter\gdef\csname @affil@\@roman\acs@affil@cnt\endcsname + {#2}% + \else + \expandafter\gdef\csname @affil@\@roman\acs@affil@cnt\endcsname + {#1}% + \fi + }% + \@ifundefined{@author@alsoaffil@\@roman\acs@author@cnt}{% + \expandafter\xdef\csname @author@alsoaffil@\@roman\acs@author@cnt + \endcsname{\the\@tempcnta}% + }{% + \expandafter\xdef\csname @author@alsoaffil@\@roman\acs@author@cnt + \endcsname{% + \csname @author@alsoaffil@\@roman\acs@author@cnt\endcsname + ,\the\@tempcnta + }% + }% + \else + \acs@warning{Affiliation with no author}% + \fi +} +\newcommand*\acs@alsoaffil@find[1]{% + \begingroup + \def\@tempa{#1}% + \@tempcnta\z@\relax + \@tempcntb\z@\relax + \acs@affil@ifdup@aux + \expandafter\endgroup + \expandafter\@tempcnta\the\@tempcnta\relax +} +\newcommand*\altaffiliation[1]{% + \ifnum\acs@author@cnt>\z@\relax + \begingroup + \acs@altaffil@ifdup{#1}{% + \expandafter\xdef\csname @author@altaffil@\@roman\acs@author@cnt + \endcsname{\the\@tempcnta}% + }{% + \global\advance\acs@affil@alt@cnt\@ne\relax + \expandafter\gdef\csname @altaffil@\@roman\acs@affil@alt@cnt + \endcsname{#1}% + \expandafter\xdef\csname @author@altaffil@\@roman\acs@author@cnt + \endcsname{\the\acs@affil@alt@cnt}% + }% + \endgroup + \else + \acs@warning{Affiliation with no author}% + \fi +} +\@onlypreamble\altaffiliation +\newcommand*\acs@altaffil@ifdup[1]{% + \def\@tempa{#1}% + \@tempswafalse + \@tempcnta\z@\relax + \ifnum\acs@affil@alt@cnt>\z@\relax + \expandafter\acs@altaffil@ifdup@aux + \fi + \if@tempswa + \expandafter\@firstoftwo + \else + \expandafter\@secondoftwo + \fi +} +\newcommand*\acs@altaffil@ifdup@aux{% + \advance\@tempcnta\@ne\relax + \expandafter\expandafter\expandafter\def\expandafter\expandafter + \expandafter\@tempb\expandafter\expandafter\expandafter + {\csname @altaffil@\@roman\@tempcnta\endcsname}% + \ifx\@tempa\@tempb + \expandafter\@tempswatrue + \else + \ifnum\@tempcnta<\acs@affil@alt@cnt\relax + \expandafter\expandafter\expandafter\acs@altaffil@ifdup@aux + \fi + \fi +} +\newcommand*\email[1]{% + \ifnum\acs@author@cnt>\z@\relax + \expandafter\gdef\csname @email@\@roman\acs@author@cnt\endcsname + {#1}% + \else + \acs@warning{E-mail with no author}% + \fi +} +\@onlypreamble\email +\newcommand*\fax[1]{% + \ifnum\acs@author@cnt>\z@\relax + \expandafter\gdef\csname @fax@\@roman\acs@author@cnt\endcsname + {#1}% + \else + \acs@warning{Fax number with no author}% + \fi +} +\@onlypreamble\fax +\newcommand*\phone[1]{% + \ifnum\acs@author@cnt>\z@\relax + \expandafter\gdef\csname @phone@\@roman\acs@author@cnt\endcsname + {#1}% + \else + \acs@warning{Phone number with no author}% + \fi +} +\@onlypreamble\phone +\newcommand*\abbreviations[1]{% + \gdef\@abbreviations{#1}% +} +\newcommand*\@abbreviations{} +\@onlypreamble\abbreviations +\newcommand*\keywords[1]{% + \gdef\@keywords{#1}% +} +\newcommand*\@keywords{} +\@onlypreamble\keywords +\newcommand*\acs@abbreviations@print{% + \ifx\@abbreviations\@empty\else + \section*{Abbreviations} + \@abbreviations + \par + \fi +} +\newcommand*\acs@keywords@print{% + \ifx\@keywords\@empty\else + \section*{Keywords} + \@keywords + \par + \fi +} +\newcommand*\acs@title@short@print{% + \section*{Running header} + \acs@title@short + \par +} +\newlength\acs@space@pre@title +\setlength\acs@space@pre@title{2em} +\newlength\acs@space@post@title +\setlength\acs@space@post@title{1.5em} +\newlength\acs@space@post@author +\setlength\acs@space@post@author{1em} +\newlength\acs@space@post@address +\setlength\acs@space@post@address{1em} +\newlength\acs@space@post@email +\setlength\acs@space@post@email{1.5em} +\newlength\acs@maketitle@width +\setlength\acs@maketitle@width{\textwidth} +\newcommand*\affilsize{\normalsize} +\newcommand*\authorsize{\large} +\newcommand*\emailsize{\normalsize} +\newcommand*\titlesize{\LARGE} +\newcommand*\affilfont{\itshape} +\newcommand*\authorfont{\sffamily} +\newcommand*\emailfont{} +\newcommand*\titlefont{\bfseries\sffamily} +\newcommand*{\ps@acs}{} +\let\ps@acs\ps@plain +\def\@maketitle{% + \pagestyle{acs}% + \ifnum\acs@author@cnt<\z@\relax + \acs@warning{No authors defined: At least one author is required}% + \fi + \newpage + \null + \vspace*{\acs@space@pre@title}% + \begin{center} + \begin{minipage}{\acs@maketitle@width} + \begin{center} + {% + \titlefont + \titlesize + \let\@fnsymbol\acs@author@fnsymbol + \let\footnote\acs@title@footnote + \acs@maketitle@suppinfo \@title + \acs@title@footnote@check + \global\acs@footnote@cnt\c@footnote\relax + \@maketitle@title@hook + \par + }% + \vspace*{\acs@space@post@title}% + {% + \authorsize + \authorfont + \frenchspacing + \acs@author@list + \par + }% + \vspace*{\acs@space@post@author}% + {% + \affilsize + \affilfont + \acs@address@list + \par + }% + \vspace*{\acs@space@post@address}% + {% + \emailsize + \emailfont + \ifacs@email + \expandafter\acs@contact@details + \fi + }% + \vspace*{\acs@space@post@email}% + \end{center} + \end{minipage} + \end{center}% +} +\newcommand*\@maketitle@title@hook{} +\newcommand*\acs@maketitle@suppinfo{% + \ifx\acs@manuscript\acs@manuscript@suppinfo + Supporting information for:\\ + \fi +} +\newcommand*\acs@title@footnote[1]{% + \footnotemark + \g@addto@macro\@thanks@hook{% + \footnotetext{#1}% + }% +} +\newcommand\acs@title@footnote@check{% + \ifx\@thanks@hook\@empty\else + \expandafter\gdef\expandafter\@thanks@hook\expandafter{% + \expandafter\begingroup + \expandafter\let\expandafter\@fnsymbol\expandafter + \acs@author@fnsymbol + \@thanks@hook + \endgroup + }% + \fi +} +\newcommand*\acs@contact@details{% + { \sffamily E-mail: \acs@email@list }% + \acs@number@list +} +\def\@thanks{% + \@thanks@hook + \ifnum\acs@affil@cnt>\@ne\relax + \expandafter\acs@affil@list + \else + \ifnum\acs@affil@alt@cnt>\z@\relax + \expandafter\expandafter\expandafter\acs@affil@list + \fi + \fi +} +\newcommand*\@thanks@hook{} +\newcommand*\acs@author@list{% + \@tempcnta\z@\relax + \ifnum\acs@author@cnt=\z@\relax\else + \expandafter\acs@author@list@main + \fi + \acs@author@list@star +} +\newcommand*\acs@author@list@star{% + \g@addto@macro\@thanks@hook{% + \setcounter{footnote}{1}% + \footnotetext{To whom correspondence should be addressed}% + }% +} +\newcommand*\acs@author@footnotes{} +\newcommand*\acs@author@list@main{% + \advance\@tempcnta\@ne\relax + \def\acs@author@footnotes{}% + \acs@author@list@and + \space + \@nameuse{@author@\@roman\@tempcnta}% + \acs@author@list@comma + \acs@author@star + \acs@author@affil + \acs@author@affil@also + \acs@author@affil@alt + \ifx\@empty\acs@author@footnotes\else + \textsuperscript{\acs@author@footnotes}% + \fi + \ifnum\@tempcnta<\acs@author@cnt\relax + \expandafter\acs@author@list@main + \fi +} +\newcommand*\acs@author@list@and{% + \ifnum\acs@author@cnt=\@ne\relax\else + \ifnum\@tempcnta=\acs@author@cnt\relax + \space and% + \fi + \fi +} +\newcommand*\acs@author@list@comma{% + \ifnum\acs@author@cnt>\tw@\relax + \ifnum\@tempcnta<\acs@author@cnt\relax + ,% + \fi + \fi +} +\newcommand*\acs@author@star{% + \acs@ifundefined{@email@\@roman\@tempcnta}{}{% + \acs@author@star@aux + }% +} +\newcommand*\acs@author@star@aux{% + \protected@edef\acs@author@footnotes{% + \acs@author@fnsymbol{\z@}% + \ifnum\acs@affil@cnt>\@ne\relax + ,% + \else + \ifnum\acs@affil@alt@cnt>\z@\relax + ,% + \fi + \fi + }% +} +\newcommand*\acs@author@affil{% + \acs@ifundefined{% + @affil@\@roman\csname @author@affil@\@roman\@tempcnta\endcsname + }{% + \acs@warning{% + No affiliation given for author\MessageBreak + \@nameuse{@author@\@roman\@tempcnta}% + }% + }{% + \acs@author@affil@aux + }% +} +\newcommand*\acs@author@affil@aux{% + \ifnum\acs@affil@cnt>\@ne\relax + \expandafter\acs@affil@marker@cnt\csname @author@affil@\@roman + \@tempcnta\endcsname\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \protected@edef\acs@author@footnotes{% + \acs@author@footnotes + \acs@author@fnsymbol{\acs@affil@marker@cnt}% + }% + \else + \ifnum\acs@affil@alt@cnt>\z@\relax + \acs@affil@marker@cnt\@ne\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \protected@edef\acs@author@footnotes{% + \acs@author@footnotes + \acs@author@fnsymbol{\acs@affil@marker@cnt}% + }% + \fi + \fi +} +\newcommand*\acs@author@affil@also{% + \acs@ifundefined{@author@alsoaffil@\@roman\@tempcnta}{}{% + \acs@author@affil@also@aux + }% +} +\newcommand*\acs@author@affil@also@aux{% + \expandafter\@for\expandafter\@tempa\expandafter:\expandafter + =\csname @author@alsoaffil@\@roman\@tempcnta\endcsname\do{% + \acs@affil@marker@cnt\@tempa\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \protected@edef\acs@author@footnotes{% + \acs@author@footnotes + ,% + \acs@author@fnsymbol{\acs@affil@marker@cnt}% + }% + }% +} +\newcommand*\acs@author@affil@alt{% + \acs@ifundefined{@author@altaffil@\@roman\@tempcnta}{}{% + \acs@author@affil@alt@aux + }% +} +\newcommand*\acs@author@affil@alt@aux{% + \expandafter\acs@affil@marker@cnt + \csname @author@altaffil@\@roman\@tempcnta\endcsname\relax + \advance\acs@affil@marker@cnt\acs@affil@cnt\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \protected@edef\acs@author@footnotes{% + \acs@author@footnotes + ,% + \acs@author@fnsymbol{\acs@affil@marker@cnt}% + }% +} +\newcommand*{\acs@author@fnsymbol}[1]{% + \ensuremath{% + \expandafter\acs@author@fnsymbol@aux\expandafter{\number#1 }% + }% +} +\newcommand*{\acs@author@fnsymbol@aux}[1]{% + \ifnum#1>10 % + \expandafter\acs@author@fnsymbol@loop + \else + \expandafter\acs@author@fnsymbol@symbol + \fi + {#1}% +} +\newcommand*{\acs@author@fnsymbol@loop}[1]{% + \acs@author@fnsymbol@loop@aux@i#1% +} +\newcommand*{\acs@author@fnsymbol@loop@aux@i}[2]{% + \acs@author@fnsymbol@symbol{\ifnum#2=0 10\else #2\fi}% + \expandafter\acs@author@fnsymbol@loop@aux@ii\romannumeral #1000Q{}% + {\acs@author@fnsymbol@symbol{\ifnum#2=0 10\else #2\fi}}% +} +\newcommand*{\acs@author@fnsymbol@loop@aux@ii}[1]{% + \@nameuse{acs@author@fnsymbol@loop@aux@#1}% +} +\def\acs@author@fnsymbol@loop@aux@m#1Q#2#3{% + \acs@author@fnsymbol@loop@aux@ii#1Q{#2#3}{#3}% +} +\newcommand*{\acs@author@fnsymbol@loop@aux@Q}[2]{#1} +\newcommand*{\acs@author@fnsymbol@symbol}[1]{% + \ifcase #1 *\or + \dagger\or + \ddagger\or + \P\or + \S\or + \|\or + \bot\or + \#\or + @\or + \triangle\or + \nabla + \fi +} +\newcommand*\acs@address@list{% + \@tempcnta\z@\relax + \ifnum\acs@affil@cnt>\z@\relax + \acs@address@list@aux + \else + \acs@warning{% + No affiliations: at least one affiliation is needed% + }% + \fi +} +\newcommand*\acs@address@list@aux{% + \advance\@tempcnta\@ne\relax + \ifnum\acs@affil@cnt>\@ne\relax + \ifnum\@tempcnta=\acs@affil@cnt\relax + and + \fi + \fi + \@nameuse{@address@\@roman\@tempcnta}% + \ifnum\@tempcnta<\acs@affil@cnt\relax + , + \expandafter\acs@address@list@aux + \fi +} +\newcommand*\acs@fnsymbol@org{} +\newcommand*\acs@affil@list{% + \let\acs@fnsymbol@org\@fnsymbol + \let\@fnsymbol\acs@author@fnsymbol + \@tempcnta\z@\relax + \@tempcntb\z@\relax + \ifnum\acs@affil@cnt>\@ne\relax + \expandafter\acs@affil@list@aux + \else + \ifnum\acs@affil@alt@cnt>\z@\relax + \acs@affil@marker@cnt\@ne\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \footnotetext[\acs@affil@marker@cnt]{\@affil@i}% + \@tempcnta\@ne\relax + \fi + \fi + \ifnum\acs@affil@alt@cnt>\z@\relax + \expandafter\acs@affil@alt@list + \fi + \let\@fnsymbol\acs@fnsymbol@org +} +\newcommand*\acs@affil@list@aux{% + \advance\@tempcnta\@ne\relax + \acs@affil@marker@cnt\@tempcnta\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \footnotetext[\acs@affil@marker@cnt]{% + \@nameuse{@affil@\@roman\@tempcnta}% + }% + \ifnum\@tempcnta<\acs@affil@cnt\relax + \expandafter\acs@affil@list@aux + \fi +} +\newcommand*\acs@affil@alt@list{% + \advance\@tempcntb\@ne\relax + \acs@ifundefined{@altaffil@\@roman\@tempcntb}{}{% + \acs@altaffil@foot@aux + } + \ifnum\@tempcntb<\acs@author@cnt\relax + \expandafter\acs@affil@alt@list + \fi +} +\newcommand*\acs@altaffil@foot@aux{% + \advance\@tempcnta\@ne\relax + \acs@affil@marker@cnt\@tempcnta\relax + \advance\acs@affil@marker@cnt\acs@footnote@cnt\relax + \footnotetext[\acs@affil@marker@cnt]{% + \@nameuse{@altaffil@\@roman\@tempcntb}% + }% +} +\newcommand*\acs@email@list@font{\sf} +\newcommand*\acs@email@list{% + \begingroup + \def\UrlFont{\acs@email@list@font}% + \@tempcnta\z@\relax + \@tempcntb\z@\relax + \acs@email@list@aux + \ifnum\@tempcntb=\z@\relax + \acs@warning{% + No e-mail given:\MessageBreak + at lest one author must have a contact e-mail% + }% + \fi + \endgroup +} +\newcommand*\acs@email@list@aux{% + \advance\@tempcnta\@ne\relax + \ifnum\@tempcnta>\acs@author@cnt\relax\else + \acs@ifundefined{@email@\@roman\@tempcnta}{}{% + \advance\@tempcntb\@ne\relax + \ifnum\@tempcntb>\@ne\relax + ; + \fi + \expandafter\expandafter\expandafter\url\expandafter + \expandafter\expandafter{% + \csname @email@\@roman\@tempcnta\endcsname + }% + }% + \expandafter\acs@email@list@aux + \fi +} +\newcommand*\acs@number@list{% + \begingroup + \acs@number@list@aux@i{phone}% + \let\@tempb\@tempa + \acs@number@list@aux@i{fax}% + \ifx\@tempa\@empty\else + \ifx\@tempb\@empty\else + \protected@edef\@tempa{% + \@tempb.\space\@tempa + }% + \fi + \fi + \ifx\@tempa\@empty\else + \par + \@tempa + \fi + \endgroup +} +\newcommand*\acs@number@list@aux@i[1]{% + \def\@tempa{}% + \@tempcnta\z@\relax + \def\acs@number@list@aux@ii{% + \advance\@tempcnta\@ne\relax + \ifnum\@tempcnta>\acs@author@cnt\relax\else + \acs@ifundefined{@#1@\@roman\@tempcnta}{}{% + \acs@ifundefined{@email@\@roman\@tempcnta}{}{% + \ifx\@tempa\@empty + \edef\@tempa{% + \@nameuse{@#1@\@roman\@tempcnta}% + }% + \else + \edef\@tempa{% + \@tempa + ; + \@nameuse{@#1@\@roman\@tempcnta}% + }% + \fi + }% + }% + \expandafter\acs@number@list@aux@ii + \fi + }% + \acs@number@list@aux@ii + \ifx\@tempa\@empty\else + \protected@edef\@tempa{% + \MakeUppercase#1: \@tempa + }% + \fi +} +\newcommand*\acs@number@list@aux@ii{} +\g@addto@macro\endabstract{% + \aftergroup\acs@abstract@extras +} +\newcommand*{\acs@abstract@extras}{% + \ifacs@abbreviations + \acs@abbreviations@print + \par + \fi + \ifacs@keywords + \acs@keywords@print + \par + \fi +} +\newcommand*\acs@maketitle@extras{% + \acs@maketitle@extras@hook +} +\newcommand*\acs@maketitle@extras@hook{} +\g@addto@macro{\maketitle}{\acs@maketitle@extras} +\g@addto@macro{\document}{\maketitle} +\newfloat{scheme}{htbp}{los} +\floatname{scheme}{Scheme} +\newfloat{chart}{htbp}{loc} +\floatname{chart}{Chart} +\newfloat{graph}{htbp}{loh} +\floatname{graph}{Graph} +\newcommand*\schemename{Scheme} +\newcommand*\chartname{Chart} +\newcommand*\graphname{Graph} +\floatplacement{table}{htbp} +\floatplacement{figure}{htbp} +\floatstyle{plaintop} +\restylefloat{table} +\let\acs@floatboxreset\@floatboxreset +\def\@floatboxreset{% + \centering + \acs@floatboxreset +} +\newcommand*\plainref{} +\AtBeginDocument{\let\plainref\ref} +\newcommand*\acs@section{} +\let\acs@section\section +\newcommand*\acs@subsection{} +\let\acs@subsection\subsection +\newcommand*\acs@subsubsection{} +\let\acs@subsubsection\subsubsection +\newcommand*\acs@startsection{} +\let\acs@startsection\@startsection +\newcommand*\acs@startsection@alt[6]{% + \if@noskipsec \leavevmode \fi + \par + \@tempskipa #4\relax + \@afterindenttrue + \ifdim\@tempskipa<\z@\relax + \@tempskipa -\@tempskipa \@afterindentfalse + \fi + \if@nobreak + \everypar{}% + \else + \addpenalty\@secpenalty + \addvspace\@tempskipa + \fi + \@ifstar{% + \@ssect{#3}{#4}{#5}{#6}% + }{% + \@ssect{#3}{#4}{#5}{#6}% + }% +} +\newcommand*\acs@sections@none{% + \@ifstar{% + \acs@sections@none@aux + }{% + \acs@sections@none@aux + }% +} +\newcommand*\acs@sections@none@aux[2][]{% + \acs@warning{% + (Sub)section `#2' ignored% + }% +} +\newcommand*\SectionNumbersOff{% + \let\@startsection\acs@startsection@alt +} +\@onlypreamble\SectionNumbersOff +\newcommand*\SectionNumbersOn{% + \let\@startsection\acs@startsection +} +\@onlypreamble\SectionNumbersOn +\newcommand*\SectionsOff{% + \let\section\acs@sections@none + \let\subsection\acs@sections@none + \let\subsubsection\acs@sections@none +} +\@onlypreamble\SectionsOff +\newcommand*\SectionsOn{% + \let\section\acs@section + \let\subsection\acs@subsection + \let\subsubsection\acs@subsubsection +} +\@onlypreamble\SectionsOn +\newenvironment{acknowledgement}{% + \acs@subsection*{\acknowledgementname}% +}{} +\newenvironment{suppinfo}{% + \acs@subsection*{\suppinfoname}% + \acs@collect\acs@suppinfo@print +}{} +\newcommand\acs@suppinfo@print[1]{% + #1 + This material is available free of charge via the Internet at + \url{http://pubs.acs.org/}. +} +\newcommand*\acknowledgementname{Acknowledgement} +\AtEndOfClass{% + \def\bibsection{% + \acs@subsection*{\refname}% + }% +} +\newcommand*\suppinfoname{Supporting Information Available} +\newcommand*\acs@abstract{} +\let\acs@abstract\abstract +\newcommand*\acs@endabstract{} +\let\acs@endabstract\endabstract +\begingroup + \catcode`{ \active + \catcode`} 12\relax + \catcode`( 1\relax + \catcode`) 2\relax + \gdef\acs@abstract@start(% + \acs@warning(% + Abstract not allowed for this\MessageBreak + manuscript type + )% + \@bsphack + \catcode`{ \active + \catcode`} 12\relax + \let\end\fi + \let{\acs@abstract@end% } + \iffalse + )%{ + \gdef\acs@abstract@end#1}(% + \def\@tempa(#1)% + \ifx\@tempa\@currenvir + \@Esphack\endgroup + \if@ignore + \global\@ignorefalse + \ignorespaces + \fi + \else + \expandafter\acs@abstract@iffalse + \fi + ) +\endgroup +\newcommand*\acs@iffalse{\iffalse} +\newcommand*\AbstractOff{% + \let\abstract\acs@abstract@start + \let\endabstract\acs@abstract@end +} +\@onlypreamble\AbstractOff +\newcommand*\AbstractOn{% + \let\abstract\acs@abstract + \let\endabstract\acs@endabstract +} +\@onlypreamble\AbstractOn +\newtoks\acs@collect@toks +\newtoks\acs@collect@empty@toks +\newcommand*\acs@collect@begins{} +\newcommand*\acs@collect@content{} +\newcommand\acs@collect[1]{% + \acs@collect@toks{% + \expandafter#1\expandafter{\the\acs@collect@toks}% + }% + \edef\acs@collect@content{% + \the\acs@collect@toks + \noexpand\end{\@currenvir}% + }% + \acs@collect@toks\acs@collect@empty@toks + \def\acs@collect@begins{b}% + \begingroup + \expandafter\let\csname\@currenvir\endcsname\acs@collect@aux + \edef\acs@collect@content{% + \expandafter\noexpand\csname\@currenvir\endcsname + }% + \acs@collect@content +} +\newcommand*\acs@collect@aux{} +\long\def\acs@collect@aux#1\end#2{% + \edef\acs@collect@begins{% + \acs@collect@begins@#1\begin\end + \expandafter\@gobble\acs@collect@begins + }% + \ifx\@empty\acs@collect@begins + \endgroup + \@checkend{#2}% + \acs@collect@body{#1}% + \else + \acs@collect@body{#1\end{#2}}% + \fi + \acs@collect@content +} +\newcommand*\acs@collect@begins@{} +\long\def\acs@collect@begins@#1\begin#2{% + \ifx\end#2\else + b\expandafter\acs@collect@begins@ + \fi +} +\newcommand\acs@collect@body[1]{% + \global\acs@collect@toks\expandafter{\the\acs@collect@toks#1}% +} +\newcommand\acs@abstract@print[1]{% + \global\long\def\acs@abstract@text{% + \if@twocolumn + \@restonecoltrue\onecolumn + \else + \@restonecolfalse\newpage + \fi + \acs@section*{Abstract}% + #1% + \if@restonecol + \twocolumn + \else + \newpage + \fi + }% + \AtEndDocument{\acs@abstract@text}% +} +\newcommand{\acs@tocentry@print}[1]{% + \gdef\acs@tocentry@text{#1}% + \AtEndDocument{% + \if@twocolumn + \@restonecoltrue\onecolumn + \else + \@restonecolfalse\newpage + \fi + \acs@tocentry@print@aux + \if@restonecol + \twocolumn + \else + \newpage + \fi + }% +} +\newcommand*{\acs@tocentry@print@aux}{% + \acs@section*{\tocentryname}% + \tocsize + \sffamily + \singlespacing + \begin{center} + \fbox + {% + \begin{minipage}{\acs@tocentry@height} + \vbox to \acs@tocentry@width{\acs@tocentry@text}% + \end{minipage}% + }% + \end{center}% + } +\newlength{\acs@tocentry@height} +\newlength{\acs@tocentry@width} +\setlength{\acs@tocentry@height}{9 cm} +\setlength{\acs@tocentry@width}{3.5 cm} +\newenvironment{tocentry}{\acs@collect\acs@tocentry@print}{} +\newcommand*\tocentryname{Graphical TOC Entry} +\newcommand*\tocsize{% + \@setfontsize\tocsize\@viiipt\@ixpt +} +\newcommand*\acs@type@list{article,communication,suppinfo} +\newcommand*\acs@type@default{article} +\newcommand*\acs@type@check{% + \@tempswafalse + \@for\@tempa:=\acs@type@list\do{% + \ifx\@tempa\acs@manuscript + \expandafter\@tempswatrue + \fi + }% + \if@tempswa\else + \acs@warning{% + Invalid manuscript type \acs@manuscript:\MessageBreak + changed to default type \acs@type@default + }% + \let\acs@manuscript\acs@type@default + \fi +} +\def\refname{% + \ifnum\the\value{bibnote}>\z@\relax + Notes and + \fi + References% +} +\newcommand*\acs@setkeys{\setkeys{acs}} +\let\acs@killabstract\AbstractOff +\let\acs@killsecs\SectionsOff +\newcommand*\acs@validtype[2][article]{% + \def\acs@type@default{#1}% + \def\acs@type@list{#2}% +} +\newcommand*\acs@par{} +\let\acs@par\par +\newcommand*\acs@layout@shared{% + \AtBeginDocument{\singlespacing}% + \twocolumn + \tolerance=2000\relax + \emergencystretch=10pt\relax + \geometry{ + letterpaper, + top = 12.7mm, + bottom = 16.8mm, + left = 19.3mm, + right = 19.3mm + }% + \setlength{\columnsep}{8.1mm}% + \setlength{\parindent}{3.3mm}% + \renewenvironment{acknowledgement}{% + \def\@tempa{acknowledgement}% + \ifx\@currenvir\@tempa + \let\par\relax + \acksize + \vspace{6pt}% + \textbf{\acknowledgementname}% + \else + \acs@subsection*{\acknowledgementname}% + \fi + }{% + \acs@par + }% + \renewenvironment{suppinfo}{% + \def\@tempa{suppinfo}% + \ifx\@currenvir\@tempa + \expandafter\acs@suppinfo@aux + \else + \acs@subsection*{\suppinfoname}% + \fi + }{% + \acs@par + }% +} +\newcommand*\acs@suppinfo@aux{% + \let\par\relax + \suppsize + \vspace{6pt}% + \textbf{\suppinfoname:} + \acs@collect\acs@suppinfo@print +} +\newcommand*\acksize{\normalsize} +\newcommand*\suppsize{\normalsize} +\newcommand*\acs@layout@nine{% + \def\@xipt{11}% + \long\def\normalsize{% + \@setfontsize\normalsize\@ixpt\@xipt + }% + \normalsize + \let\@listi\@listI + \abovedisplayskip 5\p@ \@plus2\p@ \@minus 5\p@\relax + \abovedisplayshortskip \z@ \@plus3\p@\relax + \belowdisplayshortskip 3\p@ \@plus3\p@ \@minus 3\p@\relax + \belowdisplayskip\abovedisplayskip\relax + \abovecaptionskip 5\p@\relax + \intextsep 7\p@ \@plus 2\p@ \@minus 2\p@\relax +} +\newcommand*\acs@layout@ten{% + \long\def\normalsize{% + \@setfontsize\normalsize\@xpt\@xiipt + }% + \normalsize + \@setfontsize\normalsize\@xpt\@xiipt + \let\@listi\@listI + \abovedisplayskip 10\p@ \@plus2\p@ \@minus5\p@\relax + \abovedisplayshortskip \z@ \@plus3\p@\relax + \belowdisplayshortskip 6\p@ \@plus3\p@ \@minus3\p@\relax + \belowdisplayskip \abovedisplayskip\relax +} +\InputIfFileExists{\acs@journal.cfg}{}{% + \acs@warning{% + Unknown journal `\acs@journal':\MessageBreak + using default configuration JACSAT% + }% + \input{jacsat.cfg}% +} +\acs@type@check +\ifx\acs@manuscript\acs@manuscript@note + \SectionsOff +\fi +\ifx\acs@manuscript\acs@manuscript@review + \SectionsOn + \SectionNumbersOn +\fi +\ifx\acs@manuscript\acs@manuscript@suppinfo + \setkeys{acs}{maxauthors = 0} + \def\thepage{S\arabic{page}} + \renewcommand*\thefigure{S\@arabic\c@figure} + \renewcommand*\thescheme{S\@arabic\c@scheme} + \renewcommand*\thetable{S\@arabic\c@table} + \AtBeginDocument + {% + \renewcommand*\citenumfont[1]{S#1}% + \renewcommand*\bibnumfmt[1]{(S#1)}% + } +\fi +\begingroup + \def\@tempa{twocolumn} + \ifx\acs@layout\@tempa + \aftergroup\acs@layout@shared + \fi + \def\@tempa{two-column} + \ifx\acs@layout\@tempa + \aftergroup\acs@layout@shared + \fi +\endgroup +\ifacs@super + \RequirePackage[sort&compress,numbers,super]{natbib} +\else + \RequirePackage[sort&compress,numbers,round]{natbib} + \def\citenumfont{\textit} +\fi +\RequirePackage{natmove} +\IfFileExists{mciteplus.sty}{% + \RequirePackage{mciteplus} + \providecommand*{\@mciteNatbibCiteCmdList}{}% + \edef\@tempa{\noexpand\in@{citenum}{\@mciteNatbibCiteCmdList}}% + \@tempa + \ifin@ + \else + \edef\@mciteNatbibCiteCmdList{\@mciteNatbibCiteCmdList,citenum}% + \fi + \def\@mciteSubRef[##1]##2{\plainref{\@mcitereflabelprefix:##1:##2}} +}{} +\newcommand*\acs@bibstyle{achemso} +\ifacs@biochem + \def\acs@bibstyle{biochem} + \bibliographystyle{biochem} +\else + \bibliographystyle{achemso} +\fi +\newcommand*\acs@bibliographystyle{} +\let\acs@bibliographystyle\bibliographystyle +\def\bibliographystyle#1{% + \acs@warning{\string\bibliographystyle\space ignored}% + \expandafter\acs@bibliographystyle\expandafter{\acs@bibstyle}% +} +%% +%% Originally developed by Mats Dahlgren +%% Copyright (C) 1996-1998 by Mats Dahlgren +%% Copyright (C) 2008-2014 by +%% Joseph Wright +%% +%% Part of this bundle is derived from cite.sty, to which the +%% following license applies: +%% Copyright (C) 1989-2009 by Donald Arseneau +%% These macros may be freely transmitted, reproduced, or +%% modified provided that this notice is left intact. +%% +%% It may be distributed and/or modified under the conditions of +%% the LaTeX Project Public License (LPPL), either version 1.3c of +%% this license or (at your option) any later version. The latest +%% version of this license is in the file: +%% +%% http://www.latex-project.org/lppl.txt +%% +%% This work is "maintained" (as per LPPL maintenance status) by +%% Joseph Wright. +%% +%% This work consists of the file achemso.dtx +%% and the derived files achemso.cls, +%% achemso.ins, +%% achemso.pdf, +%% achemso.sty, +%% achemso-demo.bib, +%% achemso-demo.tex, +%% natmove.sty and +%% a number of configuration files. +%% +%% +%% End of file `achemso.cls'. diff --git a/achemso.sty b/achemso.sty new file mode 100644 index 0000000..3a9daa3 --- /dev/null +++ b/achemso.sty @@ -0,0 +1,362 @@ +%% +%% This is file `achemso.sty', +%% generated with the docstrip utility. +%% +%% The original source files were: +%% +%% achemso.dtx (with options: `package') +%% ---------------------------------------------------------------- +%% achemso --- Support for submissions to American Chemical Society +%% journals +%% E-mail: joseph.wright@morningstar2.co.uk +%% Released under the LaTeX Project Public License v1.3c or later +%% See http://www.latex-project.org/lppl.txt +%% ---------------------------------------------------------------- +%% +\NeedsTeXFormat{LaTeX2e} + +\ProvidesPackage{achemso} + [2014/08/18 v3.8k Support for ACS journals] +\@ifclassloaded{achemso}{% + \PackageInfo{achemso}{% + You have already loaded the `achemso' class:\MessageBreak + loading the package will abort% + }% + \endinput +}{% + \PackageInfo{achemso}{% + When writing a submission to an ACS journal, please\MessageBreak + use the achemso document class% + }% +} +\newcommand*\acs@warning{\PackageWarning{achemso}} +\newcommand*\acs@ifundefined[1]{% + \begingroup\expandafter\expandafter\expandafter\endgroup + \expandafter\ifx\csname #1\endcsname\relax + \expandafter\@firstoftwo + \else + \expandafter\@secondoftwo + \fi +} +\RequirePackage{xkeyval} +\newcommand*\acs@keyval@bool[2]{% + \acs@ifundefined{acs@#1#2}{% + \acs@warning{Unknown option `#2' for key #1}% + }{% + \@nameuse{acs@#1#2}% + }% +} +\newif\ifacs@abbreviations +\newif\ifacs@articletitle +\newif\ifacs@biochem +\newif\ifacs@chaptertitle +\newif\ifacs@email +\newif\ifacs@hyperref +\newif\ifacs@keywords +\newif\ifacs@super +\define@key{acs}{abbreviations}[true]{% + \acs@keyval@bool{abbreviations}{#1}% +} +\define@key{acs}{articletitle}[true]{% + \acs@keyval@bool{articletitle}{#1}% +} +\define@key{acs}{biochem}[true]{% + \acs@keyval@bool{biochem}{#1}% +} +\define@key{acs}{chaptertitle}[true]{% + \acs@keyval@bool{chaptertitle}{#1}% +} +\define@key{acs}{email}[true]{% + \acs@keyval@bool{email}{#1}% +} +\define@key{acs}{hyperref}[true]{% + \acs@keyval@bool{hyperref}{#1}% +} +\define@key{acs}{keywords}[true]{% + \acs@keyval@bool{keywords}{#1}% +} +\define@key{acs}{super}[true]{% + \acs@keyval@bool{super}{#1}% +} +\define@key{acs}{usetitle}[true]{% + \acs@keyval@bool{articletitle}{#1}% +} +\newcommand*\acs@journal{jacsat} +\newcommand*\acs@layout{traditional} +\newcommand*\acs@manuscript{article} +\newcommand*\acs@maxauthors{15} +\define@key{acs}{journal}{% + \def\acs@journal{#1}% +} +\define@key{acs}{layout}{% + \def\acs@layout{#1}% +} +\define@key{acs}{manuscript}{% + \def\acs@manuscript{#1}% +} +\define@key{acs}{maxauthors}{% + \def\acs@maxauthors{#1}% +} +\newif\ifacs@etal@truncate +\define@key{acs}{etalmode}{% + \acs@ifundefined{acs@etal@#1}{% + \acs@warning{% + Unknown value `#1' for\MessageBreak etalmode option% + }% + }{% + \@nameuse{acs@etal@#1}% + }% +} +\newcommand*\acs@etal@firstonly{\acs@etal@truncatefalse} +\newcommand*\acs@etal@truncate{\acs@etal@truncatetrue} +\define@key{acs}{biochemistry}{% + \setkeys{acs}{biochem = #1}% +} +\define@key{acs}{biblabel}{% + \acs@ifundefined{acs@biblabel@#1}{% + \acs@warning{% + Unknown value `#1' for\MessageBreak biblabel option% + }% + }{% + \acs@activate@biblabel{\@nameuse{acs@biblabel@#1}}% + }% +} +\newcommand*\acs@activate@biblabel{} +\let\acs@activate@biblabel\AtEndOfPackage +\AtEndOfPackage{\let\acs@activate@biblabel\@firstofone} +\newcommand*\acs@biblabel@brackets{\def\bibnumfmt##1{(##1)}} +\newcommand*\acs@biblabel@fullstop{\def\bibnumfmt##1{##1.}} +\newcommand*\acs@biblabel@period{\def\bibnumfmt##1{##1.}} +\newcommand*\acs@biblabel@plain{\def\bibnumfmt##1{##1}} +\setkeys{acs}{ + email = true, + super = true +} +\ProcessOptionsX* +\newcommand*\acs@manuscript@communication{communication} +\newcommand*\acs@manuscript@letter{letter} +\newcommand*\acs@manuscript@note{note} +\newcommand*\acs@manuscript@review{review} +\newcommand*\acs@manuscript@suppinfo{suppinfo} +\newcommand*\acs@niib@create{% + \@namedef{ver@notes2bib.sty}{% + 2009/04/20 v1.6a Integrating notes into the bibliography (achemso + version) + }% + \@ifundefined{c@bibnote}{\newcounter{bibnote}}{} + \def\thebibnote{% + Note-\the\value{bibnote}% + }% + \DeclareRobustCommand*{\bibnote}[1][\thebibnote]{% + \stepcounter{bibnote}% + \def\acs@niib@after@text{\cite{##1}}% + \acs@niib@text{##1}% + }% + \DeclareRobustCommand*{\bibnotemark}[1][\thebibnote]{% + \stepcounter{bibnote}% + \cite{##1}% + }% + \DeclareRobustCommand*{\bibnotetext}[1][\thebibnote]{% + \let\acs@niib@after@text\relax + \acs@niib@text{##1}% + }% + \newcommand*\printbibnotes{% + \ifnum\the\value{bibnote}>\z@\relax + \nocite{achemso-control}% + \acs@bibliography{acs-\jobname}% + \fi + }% +} +\newcommand*\acs@niib@after@text{} +\newcommand*\acs@niib@text{% + \@bsphack + \if@filesw + \expandafter\acs@niib@write + \else + \expandafter\acs@niib@no@write + \fi +} +\newcommand*\acs@niib@write[1]{% + \begingroup + \let\do\@makeother + \dospecials + \catcode`\{ 1\relax + \catcode`\} 2\relax + \acs@niib@write@aux@i{#1}% +} +\newcommand*\acs@niib@write@aux@i[1]{% + \long\def\@tempa##1{% + \def\@tempa{##1}% + \@onelevel@sanitize\@tempa + \expandafter\endgroup + \expandafter\def\expandafter\@tempa\expandafter{\@tempa}% + \acs@niib@write@aux@ii{#1}% + }% + \catcode`\^^M 10\relax + \@tempa +} +\newcommand*\acs@niib@write@aux@ii[1]{% + \immediate\write\acs@bib@file{% + @Misc\string{#1,^^J% + \space\space note = \string{\@tempa\string},^^J% + \string}^^J% + }% + \@esphack + \acs@niib@after@text +} +\newcommand\acs@niib@no@write[2]{% + \@esphack + \acs@niib@after@text +} +\AtBeginDocument{ + \def\nmv@natbib@detect{% + \ifNAT@super + \expandafter\acs@nmv@activate + \else + \expandafter\acs@autonote + \fi + } +} +\newcommand*\acs@nmv@activate{% + \let\nmv@citex@nat\@citex + \let\@citex\nmv@citex + \let\nmv@cite\cite + \renewcommand*{\cite}[2][]{% + \nmv@ifmtarg{##1}{% + \nmv@citetrue + \nmv@cite{##2}% + }{% + \nocite{##2}% + \bibnote{Ref.~\citenum{##2}, ##1}% + }% + }% +} +\newcommand*\acs@autonote{% + \let\nmv@cite\cite + \renewcommand*{\cite}[2][]{% + \nmv@ifmtarg{##1}{% + \nmv@cite{##2}% + }{% + \nocite{##2}% + \bibnote{Ref.~\citenum{##2}, ##1}% + }% + }% +} +\newwrite\acs@bib@file +\newcommand*\acs@bib@message{% + This is an auxiliary file used by the `achemso' bundle.^^J% + This file may safely be deleted. It will be recreated as required.^^J +} +\newcommand*\acs@bib@name{acs-\jobname.bib} +\newcommand*\acs@bib@write{% + \if@filesw + \expandafter\acs@bib@write@aux + \fi +} +\AtBeginDocument{\acs@bib@write} +\newcommand*\acs@bib@write@aux{% + \immediate\openout\acs@bib@file\acs@bib@name\relax + \immediate\write\acs@bib@file{\acs@bib@message}% + \edef\@tempa##1##2{% + \space\space##1\space = "##2",^^J% + }% + \immediate\write\acs@bib@file{% + @Control\string{% + achemso-control,^^J% + \@tempa{ctrl-article-title\space}{% + \ifacs@articletitle yes\else no\fi + }% + \@tempa{ctrl-chapter-title\space}{% + \ifacs@chaptertitle yes\else no\fi + }% + \@tempa{ctrl-etal-number\space\space\space}{\acs@maxauthors}% + \@tempa{ctrl-etal-firstonly}{% + \ifacs@etal@truncate no\else yes\fi + }% + \string}^^J% + }% + \immediate\write\@auxout{% + \string\citation\string{achemso-control\string}% + }% + \AtEndDocument{% + \immediate\closeout\acs@bib@file\relax + }% +} +\AtBeginDocument{% + \let\acs@bibliography\bibliography + \def\bibliography#1{% + \acs@bibliography{acs-\jobname,#1}% + }% +} +\AtBeginDocument{ + \providecommand{\latin}[1]{#1} +} +\ifacs@super + \RequirePackage[sort&compress,numbers,super]{natbib} +\else + \RequirePackage[sort&compress,numbers,round]{natbib} + \def\citenumfont{\textit} +\fi +\RequirePackage{natmove} +\IfFileExists{mciteplus.sty}{% + \RequirePackage{mciteplus} + \providecommand*{\@mciteNatbibCiteCmdList}{}% + \edef\@tempa{\noexpand\in@{citenum}{\@mciteNatbibCiteCmdList}}% + \@tempa + \ifin@ + \else + \edef\@mciteNatbibCiteCmdList{\@mciteNatbibCiteCmdList,citenum}% + \fi +}{} +\newcommand*\acs@bibstyle{achemso} +\ifacs@biochem + \def\acs@bibstyle{biochem} + \bibliographystyle{biochem} +\else + \bibliographystyle{achemso} +\fi +\newcommand*\acs@bibliographystyle{} +\let\acs@bibliographystyle\bibliographystyle +\def\bibliographystyle#1{% + \acs@warning{\string\bibliographystyle\space ignored}% + \expandafter\acs@bibliographystyle\expandafter{\acs@bibstyle}% +} +\AtBeginDocument{% + \@ifpackageloaded{notes2bib}{}{% + \acs@niib@create + }% +} +%% +%% Originally developed by Mats Dahlgren +%% Copyright (C) 1996-1998 by Mats Dahlgren +%% Copyright (C) 2008-2014 by +%% Joseph Wright +%% +%% Part of this bundle is derived from cite.sty, to which the +%% following license applies: +%% Copyright (C) 1989-2009 by Donald Arseneau +%% These macros may be freely transmitted, reproduced, or +%% modified provided that this notice is left intact. +%% +%% It may be distributed and/or modified under the conditions of +%% the LaTeX Project Public License (LPPL), either version 1.3c of +%% this license or (at your option) any later version. The latest +%% version of this license is in the file: +%% +%% http://www.latex-project.org/lppl.txt +%% +%% This work is "maintained" (as per LPPL maintenance status) by +%% Joseph Wright. +%% +%% This work consists of the file achemso.dtx +%% and the derived files achemso.cls, +%% achemso.ins, +%% achemso.pdf, +%% achemso.sty, +%% achemso-demo.bib, +%% achemso-demo.tex, +%% natmove.sty and +%% a number of configuration files. +%% +%% +%% End of file `achemso.sty'. diff --git a/inoraj.cfg b/inoraj.cfg new file mode 100644 index 0000000..9014fde --- /dev/null +++ b/inoraj.cfg @@ -0,0 +1,62 @@ +%% +%% This is file `jpcbfk.cfg', +%% generated with the docstrip utility. +%% +%% The original source files were: +%% +%% achemso.dtx (with options: `jpcbfk') +%% ---------------------------------------------------------------- +%% achemso --- Support for submissions to American Chemical Society +%% journals +%% E-mail: joseph.wright@morningstar2.co.uk +%% Released under the LaTeX Project Public License v1.3c or later +%% See http://www.latex-project.org/lppl.txt +%% ---------------------------------------------------------------- +%% + +\ProvidesFile{jpcbfk.cfg} + [2014/08/18 v3.8k achemso configuration: J. Phys. Chem. B] +\def\acs@type@list{article,suppinfo} +\setkeys{acs}{ + articletitle = true, + etalmode = truncate, + maxauthors = 10, + keywords = true +} +\SectionNumbersOff +\captionsetup[table]{labelfont=bf,textfont=bf} +\g@addto@macro{\maketitle}{\newpage} +%% +%% Originally developed by Mats Dahlgren +%% Copyright (C) 1996-1998 by Mats Dahlgren +%% Copyright (C) 2008-2014 by +%% Joseph Wright +%% +%% Part of this bundle is derived from cite.sty, to which the +%% following license applies: +%% Copyright (C) 1989-2009 by Donald Arseneau +%% These macros may be freely transmitted, reproduced, or +%% modified provided that this notice is left intact. +%% +%% It may be distributed and/or modified under the conditions of +%% the LaTeX Project Public License (LPPL), either version 1.3c of +%% this license or (at your option) any later version. The latest +%% version of this license is in the file: +%% +%% http://www.latex-project.org/lppl.txt +%% +%% This work is "maintained" (as per LPPL maintenance status) by +%% Joseph Wright. +%% +%% This work consists of the file achemso.dtx +%% and the derived files achemso.cls, +%% achemso.ins, +%% achemso.pdf, +%% achemso.sty, +%% achemso-demo.bib, +%% achemso-demo.tex, +%% natmove.sty and +%% a number of configuration files. +%% +%% +%% End of file `jpcbfk.cfg'. diff --git a/natmove.sty b/natmove.sty new file mode 100644 index 0000000..51e59ec --- /dev/null +++ b/natmove.sty @@ -0,0 +1,152 @@ +%% +%% This is file `natmove.sty', +%% generated with the docstrip utility. +%% +%% The original source files were: +%% +%% achemso.dtx (with options: `natmove') +%% ---------------------------------------------------------------- +%% achemso --- Support for submissions to American Chemical Society +%% journals +%% E-mail: joseph.wright@morningstar2.co.uk +%% Released under the LaTeX Project Public License v1.3c or later +%% See http://www.latex-project.org/lppl.txt +%% ---------------------------------------------------------------- +%% +\NeedsTeXFormat{LaTeX2e} + +\ProvidesPackage{natmove} + [2010/01/15 v1.1a Automatic citation moving with natbib] +\RequirePackage{natbib} +\newcommand*\nmv@ifmtarg{} +\newcommand*\nmv@xifmtarg{} +\begingroup + \catcode`\Q 3\relax + \long\gdef\nmv@ifmtarg#1{% + \nmv@xifmtarg#1QQ\@secondoftwo\@firstoftwo\@nil + } + \long\gdef\nmv@xifmtarg#1#2Q#3#4#5\@nil{#4} +\endgroup +\newif\ifnmv@cite +\newcommand*\nmv@citex{% + \ifnmv@cite + \expandafter\nmv@citex@moving + \else + \expandafter\nmv@citex@nat + \fi +} +\newcommand*\nmv@after{} +\newcommand*\nmv@citex@moving{} +\def\nmv@citex@moving[#1][#2]#3{% + \leavevmode + \skip@\lastskip\relax + \unskip + \begingroup + \def\nmv@after{\nmv@citex@nat[#1][#2]{#3}}% + \global\nmv@citefalse + \nmv@citex@get@next\relax +} +\newcommand*\nmv@citex@end{% + \nmv@after + \endgroup +} +\newcommand*\nmv@citex@get@next[1]{% + \futurelet\nmv@citex@next\nmv@citex@punct +} +\newcommand*\nmv@citex@punct{% + \let\nmv@citex@loop\nmv@citex@end + \ifx\nmv@citex@next.\relax + \ifnum\spacefactor<\nmv@citex@sfac\else + \expandafter\expandafter\expandafter\nmv@citex@punct@undouble + \fi + \fi + \expandafter\nmv@citex@punct@aux\natmovechars\@nil + \nmv@citex@loop +} +\newcommand*\nmv@citex@punct@undouble{% + \let\nmv@citex@next\relax + \let\nmv@citex@loop\nmv@citex@get@next +} +\newcommand*\nmv@citex@loop{} +\newcommand*\nmv@citex@punct@aux[1]{% + \ifx\nmv@citex@next#1\@empty + #1% + \let\nmv@citex@loop\nmv@citex@get@next + \fi + \ifx#1\@nil\else + \expandafter\nmv@citex@punct@aux + \fi +} +\mathchardef\nmv@citex@sfac3000\relax +\expandafter\def\expandafter\frenchspacing\expandafter{% + \frenchspacing + \mathchardef\nmv@citex@sfac1001\relax + \sfcode`\.\nmv@citex@sfac + \sfcode`\?\nmv@citex@sfac + \sfcode`\!\nmv@citex@sfac +} +\ifnum\sfcode`\.=\@m + \frenchspacing +\fi +\newcommand*\nmv@citex@nat{} +\newcommand*\nmv@activate{% + \let\nmv@citex@nat\@citex + \let\@citex\nmv@citex + \let\nmv@cite\cite + \renewcommand*{\cite}[2][]{% + \nmv@ifmtarg{##1}{% + \nmv@citetrue + \nmv@cite{##2}% + }{% + \nmv@citefalse + \nmv@cite[##1]{##2}}% + }% +} +\newcommand*\nmv@natbib@detect{% + \@ifpackageloaded{natbib}{% + \ifNAT@super + \expandafter\nmv@activate + \fi + }{% + \PackageInfo{natmove}{% + The natbib package is not loaded.\MessageBreak + Loading natmove will do nothing + }% + }% +} +\AtBeginDocument{\nmv@natbib@detect} +\newcommand*\natmovechars{.,;:} +%% +%% Originally developed by Mats Dahlgren +%% Copyright (C) 1996-1998 by Mats Dahlgren +%% Copyright (C) 2008-2014 by +%% Joseph Wright +%% +%% Part of this bundle is derived from cite.sty, to which the +%% following license applies: +%% Copyright (C) 1989-2009 by Donald Arseneau +%% These macros may be freely transmitted, reproduced, or +%% modified provided that this notice is left intact. +%% +%% It may be distributed and/or modified under the conditions of +%% the LaTeX Project Public License (LPPL), either version 1.3c of +%% this license or (at your option) any later version. The latest +%% version of this license is in the file: +%% +%% http://www.latex-project.org/lppl.txt +%% +%% This work is "maintained" (as per LPPL maintenance status) by +%% Joseph Wright. +%% +%% This work consists of the file achemso.dtx +%% and the derived files achemso.cls, +%% achemso.ins, +%% achemso.pdf, +%% achemso.sty, +%% achemso-demo.bib, +%% achemso-demo.tex, +%% natmove.sty and +%% a number of configuration files. +%% +%% +%% End of file `natmove.sty'. diff --git a/paper_UAR.tex b/paper_UAR.tex new file mode 100644 index 0000000..b275c2a --- /dev/null +++ b/paper_UAR.tex @@ -0,0 +1,772 @@ +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% This is a (brief) model paper using the achemso class +%% The document class accepts keyval options, which should include +%% the target journal and optionally the manuscript type. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\documentclass[journal = jpcafh ,manuscript=article]{achemso} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% Place any additional packages needed here. Only include packages +%% which are essential, to avoid problems later. Do NOT use any +%% packages which require e-TeX (for example etoolbox): the e-TeX +%% extensions are not currently available on the ACS conversion +%% servers. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\usepackage[version=3]{mhchem} % Formula subscripts using \ce{} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% If issues arise when submitting your manuscript, you may want to +%% un-comment the next line. This provides information on the +%% version of every file you have used. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%%\listfiles + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% Place any additional macros here. Please use \newcommand* where +%% possible, and avoid layout-changing macros (which are not used +%% when typesetting). +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\newcommand*\mycommand[1]{\texttt{\emph{#1}}} + +%% Added by author +\usepackage{graphicx} +\usepackage{tikz} +\usepackage{xcolor} +\usepackage{pgfplots} +\usepackage{epstopdf} +\usepackage{multirow} +\usepackage{array} + +\newcommand{\red}[1]{{\color{red}#1}} +\newcommand{\blue}[1]{{\color{blue}#1}} + +\usetikzlibrary{calc,trees,positioning,arrows,chains,shapes.geometric,% + decorations.pathreplacing,decorations.pathmorphing,shapes,% + matrix,shapes.symbols,shadows} + +\newcolumntype{C}[1]{>{\centering\let\newline\\\arraybackslash\hspace{0pt}}m{#1}} + +\graphicspath{{images/}} + +\definecolor{cream}{RGB}{222,217,201} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% Meta-data block +%% --------------- +%% Each author should be given as a separate \author command. +%% +%% Corresponding authors should have an e-mail given after the author +%% name as an \email command. Phone and fax numbers can be given +%% using \phone and \fax, respectively; this information is optional. +%% +%% The affiliation of authors is given after the authors; each +%% \affiliation command applies to all preceding authors not already +%% assigned an affiliation. +%% +%% The affiliation takes an option argument for the short name. This +%% will typically be something like "University of Somewhere". +%% +%% The \altaffiliation macro should be used for new address, etc. +%% On the other hand, \alsoaffiliation is used on a per author basis +%% when authors are associated with multiple institutions. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\author{Kseniia A. Korchagina} +\affiliation[Universit\'{e} de Toulouse (UPS) and CNRS]{Laboratoire de Chimie et Physique Quantiques LCPQ/IRSAMC, Université\'e de Toulouse (UPS) and CNRS, 118 Route de Narbonne, F-31062 Toulouse, France} +\author{Fernand Spiegelman} +\affiliation[Universit\'{e} de Toulouse (UPS) and CNRS]{Laboratoire de Chimie et Physique Quantiques LCPQ/IRSAMC, Université\'e de Toulouse (UPS) and CNRS, 118 Route de Narbonne, F-31062 Toulouse, France} +\author{J\'er\^ome Cuny} +\affiliation[Universit\'{e} de Toulouse (UPS) and CNRS]{Laboratoire de Chimie et Physique Quantiques LCPQ/IRSAMC, Université\'e de Toulouse (UPS) and CNRS, 118 Route de Narbonne, F-31062 Toulouse, France} +\email{jerome.cuny@irsamc.ups-tlse.fr} +\phone{+33 (0)5 61 55 68 36} +\fax{+33 (0)5 61 55 60 65} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The document title should be given as usual. Some journals require +%% a running title from the author: this should be supplied as an +%% optional argument to \title. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\title[An \textsf{achemso} demo] +{Molecular Dynamics Study of the Collision-Induced Reaction of H with CO on Small Water Clusters\footnote{Molecular Dynamics Study of the Collision-Induced Reaction of H with CO on Small Water Clusters}} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% Some journals require a list of abbreviations or keywords to be +%% supplied. These should be set up here, and will be printed after +%% the title and author information, if needed. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%\abbreviations{PES,ISM,COSAC,FT-IR,MRCI+Q,CCD,CCSD(T),RCCSD(T),UCCSD(T),MP2, MBPT, BSSE, ZPE, DFT, SCC-DFTB, CM3, MD, MDPT} +\keywords{Molecular Dynamics, SCC-DFTB, HCO Radical, Collision-Induced Reaction, Water Clusters} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The manuscript does not need to include \maketitle, which is +%% executed automatically. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{document} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The "tocentry" environment can be used to create an entry for the +%% graphical table of contents. It is given here as some journals +%% require that it is printed as part of the abstract page. It will +%% be automatically moved as appropriate. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{tocentry} +\includegraphics[scale=0.1]{TOC.png} +\end{tocentry} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The abstract environment will automatically gobble the contents +%% if an abstract is not used by the target journal. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{abstract} +The successive hydrogenation of CO is supposed to be the main mechanism leading +to the formation of complex oxygenated species in the interstellar medium, possibly +mediated by ice layers or ice grains. In order to simulate the dynamical influence +of a water environment on the first step of the hydrogenation process, we achieve +molecular dynamics simulations of the reactive collision of H with CO adsorbed on +water clusters in the framework of the self-consistent-charge density functional +based tight-binding approach (SCC-DFTB) to calculate Potential Energy Surfaces. The reaction +probabilities and the reactive cross sections are determined for water cluster sizes +up to ten water molecules. The collision results are analyzed in terms of different reaction pathways: +reactive or non-reactive, sticking or desorption of the products or reactants. We show that the +HCO radical, although potentially formed as an intermediate whatever the size of the +water cluster, is significantly stabilized for cluster sizes larger than one water molecule +and may remain adsorbed on water clusters with more than three molecules. This behavior +is shown to be linked to the dissipation of the collision energy into vibrational +excitation of the water cluster. +\end{abstract} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% Start the main part of the manuscript here. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\section{Introduction} +In recent decades, the chemical composition of the Universe has been continuously +investigated, essentially via absorption spectroscopy with background stars as lamps. +It was established that all chemical elements and molecules in the InterStellar Medium +(ISM) are concentrated in three main kind of clouds: diffuse, translucent and dense clouds. +The chemical composition of these clouds is dominated by the abundance of hydrogen, +the concentration of helium is about 10\%, and other elements such as carbon, nitrogen, +and oxygen are also present in the ratio $\sim$10$^{-3}$-10$^{-4}$ of the hydrogen +density \cite{Festou}. In addition to these elemental abundances, a large number of +simple (H$_{2}$, CH, CH$^{+}$, CN, C$_{2}$, OH, CO, HCO, HCO$^{+}$, HCN, C$_{3}$) +and more complex organic molecules (CH$_{3}$OH, C$_{2}$H$_{5}$OH, C$_{2}$H$_{5}$CN, +CH$_{3}$COCH$_{3}$, CH$_{4}$, NH$_{3}$, H$_{2}$O, \textit{etc.}) were +detected \cite{churchwell1,thompson1,schutte1,grim1,cordiner1,kaiser1,herbst1,herbst2}. +Although most of those detected compounds can form through gas-phase processes, +some of them, in particular H$_{2}$, H$_{2}$O and CH$_{3}$OH are assumed to form +through chemical reactions between atoms and molecules at the surface of grains.\cite{Horn2004,Oberg2016} +The composition and structure of the outer layers of these grains can be of different nature: organic, +ice-mineral mixture, pure water-ice and ice-dust mixture grains depending, for instance, +on the incidence of UV radiation and cosmic rays\cite{schulz1}, or the atomic densities of +the environment where they are present.\cite{Taquet2012} In 2015, a unique set of experimental data on the chemical +composition of the surface of the 67P/Churyumov-Gerasimenko comet were obtained through +various instruments of the Philae module \cite{wright1,goesmann1,spohn1}. For instance, +mass spectroscopy measurements performed by the Ptolemy instrument detected H$_{2}$O, +CO$_{2}$ and CO as main volatile species in a ratio of 10:2:$>$1 \cite{wright1}. +The COmetary SAmpling and Composition (COSAC) experiment also provided a picture of +the organic composition of the comet surface.\cite{goesmann1} Sixteen molecules, +belonging to two main molecular groups, were identified by the COSAC instrument. +The first group includes the H$_{2}$O and CO molecules and the subsequent oxygen-containing +organic species such as alcohols and carbonyls. The second group includes CH$_{4}$ +and NH$_{3}$ (although not confidently identified) that lead to the formation of +nitrogen-containing organic species (amines, nitriles, amides, and isocyanates) \cite{goesmann1}. +These results provide a rather accurate picture of the 67P chemical composition +(and potentially of other comets) but no accurate information is provided on the +mechanisms that lead to the formation of these complex organic compounds in the +ISM \cite{loomis1,kalvans1}. This is an important question to address for both +theoreticians and experimentalists in order to strengthen our understanding of +the ISM chemistry. + +Currently, it is supposed that the main mechanism leading to the oxygenated +compound formation in grain mantles and comets is a process of successive +hydrogenation of CO, occurring by the consecutive addition of hydrogen +atoms:\cite{book1,tielens1,crovisier1,watanabe2,watanabe3,hidaka1} + +\begin{center} +CO $\xrightarrow{\text{H}}$ HCO $\xrightarrow{\text{H}}$ H$_{2}$CO $\xrightarrow{\text{H}}$ H$_{3}$CO $\xrightarrow{\text{H}}$ CH$_{3}$OH +\end{center} + +This mechanism has been the subject of various experimental studies. For instance, Hiraoka +and co-workers studied the reaction of H atoms with a solid CO thin film in the 10-25~K +temperature range.\cite{hiraoka1,hiraoka2} From these experiments, the authors +concluded that -(i)- H atoms do not diffuse into the CO matrix, the reaction proceeds only +at the surface -(ii)- the primary reaction product H$_{2}$CO is prone to polymerization -(iii)- the +rate constant for the first and second steps of this reaction is small at cryogenic temperature -(iv)- +formaldehyde and methanol were formed. Later, Pirim \textit{et al.} studied the same reaction +in two different ways, by simple hydrogenation of a CO surface and by co-injection of CO molecules +and H atoms \cite{pirim1}. In the former case, nothing was formed at 3~K whereas H$_{2}$CO and +CH$_{3}$OH were detected at 10~K by Fourier Transform InfraRed (FT-IR) spectroscopy. In contrast, +the co-injection at 10~K leads to the formation of both the HCO and H$_{3}$CO radicals as major +products. However, as mentioned above, the hydrogenation of CO in the ISM is likely to +occur at the surface of ice-coated grains. To understand such a situation, some groups also studied +the H addition on CO in a H$_{2}$O-CO ice \cite{watanabe1,watanabe2,pirim2}. They showed that +water molecules play two important roles in this process. On the one hand, they exhibit a catalytic +role by helping to overcome the activation barriers. On the other hand, water molecules create new +chemical pathways that enhance the reactivity. + +To complement these experimental measurements, theoretical studies were conducted on the different +steps of the sequential hydrogenation reaction of carbon monoxide, isolated or in the presence of +water molecules \cite{woon1,cao1,woon2,rimola1,peters1,Peters2013a}. In particular, the geometric and +energetic characteristics of reactants, transition states and products involved in this mechanism +have been the subject of various calculations at high levels of theory. For instance, Woon observed +that, at the QCISD$^{*}$ level of theory, the barrier of the H + H$_{2}$CO $\longrightarrow$ +CH$_{3}$O reaction is reduced from 5.04~kcal.mol$^{-1}$ for isolated CO to 4.18~kcal.mol$^{-1}$ +when adding four water molecules \cite{woon1}. The intermediates of this multi-step mechanism, +such as HCO and H$_{2}$CO, may also undergo isomerization under certain conditions and were +thus also investigated \cite{zanchet1,schreiner1,peters1}. + +However, it is certainly the first step of the sequential hydrogenation of CO that has deserved +the largest attention in the literature as it is a crucial step towards the formation of complex +oxygenated species \cite{woon1,cao1,woon2,rimola1,peters1,Peters2013a,adams1,bitter1,werner1,werner2,cho1,romanowski}. +For instance, Woon compared the structures and frequencies of CO and HCO as well as the energetics +of the H + CO $\longrightarrow$ HCO reaction (without water) with various high-accuracy schemes +such as Restricted Coupled Cluster RCCSD(T) or Davidson-corrected internally-contracted +MRCI+Q methods \cite{woon2}. The author showed that at the aug-cc-pVTZ level, MRCI+Q and +RCCSD(T) methods with ZPE correction slightly overestimate barrier heights, 4.1 and 4.2~kcal.mol$^{-1}$ +respectively, in comparison with the experimental value 2.0$\pm$0.4 kcal.mol$^{-1}$. In contrast, +the MRCI+Q and RCCSD(T) results for the reaction ergicity, -13.7 and -13.8 kcal.mol$^{-1}$, respectively, +are in a very good agreement with the experimental value of -14 kcal.mol$^{-1}$. Those calculations +were recently revisited by Peters \textit{et al.} using state-of-the-art multireference \textit{ab initio} +methods to study the energetics of the HCO/DCO formation and dissociation processes.\cite{Peters2013a} +In addition to their theoretical interest, the results of those and other \textit{ab initio} calculations +can be further used as input values for larger scale numerical simulations. For instance, the GRAINOBLE model +was used by Rimola \textit{et al.} \cite{rimola1} to describe the distribution of the H$_{2}$CO and CH$_{3}$OH +ice abundances. It leads to abundance values that are in a good agreement with the experimental data. +Although extremely informative, high-precision \textit{ab initio} wavefunction type calculations are only +achievable for very small systems. In a similar way, Density Functional Theory (DFT) can describe larger species +and has been applied to systems containing up to 32 water molecules but only in a static framework.\cite{rimola1} +Although a good description of the Potential Energy Surface (PES) of the various species +involved in the mechanism is of primary importance, a dynamical simulation of the hydrogenation +process at the molecular level is also desirable. Indeed, size and temperature effects of the water +substrate, influence of its morphology and diffusion of species at the surface of nanograins can +be important contributing factors that can hardly be included in highly accurate quantum chemical +calculations although they can have a strong impact. Furthermore, although reactions can occur at the +surface of grains between diffusing species \cite{Oberg2016}, they are also likely to occur during +collisions between molecules. This can hardly be described by static quantum chemical calculations +only and thus a more complete understanding of such a mechanism require the use of Molecular +Dynamics (MD) simulations. To the best of our knowledge, no MD study has been conducted to +explicitly simulate the reaction of H with CO in the presence of water molecules. + +In the present contribution, we present a MD study of the collision of H with CO at the surface +of water clusters, \textit{i.e.} CO-(H$_{2}$O)$_{n}$ (n=0-10), aiming at a statistical sampling of +the various possible pathways likely to occur between the two species. Such simulations are +made possible by the description of the PES at the Self-Consistent-Charge Density Functional +based Tight-Binding (SCC-DFTB) level of theory that allows to describe bond-forming and +bond-breaking at a limited computational cost. The outline of the article is as follows: the +computational model is described in Section II, the results of the simulations are presented in +Section III and the main outcomes and perspectives are summarized in the conclusion. + +\section{Computational Methods} \label{Comput_meth} + +\textbf{Computation of the PES.} +We use the SCC-DFTB \cite{elstner,koskinen,frauenheim} approach implemented in the deMonNano code \cite{heine1} +to describe the PES of the CO-(H$_{2}$O)$_{n}$ clusters. Within the SCC-DFTB formalism, the electronic +energy is given by the following equation: +% +\begin{eqnarray}\label{enr} +E^{SCC-DFTB} = \sum\limits^{occ} \langle \psi_i | \hat{H_0} | \psi_i \rangle + \sum\limits_{\alpha \beta} U_{\alpha \beta} (R_{\alpha \beta}) ++ \frac{1}{2} \sum\limits_{\alpha \beta} \Delta q_{\alpha} \Delta q_{\beta} \gamma_{\alpha \beta} +- \sum\limits_{\alpha \beta} f_{damp} \frac{C_{6}^{\alpha \beta}}{R_{\alpha \beta}^{6}} +\end{eqnarray} +% +where the 1$^{\text{st}}$ term is a tight-binding term defined from parametrized integrals and +the 2$^{\text{nd}}$ term is a repulsive interaction expressed as a sum over all atomic pairs. +In the present study, we used the mio-set for Slater-Koster integrals \cite{elstner}. +The 3$^{\text{rd}}$ term is the second-order term of the Taylor expansion expressed as a function +of the atomic charge fluctuations $\Delta q_\alpha$ and the 4$^{\text{th}}$ term describes the +London dispersion interaction. Rapacioli and co-workers proposed to improve the description of +the electrostatic interaction in molecular systems by replacing the original Mulliken charges by +the Class IV - Charge Model 3 (CM3) charges \cite{DFTB_CM3,rapacioli2}, defined as: +% +\begin{equation}\label{cm3} +q_{\alpha}^{CM_3} = q_{\alpha}^{Mull} + \sum \limits_{\alpha' \neq \alpha}^{atoms} [D_{Z_{\alpha}Z_{\alpha'}}B_{\kappa \kappa'} + C_{Z_{\alpha}Z_{\alpha'}}B^{2}_{\kappa \kappa'}] +\end{equation} +% +where $B_{\kappa \kappa'}$ is the Mayer's bond order whereas $C_{Z_{\alpha}Z_{\alpha'}}$ and +$D_{Z_{\alpha}Z_{\alpha'}}$ are empirical parameters to define. We used the D$_{\text{OH}}$=0.129 +value previously proposed by Simon and Spiegelman in their study on water clusters \cite{simon1,simon2,simon3}. +We fitted the D$_{\text{CO}}$ parameter to reproduce the experimental dipole moment of CO which +leads to D$_{\text{OC}}$=0.012. We set D$_{\text{CH}}$=0.0. + +A difficulty in the description of the H+CO reaction lies in the fact that it involves, +at small distances, a potential crossing between the $^{2}\Pi$ electronic ground-state +(which dissociates to ground state products H($^{2}S$) + CO($^{1}\Sigma^{+}$)) and a +$^{2}\Sigma^{+}$ excited state of the formyl radical correlated with H($^2S$)+CO($^3\Pi$). +Therefore, at the intersection of the electronic states, the treatment of the problem with +a mean-field single determinant scheme arises, and self-consistency convergence problems +occur. To solve this problem, we used a Fermi-Dirac orbital occupation defined by an +electronic temperature of 1000~K which allows to achieve a continuous switch from +one state to the other in the near vicinity of the crossing. + +\textbf{Exploration of the PES.} +Before performing the collisional trajectories between H and CO, we first optimized the +geometry of the considered CO-(H$_{2}$O)$_{n}$ clusters in order to start our trajectories +as close as possible to the equilibrium configurations at low temperature. To explore the +PES of the clusters in an exhaustive way, we used the Molecular Dynamics Parallel-Tempering +(MDPT) algorithm \cite{sugita1,sugita2,earl1}, which allows for replica +exchanges between trajectories at different temperatures. This scheme increases +the ergodicity of the MD simulations and thus speeds up the exploration of the PES at a determined +temperature. We used a temperature range going from 20 to 320~K by steps of 5~K which correspond +to 60 distinct temperatures. All the MD trajectories were 4~ns long with a timestep of 0.2 fs. +The PT replica exchanges were attempted every 400 fs. In order to achieve canonical simulations, +we used a Nos\'e-Hoover chain of five thermostats defined by a unique frequency of 800 cm$^{-1}$ \cite{nose,hoover}. + +In order to find the lowest-energy configurations on each PES, local geometry optimizations +of the CO-(H$_{2}$O)$_{n}$ clusters were subsequently performed using the following procedure: +for one out of four temperatures, \textit{i.e.} every 20~K, one thousand different geometries +were periodically selected and locally optimized using a conjugate gradient algorithm. This lead +to a total of 15000 geometry relaxations per CO-(H$_{2}$O)$_{n}$ cluster, from which the +lowest energy one was retained. + +\textbf{MD Collision Trajectories.} +The first step of the MD simulation consisted in the sampling of the initial conditions, namely +-(i)- the initial positions and velocities of the CO-(H$_{2}$O)$_{n}$ clusters, -(ii)- the angular +orientations of the clusters and -(iii)- the impact parameter of the collision. In order to sample +the initial positions and velocities, we achieved thermalisation of the CO-(H$_{2}$O)$_{n}$ +clusters at 70~K via a 200~ps long MD simulation in the canonical ensemble using the previously +obtained lowest-energy +configuration as initial geometry. The last geometries and corresponding velocities were then taken +as initial conditions for subsequent collisional trajectories. These initial positions of the +CO-(H$_{2}$O)$_{n}$ clusters were further evenly rotated along the three Cartesian axes to obtain +64 initial angular conditions. For each orientation, the impact parameters +defining the initial position of the colliding hydrogen atom were randomly generated in a disk +of radius R (R$>$R$_{\text{cluster}}$) centered at 10 \AA \ from the center of mass of +the cluster. For the CO-(H$_{2}$O)$_{n}$ clusters with n=0-5, 53 different impact parameters +were generated per angular orientation leading to a sampling of 3392 initial conditions. +In the case of CO-(H$_{2}$O)$_{10}$, 2000 initial positions of the hydrogen atom were generated +opposite to the surface containing the CO molecule in order to describe quasi-frontal collisions only. +The initial velocity of the hydrogen atom was set to 0.01 \AA.fs$^{-1}$ which is consistent with +the temperature of the cluster at 70~K. The time length of each collision trajectory was set equal to 10~ps. + +\textbf{Wavefunction and DFT Calculations.} +In order to establish reference equilibrium geometries and intermolecular interaction energies +of the CO-H$_{2}$O isomers, we performed \textit{ab initio} MP2 and CCSD(T) calculations in +combination with the Pople-style 6-311++G(d,p) basis set \cite{krishnan1} and the aug-cc-pVTZ +basis set of Dunning and co-workers \cite{dunning1,kendall1}, respectively. To further check +the performances of the SCC-DFTB approach, we also carried out DFT calculations using the +B3LYP,\cite{becke1,lee1,vosko1} B3LYP-D3\cite{Grimme2010} and B97D\cite{Grimme2006} +exchange-correlation functional in combination with the 6-311++G(d,p) basis set. The latter +functional was tested as it was shown by Peters \textit{et al.} to provide a satisfactory value +for the formation barrier of the H + CO $\rightleftharpoons$ HCO reaction in vacuum.\cite{Peters2013a} +Basis set superposition errors (BSSE) were taken into account using the counterpoise method of Boys +and Bernardi.\cite{Boys2002} All DFT and wavefunction calculations were performed with the Gaussian +09 package \cite{g09}. + +All the binding energies between CO and the water clusters discussed in the text were defined as the energy of the +relaxed CO-(H$_{2}$O)$_{n}$ complex minus the energy of the water cluster minus the energy of CO both taken in +their geometry in the optimized complex. In the same way, formation energies for the H+CO-(H$_{2}$O)$_{n}$ reaction +were defined as the energy of the relaxed HCO-(H$_{2}$O)$_{n}$ complex minus the energy of one hydrogen minus the +energy CO-(H$_{2}$O)$_{n}$ considering its geometry in the optimized complex. + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\section{Results and Discussion} \label{resul_disc} + +\subsection{Validation of SCC-DFTB Potential.} + +The SCC-DFTB method is a parametrized approach. The D$_{\text{OH}}$ parameter involved in the +definition of the CM3 charges for the O--H pair was shown by Simon \textit{et al.} to yield +good results for the description of water clusters.\cite{simon1,simon2,simon3} +For instance, in the water dimer, it provides an oxygen-oxygen distance of 2.92 \AA \ to be +compared with the experimental value of 2.98 \AA \cite{odutola}. The validity of the +D$_{\text{CO}}$ and D$_{\text{CH}}$ parameters determined in the present work had to be +checked. For this purpose, we compared the structural and energetic characteristics of +the two well-known CO-H$_{2}$O isomers to fully \textit{ab initio} calculations. +Figure~\ref{str} shows the structure of these two CO-H$_{2}$O isomers. The first one +(C-structure) corresponds to a bonding between an H atom of water and the C atom of +CO while the second one (O-structure) corresponds to the interaction between an H atom +of water and the O atom of CO. + +\begin{figure}[h!] +\centering +\includegraphics[scale=0.40]{H2O_CO_OC.png} +\caption{MP2/6-311++G(d,p) geometries of the global (C-structure) and local (O-structure) minima of +CO-H$_{2}$O.} \label{str} +\end{figure} + +\begin{table}[h] +\small +\centering +\caption{Equilibrium geometries and intermolecular interaction energies of the C- and O-structures of +CO-H$_{2}$O obtained from SCC-DFTB, DFT/B3LYP, DFT/B3LYP-D3, DFT/B97D and MP2 with the 6-311++G(d,p) +basis set and CCSD(T) with the aug-cc-pVTZ basis set.} +\label{r_e} +\begin{tabular}{|c|c|c|c|c|} +\hline +\multirow{2}{*}{Method} & \multicolumn{2}{c|}{C-structure} & \multicolumn{2}{c|}{O-structure} \\ \cline{2-5} + & $r_{min}$, \AA & \begin{tabular}[c]{@{}c@{}}E$_{\text{int.}}$,\\ kcal.mol$^{-1}$\end{tabular} & $r_{min}$, \AA & \begin{tabular}[c]{@{}c@{}}E$_{\text{int.}}$,\\ kcal.mol$^{-1}$\end{tabular} \\ \hline +SCC-DFTB & 2.20 & -0.72 & 2.18 & -0.44 \\ \hline +MP2 & 2.45 & -1.84 & 2.41 & -1.02 \\ \hline +MP2/BSSE & 2.52 & -1.51 & 2.53 & -0.61 \\ \hline +B3LYP & 2.44 & -1.49 & 2.41 & -0.79 \\ \hline +B3LYP/BSSE & 2.42 & -1.36 & 2.40 & -0.66 \\ \hline +B3LYP-D3 & 2.38 & -2.03 & 2.33 & -1.47 \\ \hline +B3LYP-D3/BSSE & 2.40 & -1.89 & 2.36 & -1.28 \\ \hline +B97D & 2.51 & -1.82 & 2.50 & -1.06 \\ \hline +B97D/BSSE & 2.53 & -1.68 & 2.52 & -0.92 \\ \hline +CCSD(T)$^a$ & - & -2.05 & - & -1.21 \\ \hline +CCSD(T)/BSSE$^b$ & - & -1.65 & - & -0.90 \\ \hline +\end{tabular}\\ +$^a$ CCSD(T) energy calculations were performed using the MP2 optimized geometry\\ +$^b$ CCSD(T)/BSSE energy calculations were performed using the MP2/BSSE optimized geometry\\ +\end{table} + +The structural and energetic characteristics of these dimers are given in Table~\ref{r_e}. +The interaction distances calculated by the SCC-DFTB method are 2.20 and 2.18 \AA~for r(H$_{2}$-C) +and r(H$_{2}$-O$_{2}$), respectively, somewhat smaller than the data obtained from MP2/6-311++G(d,p) +calculations, namely 2.45 and 2.41 \AA, respectively. From an energy standpoint, the CO-H$_{2}$O is +a very weakly bound complex (both C- and O-structures), where the interaction energy includes about +40 \% of electrostatic, 35 \% of induction and 25 \% of dispersion contributions \cite{vilela1,wheatley1,yaron1,sadlej1}. +Referring to such a very small value of the interaction energy, an accurate description using +density functional or semi-empirical methods is a very difficult task. Thus, although the SCC-DFTB +correctly predicts the energetic ordering of the two isomers, the interaction energies are somewhat +underestimated, even-though it appears from Table~\ref{r_e} that the exact value of the interaction +energy is highly dependent on the method, basis set, and applied corrections. Indeed, the three +DFT calculations (B3LYP, B3LYP-D3 and B97D) leads to quite different values for the interaction energy. +Interestingly, the B97D functional in combination with the 6-311++G(d,p) basis set provides geometries +that are very close to MP2/BSSE structures, and interaction energies almost equal to CCSD(T)/BSSE ones. +This confirms the good performances of B97D to describe carbon monoxide.\cite{Peters2013a} +From the Table~\ref{r_e}, the SCC-DFTB results for CO-H$_{2}$O are thus qualitatively similar to \textit{ab initio} +data and one can expect that the observed differences will not affect too seriously the present dynamical simulations. +As shown in the Table~\ref{e_bind}, with increasing cluster size, the SCC-DFTB binding energies converge rather +quickly from 0.72 kcal.mol$^{-1}$ to 1.00 kcal.mol$^{-1}$ and reach convergence at n=4-5. A similar behavior is +obtained at the B97D and MP2 levels of theory while B3LYP-D3 values display larger fluctuations. Consequently, +although the SCC-DFTB binding energies are still underestimated for larger clusters with respect to DFT and MP2 values, +the rapid convergence trend is expected to be reliable and certainly important for the reactive collisional behavior +discussed in the next section. + +\subsection{Results} +\begin{figure}[h!] +\centering +\includegraphics[scale=0.45]{co_h2o_figures.png} +\caption{Geometries of the global SCC-DFTB minima of the +CO-(H$_{2}$O)$_{n}$ (n=1--5,10) clusters.} \label{str_2} +\end{figure} + +\begin{table}[] +\centering +\caption{Binding energies between the CO (second column) and HCO (third column) molecules and (H$_{2}$O)$_{n}$ +clusters obtained with SCC-DFTB as well as B3LYP-D3, B97D and MP2 in combination with the 6-311++G(d,p) +basis set. \textit{Ab initio} values are reported including BSSE corrections. +SCC-DFTB HCO formation energy for H+CO-(H$_{2}$O)$_{n}$ along with B97D results +obtained by Peters \textit{et al.}\cite{} (Fourth column). All energies are in kcal.mol$^{-1}$.} +\label{e_bind} +\begin{tabular}{|c|cccc|cccc|c|} +\hline + & \multicolumn{4}{c|}{CO-(H$_{2}$O)$_{n}$} & \multicolumn{4}{c|}{HCO-(H$_{2}$O)$_{n}$} & H+CO-(H$_{2}$O)$_{n}$ \\ + \multirow{-2}{*}{n} & DFTB & B3LYP-D3 & B97D & MP2 & DFTB & B3LYP-D3 & B97D & MP2 & DFTB \\ \hline +0 & - & - & - & - & - & - & - & - & -31.18 (\textit{-25.69}$^a$) \\ \hline +1 & -0.72 & -1.89 & -1.68 &-1.51 &-5.32 &-3.38 &-2.71 &-2.46 & - 26.25 \\ \hline +2 & -0.93 & -3.62 & -2.86 &-2.52 & -10.86 &-8.22 &-6.63 &-5.50 & - 33.43 \\ \hline +3 & -1.18 & -2.30 &-1.89 & -1.57 & -7.69 &-9.44 &-8.75 &-6.35 & - 27.95 (\textit{-26.76}$^a$) \\ \hline +4 & -1.00 & -2.43 & -1.74 &-1.45 & -11.96 &-10.21 &-8.58 &-6.84 & - 26.22 \\ \hline +5 & -1.00 & -1.99 & -1.78 & -1.53 &-4.77 &-5.87 &-4.62 &-3.47 & - 27.68 (\textit{-26.68}$^a$) \\ \hline +10 & -1.01 &-1.88 &-1.92 & -1.81 &-3.54 & -3.93 &-2.84 &-1.26 & - 26.57 \\ \hline +\end{tabular} \\ +$^a$ B97D results of Peters \textit{et al.}\cite{Peters2013a,Phillip2013}\\ +\end{table} + +To ensure that statistical convergence is reached, we checked the distributions of the initial +positions of the hydrogen atom with respect to the cluster in the 3392 starting configurations. +For visualisation, the distribution maps of the initial positions of hydrogen for CO-(H$_{2}$O)$_{n}$ (n=1,2,3) +are displayed in Figure~\ref{maps}. Similar data are obtained for CO-(H$_{2}$O)$_{n}$ (n=4,5). +From those pictures, it appears that the input geometries provide a reasonably uniform distribution +of hydrogen projectiles around the clusters. + +\begin{figure*} +\centering +\includegraphics[scale=0.45]{Maps_CO_H2O.png} +\caption{Distribution of the initial positions of the incident hydrogen atom around the CO-(H$_{2}$O)$_{n}$ + (n=1,2,3) clusters.} \label{maps} +\end{figure*} + +For each cluster size, we investigated and analyzed all trajectories according to seven +scenari (also called variants) characterizing the issue of the collision. A schematic +description of these mechanisms is shown in Figure~\ref{Variants}. + +\begin{figure*} +\centering +\includegraphics[scale=1.2]{Variants.png} +\caption{Possible pathways (variants) characterizing the issue of the H + CO collision.} \label{Variants} +\end{figure*} + +Variant 1 corresponds to the case where the two following conditions are fulfilled simultaneously: +-(i)- during the collision, the reaction occurred and the HCO radical was formed, +and -(ii)- this radical remained connected to the cluster till the end of the simulation. +Geometric characteristics of the formyl radical such as R$_{\text{CO}}$ and R$_{\text{CH}}$ +were chosen to monitor the formation process. Recent studies by Adams and Purvis +provide the accurate equilibrium bond lengths of HCO using Many-Body Perturbation Theory +(MBPT) or Coupled-Cluster with Doubles excitations (CCD) calculations. The CCD values are +R$_{\text{CO}}$=1.188 \AA \ and R$_{\text{CH}}$=1.111 \AA~ \cite{adams1,marenich1}. +The present SCC-DFTB characteristics are R$_{\text{CO}}$=1.167 \AA \ and R$_{\text{CH}}$=1.197 \AA. +The criterion for HCO formation during the dynamics was thus chosen as follows: if during the simulation +the distances were fluctuating in the range 0.9-1.3 \AA~for C-O and 1.0-1.5 \AA~for C-H, +we assumed that HCO was formed. To ensure that the radical remains bonded to the surface, +we calculated the distances between the hydrogen atom of HCO and all oxygen atoms of the water +cluster (R$_{\text{H--O}}$), and the distances between the carbon atom of HCO and all oxygen atoms +of the water cluster (R$_{\text{C--O}}$). If at least one value of the R$_{\text{H--O}}$ +distance and one value of the R$_{\text{C--O}}$ distance were less than 4 \AA~at a given +MD step, the radical was assumed to be associated with the water cluster. + +The second variant describes the situation where the HCO radical was formed, but then desorbed from the +cluster (`Variant 2' in the Figure~\ref{Variants}). Similarly to CO, the binding energy between the formyl radical +and a water molecule is very small.Indeed, Cao \textit{et al.} calculated at the UCCSD(T)/aug-cc-pVTZ +level of theory, corrected for BSSE and vibrational zero-point energies, the interaction energies of three stable +isomers of HCO--H$_{2}$O. They obtained the three following values: -0.83, -1.70 and -1.61~kcal.mol$^{-1}$.\cite{cao1} +The corresponding values without vibrational zero-point energies are -2.24, -2.62 and -3.35~kcal.mol$^{-1}$. +This weak interaction energy confirms that Variant 2 is likely to occur if the incident hydrogen atom has enough +kinetic energy. It should also be noted that, similarly to CO, the HCO--(H$_{2}$O)$_{n}$ binding energies +are rather low and quite sensitive to the computational details. This is illustrated in the Table~\ref{e_bind} for +different DFT and MP2 calculations. Although the binding energies for HCO--(H$_{2}$O) and HCO--(H$_{2}$O)$_{2}$ +are somewhat overestimated, the DFTB values for larger species fall in the range of the DFT and MP2 values. +The next variant (`Variant 3' in the Figure~\ref{Variants}) +corresponds to the case where the reaction between H and CO did not occur while both reactants +remained stuck to the water cluster. The group of variants 4-6 may +occur whenever the kinetic energy of the incident hydrogen is above the energy required for +the formation of the radical. They can be briefly described as follows: Variant 4: the HCO +radical was not formed and H desorbed from the cluster while CO remained adsorbed; +Variant 5: the HCO radical was not formed, H was adsorbed while CO desorbed; Variant 6: + the HCO radical was not formed, both H and CO desorbed. It is worth pointing out that +those three variants can be encountered despite the transient formation of the HCO radical +if it dissociates during the trajectory. The last mechanism in our scheme (`Variant 7' in the Figure~\ref{Variants}) +is the situation where HCO is formed during some time of the simulation but finally dissociate +and both reactants remain bonded to the water cluster. The likelihood of each variant for clusters +CO-(H$_{2}$O)$_{n}$ (n=0-5,10) are listed in the Table~\ref{result_ratio}. + +\begin{table*} +\small +\centering +\caption{Probability (in percent) of each collisional pathway as a function of the cluster size.} +\label{result_ratio} +\begin{tabular}[t]{C{2.1cm} C{1.4cm} C{1.4cm} C{1.4cm} C{1.4cm} C{1.4cm} C{1.4cm} C{1.4cm}} +\hline \hline +\small{System} & \small{V.1 (\%)} & \small{V.2 (\%)} & \small{V.3 (\%)} & \small{V.4 (\%)} & \small{V.5 (\%)} & \small{V.6 (\%)} & \small{V.7 (\%)} \\ +\hline +\small{CO} & 0.0 & 0.0 & 0.0 & 0.0 & 0.0 & 0.0 & \textbf{35.3} \\ +\small{CO-H$_{2}$O} & 0.0 & 3.1 & 0.0 & \textbf{63.2} & 9.1 & 10.2 & 7.5 \\ +\small{CO-(H$_{2}$O)$_{2}$} & 2.3 & \textbf{58.1} & 0.3 & 5.0 & 9.7 & 0.0 & \textbf{24.6} \\ +\small{CO-(H$_{2}$O)$_{3}$} & \textbf{10.1} & \textbf{50.9} & 1.3 & 0.9 & \textbf{31.4} & 0.0 & 5.4 \\ +\small{CO-(H$_{2}$O)$_{4}$} & \textbf{58.0} & 0.0 & \textbf{35.8} & 0.9 & \textbf{0.0} & 0.0 & 5.4 \\ +\small{CO-(H$_{2}$O)$_{5}$} & \textbf{61.4} & 0.0 & 7.4 & 1.1 & \textbf{26.9} & 0.1 & 0.8 \\ +\small{CO-(H$_{2}$O)$_{10}$} & \textbf{34.8} & 5.0 & \textbf{32.4} & 3.0 & \textbf{20.8} & 0.0 & 4.0 \\ +\hline \hline +\end{tabular} +\end{table*} + +In the gas phase conditions, \textit{i.e} without water molecule, the formation of the HCO radical with a favorable +geometry occurred in 35.3 \% of trajectories, while in other cases, the hydrogen atom flew away +from the collision area. However, even in the favorable cases, the HCO radical always dissociated +at some point of the simulations. Indeed, after a successful reaction, the kinetic energy of the incident +hydrogen distributes into the few vibrational modes of the radical which leads to its dissociation. +To support this point and to highlight the role of the water cluster, Figure~\ref{r_ch} displays +a typical example of the time-evolution of the C--H distance for the HCO and HCO-(H$_{2}$O)$_{5}$ +species. Immediately after the radical formation, the fluctuations of the C--H distance in the two +systems are of the same magnitude. However, after $\sim$1~ps, those fluctuations significantly +decrease for HCO-(H$_{2}$O)$_{5}$ highlighting the dissipation of kinetic energy towards the water +molecules. This leads to a stable HCO molecule. In contrast, the fluctuations are constant in the +simulation of pure HCO which can result in its dissociation. + +\begin{figure}[h!] +\centering +\includegraphics[scale=0.20]{rch_fluctuations.png} +\caption{Time-evolution of the C--H distance for HCO-(H$_{2}$O)$_{5}$ (top) and HCO (bottom) +immediately after the radical formation. $\Delta_{R_{C-H}}$ represents the amplitude of the +distance fluctuations.} \label{r_ch} +\end{figure} + +The same behavior is observed for CO-(H$_{2}$O). Indeed, $\sim$12 \% of the trajectories +lead to the formation of HCO although it is stable in only $\sim$3 \% of them. Variant +4, \textit{i.e.} with desorption of the hydrogen from the water molecule, is an important +pathway for this species as it encompasses $\sim$80 \% of the trajectories. For CO-(H$_{2}$O)$_{2}$ +and CO-(H$_{2}$O)$_{3}$, the HCO radical is obtained in more than 50 \% of cases. Due to the +small binding energy of HCO with water molecules (see discussion above), most of the +successfully formed radicals desorb from the cluster. This is demonstrated +by the predominance of the Variant 2 pathway. It is worth pointing out that the exact amount of +this latter pathway would be highly influenced by the level of theory used to describe the PES of +those systems. CO-(H$_{2}$O)$_{2}$ displays a significant amount +of dissociated radicals (24.6 \%) which supposes that two water molecules is not enough to +accommodate the excess kinetic energy of the hydrogen. In both CO-(H$_{2}$O)$_{2}$ and +CO-(H$_{2}$O)$_{3}$, only a few trajectories lead to a stable HCO radical adsorbed on the +water cluster, 2.3 and 10.1 \%, respectively. + +Things are completely different for CO-(H$_{2}$O)$_{4}$ and CO-(H$_{2}$O)$_{5}$. Indeed, +there is no desorption of HCO from the cluster and only a few cases of HCO dissociation, +5.4 and 0.8 \%, respectively. The majority of the simulations lead to a stable HCO radical +adsorbed on the water molecules. This allows us to assume that the second step of the +successive CO hydrogenation is likely to occur on complexes composed of four or more water +molecules. The main difference between those two species is the amount of Variant 3 and 5 +pathways that seems to be opposed. In particular, CO-(H$_{2}$O)$_{4}$ displays a 0.0 \% +amount of Variant 5, in contrast to the other species. This could likely be attributed to the +planar square conformation of (H$_{2}$O)$_{4}$. +Surprisingly, despite performing quasi-frontal collisions only, for CO-(H$_{2}$O)$_{10}$, +the probability for an adsorbed HCO radical to be formed (34.8 \%) is about twice as small as +for CO-(H$_{2}$O)$_{4}$ and CO-(H$_{2}$O)$_{5}$. However, this is also the only species +displaying a significant amount of both Variant 3 and 5, 32.4 \%~and 20.8 \%, respectively. +Furthermore, the likelihood of Variant 3 and 1 are equivalent as 32.4 \%~of the trajectories lead +to an H atom stuck on the water molecules. This results from the larger surface area +of CO-(H$_{2}$O)$_{10}$ as compared to the other aggregates. It should also be noted that +in those cases, the hydrogen does not diffuse to the CO molecule in the time length of the simulations. + +In order to get more dynamical, \textit{i.e.} time-dependent, insights into the H + CO +recombination mechanism, we calculated the probability for HCO formation along the MD simulations. +Two different functions, P1(t) and P2(t), were computed from all the trajectories, regardless of +the corresponding Variants. They are defined as follow: -(i)- P1(t) is the cumulative probability that +the HCO radical was formed for the first time at time \textit{t} during the simulation without considering +any further dissociation or recombination; -(ii)- P2(t) is the cumulative probability that HCO was +formed a time \textit{t} and remains stable till the end of the simulation. From these definitions, +P1(t) is mainly influenced by Variants 1, 2 and 7, at a lesser extent it is also influenced by the other +Variants, and P2(t) by trajectories belonging to Variants 1 and 2, only. Figure~\ref{time_func} displays +the P1(t) and P2(t) functions for CO-(H$_{2}$O)$_{n}$ (n=1, 3, 5 and 10). + +\begin{figure}[h!] +\includegraphics[scale=1.2]{new_time.png} +\caption{Cumulative probability of HCO formation as a function of time for the CO-(H$_{2}$O)$_{n}$ +(n=1, 3, 5 and 10) clusters.} \label{time_func} +\end{figure} + +We can see different dynamical pictures depending on the species. For CO-(H$_{2}$O), +formation of the HCO radical occurs very rapidly. The curve P1(t) reaches its maximum +during the first two picoseconds of simulation. Then, it retains a constant value of 11.6 \%. +This latter value correlates with the sum of the probabilities of Variants 2 and 7 in the +Table~\ref{result_ratio} (10.6 \%). It should be noted that the small difference between +these values results from the definition of both P1(t) and the Variants. Indeed, P1(t) does +not take into account the possible dissociation of HCO and subsequent disconnection of +the reactant from the water cluster. Those mechanisms correspond to Variants 4 to 6. Thus, +in 1\% \ of the trajectories, which belong to Variants 4, 5 or 6, there is the transient +formation of HCO before dissociation and desorption of one or both reactants. +P2(t) shows that a stable radical is formed only in 4.5 \% of cases. +However, this function increases only during the last picosecond of the trajectory. This +demonstrates that the HCO-(H$_{2}$O) aggregate is in a regime of successive formation-dissociation. +The increase of P2(t) at the end of the simulation thus results from the finite time length of the simulations. + +For CO-(H$_{2}$O)$_{3}$ and CO-(H$_{2}$O)$_{5}$, other behaviors are observed. Indeed, in the former case, +HCO formation occurs gradually from 0.5 to 6~ps. This strongly contrast with CO-(H$_{2}$O). The maximum +value of P1(t) (66.5 \%) corresponds to the sum of the probabilities of Variants 1, 2 and 7, which is equal to 66.4 \%. +Consequently, a negligible amount of trajectories where HCO is formed lead to its dissociation and the desorption +of the reactants. In addition, in contrast with CO-(H$_{2}$O), a large amount of the successfully formed HCO +remain stable +until the end of the trajectories. 61.5 \%~of them, corresponding to Variants 1 and 2, lead to a stable radical. Again, +the increase of the P2(t) curve during the last picosecond of simulation is only an artefact. +In CO-(H$_{2}$O)$_{5}$, a faster HCO formation is observed as revealed by the sharp rise of the P1(t) +curve between 0.5 and 1~ps. After 1~ps, it smoothly increases till 8~ps. The probability of HCO formation is +63 \%, which correlates with the corresponding Variants in the Table~\ref{result_ratio} (V.1+V.2+V.7 = 62.2 \%). +Similarly, the maximum of the P2(t) curve, 62.1 \%, correspond to the sum of the Variants 1 and 2 (61.4 \%). +Consequently, most of the radicals that are formed remain stable during the considered time length. +The curves for CO-(H$_{2}$O)$_{3}$ and CO-(H$_{2}$O)$_{5}$ in the Figure~\ref{time_func} display a +time lag between the increase of the P1(t) and P2(t) functions. The faster rise of P1(t) compared to P2(t) +shows that HCO is formed in a number of trajectories but immediately dissociates due to the excess +kinetic energy of the proton. This reveals that a small amount of time is needed to dissipate this energy, +which then allows for the formation of stable HCO and the rise of P2(t). This rise is faster for +CO-(H$_{2}$O)$_{5}$ due to the larger number of water molecules contributing to energy dissipation. +Finally, a plateau is observed for the P1(t) curve of CO-(H$_{2}$O)$_{5}$ at $\sim$1.2~ps. The subsequent +increase of P1(t) can be interpreted as the reaction of CO with hydrogen atoms initially stuck to +water molecules. A visual analysis of the trajectories reveal that only hydrogen atoms that are initially +very close to CO can lead to HCO formation as no diffusion over several water molecules is observed. +This is facilitated by the re-orientation of the CO molecule that allows for the hydrogen capture. +However, this process is rather long which explains the slow rise of the P1(t) and P2(t) curves for +CO-(H$_{2}$O)$_{5}$. The CO-(H$_{2}$O)$_{10}$ curves are very similar to the ones of CO-(H$_{2}$O)$_{5}$ +which suggests a similar behavior. The two main differences between those two species are: +a small time lag for the rise of P1(t) for CO-(H$_{2}$O)$_{10}$, which is attributed to a different initial +orientation of CO with respect to the colliding hydrogen, and a lower intensity of P1(t) and P2(t), attributed +to the larger amount of trajectories leading to the sticking of the hydrogen on the surface. + +Finally, we determined the reaction cross section for the investigated H + CO-(H$_{2}$O)$_{n}$ +(n=0-5, 10) reaction, defined as: + +\begin{eqnarray}\label{cross} +\Omega=\int_{0}^{b_{max}} p(b)2\pi bdb +\end{eqnarray} +where $b$ is the impact parameter and $p(b)$ the probability for a successful HCO formation at +impact parameter $b$. We considered as successful simulations corresponding to Variants 1 and 2, +only. Figure~\ref{size} shows the evolution of the reaction cross section $\Omega$ with increasing +cluster size from 0 to 10 water molecules. + +\begin{figure}[h!] +\includegraphics[scale=1.0]{cs_size.png} +\caption{Reaction cross section for H + CO formation as a function of water cluster size.} \label{size} +\end{figure} + +In the case of a single CO molecule, the reaction cross section is null, since a stable HCO radical +is never formed. When we go from one to two water molecules, although the size of CO-H$_{2}$O +and CO-(H$_{2}$O)$_{2}$ is similar (the distance between the two most distant atoms is 4.22 and +4.19 \AA, respectively), a significant increase of $\Omega$ is observed. Again, this shows that +the second water molecule assists the capture of the incident hydrogen and makes the +collision-induced reaction more effective. These data are consistent with the previous +analysis of the trajectories. +From two to four water molecules, the reaction cross section does not significantly change. For five +water molecules, a second small increase of $\Omega$ can be observed. Consequently, up to 5 +water molecules, the present results suggest that the reaction cross section increases with cluster +size, and hence, the probability of the HCO radical formation also increases. +In the case of CO-(H$_{2}$O)$_{10}$, as previously mentioned for the probabilities of +the collisional pathways, the surface area of (H$_{2}$O)$_{10}$ significantly increases and the probability +for a successful reaction between H and CO drastically decreases. Indeed, despite considering +frontal collisions only and no orientational sampling, $\Omega$ decreases to $\sim$3~\AA. +This precludes from calculating a cross section to be directly compared with the smaller clusters. + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\section{Conclusions} \label{Concl} + +In the present study, a statistical analysis of the collision-induced reaction between hydrogen +and carbon monoxide on water clusters (H$_{2}$O)$_{n}$ (n=0-5,10) was achieved +using molecular dynamics simulation in combination with SCC-DFTB calculations of the energies +and forces. SCC-DFTB allows to describe covalent bonding in a quantum mechanical scheme +and charge relaxation along the dynamics and is thus well suited to study reactivity. +We show that the SCC-DFTB approach allows to satisfactorily describe the interaction between +the weakly bounded CO and H$_{2}$O molecules and can further be used to reaction study. +In a subsequent step, the classical collision-induced reaction of H with CO in CO-(H$_{2}$O)$_{n}$ +was investigated dynamically and the various pathways for the collision were analysed statistically. +We show that stable HCO radicals can be formed in species containing two or more water molecules. +Those water molecules play a key role in the collisional mechanism as they allow to dissipate the excess +kinetic energy of the colliding hydrogen. +However, in the case of (H$_{2}$O)$_{2}$ and (H$_{2}$O)$_{3}$, HCO returns to the gas phase in most cases +as dissociation between the radical and the water molecules is almost always observed. However, +starting from four water molecules, the successfully formed HCO remains associated +with the surface. This is an important feature for further hydrogenation steps that would lead to methanol. +For three water molecules and above, a large number of collisions lead to the sticking of the hydrogen +atom on the water molecules. In most cases, no subsequent HCO formation is observed in the simulation +time length. This suggests that the diffusion of H on the water cluster and its subsequent meeting with CO +(referred to as the Langmuir-Hinshelwood mechanism) either is damped by the cluster character of the +surface (with respect to perfect ice) or occurs at longer time than described by the present simulations. +In a few cases, when H is initially stuck close to CO, recombination can occur thanks to the +re-orientation of the CO molecule on the cluster allowing for the subsequent formation of HCO. This +process is observed mainly for (H$_{2}$O)$_{5}$ and (H$_{2}$O)$_{10}$. The recombination cross section +is of the order of $\approx$ 4 to 5~\AA \ for systems containing 3-5 water molecules. When increasing +the number of water molecules up to ten, this value drops drastically due to the sticking of H to the +cluster. Finally, it is worth point out that the size of the considered aggregates as well as the initial +conditions and length time of the trajectories favour the Eley-Rideal process with respect to the HCO +formation following the Langmuir-Hinshelwood mechanism, \textit{i.e.} the diffusion of hydrogen over the +water cluster. This latter would require a completely different set-up of the simulations to be properly +described. + +Certainly, the present quantitative results are subject to the accuracy of the SCC-DFTB method and the +limitation of the dynamical parameters, such as the number of trajectories and their time length. +Nevertheless, we think that the present results are statistically meaningful and provide clear information +on the influence of water molecules on the H + CO reaction process in a dynamical picture. +The present work +could be extended in the following directions: -(i)- increase the CO coverage of the water clusters, +which would avoid the isolation of CO on a large nanodroplet, possibly with a factor dependence +of the surface area of the nanodroplet; -(ii)- perform simulations on real ice surface, ordered or +disordered, using periodic boundary conditions. We hope that the present work brings some +confirmation and new insights for the hydrogenation chain of CO up to methanol and contribute to +the understanding of the chemistry of the ISM. + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The "Acknowledgement" section can be given in all manuscript +%% classes. This should be given within the "acknowledgement" +%% environment, which will make the correct section or running title. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{acknowledgement} +The authors acknowledge the supercomputing facility of CALMIP for generous allocation +of computer resources (projects P1320 and P0059). The authors declare that there has +been no significant financial support for this work. +\end{acknowledgement} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The same is true for Supporting Information, which should use the +%% suppinfo environment. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%% The appropriate \bibliography command should be placed here. +%% Notice that the class file automatically sets \bibliographystyle +%% and also names the section correctly. +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\bibliography{Ref} + +\end{document} \ No newline at end of file