2376 lines
122 KiB
TeX
2376 lines
122 KiB
TeX
\documentclass[journal=jctcce,manuscript=article]{achemso}
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\usepackage{graphicx,dcolumn,bm,xcolor,microtype,hyperref,multirow,amsmath,amssymb,amsfonts,physics,float,lscape,soul,rotating,longtable,tabularx}
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\usepackage[version=4]{mhchem}
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\newcommand{\alert}[1]{\textcolor{red}{#1}}
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\newcommand{\mc}{\multicolumn}
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\newcommand{\mcc}[1]{\multicolumn{1}{c}{#1}}
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\newcommand{\mr}{\multirow}
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\newcommand{\EFCI}{E_\text{FCI}}
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\newcommand{\EexCI}{E_\text{exCI}}
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\newcommand{\EsCI}{E_\text{sCI}}
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\newcommand{\EPT}{E_\text{PT2}}
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\newcommand{\PsisCI}{\Psi_\text{sCI}}
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\newcommand{\Ndet}{N_\text{det}}
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\newcommand{\ex}[6]{$^{#1}#2_{#3}^{#4}(#5 \rightarrow #6)$}
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\newcommand{\pis}{\pi^\star}
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\newcommand{\si}{\sigma}
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\newcommand{\sis}{\sigma^\star}
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% methods
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\newcommand{\TDDFT}{TD-DFT}
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\newcommand{\CASSCF}{CASSCF}
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\newcommand{\CASPT}{CASPT2}
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\newcommand{\ADC}[1]{ADC(#1)}
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\newcommand{\AD}{ADC(2)}
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\newcommand{\CCD}{CC2}
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\newcommand{\CCT}{CC3}
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\newcommand{\STEOM}{STEOM-CCSD}
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\newcommand{\AT}{ADC(3)}
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\newcommand{\CC}[1]{CC#1}
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\newcommand{\CCSD}{CCSD}
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\newcommand{\EOMCCSD}{EOM-CCSD}
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\newcommand{\CCSDT}{CCSDT}
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\newcommand{\CCSDTQ}{CCSDTQ}
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\newcommand{\CI}{CI}
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\newcommand{\sCI}{sCI}
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\newcommand{\exCI}{exFCI}
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\newcommand{\FCI}{FCI}
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% basis
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\newcommand{\Pop}{6-31+G(d)}
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\newcommand{\AVDZ}{\emph{aug}-cc-pVDZ}
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\newcommand{\AVTZ}{\emph{aug}-cc-pVTZ}
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\newcommand{\DAVTZ}{d-\emph{aug}-cc-pVTZ}
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\newcommand{\AVQZ}{\emph{aug}-cc-pVQZ}
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\newcommand{\DAVQZ}{d-\emph{aug}-cc-pVQZ}
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\newcommand{\TAVQZ}{t-\emph{aug}-cc-pVQZ}
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\newcommand{\AVFZ}{\emph{aug}-cc-pV5Z}
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\newcommand{\DAVFZ}{d-\emph{aug}-cc-pV5Z}
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% units
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\newcommand{\IneV}[1]{#1 eV}
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\newcommand{\InAU}[1]{#1 a.u.}
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\newcommand{\Ryd}{\mathrm{R}}
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\newcommand{\Val}{\mathrm{V}}
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\newcommand{\Fl}{\mathrm{F}}
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\newcommand{\ra}{\rightarrow}
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\newcommand{\SI}{Supporting Information}
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\setcounter{table}{0}
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\setcounter{figure}{0}
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\setcounter{page}{1}
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\setcounter{equation}{0}
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\renewcommand{\thepage}{S\arabic{page}}
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\renewcommand{\thefigure}{S\arabic{figure}}
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\renewcommand{\theequation}{S\arabic{equation}}
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\renewcommand{\thetable}{S\arabic{table}}
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\renewcommand{\thesection}{S\arabic{section}}
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\renewcommand\floatpagefraction{.99}
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\renewcommand\topfraction{.99}
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\renewcommand\bottomfraction{.99}
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\renewcommand\textfraction{.01}
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% addresses
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\newcommand{\LCPQ}{Laboratoire de Chimie et Physique Quantiques, CNRS et Universit\'e Toulouse III - Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France}
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\newcommand{\CEISAM}{Laboratoire CEISAM - UMR CNRS 6230, Universit\'e de Nantes, 2 Rue de la Houssini\`ere, BP 92208, 44322 Nantes Cedex 3, France}
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\newcommand{\Pisa}{Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Moruzzi 3, 56124 Pisa, Italy}
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\title{A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules\\Supporting Information}
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\author{Pierre-Fran{\c c}ois Loos}
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\email{loos@irsamc.ups-tlse.fr}
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\affiliation[LCPQ, Toulouse]{\LCPQ}
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\author{Filippo Lipparini}
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\affiliation[DC, Pisa]{\Pisa}
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\email{filippo.lipparini@unipi.it}
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\author{Martial Boggio-Pasqua}
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\affiliation[LCPQ, Toulouse]{\LCPQ}
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\author{Anthony Scemama}
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\affiliation[LCPQ, Toulouse]{\LCPQ}
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\author{Denis Jacquemin}
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\email{Denis.Jacquemin@univ-nantes.fr}
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\affiliation[UN, Nantes]{\CEISAM}
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\begin{document}
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\clearpage
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\section{Basis set and frozen-core effects}
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\subsection{Cyanoacetylene, cyanogen, and diacetylene}
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies of cyanoacetylene, cyanogen, and diacetylene using various atomic basis sets.
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FC stands for frozen core. All values are in eV.}
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\label{Table-S1}
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\begin{small}
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\begin{tabular}{l|cccccccc}
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\hline
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& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & {\AVFZ} \\
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& FC & FC &FC & FC & Full & FC & Full & FC \\
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\hline
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& \multicolumn{8}{c}{Cyanoacetylene} \\
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\hline
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$^1\Sigma^-$ &6.02 &5.92 &5.80 &5.79 &5.79 &5.79 &5.79 &5.79 \\
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$^1\Delta$ &6.29 &6.17 &6.08 &6.06 &6.07 &6.06 &6.07 &6.06 \\
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$^3\Sigma^+$ &4.44 &4.43 &4.45 &4.46 &4.46 &4.46 &4.46 &4.47 \\
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$^3\Delta$ &5.35 &5.28 &5.22 &5.22 &5.21 &5.22 &5.21 &5.22 \\
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$^1A''$[F] &3.70 &3.60 &3.54 &3.54 &3.54 & & & \\
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\hline
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& \multicolumn{8}{c}{Cyanogen} \\
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\hline
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$^1\Sigma_u^-$ &6.62 &6.52 &6.39 &6.38 &6.38 &6.38 &6.38 &6.38 \\
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$^1\Delta_u$ &6.88 &6.77 &6.66 &6.64 &6.65 &6.64 &6.65 &6.64 \\
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$^3\Sigma_u^+$ &4.92 &4.89 &4.90 &4.91 &4.91 &4.91 &4.91 &4.92 \\
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$^1\Sigma_u^-$[F] &5.27 &5.19 &5.06 &5.05 &5.05 &5.05 &5.05 &5.04 \\
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\hline
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& \multicolumn{8}{c}{Diacetylene} \\
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\hline
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$^1\Sigma_u^-$ &5.57 &5.44 &5.34 &5.33 &5.34 &5.33 &5.34 &5.33 \\
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$^1\Delta_u$ &5.83 &5.69 &5.61 &5.60 &5.60 &5.60 &5.60 &5.60 \\
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$^3\Sigma_u^+$ &4.07 &4.06 &4.08 &4.10 &4.09 &4.10 &4.09 &4.11 \\
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$^3\Delta_u$ &4.93 &4.86 &4.80 &4.80 &4.80 &4.80 &4.80 &4.80 \\
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\hline
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\end{tabular}
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\end{small}
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\end{table}
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\clearpage
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\subsection{Cyclopropenone, cyclopropenethione, and methylenecyclopropene}
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies of cyclopropenone, cyclopropenethione, and methylenecyclopropene using various atomic basis sets.
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FC stands for frozen core. All values are in eV.}
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\label{Table-S2}
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\begin{small}
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\begin{tabular}{l|ccccccc}
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\hline
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& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} & {\AVFZ} \ \\
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& FC & FC &FC & FC & Full & FC & FC \\
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\hline
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& \multicolumn{7}{c}{Cyclopropenone} \\
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\hline
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$^1B_1 (n \rightarrow \pi^\star)$ &4.32 &4.22 &4.21 &4.23 &4.22& 4.23 & 4.23\\
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$^1A_2 (n \rightarrow \pi^\star)$ &5.68 &5.59 &5.57 &5.58 &5.57& 5.58 & 5.58\\
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$^1B_2 (n \rightarrow 3s)$ &6.39 &6.21 &6.32 &6.37 &6.38& 6.36 & 6.38\\%
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$^1B_2 (\pi \rightarrow \pi^\star)$ &6.70 &6.56 &6.54 &6.56 &6.56& 6.56 & 6.56\\
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$^1B_2 (n \rightarrow 3p)$ &6.92 &6.88 &6.96 &6.99 &7.00& 6.96 & 6.99\\
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$^1A_1 (n \rightarrow 3p)$ &7.00 &6.88 &7.00 &7.05 &7.06& 7.03 & 7.06\\
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$^1A_1 (\pi \rightarrow \pi^\star)$ &8.51 &8.32 &8.28 &8.28 &8.28& 8.22 & 8.26\\
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$^3B_1 (n \rightarrow \pi^\star)$ &4.02 &3.90 &3.91 &3.93 &3.92& 3.93 & 3.94\\
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$^3B_2 (\pi \rightarrow \pi^\star)$ &4.92 &4.90 &4.89 &4.91 &4.90& 4.91 & 4.92\\
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$^3A_2 (n \rightarrow \pi^\star)$ &5.48 &5.38 &5.37 &5.39 &5.37& 5.39 & 5.39\\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &6.89 &6.79 &6.83 &6.84 &6.83& 6.84 & 6.85\\
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\hline
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& \multicolumn{7}{c}{Cyclopropenethione} \\
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\hline
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$^1A_2 (n \rightarrow \pi^\star)$ &3.46 &3.47 &3.43 &3.44 &3.42& 3.44 & 3.43 \\
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$^1B_1 (n \rightarrow \pi^\star)$ &3.45 &3.42 &3.43 &3.45 &3.43& 3.45 & 3.46\\
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$^1B_2 (\pi \rightarrow \pi^\star)$ &4.67 &4.66 &4.64 &4.66 &4.64& 4.66 & 4.66 \\
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$^1B_2 (n \rightarrow 3s)$ &5.26 &5.23 &5.34 &5.39 &5.39& 5.38 & 5.40 \\
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$^1A_1 (\pi \rightarrow \pi^\star)$ &5.53 &5.52 &5.49 &5.49 &5.48& 5.49 & 5.49\\
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$^1B_2 (n \rightarrow 3p)$ &5.83 &5.86 &5.93 &5.95 &5.95& 5.91 & 5.95 \\%$^a$, mais les autres aussi !!
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$^3A_2 (n \rightarrow \pi^\star)$ &3.33 &3.34 &3.31 &3.31 &3.29& 3.31 & 3.31 \\
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$^3B_1 (n \rightarrow \pi^\star)$ &3.34 &3.30 &3.31 &3.34 &3.32& 3.34 & 3.35\\
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$^3B_2 (\pi \rightarrow \pi^\star)$ &4.01 &4.03 &4.02 &4.04 &4.03& 4.04 & 4.05 \\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &4.06 &4.09 &4.03 &4.04 &4.02& 4.04& 4.03 \\
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\hline
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& \multicolumn{7}{c}{Methylenecyclopropene} \\
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\hline
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$^1B_2 (\pi \rightarrow \pi^\star)$ &4.38 &4.32 &4.31 &4.31 &4.31& 4.31& 4.32 \\
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$^1B_1 (\pi \rightarrow 3s)$ &5.65 &5.35 &5.44 &5.47 &5.48& 5.46& 5.47\\
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$^1A_2 (\pi \rightarrow 3p)$ &5.97 &5.86 &5.95 &5.98 &5.99& 5.96& 5.97\\
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$^1A_1 (\pi \rightarrow \pi^\star)$ &6.17 &6.15 &6.13 &6.09 &6.10& 5.98& 6.04\\
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$^3B_2 (\pi \rightarrow \pi^\star)$ &3.50 &3.49 &3.50 &3.50 &3.50& 3.50& 3.51\\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &4.74 &4.74 &4.74 &4.75 &4.74& 4.74& 4.75\\
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\hline
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\end{tabular}
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\begin{flushleft}
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%$^a${Significant mixing.}
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\end{flushleft}
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\end{small}
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\end{table}
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\clearpage
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\subsection{Acrolein, butadiene, and glyoxal}
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\begin{sidewaystable}[htp]
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\caption{\small CC3 vertical transition energies of acrolein, butadiene, and glyoxal using various atomic basis sets.
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FC stands for frozen core. All values are in eV.}
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\label{Table-S3}
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\begin{small}
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\begin{tabular}{l|ccccccc}
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\hline
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& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} &{\AVFZ}\\
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& FC & FC &FC & FC & Full & FC & FC \\
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\hline
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& \multicolumn{6}{c}{Acrolein} \\
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\hline
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$^1A'' (n \rightarrow \pi^\star)$ &3.83 &3.77 &3.74 &3.75 &3.74\\
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$^1A' (\pi \rightarrow \pi^\star)$ &6.83 &6.67 &6.65 &6.65 &6.65\\
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$^1A'' (n \rightarrow \pi^\star)$ &6.94 &6.75 &6.75 &6.77 &6.76\\
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$^1A' (n \rightarrow 3s)$ &7.22 &6.99 &7.07 &7.11 &7.11\\
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$^3A'' (n \rightarrow \pi^\star)$ &3.55 &3.47 &3.46 &3.47 &3.46\\
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$^3A' (\pi \rightarrow \pi^\star)$ &3.94 &3.95 &3.94 &3.95 &3.94\\
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$^3A' (\pi \rightarrow \pi^\star)$ &6.25 &6.22 &6.19 &6.20 &6.19\\
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$^3A'' (n \rightarrow \pi^\star)$ &6.81 &6.60 &6.61 &6.63 &6.62\\
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\hline
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& \multicolumn{6}{c}{Butadiene} \\
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\hline
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$^1B_u (\pi \rightarrow \pi^\star)$ &6.41 &6.25 &6.22 &6.21 &6.22\\
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$^1B_g (\pi \rightarrow 3s)$ &6.53 &6.26 &6.33 &6.35 &6.36\\
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$^1A_g (\pi \rightarrow \pi^\star)$ &6.73 &6.68 &6.67 &6.67 &6.67& 6.67\\
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$^1A_u (\pi \rightarrow 3p)$ &6.87 &6.57 &6.64 &6.66 &6.67\\
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$^1A_u (\pi \rightarrow 3p)$ &6.93 &6.73 &6.80 &6.82 &6.83\\
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$^1B_u (\pi \rightarrow 3p)$ &7.98 &7.86 &7.68 &7.54 &7.55\\
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$^3B_u (\pi \rightarrow \pi^\star)$ &3.35 &3.36 &3.36 &3.37 &3.36\\
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$^3A_g (\pi \rightarrow \pi^\star)$ &5.22 &5.21 &5.20 &5.21 &5.20\\
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$^3B_g (\pi \rightarrow 3s)$ &6.46 &6.20 &6.28 &6.30 &6.31\\
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\hline
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& \multicolumn{6}{c}{Glyoxal} \\
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\hline
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$^1A_u (n \rightarrow \pi^\star)$ &2.94 &2.90 &2.88 &2.88 &2.87& 2.88& 2.88\\
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$^1B_g (n \rightarrow \pi^\star)$ &4.34 &4.30 &4.27 &4.27 &4.27& 4.27& 4.28 \\
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$^1A_g (n,n \rightarrow \pi^\star,\pi^\star)$&6.74 &6.70 &6.76 &6.76 &6.74& 6.76& 6.75 \\
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$^1B_g (n \rightarrow \pi^\star)$ &6.81 &6.59 &6.58 &6.59 &6.58& 6.58& 6.59 \\
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$^1B_u (n \rightarrow3p)$ &7.72 &7.55 &7.67 &7.72 &7.73& 7.72& 7.74\\
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$^3A_u (n \rightarrow \pi^\star)$ &2.55 &2.49 &2.49 &2.49 &2.49& 2.49& 2.50\\
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$^3B_g (n \rightarrow \pi^\star)$ &3.97 &3.91 &3.90 &3.91 &3.90& 3.91& 3.92\\
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$^3B_u (\pi \rightarrow \pi^\star)$ &5.22 &5.20 &5.17 &5.18 &5.17& 5.18& 5.19\\
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$^3A_g (\pi \rightarrow \pi^\star)$ &6.35 &6.34 &6.30 &6.31 &6.30& 6.31& 6.31\\
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\hline
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\end{tabular}
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\end{small}
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\end{sidewaystable}
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\clearpage
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\subsection{Acetone, cyanoformaldehyde, isobutene, propynal, thioacetone, and thiopropynal}
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies of acetone, cyanoformaldehyde, isobutene, propynal, thioacetone, and thiopropynal using various atomic basis sets.
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FC stands for frozen core. All values are in eV.}
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\label{Table-S4}
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\begin{small}
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\begin{tabular}{l|cccccc}
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\hline
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& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} \\
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& FC & FC &FC & FC & Full & FC\\
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\hline
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& \multicolumn{6}{c}{Acetone} \\
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\hline
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$^1A_2 (n \rightarrow \pi^\star)$ &4.55 &4.50 &4.48 &4.49 &4.48\\
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$^1B_2 (n \rightarrow 3s)$ &6.65 &6.31 &6.43 &6.48 &6.49\\
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$^1A_2 (n \rightarrow 3p)$ &7.83 &7.37 &7.45 &7.48 &7.49\\
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$^1A_1 (n \rightarrow 3p)$ &7.81 &7.39 &7.48 &7.52 &7.53\\
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$^1B_2 (n \rightarrow 3p)$ &7.87 &7.56 &7.59 &7.60 &7.61\\
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$^3A_2 (n \rightarrow \pi^\star)$ &4.21 &4.16 &4.15 &4.17 &4.16\\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &6.32 &6.31 &6.28 &6.30 &6.28\\
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\hline
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& \multicolumn{6}{c}{Cyanoformaldehyde} \\
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\hline
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$^1A'' (n \rightarrow \pi^\star)$ &3.91 &3.86 &3.83 &3.84 &3.83 &3.84\\
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$^1A'' (\pi \rightarrow \pi^\star)$ &6.64 &6.51 &6.42 &6.41 &6.41 &6.41\\
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$^3A'' (n \rightarrow \pi^\star)$ &3.53 &3.47 &3.46 &3.47 &3.46 &3.47\\
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$^3A' (\pi \rightarrow \pi^\star)$ &5.07 &5.03 &5.01 &5.02 &5.01 &5.02\\
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\hline
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& \multicolumn{6}{c}{Isobutene} \\
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\hline
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$^1B_1 (\pi \rightarrow 3s)$ &6.77 &6.39 &6.45 &6.47 &6.49\\
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$^1A_1 (\pi \rightarrow 3p)$ &7.16 &7.00 &7.00 &6.99 &7.00\\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &4.52 &4.54 &4.53 &4.54 &4.54\\
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\hline
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& \multicolumn{6}{c}{Propynal} \\
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\hline
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$^1A'' (n \rightarrow \pi^\star)$ &3.90 &3.85 &3.82 &3.83 &3.82 &3.83\\
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$^1A'' (\pi \rightarrow \pi^\star)$ &5.69 &5.59 &5.51 &5.50 &5.50 &5.50\\
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$^3A'' (n \rightarrow \pi^\star)$ &3.56 &3.50 &3.49 &3.50 &3.49 &3.50\\
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$^3A' (\pi \rightarrow \pi^\star)$ &4.46 &4.40 &4.43 &4.44 &4.43 &4.44\\
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\hline
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& \multicolumn{6}{c}{Thioacetone} \\
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\hline
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$^1A_2 (n \rightarrow \pi^\star)$ &2.58 &2.59 &2.55 &2.56 &\\
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$^1B_2 (n \rightarrow 4s)$ &5.65 &5.44 &5.55 &5.60 &\\
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$^1A_1 (\pi \rightarrow \pi^\star)$ &6.09 &5.97 &5.90 &5.88 &5.87\\
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$^1B_2 (n \rightarrow 4p)$ &6.59 &6.45 &6.51 &6.52 &\\
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$^1A_1 (n \rightarrow 4p)$ &6.95 &6.54 &6.61 &6.64 &6.64\\
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$^3A_2 (n \rightarrow \pi^\star)$ &2.36 &2.36 &2.34 &2.35 &\\
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$^3A_1 (\pi \rightarrow \pi^\star)$ &3.45 &3.51 &3.46 &3.47 &3.46\\
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\hline
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& \multicolumn{5}{c}{Thiopropynal} \\
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|
\hline
|
|
$^1A'' (n \rightarrow \pi^\star)$ &2.09 &2.09 &2.05 &2.06 &2.04\\
|
|
$^3A'' (n \rightarrow \pi^\star)$ &1.84 &1.83 &1.81 &1.82 &1.81\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
\clearpage
|
|
|
|
|
|
\subsection{Cyclopentadiene, furan, imidazole, pyrrole, and thiophene}
|
|
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of furan and pyrrole using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S5}
|
|
\begin{small}
|
|
\begin{tabular}{l|ccccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{{\AVQZ}} \\
|
|
& FC & FC &FC & FC & Full \\
|
|
\hline
|
|
& \multicolumn{5}{c}{Furan} \\
|
|
\hline
|
|
$^1A_2 (\pi \rightarrow 3s)$ &6.26 &6.00 &6.08 &6.10 &6.12\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &6.50 &6.37 &6.34 &6.34 &6.34\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &6.71 &6.62 &6.58 &6.58 &6.58\\
|
|
$^1B_1 (\pi \rightarrow 3p)$ &6.76 &6.55 &6.63 &6.65 &6.67\\
|
|
$^1A_2 (\pi \rightarrow 3p)$ &6.97 &6.73 &6.80 &6.82 &6.83\\
|
|
$^1B_2 (\pi \rightarrow 3p)$ &7.53 &7.39 &7.23 &7.13 &7.14\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &4.28 &4.25 &4.22 &4.22 &4.22\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &5.56 &5.51 &5.48 &5.49 &5.48\\
|
|
$^3A_2 (\pi \rightarrow 3s)$ &6.18 &5.94 &6.02 &6.05 &6.07\\
|
|
$^3B_1 (\pi \rightarrow 3p)$ &6.69 &6.51 &6.59 &6.61 &6.63\\
|
|
\hline
|
|
& \multicolumn{5}{c}{Pyrrole} \\
|
|
\hline
|
|
$^1A_2 (\pi \rightarrow 3s)$ &5.25 &5.15 &5.24 &5.27 &5.28 \\
|
|
$^1B_1 (\pi \rightarrow 3p)$ &5.99 &5.89 &5.98 &6.01 &6.02 \\
|
|
$^1A_2 (\pi \rightarrow 3p)$ &6.27 &5.94 &6.01 &6.03 &6.05 \\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &6.33 &6.28 &6.25 &6.22 &6.23 \\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &6.43 &6.35 &6.32 &6.31 &6.31 \\
|
|
$^1B_2 (\pi \rightarrow 3p)$ &7.20 &7.00 &6.83 &6.74 &6.75 \\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &4.59 &4.56 &4.53 &4.53 &4.52 \\
|
|
$^3A_2 (\pi \rightarrow 3s)$ &5.22 &5.12 &5.21 &5.24 &5.26 \\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &5.54 &5.49 &5.46 &5.47 &5.46 \\
|
|
$^3B_1 (\pi \rightarrow 3p)$ &5.91 &5.82 &5.92 &5.95 &5.97 \\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of cyclopentadiene, imidazole, and thiophene using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S6}
|
|
\begin{small}
|
|
\begin{tabular}{l|cccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & {{\AVQZ}} \\
|
|
& FC & FC &FC & FC \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Cyclopentadiene} \\
|
|
\hline
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &5.79 &5.59 &5.54 &5.53 \\
|
|
$^1A_2 (\pi \rightarrow 3s)$ &6.08 &5.70 &5.77 &5.79 \\
|
|
$^1B_1 (\pi \rightarrow 3p)$ &6.57 &6.34 &6.40 &6.42 \\
|
|
$^1A_2 (\pi \rightarrow 3p)$ &6.67 &6.39 &6.45 &6.46 \\
|
|
$^1B_2 (\pi \rightarrow 3p)$ &7.06 &6.55 &6.56 &6.55 \\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &6.67 &6.59 &6.57 &6.57 \\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &3.33 &3.32 &3.32 &3.32 \\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &5.16 &5.14 &5.12 &5.13 \\
|
|
$^3A_2 (\pi \rightarrow 3s)$ &6.01 &5.65 &5.73 &5.75 \\
|
|
$^3B_1 (\pi \rightarrow 3p)$ &6.51 &6.30 &6.36 &6.38 \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Imidazole} \\
|
|
\hline
|
|
$^1A'' (\pi \rightarrow 3s)$ &5.77 &5.60 &5.71 &5.73 \\
|
|
$^1A' (\pi \rightarrow \pi^\star)$ &6.51 &6.43 &6.41 &6.41 \\
|
|
$^1A'' (n \rightarrow \pi^\star)$ &6.66 &6.42 &6.50 &6.53 \\
|
|
$^1A' (\pi \rightarrow 3p)$ &7.04 &6.93 &6.87 &6.86 \\
|
|
$^3A' (\pi \rightarrow \pi^\star)$ &4.83 &4.78 &4.75 &4.76 \\
|
|
$^3A'' (\pi \rightarrow 3s)$ &5.72 &5.57 &5.67 &5.70 \\
|
|
$^3A' (\pi \rightarrow \pi^\star)$ &5.88 &5.78 &5.74 &5.75 \\
|
|
$^3A'' (n \rightarrow \pi^\star)$ &6.48 &6.37 &6.33 &6.33 \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Thiophene} \\
|
|
\hline
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &5.79 &5.70 &5.65 &5.64\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &6.23 &6.05 &5.96 &5.94\\
|
|
$^1A_2 (\pi \rightarrow 3s)$ &6.26 &6.07 &6.14 &6.16\\
|
|
$^1B_1 (\pi \rightarrow 3p)$ &6.18 &6.19 &6.14 &6.11\\
|
|
$^1A_2 (\pi \rightarrow 3p)$ &6.32 &6.33 &6.25 &6.22\\
|
|
$^1B_1 (\pi \rightarrow 3s)$ &6.62 &6.42 &6.50 &6.53\\
|
|
$^1B_2 (\pi \rightarrow 3p)$ &7.45 &7.45 &7.29 &7.18\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &7.50 &7.41 &7.35 &7.33\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &3.95 &3.96 &3.94 &3.93\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &4.90 &4.82 &4.77 &4.77\\
|
|
$^3B_1 (\pi \rightarrow 3p)$ &6.00 &6.01 &5.95 &5.92\\
|
|
$^3A_2 (\pi \rightarrow 3s)$ &6.20 &6.01 &6.09 &5.99\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
|
|
\clearpage
|
|
|
|
\subsection{Benzene, pyrazine, and tetrazine}
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of benzene using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S7}
|
|
\begin{small}
|
|
\begin{tabular}{l|cccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & {\AVQZ} \\
|
|
& FC & FC &FC & FC \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Benzene} \\
|
|
\hline
|
|
$^1B_{2u} (\pi \rightarrow \pi^\star)$ &5.13 &5.11 &5.09 &5.09\\
|
|
$^1B_{1u} (\pi \rightarrow \pi^\star)$ &6.68 &6.50 &6.44 &6.43\\
|
|
$^1E_{1g} (\pi \rightarrow 3s)$ &6.75 &6.46 &6.52 &6.54\\
|
|
$^1A_{2u} (\pi \rightarrow 3p)$ &7.24 &7.02 &7.08 &7.10\\
|
|
$^1E_{2u} (\pi \rightarrow 3p)$ &7.34 &7.09 &7.15 &7.16\\
|
|
$^3B_{1u} (\pi \rightarrow \pi^\star)$ &4.18 &4.19 &4.18 &4.19\\
|
|
$^3E_{1u}(\pi \rightarrow \pi^\star)$ &4.95 &4.89 &4.86 &4.87\\
|
|
$^3B_{2u} (\pi \rightarrow \pi^\star)$ &6.06 &5.86 &5.81 &5.81\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
\clearpage
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of pyrazine and tetrazine using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S8}
|
|
\begin{small}
|
|
\begin{tabular}{l|ccccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{{\AVQZ}} \\
|
|
& FC & FC &FC & FC & Full \\
|
|
\hline
|
|
& \multicolumn{5}{c}{Pyrazine} \\
|
|
\hline
|
|
$^1B_{3u} (n \rightarrow \pi^\star)$ & 4.28 &4.19 &4.14 &4.14& 4.13\\
|
|
$^1A_{u} (n \rightarrow \pi^\star)$ & 5.08 &4.98 &4.97 &4.98& 4.97\\
|
|
$^1B_{2u} (\pi \rightarrow \pi^\star)$ & 5.10 &5.07 &5.03 &5.02& 5.02\\
|
|
$^1B_{2g} (n \rightarrow \pi^\star)$ & 5.86 &5.78 &5.71 &5.71& 5.69\\
|
|
$^1A_{g} (n \rightarrow 3s)$ & 6.74 &6.54 &6.66 &6.70& 6.71\\
|
|
$^1B_{1g} (n \rightarrow \pi^\star)$ & 6.87 &6.75 &6.73 &6.73& 6.71\\
|
|
$^1B_{1u} (\pi \rightarrow \pi^\star)$ & 7.10 &6.92 &6.86 &6.85& 6.85\\
|
|
$^1B_{1g} (\pi \rightarrow 3s)$ & 7.36 &7.13 &7.20 &7.23& 7.24\\
|
|
$^1B_{2u} (n \rightarrow 3p)$ & 7.39 &7.14 &7.25 &7.29& 7.30\\
|
|
$^1B_{1u} (n \rightarrow 3p)$ & 7.56 &7.38 &7.45 &7.48& 7.49\\
|
|
$^1B_{1u} (\pi \rightarrow \pi^\star)$ & 8.19 &7.99 &7.94 &7.93& 7.93\\
|
|
$^3B_{3u} (n \rightarrow \pi^\star)$ & 3.68 &3.60 &3.59 &3.59& 3.59\\
|
|
$^3B_{1u} (\pi \rightarrow \pi^\star)$ & 4.39 &4.40 &4.39 &4.40& 4.39\\
|
|
$^3B_{2u} (\pi \rightarrow \pi^\star)$ & 4.56 &4.46 &4.40 &4.40& 4.40\\
|
|
$^3A_{u} (n \rightarrow \pi^\star)$ & 5.05 &4.93 &4.93 &4.94& 4.93\\
|
|
$^3B_{2g} (n \rightarrow \pi^\star)$ & 5.18 &5.11 &5.08 &5.09& 5.07\\
|
|
$^3B_{1u} (\pi \rightarrow \pi^\star)$ & 5.38 &5.32 &5.29 &5.29& 5.28\\
|
|
\hline
|
|
& \multicolumn{5}{c}{Tetrazine} \\
|
|
\hline
|
|
$^1B_{3u} (n \rightarrow \pi^\star)$ & 2.53 &2.49 &2.46 &2.45 &2.45\\
|
|
$^1A_{u} (n \rightarrow \pi^\star)$ & 3.75 &3.69 &3.67 &3.68 &3.67\\
|
|
$^1A_{g} (n,n \rightarrow \pi^\star, \pi^\star)$ & 6.22 &6.22 &6.21 &6.19 &6.17\\
|
|
$^1B_{1g} (n \rightarrow \pi^\star)$ & 5.01 &4.97 &4.91 &4.90 &4.88\\
|
|
$^1B_{2u} (\pi \rightarrow \pi^\star)$ & 5.29 &5.27 &5.23 &5.22 &5.21\\
|
|
$^1B_{2g} (n \rightarrow \pi^\star)$ & 5.56 &5.53 &5.46 &5.46 &5.45\\
|
|
$^1A_{u} (n \rightarrow \pi^\star)$ & 5.61 &5.59 &5.52 &5.52 &5.50\\
|
|
$^1B_{3g} (n,n \rightarrow \pi^\star, \pi^\star)$ & 7.64 &7.62 &7.62 &7.60 &7.58\\
|
|
$^1B_{2g} (n \rightarrow \pi^\star)$ & 6.24 &6.17 &6.13 &6.13 &6.10\\
|
|
$^1B_{1g} (n \rightarrow \pi^\star)$ & 7.04 &6.98 &6.92 &6.92 &6.91\\
|
|
$^3B_{3u} (n \rightarrow \pi^\star)$ & 1.87 &1.86 &1.85 &1.86 &1.85\\
|
|
$^3A_{u} (n \rightarrow \pi^\star)$ & 3.48 &3.43 &3.44 &3.45 &3.43\\
|
|
$^3B_{1g} (n \rightarrow \pi^\star)$ & 4.25 &4.23 &4.20 &4.21 &4.18\\
|
|
$^3B_{1u} (\pi \rightarrow \pi^\star)$ & 4.54 &4.54 &4.54 &4.54 &4.53\\
|
|
$^3B_{2u} (\pi \rightarrow \pi^\star)$ & 4.65 &4.58 &4.52 &4.52 &4.51\\
|
|
$^3B_{2g} (n \rightarrow \pi^\star)$ & 5.11 &5.09 &5.05 &5.05 &5.04\\
|
|
$^3A_{u} (n \rightarrow \pi^\star)$ & 5.17 &5.15 &5.11 &5.11 &5.10\\
|
|
$^3B_{3g} (n,n \rightarrow \pi^\star, \pi^\star)$ & 7.35 &7.33 &7.35 &7.34 &7.32\\
|
|
$^3B_{1u} (\pi \rightarrow \pi^\star)$ & 5.51 &5.46 &5.42 &5.43 &5.42\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
\clearpage
|
|
|
|
\subsubsection{Pyridazine, pyridine, pyrimidine and triazine}
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of pyridazine and pyridine using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S9}
|
|
\begin{small}
|
|
\begin{tabular}{l|cccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & {\AVQZ} \\
|
|
& FC & FC &FC & FC \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Pyridazine} \\
|
|
\hline
|
|
$^1B_1 (n \rightarrow \pi^\star)$ &3.95 &3.86 &3.83 &3.83\\
|
|
$^1A_2 (n \rightarrow \pi^\star)$ &4.49 &4.39 &4.37 &4.38\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &5.36 &5.33 &5.29 &5.29\\
|
|
$^1A_2 (n \rightarrow \pi^\star)$ &5.88 &5.80 &5.74 &5.74\\
|
|
$^1B_2 (n \rightarrow 3s)$ &6.26 &6.06 &6.17 &6.21\\
|
|
$^1B_1 (n \rightarrow \pi^\star)$ &6.51 &6.41 &6.37 &6.37\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &6.96 &6.79 &6.74 &6.73\\
|
|
$^3B_1 (n \rightarrow \pi^\star)$ &3.27 &3.20 &3.19 &3.20\\
|
|
$^3A_2 (n \rightarrow \pi^\star)$ &4.19 &4.11 &4.11 &4.12\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &4.39 &4.39 &4.38 &4.39\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &4.93 &4.87 &4.83 &4.82\\
|
|
\hline
|
|
& \multicolumn{4}{c}{Pyridine} \\
|
|
\hline
|
|
$^1B_1 (n \rightarrow \pi^\star)$ &5.12 &5.01 &4.96& 4.96\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &5.23 &5.21 &5.17& 5.17\\
|
|
$^1A_2 (n \rightarrow \pi^\star)$ &5.55 &5.41 &5.40& 5.41\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &6.84 &6.64 &6.63& 6.62\\
|
|
$^1A_1 (n \rightarrow 3s)$ &6.92 &6.71 &6.76& 6.80\\
|
|
$^1A_2 (\pi \rightarrow 3s)$ &6.98 &6.74 &6.81& 6.83\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ &7.50 &7.40 &7.38& 7.40\\
|
|
$^1B_1 (\pi \rightarrow 3p)$ &7.54 &7.32 &7.38& 7.40\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &7.56 &7.34 &7.39& 7.40\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &4.33 &4.34 &4.33& 4.34\\
|
|
$^3B_1 (n \rightarrow \pi^\star)$ &4.57 &4.47 &4.46& 4.47\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &4.92 &4.83 &4.79& 4.79\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &5.14 &5.08 &5.05& 5.05\\
|
|
$^3A_2 (n \rightarrow \pi^\star)$ &5.51 &5.37 &5.35& 5.37\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ &6.46 &6.30 &6.25& 6.25\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
\clearpage
|
|
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small CC3 vertical transition energies of pyrimidine and triazine using various atomic basis sets.
|
|
FC stands for frozen core. All values are in eV.}
|
|
\label{Table-S10}
|
|
\begin{small}
|
|
\begin{tabular}{l|cccc}
|
|
\hline
|
|
& {\Pop} & {\AVDZ} & {\AVTZ} & {\AVQZ} \\
|
|
& FC & FC &FC & FC \\
|
|
\hline
|
|
& \multicolumn{4}{c}{Pyrimidine} \\
|
|
\hline
|
|
$^1B_1 (n \rightarrow \pi^\star)$ & 4.58 &4.48 &4.44 &4.45\\
|
|
$^1A_2 (n \rightarrow \pi^\star)$ & 4.99 &4.89 &4.86 &4.87\\
|
|
$^1B_2 (\pi \rightarrow \pi^\star)$ & 5.47 &5.44 &5.41 &5.40\\
|
|
$^1A_2 (n \rightarrow \pi^\star)$ & 6.07 &5.98 &5.93 &5.93\\
|
|
$^1B_1 (n \rightarrow \pi^\star)$ & 6.39 &6.29 &6.26 &6.27\\
|
|
$^1B_2 (n \rightarrow 3s)$ & 6.81 &6.61 &6.72 &6.76\\
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ & 7.08 &6.93 &6.87 &6.86\\
|
|
$^3B_1 (n \rightarrow \pi^\star)$ & 4.20 &4.12 &4.10 &4.11\\
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ & 4.55 &4.56 &4.55 &4.56\\
|
|
$^3A_2 (n \rightarrow \pi^\star)$ & 4.77 &4.67 &4.66 &4.67\\
|
|
$^3B_2 (\pi \rightarrow \pi^\star)$ & 5.08 &5.00 &4.96 &4.96\\
|
|
\hline
|
|
& \multicolumn{4}{c}{Triazine} \\
|
|
\hline
|
|
$^1A_1'' (n \rightarrow \pi^\star)$ & 4.85 &4.76 &4.73 &4.74\\
|
|
$^1A_2'' (n \rightarrow \pi^\star)$ & 4.84 &4.78 &4.74 &4.74\\
|
|
$^1E'' (n \rightarrow \pi^\star)$ & 4.89 &4.82 &4.78 &4.79\\
|
|
$^1A_2' (\pi \rightarrow \pi^\star)$ & 5.84 &5.81 &5.78 &5.78\\
|
|
$^1A_1' (\pi \rightarrow \pi^\star)$ & 7.45 &7.31 &7.24 &7.23\\
|
|
$^1E' (n \rightarrow 3s)$ & 7.44 &7.24 &7.35 &7.39\\
|
|
$^1E'' (n \rightarrow \pi^\star)$ & 7.89 &7.82 &7.79 &7.78\\
|
|
$^1E' (\pi \rightarrow \pi^\star)$ & 8.12 &7.97 &7.92 &7.92\\
|
|
$^3A_2'' (n \rightarrow \pi^\star)$ & 4.40 &4.35 &4.33 &4.34\\
|
|
$^3E'' (n \rightarrow \pi^\star)$ & 4.59 &4.52 &4.51 &4.51\\
|
|
$^3A_1'' (n \rightarrow \pi^\star)$ & 4.87 &4.78 &4.75 &4.76\\
|
|
$^3A_1' (\pi \rightarrow \pi^\star)$ & 4.88 &4.88 &4.88 &4.89\\
|
|
$^3E' (\pi \rightarrow \pi^\star)$ & 5.70 &5.64 &5.61 &5.61\\
|
|
$^3A_2' (\pi \rightarrow \pi^\star)$ & 6.85 &6.69 &6.63 &6.62\\
|
|
\hline
|
|
\end{tabular}
|
|
\end{small}
|
|
\end{table}
|
|
|
|
\clearpage
|
|
|
|
|
|
|
|
\clearpage
|
|
|
|
\section{Multiconfigurational results}
|
|
|
|
\subsection{Basis set effects}
|
|
|
|
\begin{table}[htp]
|
|
\caption{\small Vertical transition energies of cyanoacetylene, cyanogen, and diacetylene using various atomic basis sets and
|
|
multi-reference methods. All values are in eV and have been obtained within the FC approximation. The CASPT2 calculations
|
|
are performed with a level shift of 0.3 and a IPEA of 0.25. Pop, AVDZ, AVTZ, and AVQZ respectively stand for {\Pop}, {\AVDZ},
|
|
{\AVTZ}, and {\AVQZ}. }
|
|
\label{Table-S1b}
|
|
\begin{footnotesize}
|
|
\begin{tabular}{l|cccccccccccc}
|
|
\hline
|
|
& \multicolumn{4}{c}{CASPT2(8,8)} & \multicolumn{4}{c}{PC-NEVPT2(8,8)} & \multicolumn{4}{c}{SC-NEVPT2(8,8)} \\
|
|
& Pop &AVDZ & AVTZ & AVQZ & Pop &AVDZ & AVTZ & AVQZ& Pop &AVDZ & AVTZ & AVQZ \\
|
|
\hline
|
|
& \multicolumn{12}{c}{Cyanoacetylene} \\
|
|
\hline
|
|
$^1\Sigma^-$ & & 6.00 & 5.86 & & & 5.93 & 5.78 & & & 5.98 & 5.83 & \\
|
|
$^1\Delta$ & & 6.26 & 6.13 & & & 6.22 & 6.10 & & & 6.27 & 6.14 & \\
|
|
$^3\Sigma^+$ & & 4.47 & 4.45 & & & 4.46 & 4.45 & & & 4.51 & 4.49 & \\
|
|
$^3\Delta$ & & 5.30 & 5.21 & & & 5.28 & 5.19 & & & 5.31 & 5.23 & \\
|
|
\hline
|
|
& \multicolumn{12}{c}{Cyanogen} \\
|
|
\hline
|
|
$^1\Sigma_u^-$ & 6.63 & 6.56 & 6.40 & 6.37 & 6.56 & 6.49 & 6.32 & 6.29 & 6.61 & 6.54 & 6.37 & 6.34 \\
|
|
$^1\Delta_u$ & 6.93 & 6.84 & 6.70 & 6.66 & 6.91 & 6.81 & 6.66 & 6.63 & 6.95 & 6.86 & 6.71 & 6.68 \\
|
|
$^3\Sigma_u^+$ & 4.91 & 4.89 & 4.86 & 4.86 & 4.92 & 4.91 & 4.88 & 4.89 & 4.96 & 4.95 & 4.92 & 4.93 \\
|
|
$^1\Sigma_u^-$[F] & & 5.23 & 5.07 & & & 5.14 & 4.97 & & & 5.17 & 5.01 & \\
|
|
\hline
|
|
& \multicolumn{12}{c}{Diacetylene} \\
|
|
\hline
|
|
$^1\Sigma_u^-$ & & 5.56 & 5.43 & & & 5.47 & 5.33 & & & 5.53 & 5.39 & \\
|
|
$^1\Delta_u$ & & 5.80 & 5.68 & & & 5.73 & 5.61 & & & 5.78 & 5.67 & \\
|
|
$^3\Sigma_u^+$ & & 4.12 & 4.11 & & & 4.09 & 4.08 & & & 4.14 & 4.13 & \\
|
|
$^3\Delta_u$ & & 4.89 & 4.81 & & & 4.86 & 4.78 & & & 4.90 & 4.82 & \\
|
|
\hline
|
|
\end{tabular}
|
|
\end{footnotesize}
|
|
\end{table}
|
|
\clearpage
|
|
|
|
\subsection{Active Spaces}
|
|
|
|
In the following tables, NEVPT2 vertical transition energies are provided using different sizes of active space.
|
|
The composition of the active space is specified in terms of number of active orbitals per irreducible representation only for the NEVPT2 result chosen in the article (Tables $1$--$4$).
|
|
Similarly, the state-averaging procedure and the CASSCF vertical transition energies given correspond to the underlying reference calculation for the final NEVPT2 values of the article.
|
|
Note that, in all these calculations, the ground state is always included in the state averaging procedure.
|
|
In addition, we chose carefully the states to be averaged in the case of non-abelian point groups in order to describe correctly the degeneracy of doubly-degenerate states (e.g., $\Delta$ states of cyanoacetylene, cyanogen and diacetylene, and $E$ states of benzene and triazine).
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acetone.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_2 (\Val; n \ra \pis)$ &(2,3,1,0) &(1,0,0,2) &4.77$^b$ &4.57$^a$,4.48$^b$ \\
|
|
$^1B_2 (\Ryd; n \ra 3s)$ &(4,2,1,0) &(1,0,2,0) &5.50$^c$ &6.81$^c$ \\
|
|
$^1A_2 (\Ryd; n \ra 3p)$ &(2,3,1,0) &(1,0,0,2) &7.46$^b$ &7.65$^b$ \\
|
|
$^1A_1 (\Ryd; n \ra 3p)$ &(2,2,2,0) &(2,0,0,0) &7.03$^d$ &7.75$^d$ \\
|
|
$^1B_2 (\Ryd; n \ra 3p)$ &(4,2,1,0) &(1,0,2,0) &6.44$^c$ &7.91$^c$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ &(2,2,1,0) &(1,0,0,1) &4.47$^a$ &4.20$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ &(2,2,0,0) &(2,0,0,0) &6.22$^e$ &6.28$^e$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,5o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $3p_x$ orbitals.
|
|
$^c$Using reference (6e,7o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$, $3s$ and $3p_z$ orbitals.
|
|
$^d$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $3p_y$ orbitals.
|
|
$^e$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acrolein.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a',a'')$ & $(A',A'')$ \\
|
|
\hline
|
|
$^1A'' (\Val; n \ra \pis)$ & (8,4) & (1,3) & 4.02$^a$ &3.76$^a$,3.73$^b$ \\
|
|
$^1A' (\Val; \pi \ra \pis)$ & (8,4) & (4,0) & 8.24$^a$ &6.67$^a$ \\
|
|
$^1A'' (\Val; n \ra \pis)$ & (8,4) & (1,3) & 7.63$^a$ &7.16$^{a,c}$,7.57$^{b,c}$ \\
|
|
$^1A' (\Ryd; n \ra 3s)$ & (8,4) & (4,0) & 6.98$^a$ &7.05$^a$ \\
|
|
$^3A'' (\Val; n \ra \pis)$ & (8,4) & (1,3) & 3.86$^a$ &3.46$^a$,3.44$^b$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ & (8,4) & (4,0) & 4.31$^a$ &3.95$^a$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ & (8,4) & (4,0) & 6.76$^a$ &6.23$^a$ \\
|
|
$^3A'' (\Val; n \ra \pis)$ & (8,4) & (1,3) & 7.47$^a$ &6.83$^{a,d}$,7.06$^{b,d}$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (12e,12o) active space including valence $\pi$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$, $n_\text{O}$ and $3s$ orbitals.
|
|
$^b$Using reference (12e,13o) active space including valence $\pi$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$, $n_\text{O}$, $3s$ and $3p_z$ orbitals.
|
|
$^c$Substantial Rydberg and doubly-excited character.
|
|
$^d$Substantial doubly-excited character.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of benzene.}
|
|
\small
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_g,b_{3u},b_{2u},b_{1g},$ & $(A_g,B_{3u},B_{2u},B_{1g},$ \\
|
|
& $b_{1u},b_{2g},b_{3g},a_u)$ & $B_{1u},B_{2g},B_{3g},A_u)$ \\
|
|
\hline
|
|
$^1B_{2u} (\Val; \pi \ra \pis)$ & (0,0,0,0,2,1,2,1) & (1,1,0,0,0,0,0,0) & 4.98$^a$ &5.32$^a$,5.32$^b$ \\
|
|
$^1B_{1u} (\Val; \pi \ra \pis)$ & (0,0,0,0,4,1,2,2) & (1,1,2,0,0,0,0,0) & 7.27$^b$ &6.01$^a$,6.43$^b$ \\
|
|
$^1E_{1g} (\Ryd; \pi \ra 3s)$ & (1,0,0,0,2,1,2,1) & (1,0,0,0,0,1,1,0) & 5.90$^c$ &6.75$^c$ \\
|
|
$^1A_{2u} (\Ryd; \pi \ra 3p)$ & (0,1,1,0,2,1,2,1) & (1,0,0,0,2,0,0,1) & 6.14$^d$ &7.40$^d$\\
|
|
$^1E_{2u} (\Ryd; \pi \ra 3p)$ & (0,1,1,0,2,1,2,1) & (1,0,0,0,2,0,0,1) & 6.21$^d$ &7.45$^d$ \\
|
|
$^3B_{1u} (\Val; \pi \ra \pis)$ & (0,0,0,0,4,1,2,2) & (1,0,1,0,0,0,0,0) & 3.85$^b$ &4.44$^a$,4.32$^b$\\
|
|
$^3E_{1u}(\Val; \pi \ra \pis)$ & (0,0,0,0,4,1,2,2) & (1,1,1,0,0,0,0,0) & 4.85$^b$ &4.99$^a$,4.92$^b$\\
|
|
$^3B_{2u} (\Val; \pi \ra \pis)$ & (0,0,0,0,4,1,2,2) & (1,1,0,0,0,0,0,0) & 6.75$^b$ &5.30$^a$,5.51$^b$\\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^b$Using reference (6e,9o) active space including valence $\pi$ and three $3p_z$ orbitals.
|
|
$^c$Using reference (6e,7o) active space including valence $\pi$ and $3s$ orbitals.
|
|
$^d$Using reference (6e,8o) active space including valence $\pi$, $3p_x$ and $3p_y$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of butadiene.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_g,a_u,b_u,b_g)$ & $(A_g,A_u,B_u,B_g)$ \\
|
|
\hline
|
|
$^1B_u (\Val; \pi \ra \pis)$ & (0,4,0,4) & (1,0,2,0) & 6.65$^c$ &6.04$^a$,6.73$^b$,6.68$^c$ \\
|
|
$^1B_g (\Ryd; \pi \ra 3s)$ & (4,2,3,2) & (1,0,0,1) & 5.94$^d$ &6.44$^d$ \\
|
|
$^1A_g (\Val; \pi \ra \pis)$ & (3,2,3,2) & (2,0,0,0) & 6.99$^a$ &6.70$^a$ \\
|
|
$^1A_u (\Ryd; \pi \ra 3p)$ & (3,2,5,2) & (1,2,0,0) & 5.95$^e$ &6.84$^e$ \\
|
|
$^1A_u (\Ryd; \pi \ra 3p)$ & (3,2,5,2) & (1,2,0,0) & 6.12$^e$ &7.01$^e$ \\
|
|
$^1B_u (\Ryd; \pi \ra 3p)$ & (0,4,0,4) & (1,0,2,0) & 7.93$^c$ &6.99$^b$,7.45$^c$ \\
|
|
$^3B_u (\Val; \pi \ra \pis)$ & (3,2,3,2) & (1,0,1,0) & 3.55$^a$ &3.40$^a$ \\
|
|
$^3A_g (\Val; \pi \ra \pis)$ & (3,2,3,2) & (2,0,0,0) & 5.52$^a$ &5.30$^a$ \\
|
|
$^3B_g (\Ryd; \pi \ra 3s)$ & (4,2,3,2) & (1,0,0,1) & 5.89$^d$ &6.38$^d$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (10e,10o) active space including valence $\pi$, $\si_\text{CC}$ and $\si^*_\text{CC}$ orbitals.
|
|
$^b$Using reference (10e,11o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3p_z$ orbitals.
|
|
$^c$Using reference (4e,8o) active space including valence $\pi$ and four $3p_z$.
|
|
$^d$Using reference (10e,11o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3s$ orbitals.
|
|
$^e$Using reference (10e,12o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$, $3p_x$ and $3p_y$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoacetylene.}
|
|
\begin{tabularx}{\textwidth}{p{4cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF$^a$ & NEVPT2$^a$ \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1\Sigma^- (\Val; \pi \ra \pis)$ & (0,4,4,0) & (1,0,0,1) & 6.54 & 5.78 \\
|
|
$^1\Delta (\Val; \pi \ra \pis)$ & (0,4,4,0) & (2,0,0,1) & 6.80 & 6.10 \\
|
|
$^3\Sigma^+ (\Val; \pi \ra \pis)$ & (0,4,4,0) & (2,0,0,0) & 4.86 & 4.45 \\
|
|
$^3\Delta (\Val; \pi \ra \pis)$ & (0,4,4,0) & (2,0,0,1) & 5.64 & 5.19 \\
|
|
$^1A'' [\mathrm{F}] (\Val; \pi \ra \pis)$ & ($a'$:4,$a''$:4) & ($A'$:1,$A''$:2) & 4.30 & 3.50 \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoformaldehyde.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a',a'')$ & $(A',A'')$ \\
|
|
\hline
|
|
$^1A'' (\Val; n \ra \pis)$ & (3,4) & (1,2) & 4.02$^a$ & 3.98$^a$ \\
|
|
$^1A'' (\Val; \pi \ra \pis)$ & (3,4) & (1,2) & 7.61$^a$ & 6.44$^a$ \\
|
|
$^3A'' (\Val; n \ra \pis)$ & (3,4) & (1,1) & 3.52$^a$ & 3.58$^a$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ & (2,4) & (2,0) & 4.98$^b$ & 5.35$^b$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$ Using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
|
|
$^b$ Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanogen.}
|
|
\begin{tabularx}{\textwidth}{p{3.5cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF$^a$ & NEVPT2$^a$ \\
|
|
& $(a_g,b_{3u},b_{2u},b_{1g},$ & $(A_g,B_{3u},B_{2u},B_{1g},$ \\
|
|
& $b_{1u},b_{2g},b_{3g},a_u)$ & $B_{1u},B_{2g},B_{3g},A_u)$ \\
|
|
\hline
|
|
$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,0,0,0,1) & 7.14 & 6.32 \\
|
|
$^1\Delta_u (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,1,0,0,1) & 7.46 & 6.66 \\
|
|
$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,1,0,0,0) & 5.28 & 4.88 \\
|
|
$^1\Sigma_u^- [\mathrm{F}] (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,0,0,0,1) & 5.68 & 4.97 \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopentadiene.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (1,0,2,0) & 6.71$^c$ & 4.96$^a$,4.92$^b$,5.65$^c$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3s)$ & (2,2,0,2) & (1,0,0,2) & 5.21$^d$ & 5.92$^d$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3p)$ & (0,2,1,2) & (1,1,0,0) & 6.08$^e$ & 6.42$^e$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3p)$ & (2,2,0,2) & (1,0,0,2) & 5.78$^d$ & 6.59$^d$ \\
|
|
$^1B_2 (\Ryd; \pi \ra 3p)$ & (0,4,0,2) & (1,0,2,0) & 6.16$^c$ & 6.58$^b$,6.60$^c$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,2,0,2) & (3,0,0,0) & 6.49$^{a,f}$ & 6.75$^{a,f}$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,2,0,2) & (1,0,1,0) & 3.26$^a$ & 3.41$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,2,0,2) & (3,0,0,0) & 4.92$^a$ & 5.30$^a$ \\
|
|
$^3A_2 (\Ryd; \pi \ra 3s)$ & (1,2,0,2) & (1,0,0,1) & 5.53$^g$ & 5.73$^g$ \\
|
|
$^3B_1 (\Ryd; \pi \ra 3p)$ & (0,2,1,2) & (1,1,0,0) & 6.05$^e$ & 6.40$^e$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (4e,4o) active space including valence $\pi$ orbitals.
|
|
$^b$Using reference (4e,5o) active space including valence $\pi$ and $3p_x$ orbitals.
|
|
$^c$Using reference (4e,6o) active space including valence $\pi$ and two $3p_x$ orbitals.
|
|
$^d$Using reference (4e,6o) active space including valence $\pi$, $3s$ and $3p_z$ orbitals.
|
|
$^e$Using reference (4e,5o) active space including valence $\pi$ and $3p_y$ orbitals.
|
|
$^f$Strong double-excitation character.
|
|
$^g$Using reference (4e,5o) active space including valence $\pi$ and $3s$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenone.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF$^a$ & NEVPT2$^a$ \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_1 (\Val; n \ra \pis)$ & (2,3,1,1) & (1,3,0,0) & 4.92 & 4.04 \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (0,4,2,1) & (1,0,0,3) & 5.64 & 5.85 \\
|
|
$^1B_2 (\Ryd; n \ra 3s)$ & (2,3,1,1) & (1,0,3,0) & 5.68 & 6.51 \\
|
|
$^1B_2 (\Val; \pi \ra \pis$) & (2,3,1,1) & (1,0,3,0) & 6.40 & 6.82 \\
|
|
$^1B_2 (\Ryd; n \ra 3p)$ & (2,3,1,1) & (1,0,3,0) & 6.35 & 7.07 \\
|
|
$^1A_1 (\Ryd; n \ra 3p)$ & (0,4,2,1) & (4,0,0,0) & 6.84 & 7.28 \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,4,2,1) & (4,0,0,0) & 10.42 & 8.19 \\
|
|
$^3B_1 (\Val; n \ra \pis)$ & (2,3,1,1) & (1,3,0,0) & 4.72 & 3.51 \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (2,3,1,1) & (1,0,3,0) & 4.39 & 5.10 \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (0,4,2,1) & (1,0,0,3) & 5.40 & 5.60 \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,4,2,1) & (4,0,0,0) & 6.59 & 7.16 \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$All calculations using reference (6e,7o) active space.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenethione.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_2 (\Val; n \ra \pis)$ & (0,3,1,1) & (1,0,0,1) & 3.44$^a$ &3.52$^a$ \\
|
|
$^1B_1 (\Val; n \ra \pis)$ & (0,3,1,1) & (1,1,0,0) & 3.57$^a$ &3.50$^a$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (2,3,1,1) & (1,0,3,0) & 4.51$^b$ &4.77$^b$ \\
|
|
$^1B_2 (\Ryd; n \ra 3s)$ & (2,3,1,1) & (1,0,3,0) & 4.59$^b$ &5.35$^b$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,1) & (2,0,0,0) & 6.46$^c$ &5.54$^c$ \\
|
|
$^1B_2 (\Ryd; n \ra 3p)$ & (2,3,1,1) & (1,0,3,0) & 5.27$^b$ &5.99$^b$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (0,3,1,1) & (1,0,0,1) & 3.26$^a$ &3.38$^a$ \\
|
|
$^3B_1 (\Val; n \ra \pis)$ & (0,3,1,1) & (1,1,0,0) & 3.51$^a$ &3.40$^a$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (2,3,1,1) & (1,0,3,0) & 3.80$^b$ &4.21$^c$,4.17$^b$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,3,0,1) & (2,0,0,0) & 3.83$^c$ &4.13$^c$ \\
|
|
\hline& & &
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,5o) active space.
|
|
$^b$Using reference (6e,7o) active space.
|
|
$^c$Using reference (4e,4o) active space.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of diacetylene.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF$^a$ & NEVPT2$^a$ \\
|
|
& $(a_g,b_{3u},b_{2u},b_{1g},$ & $(A_g,B_{3u},B_{2u},B_{1g},$ \\
|
|
& $b_{1u},b_{2g},b_{3g},a_u)$ & $B_{1u},B_{2g},B_{3g},A_u)$ \\
|
|
\hline
|
|
$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,0,0,0,1) & 6.13 & 5.33 \\
|
|
$^1\Delta_u (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,1,0,0,1) & 6.39 & 5.61 \\
|
|
$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,1,0,0,0) & 4.54 & 4.08 \\
|
|
$^3\Delta_u (\Val; \pi \ra \pis)$ & (0,2,2,0,0,2,2,0) & (1,0,0,0,1,0,0,1) & 5.28 & 4.78 \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of furan.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_2 (\Ryd; \pi \ra 3s)$ & (2,3,0,2) & (1,0,0,2) & 5.26$^a$ & 6.28$^a$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (1,0,2,0) & 7.78$^c$ & 5.92$^b$,6.20$^{c,d}$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 6.73$^{b,e}$ & 6.77$^{b,e}$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 6.07$^f$ & 6.71$^f$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3p)$ & (2,3,0,2) & (1,0,0,2) & 5.87$^a$ & 6.99$^a$ \\
|
|
$^1B_2 (\Ryd; \pi \ra 3p)$ & (0,4,0,2) & (1,0,2,0) & 6.54$^c$ & 7.01$^{c,d}$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (1,0,1,0) & 3.94$^b$ & 4.42$^b$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 5.41$^b$ & 5.60$^b$ \\
|
|
$^3A_2 (\Ryd; \pi \ra 3s)$ & (1,3,0,2) & (1,0,0,1) & 5.57$^g$ & 6.08$^g$ \\
|
|
$^3B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 6.04$^f$ & 6.68$^f$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,7o) active space including valence $\pi$, $3s$ and $3p_z$ orbitals.
|
|
$^b$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
|
$^d$Increasing the $\pi$ $3p_x$ active space leads to strong mixing in the zeroth-order wavefunction requiring QD-NEVPT2 (see Pastore et al., Chem. Phys. Lett. 2006, 426, 445--451).
|
|
$^e$Strong double-excitation character.
|
|
$^f$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
|
$^g$Using reference (6e,6o) active space including valence $\pi$ and $3s$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of glyoxal.}
|
|
\begin{tabularx}{\textwidth}{p{4cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_g,a_u,b_u,b_g)$ & $(A_g,A_u,B_u,B_g)$ \\
|
|
\hline
|
|
$^1A_u (\Val; n \ra \pis)$ & (4,2,4,2) & (1,1,0,0) & 3.42$^a$ & 2.90$^a$ \\
|
|
$^1B_g (\Val; n \ra \pis)$ & (4,2,4,3) & (1,0,0,2) & 4.68$^b$ & 4.31$^a$,4.30$^b$ \\
|
|
$^1A_g (\Val; n,n \ra \pis,\pis)$ & (4,2,4,2) & (2,0,0,0) & 5.92$^a$ & 5.52$^a$ \\
|
|
$^1B_g (\Val; n \ra \pis)$ & (4,2,4,3) & (1,0,0,2) & 7.35$^b$ & 6.91$^{a,c}$,6.64$^{b,c}$ \\
|
|
$^1B_u (\Ryd; n \ra 3p)$ & (4,2,5,2) & (1,0,1,0) & 7.04$^d$ & 7.84$^d$ \\
|
|
$^3A_u (\Val; n \ra \pis)$ & (4,2,4,2) & (1,1,0,0) & 3.06$^a$ & 2.49$^a$ \\
|
|
$^3B_g (\Val; n \ra \pis)$ & (4,2,4,2) & (1,0,0,1) & 4.61$^a$ & 3.99$^a$ \\
|
|
$^3B_u (\Val; \pi \ra \pis)$ & (4,2,4,2) & (1,0,1,0) & 5.46$^a$ & 5.17$^a$ \\
|
|
$^3A_g (\Val; \pi \ra \pis)$ & (4,2,4,2) & (2,0,0,0) & 6.69$^a$ & 6.33$^a$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (14e,12o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$ and $\si^*_\text{CO}$ orbitals.
|
|
$^b$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_z$ orbitals.
|
|
$^c$Non-negligible doubly-excited and Rydberg character.
|
|
$^d$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_x$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of imidazole.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a',a'')$ & $(A',A'')$ \\
|
|
\hline
|
|
$^1A'' (\Ryd; \pi \ra 3s)$ &(2,5) &(1,3) &5.04$^b$ &5.97$^a$,5.93$^b$ \\
|
|
$^1A' (\Val; \pi \ra \pis)$ &(0,9) &(3,0) &6.18$^e$ &6.86$^c$,6.81$^d$,6.73$^e$ \\
|
|
$^1A'' (\Val; n \ra \pis)$ &(2,5) &(1,3) &7.13$^b$ &6.97$^f$,6.96$^b$ \\
|
|
$^1A' (\Ryd; \pi \ra 3p)$ &(0,9) &(3,0) &6.73$^e$ &7.08$^d$,7.00$^e$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ &(0,9) &(3,0) &4.55$^e$ &4.98$^c$,4.86$^e$ \\
|
|
$^3A'' (\Ryd; \pi \ra 3s)$ &(2,5) &(1,3) &5.03$^b$ &5.93$^a$,5.91$^b$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ &(0,9) &(3,0) &5.69$^e$ &6.09$^c$,5.91$^e$ \\
|
|
$^3A'' (\Val; n \ra \pis)$ &(2,5) &(1,3) &6.58$^b$ &6.49$^f$,6.48$^b$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,6o) active space including valence $\pi$ and $3s$ orbitals.
|
|
$^b$Using reference (8e,7o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^c$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
|
$^d$Using reference (6e,6o) active space including valence $\pi$ and one $3p_z$ orbitals.
|
|
$^e$Using reference (6e,9o) active space including valence $\pi$ and four $3p_z$ orbitals.
|
|
$^f$Using reference (8e,6o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of isobutene.}
|
|
\begin{tabularx}{\textwidth}{p{3.5cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_1 (\Ryd; \pi \ra 3s)$ &(3,2,0,0) &(1,1,0,0) &6.12$^a$ &6.63$^a$ \\
|
|
$^1A_1 (\Ryd; \pi \ra 3p)$ &(2,3,0,0) &(2,0,0,0) &6.90$^b$ &7.20$^b$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ &(2,2,0,0) &(2,0,0,0) &4.66$^c$ &4.61$^c$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (4e,5o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3s$ orbitals.
|
|
$^b$Using reference (4e,5o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3p_x$ orbitals.
|
|
$^c$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CC}$ and $\si^*_\text{CC}$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of methylenecyclopropene.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,3,0,1) & (1,0,1,0) & 4.47$^a$ &4.37$^a$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3s)$ & (1,3,0,1) & (1,1,0,0) & 4.92$^c$ &5.51$^b$,5.49$^c$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3p)$ & (0,3,1,1) & (1,0,0,1) & 5.37$^c$ &6.00$^c$ \\
|
|
$^1A_1(\Val; \pi \ra \pis)$ & (0,6,0,1) & (5,0,0,0) & 5.37$^e$ &6.33$^d$,6.36$^e$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,3,0,1) & (1,0,1,0) & 3.44$^a$ &3.66$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,5,0,1) & (4,0,0,0) & 4.60$^d$ &4.87$^d$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (4e,4o) active space.
|
|
$^b$Using reference (6e,6o) active space.
|
|
$^c$Using reference (4e,5o) active space.
|
|
$^d$Using reference (4e,6o) active space.
|
|
$^e$Using reference (4e,7o) active space.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of propynal.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a',a'')$ & $(A',A'')$ \\
|
|
\hline
|
|
$^1A'' (\Val; n \ra \pis)$ & (3,4) & (1,2) & 4.00$^a$ & 3.95$^a$ \\
|
|
$^1A'' (\Val; \pi \ra \pis)$ & (3,4) & (1,2) & 6.62$^a$ & 5.50$^a$ \\
|
|
$^3A'' (\Val; n \ra \pis)$ & (3,4) & (1,1) & 3.52$^a$ & 3.59$^a$ \\
|
|
$^3A' (\Val; \pi \ra \pis)$ & (2,4) & (2,0) & 4.69$^b$ & 4.63$^b$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrazine.}
|
|
\begin{tabularx}{\textwidth}{p{3.5cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_g,b_{3u},b_{2u},b_{1g},$ & $(A_g,B_{3u},B_{2u},B_{1g},$ \\
|
|
& $b_{1u},b_{2g},b_{3g},a_u)$ & $B_{1u},B_{2g},B_{3g},A_u)$ \\
|
|
\hline
|
|
$^1B_{3u} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,1,0,0,0,0,0,0) & 4.76$^a$ & 4.17$^a$ \\
|
|
$^1A_{u} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,0,0,0,0,0,0,1) & 5.90$^a$ & 4.77$^a$ \\
|
|
$^1B_{2u} (\Val; \pi \ra \pis)$ & (0,2,0,1,0,2,0,1) & (1,0,1,0,0,0,0,0) & 4.97$^b$ & 5.32$^b$,5.37$^c$ \\
|
|
$^1B_{2g} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,0,0,0,0,1,0,0) & 5.80$^a$ & 5.88$^a$ \\
|
|
$^1A_{g} (\Ryd; n \ra 3s)$ & (2,2,0,1,1,2,0,1) & (2,0,0,0,0,0,0,0) & 6.69$^d$ & 6.70$^d$\\
|
|
$^1B_{1g} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,0,0,1,0,0,0,0) & 7.16$^a$ & 6.75$^a$ \\
|
|
$^1B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,3,0,0,0) & 8.04$^f$ & 6.38$^b$,6.31$^e$,6.81$^f$ \\
|
|
$^1B_{1g} (\Ryd; \pi \ra 3s)$ & (1,2,0,1,0,2,0,1) & (1,0,0,1,0,0,0,0) & 6.73$^g$ & 7.33$^g$ \\
|
|
$^1B_{2u} (\Ryd; n \ra 3p)$ & (1,2,1,1,1,2,0,1) & (1,0,2,0,0,0,0,0) & 7.49$^c$ & 7.25$^c$ \\
|
|
$^1B_{1u} (\Ryd; n \ra 3p)$ & (1,2,0,1,2,2,0,1) & (1,0,0,0,3,0,0,0) & 7.83$^e$ & 7.42$^e$ \\
|
|
$^1B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,3,0,0,0) & 9.65$^f$ & 7.29$^b$,6.96$^e$,8.25$^f$\\
|
|
$^3B_{3u} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,1,0,0,0,0,0,0) & 4.16$^a$ & 3.56$^a$ \\
|
|
$^3B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,2,0,0,0) & 3.98$^f$ & 4.68$^b$,4.57$^f$ \\
|
|
$^3B_{2u} (\Val; \pi \ra \pis)$ & (0,2,0,1,0,2,0,1) & (1,0,1,0,0,0,0,0) & 4.62$^b$ & 4.42$^b$ \\
|
|
$^3A_{u} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,0,0,0,0,0,0,1) & 5.85$^a$ & 4.75$^a$ \\
|
|
$^3B_{2g} (\Val; n \ra \pis)$ & (1,2,0,1,1,2,0,1) & (1,0,0,0,0,1,0,0) & 5.25$^a$ & 5.21$^a$ \\
|
|
$^3B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,2,0,0,0) & 5.15$^f$ & 5.43$^b$,5.35$^f$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3p_y$ orbitals.
|
|
$^d$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^e$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3p_z$ orbitals.
|
|
$^f$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
|
$^g$Using reference (6e,7o) active space including valence $\pi$ and $3s$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
\clearpage
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyridazine.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_1 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,1,0,0) & 4.29$^a$ & 3.80$^a$ \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,0,0,1) & 4.83$^a$ & 4.40$^a$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,3) & (2,0,0,0) & 5.12$^b$ & 5.58$^b$ \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,0,0,2) & 6.26$^a$ & 5.88$^a$ \\
|
|
$^1B_2 (\Ryd; n \ra 3s)$ & (2,3,1,3) & (1,0,1,0) & 5.99$^c$ & 6.21$^c$ \\
|
|
$^1B_1 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,2,0,0) & 7.16$^a$ & 6.64$^a$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,6,0,6) & (1,0,3,0) & 7.58$^e$ & 7.82$^b$,7.19$^d$,7.10$^e$ \\
|
|
$^3B_1 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,1,0,0) & 3.60$^a$ & 3.13$^a$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (1,3,1,3) & (1,0,0,1) & 4.49$^a$ & 4.14$^a$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,6,0,6) & (1,0,1,0) & 4.06$^e$ & 4.65$^b$,4.55$^d$,4.49$^e$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,3,0,3) & (2,0,0,0) & 4.93$^b$ & 4.94$^b$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^d$Using reference (6e,9o) active space including valence $\pi$, $n_\text{N}$ and three $3p_x$ orbitals.
|
|
$^e$Using reference (6e,12o) active space including valence $\pi$, $n_\text{N}$ and six $3p_x$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyridine.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_1 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,2,0,0) & 5.43$^b$ & 5.17$^a$,5.15$^b$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,7,0,3) & (1,0,2,0) & 5.03$^d$ & 5.44$^c$,5.31$^d$ \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (2,4,0,2) & (1,0,0,2) & 6.30$^e$ & 5.32$^a$,5.29$^e$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (2,0,0,0) & 7.90$^c$ & 6.69$^c$ \\
|
|
$^1A_1 (\Ryd; n \ra 3s)$ & (2,4,0,2) & (2,0,0,0) & 6.40$^e$ & 6.99$^e$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3s)$ & (2,4,0,2) & (1,0,0,2) & 6.60$^e$ & 6.96$^f$,6.86$^e$\\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,7,0,3) & (1,0,2,0) & 7.45$^d$ & 8.61$^a$,7.83$^d$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3p)$ & (1,4,1,2) & (1,2,0,0) & 7.12$^b$ & 7.57$^g$,7.45$^b$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (4,0,0,0) & 9.49$^c$ & 6.97$^c$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (2,0,0,0) & 3.98$^c$ & 4.60$^c$ \\
|
|
$^3B_1 (\Val; n \ra \pis)$ & (1,4,0,2) & (1,1,0,0) & 4.65$^a$ & 4.58$^a$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,7,0,3) & (1,0,2,0) & 4.83$^d$ & 4.90$^c$,4.88$^d$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,4,0,2) & (3,0,0,0) & 5.11$^c$ & 5.19$^c$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (1,4,0,2) & (1,0,0,1) & 5.94$^a$ & 5.33$^a$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,7,0,3) & (1,0,2,0) & 6.93$^d$ & 7.00$^c$,6.29$^d$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
$^b$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and $3p_y$ orbitals.
|
|
$^c$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^d$Using reference (6e,10o) active space including valence $\pi$ and four $3p_x$ orbitals.
|
|
$^e$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^d$Using reference (6e,8o) active space including valence $\pi$ and $3s$ orbitals.
|
|
$^g$Using reference (6e,7o) active space including valence $\pi$ and $3p_y$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrimidine.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1B_1 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,1,0,0) & 4.85$^a$ & 4.55$^a$ \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,0,0,1) & 5.52$^a$ & 4.84$^a$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,7,0,4) & (1,0,1,0) & 5.23$^e$ & 5.71$^b$,5.57$^d$,5.53$^e$ \\
|
|
$^1A_2 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,0,0,2) & 6.70$^a$ & 6.02$^a$ \\
|
|
$^1B_1 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,2,0,0) & 7.20$^a$ & 6.40$^a$ \\
|
|
$^1B_2 (\Ryd; n \ra 3s)$ & (2,4,1,2) & (1,0,2,0) & 6.86$^c$ & 6.77$^c$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,7,0,4) & (2,0,0,0) & 7.62$^e$ & 7.47$^b$,7.11$^e$ \\
|
|
$^3B_1 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,1,0,0) & 4.45$^a$ & 4.17$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,7,0,4) & (2,0,0,0) & 4.25$^e$ & 4.84$^b$,4.67$^e$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (1,4,1,2) & (1,0,0,1) & 5.20$^a$ & 4.72$^a$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,7,0,4) & (1,0,1,0) & 5.00$^e$ & 5.08$^b$,5.01$^e$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^d$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
|
$^e$Using reference (6e,11o) active space including valence $\pi$ and five $3p_x$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrrole.}
|
|
\begin{tabularx}{\textwidth}{p{3.5cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_2 (\Ryd; \pi \ra 3s)$ & (1,3,0,2) & (1,0,0,1) & 4.49$^a$ & 5.51$^a$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 5.22$^b$ & 6.32$^b$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3p)$ & (2,3,0,2) & (1,0,0,2) & 4.89$^c$ & 6.44$^c$ \\
|
|
$^1B_2 (\Val; (\pi \ra \pis)$ & (0,4,0,2) & (1,0,2,0) & 7.73$^e$ & 6.48$^{e,f}$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 6.47$^d$ & 6.53$^d$ \\
|
|
$^1B_2 (\Ryd; \pi \ra 3p)$ & (0,4,0,2) & (1,0,2,0) & 5.82$^e$ & 6.50$^d$,6.62$^{e,f}$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (1,0,1,0) & 4.24$^d$ & 4.74$^d$ \\
|
|
$^3A_2 (\Ryd; \pi \ra 3s)$ & (1,3,0,2) & (1,0,0,1) & 4.47$^a$ & 5.49$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 5.52$^d$ & 5.56$^d$ \\
|
|
$^3B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 5.18$^b$ & 6.28$^b$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,6o) active space including valence $\pi$ and $3s$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
|
$^c$Using reference (6e,7o) active space including valence $\pi$, $3s$ and $3p_z$ orbitals.
|
|
$^d$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
|
$^e$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
|
$^f$Increasing the $\pi$ $3p_x$ active space leads to strong mixing in the zeroth-order wavefunction requiring a multi-state treatment (see Roos et al., J. Chem. Phys. 2002, 116, 7526--7536).
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of tetrazine.}
|
|
\begin{tabularx}{\textwidth}{p{4cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_g,b_{3u},b_{2u},b_{1g},$ & $(A_g,B_{3u},B_{2u},B_{1g},$ \\
|
|
& $b_{1u},b_{2g},b_{3g},a_u)$ & $B_{1u},B_{2g},B_{3g},A_u)$ \\
|
|
\hline
|
|
$^1B_{3u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,1,0,0,0,0,0,0) & 2.99$^a$ & 2.35$^a$ \\
|
|
$^1A_{u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,0,1) & 4.37$^a$ & 3.58$^a$ \\
|
|
$^1A_{g} (\Val; n,n \ra \pis, \pis)$ & (1,2,1,1,1,2,1,1) & (2,0,0,0,0,0,0,0) & 5.42$^a$ & 4.61$^a$ \\
|
|
$^1B_{1g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,1,0,0,0,0) & 5.41$^a$ & 4.95$^a$ \\
|
|
$^1B_{2u} (\Val; \pi \ra \pis)$ & (0,2,0,1,0,2,0,1) & (1,0,1,0,0,0,0,0) & 5.04$^b$ & 5.56$^b$ \\
|
|
$^1B_{2g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,1,0,0) & 5.43$^a$ & 5.63$^a$ \\
|
|
$^1A_{u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,0,2) & 6.37$^a$ & 5.62$^a$ \\
|
|
$^1B_{3g} (\Val; n,n \ra \pis, \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,1,0) & 6.59$^a$ & 6.15$^a$ \\
|
|
$^1B_{2g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,2,0,0) & 6.79$^a$ & 6.13$^a$ \\
|
|
$^1B_{1g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,2,0,0,0,0) & 7.18$^a$ & 6.76$^a$ \\
|
|
$^3B_{3u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,1,0,0,0,0,0,0) & 2.38$^a$ & 1.73$^a$ \\
|
|
$^3A_{u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,0,1) & 4.06$^a$ & 3.36$^a$ \\
|
|
$^3B_{1g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,1,0,0,0,0) & 4.66$^a$ & 4.24$^a$ \\
|
|
$^3B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,2,0,0,0) & 3.90$^c$ & 4.80$^b$,4.70$^a$ \\
|
|
$^3B_{2u} (\Val; \pi \ra \pis)$ & (0,2,0,1,0,2,0,1) & (1,0,1,0,0,0,0,0) & 4.68$^b$ & 4.58$^b$ \\
|
|
$^3B_{2g} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,1,0,0) & 5.17$^a$ & 5.27$^a$ \\
|
|
$^3A_{u} (\Val; n \ra \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,0,2) & 6.12$^a$ & 5.13$^a$ \\
|
|
$^3B_{3g} (\Val; n,n \ra \pis, \pis)$ & (1,2,1,1,1,2,1,1) & (1,0,0,0,0,0,1,0) & 6.56$^a$ & 5.51$^a$ \\
|
|
$^3B_{1u} (\Val; \pi \ra \pis)$ & (0,4,0,1,0,2,0,2) & (1,0,0,0,2,0,0,0) & 5.32$^c$ & 5.64$^b$,5.56$^c$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (14e,10o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thioacetone.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_2 (\Val; n \ra \pis)$ & (2,2,1,0) & (1,0,0,1) & 2.72$^a$ & 2.55$^a$ \\
|
|
$^1B_2 (\Ryd; n \ra 4s)$ & (4,2,1,0) & (1,0,2,0) & 4.80$^b$ & 5.72$^b$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (2,2,2,0) & (3,0,0,0) & 6.94$^d$ & 6.09$^c$,6.24$^d$ \\
|
|
$^1B_2 (\Ryd; n \ra 4p)$ & (4,2,1,0) & (1,0,2,0) & 5.57$^b$ & 6.62$^b$ \\
|
|
$^1A_1 (\Ryd; n \ra 4p)$ & (2,2,2,0) & (3,0,0,0) & 6.24$^d$ & 6.52$^d$ \\
|
|
$^3A_2 (\Val; n \ra \pis)$ & (2,2,1,0) & (1,0,0,1) & 2.52$^a$ & 2.32$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (2,2,0,0) & (2,0,0,0) & 3.52$^c$ & 3.48$^c$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,5o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
|
$^b$Using reference (6e,7o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$, 4s and $4p_z$ orbitals.
|
|
$^c$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
|
$^d$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $4p_y$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thiophene.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 6.11$^a$ & 5.84$^a$ \\
|
|
$^1B_2 (\Val; \pi \ra \pis)$ & (0,5,0,2) & (1,0,2,0) & 6.94$^c$ & 5.64$^a$,5.54$^b$,6.10$^c$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3s)$ & (1,3,0,2) & (1,0,0,1) & 5.70$^d$ & 6.20$^d$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 6.02$^e$ & 6.19$^e$ \\
|
|
$^1A_2 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,0,0,1) & 6.05$^e$ & 6.40$^e$,6.52$^f$ \\
|
|
$^1B_1 (\Ryd; \pi \ra 3s)$ & (1,3,1,2) & (1,2,0,0) & 5.78$^f$ & 6.73$^d$, 6.71$^f$ \\
|
|
$^1B_2 (\Ryd; \pi \ra 3p)$ & (0,5,0,2) & (1,0,2,0) & 6.80$^c$ & 7.42$^b$,7.25$^c$ \\
|
|
$^1A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 8.29$^{a,g}$ & 7.39$^{a,g}$ \\
|
|
$^3B_2 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (1,0,1,0) & 3.68$^a$ & 4.13$^a$ \\
|
|
$^3A_1 (\Val; \pi \ra \pis)$ & (0,3,0,2) & (3,0,0,0) & 4.97$^a$ & 4.84$^a$ \\
|
|
$^3B_1 (\Ryd; \pi \ra 3p)$ & (0,3,1,2) & (1,1,0,0) & 5.86$^e$ & 5.98$^e$ \\
|
|
$^3A_2 (\Ryd; \pi \ra 3s)$ & (1,3,0,2) & (1,0,0,1) & 5.65$^d$ & 6.14$^d$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
|
$^c$Using reference (6e,7o) active space including valence $\pi$ and two $3p_x$ orbitals.
|
|
$^d$Using reference (6e,6o) active space including valence $\pi$ and $3s$ orbitals.
|
|
$^e$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
|
$^f$Using reference (6e,7o) active space including valence $\pi$, $3s$ and $3p_y$ orbitals.
|
|
$^g$Strong double-excitation character.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thiopropynal.}
|
|
\begin{tabularx}{\textwidth}{XXXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF$^a$ & NEVPT2$^a$ \\
|
|
& $(a',a'')$ & $(A',A'')$ \\
|
|
\hline
|
|
$^1A'' (\Val; n \ra \pis)$ & (3,4) & (1,1) & 2.06 & 2.05 \\
|
|
$^3A'' (\Val; n \ra \pis)$ & (3,4) & (1,1) & 1.85 & 1.81 \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$All calculations using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\begin{table}
|
|
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of triazine.}
|
|
\begin{tabularx}{\textwidth}{p{3.5cm}XXXX}
|
|
\hline
|
|
State & Active space & State average & CASSCF & NEVPT2 \\
|
|
& $(a_1,b_1,b_2,a_2)$ & $(A_1,B_1,B_2,A_2)$ \\
|
|
\hline
|
|
$^1A_1'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,2,0,2) & 5.88$^a$ & 4.61$^a$ \\
|
|
$^1A_2'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,1,0,0) & 5.14$^a$ & 4.89$^a$ \\
|
|
$^1E'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,2,0,2) & 5.51$^a$ & 4.88$^a$ \\
|
|
$^1A_2' (\Val; \pi \ra \pis)$ & (0,6,0,3) & (1,0,1,0) & 5.55$^d$ & 6.10$^b$,6.15$^c$,5.95$^d$ \\
|
|
$^1A_1' (\Val; \pi \ra \pis)$ & (0,6,0,3) & (2,0,0,0) & 8.20$^d$ & 7.06$^b$,7.30$^d$ \\
|
|
$^1E' (\Ryd; n \ra 3s)$ & (3,4,1,2) & (2,0,2,0) & 6.15$^c$ & 7.45$^c$ \\
|
|
$^1E'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,1,0,1) & 8.26$^a$ & 7.98$^a$ \\
|
|
$^1E' (\Val; \pi \ra \pis)$ & (0,6,0,3) & (4,0,3,0) & 10.03$^d$ & 7.74$^b$,8.34$^d$ \\
|
|
$^3A_2'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,1,0,0) & 4.74$^a$ & 4.51$^a$ \\
|
|
$^3E'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,2,0,2) & 5.14$^a$ & 4.61$^a$ \\
|
|
$^3A_1'' (\Val; n \ra \pis)$ & (2,4,1,2) & (1,2,0,2) & 5.88$^a$ & 4.71$^a$ \\
|
|
$^3A_1' (\Val; \pi \ra \pis)$ & (0,6,0,3) & (2,0,0,0) & 4.46$^d$ & 5.20$^b$,5.05$^d$ \\
|
|
$^3E' (\Val; \pi \ra \pis)$ & (0,6,0,3) & (3,0,1,0) & 5.57$^d$ & 5.83$^b$,5.73$^d$ \\
|
|
$^3A_2' (\Val; (\pi \ra \pis)$ & (0,6,0,3) & (1,0,1,0) & 7.70$^d$ & 5.83$^b$,6.36$^d$ \\
|
|
\hline
|
|
\end{tabularx}
|
|
\begin{flushleft}
|
|
\begin{footnotesize}
|
|
$^a$Using reference (12e,9o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
|
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
|
$^c$Using reference (12e,10o) active space including valence $\pi$, $n_\text{N}$ and $3s$ orbitals.
|
|
$^d$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
|
\end{footnotesize}
|
|
\end{flushleft}
|
|
\end{table}
|
|
|
|
|
|
\clearpage
|
|
|
|
\section{Selected CI results}
|
|
|
|
\begin{landscape}
|
|
\begin{footnotesize}
|
|
\begin{longtable}{p{3.5cm}p{3.5cm}p{2cm}p{1.2cm}p{2.8cm}p{2cm}p{1.2cm}p{2.8cm}}
|
|
\caption{
|
|
Vertical excitations (in eV) for various states of the studied molecules computed with an extrapolated SCI method (exFCI).
|
|
The number of determinants $N_\text{det}$ of the largest SCI wave functions and their corresponding excitation energies are also reported.
|
|
The extrapolation error is estimated as the difference in excitation energy between the largest SCI wave function and its corresponding extrapolated value.
|
|
\label{tab:sCI}}
|
|
\\
|
|
\hline
|
|
Molecule & Transition & \mc{3}{c}{\Pop} & \mc{3}{c}{\AVDZ} \\
|
|
\cline{3-5} \cline{6-8}
|
|
& & $\Ndet$ & SCI & exFCI & $\Ndet$ & SCI & exFCI \\
|
|
\hline
|
|
\endfirsthead
|
|
\hline
|
|
Molecule & Transition & \mc{3}{c}{\Pop} & \mc{3}{c}{\AVDZ} \\
|
|
\cline{3-5} \cline{6-8}
|
|
& & $\Ndet$ & SCI & exFCI & $\Ndet$ & SCI & exFCI \\
|
|
\hline
|
|
\endhead
|
|
\hline \multicolumn{8}{r}{{Continued on next page}} \\
|
|
\endfoot
|
|
\hline
|
|
\endlastfoot
|
|
Acetone & $^1A_2 (\Val; n \ra \pis)$ & $26\,526\,782$ & $4.55$ & $4.60\pm0.05$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3s)$ & $25\,1675\,94$ & $6.91$ & $6.83\pm0.08$ \\ %TO BE CHECKED !!!!!
|
|
% & $^1A_2 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
% & $^1A_1 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
& $^3A_2 (\Val; n \ra \pis)$ & $26\,553\,941$ & $4.22$ & $4.18\pm0.04$ \\
|
|
% & $^3A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
Acrolein & $^1A'' (\Val; n \ra \pis)$ & $23\,273\,572$ & $3.84$ & $3.85\pm0.01$ \\
|
|
% & $^1A' (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^1A'' (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^1A' (\Ryd; n \ra 3s)$ & $$ & $$ & $$ \\
|
|
& $^3A'' (\Val; n \ra \pis)$ & $26\,531\,491$ & $3.59$ & $3.60\pm0.01$
|
|
& $15\,827\,189$ & $3.58$ & $3.51\pm0.07$ \\
|
|
& $^3A' (\Val; \pi \ra \pis)$ & $37\,480\,261$ & $4.01$ & $3.98\pm0.03$
|
|
& $15\,827\,189$ & $4.05$ & $3.96\pm0.09$ \\
|
|
% & $^3A' (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^3A'' (\Ryd; \pi \ra 3s)$ & $$ & $$ & $$ \\
|
|
Butadiene & $^1B_u (\Val; \pi \ra \pis)$ & $20\,552\,493$ & $6.43$ & $6.41\pm0.02$ \\
|
|
% & $^1B_g (\Ryd; \pi \ra 3s)$ & $$ & $$ & $$ \\
|
|
% & $^1A_g (\Val; \pi \ra \pis)$ & $92\,506\,300$ & $6.59$ & $6.55\pm0.04$
|
|
% & $59\,594\,588$ & $6.58$ & $6.51\pm0.07$ \\
|
|
% & $^1A_u (\Ryd; \pi \ra 3p)$ & $$ & $$ & $$ \\
|
|
& $^1A_u (\Ryd; \pi \ra 3p)$ & $20\,552\,493$ & $6.96$ & $6.95\pm0.01$
|
|
& $12\,521\,242$ & $6.72$ & $6.72\pm0.00$ \\
|
|
% & $^1B_u (\Ryd; \pi \ra 3p)$ & $$ & $$ & $$ \\
|
|
& $^3B_u (\Val; \pi \ra \pis)$ & $49\,847\,526$ & $3.40$ & $3.37\pm0.03$ \\
|
|
& $^3A_g (\Val; \pi \ra \pis)$ & & &
|
|
& $17\,235\,280$ & $6.29$ & $6.21\pm0.08$ \\
|
|
& $^3B_g (\Val; \pi \ra 3s)$ & $49\,847\,526$ & $6.43$ & $6.40\pm0.03$ \\
|
|
Cyanoacetylene & $^1\Sigma^- (\Val; \pi \ra \pis)$ & $21\,269\,249$ & $6.01$ & $6.02\pm0.01$
|
|
& $11\,023\,351$ & $5.93$ & $5.84\pm0.09$ \\
|
|
& $^1\Delta (\Val; \pi \ra \pis)$ & $21\,269\,249$ & $6.29$ & $6.28\pm0.01$
|
|
& $11\,023\,351$ & $6.19$ & $6.14\pm0.05$ \\
|
|
& $^3\Sigma^+ (\Val; \pi \ra \pis)$ & $18\,198\,954$ & $4.48$ & $4.45\pm0.03$
|
|
& $25\,646\,703$ & $4.47$ & $4.41\pm0.06$ \\
|
|
& $^3\Delta (\Val; \pi \ra \pis)$ & $18\,198\,954$ & $5.35$ & $5.32\pm0.03$
|
|
& $25\,646\,703$ & $5.28$ & $5.20\pm0.08$ \\
|
|
& $^1A'' [\Fl] (\Val; \pi \ra \pis)$ & $104\,485\,975$ & $3.70$ & $3.67\pm0.03$
|
|
& $62\,248\,690$ & $3.61$ & $3.50\pm0.02$ \\
|
|
Cyanoformaldehyde & $^1A'' (\Val; n \ra \pis)$ & $17\,778\,047$ & $3.94$ & $3.92\pm0.02$
|
|
& $19\,020\,785$ & $3.93$ & $3.98\pm0.05$ \\
|
|
& $^1A'' (\Val; \pi \ra \pis)$ & $17\,778\,047$ & $6.67$ & $6.60\pm0.07$
|
|
& $19\,020\,785$ & $6.57$ & $6.58\pm0.01$ \\
|
|
& $^3A'' (\Val; n \ra \pis)$ & $21\,011\,221$ & $3.54$ & $3.48\pm0.06$
|
|
& $48\,532\,729$ & $3.51$ & $3.52\pm0.01$ \\
|
|
& $^3A' (\Val; \pi \ra \pis)$ & & &
|
|
& $48\,5327\,29$ & $5.10$ & $5.07\pm0.03$ \\
|
|
Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & $12\,1991\,55$ & $6.61$ & $6.58\pm0.03$
|
|
& $20\,9495\,13$ & $6.52$ & $6.44\pm0.08$ \\
|
|
& $^1\Delta_u (\Val; \pi \ra \pis)$ & $12\,1991\,55$ & $6.89$ & $6.87\pm0.02$
|
|
& $20\,9495\,13$ & $6.78$ & $6.74\pm0.04$ \\
|
|
& $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & $34\,1277\,36$ & $4.97$ & $4.91\pm0.06$
|
|
& $25\,7606\,68$ & $4.94$ & $4.87\pm0.07$ \\
|
|
& $^1\Sigma_u^- [\Fl] (\Val; \pi \ra \pis)$ & $21\,4163\,04$ & $5.36$ & $5.31\pm0.05$
|
|
& $28\,8841\,38$ & $5.17$ & $5.26\pm0.09$ \\
|
|
Cyclopropenone & $^1B_1 (\Val; n \ra \pis)$ & $48\,8976\,96$ & $4.40$ & $4.38\pm0.02$ \\
|
|
& $^1A_2 (\Val; n \ra \pis)$ & $24\,5411\,16$ & $5.70$ & $5.64\pm0.06$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3s)$ & $$ & $$ & $$ \\
|
|
% & $^1B_2 (\Val; \pi \ra \pis$) & $$ & $$ & $$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
% & $^1A_1 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
% & $^1A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
& $^3B_1 (\Val; n \ra \pis)$ & $24\,008\,328$ & $4.07$ & $4.00\pm0.07$ \\
|
|
& $^3B_2 (\Val; \pi \ra \pis)$ & $48\,311\,362$ & $4.95$ & $4.95\pm0.00$ \\
|
|
% & $^3A_2 (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^3A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
Cyclopropenethione & $^1A_2 (\Val; n \ra \pis)$ & $39\,385\,657$ & $3.46$ & $3.45\pm0.01$ \\
|
|
& $^1B_1 (\Val; n \ra \pis)$ & $39\,385\,657$ & $3.50$ & $3.44\pm0.05$ \\
|
|
& $^1B_2 (\Val; \pi \ra \pis)$ & $39\,385\,657$ & $4.68$ & $4.59\pm0.09$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3s)$ & $$ & $$ & $$ \\
|
|
% & $^1A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
& $^3A_2 (\Val; n \ra \pis)$ & $23\,904\,962$ & $3.32$ & $3.29\pm0.03$ \\
|
|
% & $^3B_1 (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
& $^3B_2 (\Val; \pi \ra \pis)$ & $23\,904\,962$ & $4.06$ & $4.03\pm0.03$ \\
|
|
% & $^3A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
Diacetylene & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & $18\,955\,451$ & $5.58$ & $5.52\pm0.06$
|
|
& $19\,192\,556$ & $5.45$ & $5.47\pm0.02$ \\
|
|
& $^1\Delta_u (\Val; \pi \ra \pis)$ & $18\,955\,451$ & $5.85$ & $5.84\pm0.01$
|
|
& $19\,192\,556$ & $5.45$ & $5.69\pm0.02$ \\
|
|
& $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & $13\,777\,757$ & $4.11$ & $4.04\pm0.07$
|
|
& $26\,668\,471$ & $4.11$ & $4.07\pm0.04$ \\
|
|
& $^3\Delta_u (\Val; \pi \ra \pis)$ & $13\,777\,757$ & $4.93$ & $4.94\pm0.01$
|
|
& $26\,668\,471$ & $4.87$ & $4.85\pm0.02$ \\
|
|
Glyoxal & $^1A_u (\Val; n \ra \pis)$ & $51\,656\,090$ & $2.96$ & $2.93\pm0.03$
|
|
& $34\,125\,394$ & $2.94$ & $2.93\pm0.01$ \\
|
|
& $^1B_g (\Val; n \ra \pis)$ & $24\,394\,242$ & $4.34$ & $4.28\pm0.06$ \\
|
|
% & $^1A_g (\Val; n,n \ra \pis,\pis)$ & $118\,275\,835$ & $5.69$ & $5.60\pm0.09$ \\
|
|
% & $^1B_g (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^1B_u (\Ryd; n \ra 3p)$ & $$ & $$ & $$ \\
|
|
& $^3A_u (\Val; n \ra \pis)$ & $47\,693\,908$ & $2.58$ & $2.54\pm0.04$ \\
|
|
% & $^3B_g (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^3B_u (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^3A_g (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
Isobutene & $^1B_1 (\Ryd; \pi \ra 3s)$ & $28\,095\,377$ & $6.86$ & $6.78\pm0.08$ \\
|
|
& $^1A_1 (\Ryd; \pi \ra 3p)$ & $59\,728\,169$ & $7.22$ & $7.16\pm0.02$ \\
|
|
& $^3A_1 \Val; (\pi \ra \pis)$ & $32\,440\,621$ & $4.54$ & $4.56\pm0.02$ \\
|
|
Methylenecyclopropene & $^1B_2 (\Val; \pi \ra \pis)$ & $51\,918\,524$ & $4.35$ & $4.32\pm0.03$ \\
|
|
% & $^1B_1 (\Ryd; \pi \ra \sigma^\star)$ & $$ & $$ & $$ \\
|
|
& $^1A_2 (\Ryd; \pi \ra 3p)$ & $25\,146\,911$ & $6.02$ & $5.92\pm0.10$ \\
|
|
& $^1A_1(\Val; \pi \ra \pis)$ & $31\,721\,213$ & $6.21$ & $6.20\pm0.01$ \\
|
|
& $^3B_2 (\Val; \pi \ra \pis)$ & $24\,379\,551$ & $3.50$ & $3.44\pm0.06$
|
|
& $43\,090\,114$ & $3.49$ & $3.45\pm0.04$ \\
|
|
& $^3A_1 (\Val; \pi \ra \pis)$ & $24\,379\,551$ & $4.77$ & $4.67\pm0.10$
|
|
& $43\,090\,114$ & $4.77$ & $4.79\pm0.02$ \\
|
|
Propynal & $^1A'' (\Val; n \ra \pis)$ & $48\,945\,252$ & $3.90$ & $3.84\pm0.06$
|
|
& $28\,249\,344$ & $3.92$ & $3.89\pm0.03$ \\
|
|
& $^1A'' (\Val; \pi \ra \pis)$ & $26\,554\,616$ & $5.72$ & $5.64\pm0.08$
|
|
& $28\,249\,344$ & $5.72$ & $5.63\pm0.09$ \\
|
|
& $^3A'' (\Val; n \ra \pis)$ & $23\,182\,284$ & $3.58$ & $3.54\pm0.04$ \\
|
|
& $^3A' (\Val; \pi \ra \pis)$ & $39\,375\,360$ & $4.52$ & $4.44\pm0.08$ \\
|
|
Thioacetone & $^1A_2 (\Val; n \ra \pis)$ & $26\,515\,070$ & $2.56$ & $2.61\pm0.05$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 4s)$ & $??$ & $??$ & $5.60\pm0.04$ \\
|
|
% & $^1A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
% & $^1A_1 (\Ryd; n \ra 4p)$ & $$ & $$ & $$ \\
|
|
% & $^1B_2 (\Ryd; n \ra 4p)$ & $$ & $$ & $$ \\
|
|
& $^3A_2 (\Val; n \ra \pis)$ & $63\,669\,401$ & $2.36$ & $2.36\pm0.00$ \\
|
|
% & $^3A_1 (\Val; \pi \ra \pis)$ & $$ & $$ & $$ \\
|
|
Thiopropynal & $^1A'' (\Val; n \ra \pis)$ & $15\,782\,429$ & $2.07$ & $2.08\pm0.01$ \\
|
|
% & $^3A'' (\Val; n \ra \pis)$ & $$ & $$ & $$ \\
|
|
\end{longtable}
|
|
\end{footnotesize}
|
|
\begin{flushleft}\begin{footnotesize}
|
|
%$^a${CI convergence too slow to provide reliable estimate.}
|
|
\end{footnotesize}\end{flushleft}
|
|
|
|
\end{landscape}
|
|
|
|
\clearpage
|
|
|
|
\section{Benchmarks}
|
|
|
|
\subsection{Raw data}
|
|
|
|
|
|
\clearpage
|
|
|
|
\begin{landscape}
|
|
\renewcommand*{\arraystretch}{.55}
|
|
\LTcapwidth=\textwidth
|
|
\begin{footnotesize}
|
|
\begin{longtable}{p{3.73cm}p{3.6cm}p{.55cm}|p{1.2cm}p{1.2cm}p{1.2cm}p{1.2cm}p{1.2cm}p{1.6cm}p{1.2cm}p{1.2cm}}\\
|
|
\caption{Comparisons between the TBE(FC)/{\AVTZ} benchmark (see Table 11) and the results obtained with various computational
|
|
approaches using the same basis set. STEOM stands for STEOM-CCSD and CC(3) for CCSDR(3).} \label{Table-SI-b1}\\
|
|
\hline
|
|
Compound & State & TBE & CIS(D) & CC2 & CCSD & STEOM & CC(3) &CCSDT-3& CC3& ADC(2) \\
|
|
\hline
|
|
\endfirsthead
|
|
\hline
|
|
Compound & State & TBE & CIS(D) & CC2 & CCSD & STEOM & CC(3) &CCSDT-3& CC3& ADC(2) \\
|
|
\hline
|
|
\endhead
|
|
\hline \multicolumn{11}{r}{{Continued on next page}} \\
|
|
\endfoot
|
|
\hline
|
|
\endlastfoot
|
|
Acetone &$^1A_2 (\Val; n \ra \pis)$ & 4.47 &4.51 &4.55 &4.54& 4.40 &4.48 &4.49 &4.48 &4.37 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3s)$ & 6.46 &5.91 &5.91 &6.59& 6.62 &6.46 &6.50 &6.43 &5.87 \\
|
|
&$^1A_2 (\mathrm{R}; n \ra 3p)$ & 7.47 &6.83 &6.84 &7.57& &7.47 &7.51 &7.45 &6.81 \\
|
|
&$^1A_1 (\mathrm{R}; n \ra 3p)$ & 7.51 &7.04 &6.89 &7.63& 7.68 &7.52 &7.55 &7.48 &6.85 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3p)$ & 7.62 &6.93 &7.02 &7.72& &7.61 &7.65 &7.59 &6.99 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 4.13 &4.15 &4.16 &4.15& 4.05 & & &4.15 &4.00 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 6.25 &6.50 &6.50 &6.19& 6.05 & & &6.28 &6.37 \\
|
|
Acrolein &$^1A'' (\Val; n \ra \pis)$ & 3.78 &3.89 &3.85 &3.91& 3.85 &3.80 &3.78 &3.74 &3.68 \\
|
|
&$^1A' (\Val; \pi \ra \pis)$ & 6.69 &6.88 &6.80 &6.87& &6.69 &6.71 &6.65 &6.74 \\
|
|
&$^1A'' (\Val; n \ra \pis)$ & \emph{6.72} &7.76 &6.68 &7.27& 6.98 &6.94 &6.89 &6.75 &6.59 \\
|
|
&$^1A' (\mathrm{R}; n \ra 3s)$ & 7.08 &6.92 &6.40 &7.24& 7.25 &7.12 &7.15 &7.07 &6.35 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 3.51 &3.56 &3.49 &3.55& 3.48 & & &3.46 &3.33 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 3.94 &4.14 &4.06 &3.88& 3.72 & & &3.94 &4.05 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 6.18 &6.42 &6.37 &6.14& 6.00 & & &6.19 &6.31 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & \emph{6.54} & &6.55 &7.09& & & &6.61 &6.47 \\
|
|
Benzene &$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.06 &5.32 &5.26 &5.20& 5.01 &5.14 &5.11 &5.09 &5.27 \\
|
|
&$^1B_{1u} (\Val; \pi \ra \pis)$ & 6.45 &6.61 &6.48 &6.50& 6.51 &6.47 &6.45 &6.44 &6.45 \\
|
|
&$^1E_{1g} (\mathrm{R}; \pi \ra 3s)$ & 6.52 &6.57 &6.47 &6.58& 6.65 &6.54 &6.54 &6.52 &6.52 \\
|
|
&$^1A_{2u} (\mathrm{R}; \pi \ra 3p)$ & 7.08 &7.08 &7.00 &7.12& 7.17 &7.10 &7.09 &7.08 &7.06 \\
|
|
&$^1E_{2u} (\mathrm{R}; \pi \ra 3p)$ & 7.15 &7.14 &7.06 &7.20& &7.17 &7.16 &7.15 &7.12 \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.16 &4.47 &4.37 &4.00& & & &4.18 &4.37 \\
|
|
&$^3E_{1u}(\Val; \pi \ra \pis)$ & 4.85 &5.12 &5.08 &4.93& 4.88 & & &4.86 &5.07 \\
|
|
&$^3B_{2u} (\Val; \pi \ra \pis)$ & 5.81 &5.95 &5.89 &5.77& 5.78 & & &5.81 &5.87 \\
|
|
Butadiene &$^1B_u (\Val; \pi \ra \pis)$ & 6.22 &6.24 &6.16 &6.35& 6.33 &6.21 &6.24 &6.22 &6.12 \\
|
|
&$^1B_g (\mathrm{R}; \pi \ra 3s)$ & 6.33 &6.34 &6.26 &6.40& 6.38 &6.33 &6.34 &6.33 &6.31 \\
|
|
&$^1A_g (\Val; \pi \ra \pis)$ & 6.50 &7.35 &7.09 &7.12& &6.86 &6.76 &6.67 &7.14 \\
|
|
&$^1A_u (\mathrm{R}; \pi \ra 3p)$ & 6.64 &6.65 &6.57 &6.71& 6.69 &6.65 &6.66 &6.64 &6.63 \\
|
|
&$^1A_u (\mathrm{R}; \pi \ra 3p)$ & 6.80 &6.78 &6.70 &6.87& 6.92 &6.80 &6.81 &6.80 &6.76 \\
|
|
&$^1B_u (\mathrm{R}; \pi \ra 3p)$ & 7.68 &7.71 &7.63 &7.76& 7.76 &7.68 & &7.68 &7.48 \\
|
|
&$^3B_u (\Val; \pi \ra \pis)$ & 3.36 &3.55 &3.45 &3.29& 3.17 & & &3.36 &3.46 \\
|
|
&$^3A_g (\Val; \pi \ra \pis)$ & 5.20 &5.33 &5.30 &5.17& 5.03 & & &5.20 &5.27 \\
|
|
&$^3B_g (\mathrm{R}; \pi \ra 3s)$ & 6.29 &6.31 &6.21 &6.33& 6.42 & & &6.28 &6.27 \\
|
|
Cyanoacetylene &$^1\Sigma^- (\Val; \pi \ra \pis)$ & 5.80 &6.14 &6.03 &5.88& 5.87 &5.84 &5.81 &5.80 &5.99 \\
|
|
&$^1\Delta (\Val; \pi \ra \pis)$ & 6.07 &6.41 &6.30 &6.15& 6.20 &6.11 &6.09 &6.08 &6.25 \\
|
|
&$^3\Sigma^+ (\Val; \pi \ra \pis)$ & 4.44 &4.89 &4.80 &4.38& 4.35 & & &4.45 &4.77 \\
|
|
&$^3\Delta (\Val; \pi \ra \pis)$ & 5.21 &5.60 &5.50 &5.24& 5.22 & & &5.22 &5.46 \\
|
|
&$^1A'' [\mathrm{F}] (\Val; \pi \ra \pis)$ & 3.54 &3.83 &3.79 &3.58& 3.52 &3.58 &3.54 &3.54 &3.63 \\
|
|
Cyanoformaldehyde &$^1A'' (\Val; n \ra \pis)$ & 3.81 &3.98 &3.97 &3.94& 3.80 &3.87 &3.86 &3.83 &3.83 \\
|
|
&$^1A'' (\Val; \pi \ra \pis)$ & 6.46 &7.10 &6.74 &6.67& 6.56 &6.50 &6.47 &6.42 &6.73 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 3.44 &3.54 &3.51 &3.49& 3.42 & & &3.46 &3.37 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 5.01 &5.43 &5.34 &4.97& 4.89 & & &5.01 &5.27 \\
|
|
Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 6.39 &6.85 &6.72 &6.50& 6.46 &6.44 &6.40 &6.39 &6.67 \\
|
|
& $^1\Delta_u (\Val; \pi \ra \pis)$ & 6.66 &7.15 &7.02 &6.78& 6.80 &6.72 &6.68 &6.66 &6.95 \\
|
|
& $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.91 &5.44 &5.35 &4.84& 4.81 & & &4.90 &5.31 \\
|
|
& $^1\Sigma_u^- [\mathrm{F}] (\Val; \pi \ra \pis)$ & 5.05 &5.61 &5.48 &5.13& 5.07 &5.14 &5.06 &5.06 &5.39 \\
|
|
Cyclopentadiene &$^1B_2 (\Val; \pi \ra \pis)$ & 5.56 &5.62 &5.52 &5.67& 5.59 &5.53 &5.56 &5.54 &5.49 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3s)$ & 5.78 &5.75 &5.66 &5.83& 5.80 &5.78 &5.78 &5.77 &5.71 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.41 &6.33 &6.26 &6.45& 6.44 &6.41 &6.41 &6.40 &6.31 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3p)$ & 6.46 &6.37 &6.30 &6.50& 6.60 &6.46 &6.46 &6.45 &6.35 \\
|
|
&$^1B_2 (\mathrm{R}; \pi \ra 3p)$ & 6.56 &6.50 &6.42 &6.61& 6.65 &6.57 &6.56 &6.56 &6.48 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & \emph{6.52} &7.63 &6.86 &6.96& &6.71 &6.66 &6.57 &6.91 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 3.31 &3.52 &3.42 &3.24& 3.11 & & &3.32 &3.42 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.11 &5.30 &5.36 &5.09& 4.79 & & &5.12 &5.23 \\
|
|
&$^3A_2 (\mathrm{R}; \pi \ra 3s)$ & 5.73 &5.73 &5.62 &5.78& 5.86 & & &5.73 &5.67 \\
|
|
&$^3B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.36 &6.31 &6.22 &6.40& 6.47 & & &6.36 &6.27 \\
|
|
Cyclopropenone &$^1B_1 (\Val; n \ra \pis)$ & 4.26 &4.27 &4.01 &4.53& 4.18 &4.28 &4.31 &4.21 &3.88 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.55 &5.65 &5.65 &5.40& &5.59 &5.59 &5.57 &5.47 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3s)$ & 6.34 &6.32 &5.84 &6.44& 6.36 &6.35 &6.38 &6.32 &5.79 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis$) & 6.54 &6.60 &6.46 &6.82& &6.59 &6.61 &6.54 &6.33 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3p)$ & 6.98 &6.48 &6.56 &7.09& 7.07 &6.98 & &6.96 &6.43 \\
|
|
&$^1A_1 (\mathrm{R}; n \ra 3p)$ & 7.02 &6.54 &6.47 &7.12& &7.02 &7.06 &7.00 &6.41 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 8.28 &8.22 &8.28 &8.35& 8.19 &8.29 & &8.28 &8.10 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 3.93 &4.15 &3.73 &4.18& 4.13 & & &3.91 &3.62 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.88 &5.26 &4.99 &4.91& 4.88 & & &4.89 &4.90 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 5.35 &5.96 &5.45 &5.40& 5.01 & & &5.37 &5.28 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 6.79 &6.97 &7.02 &6.76& 6.39 & & &6.83 &6.84 \\
|
|
Cyclopropenethione &$^1A_2 (\Val; n \ra \pis)$ & 3.41 &3.45 &3.53 &3.51& 3.34 &3.43 &3.46 &3.43 &3.38 \\
|
|
&$^1B_1 (\Val; n \ra \pis)$ & 3.45 &3.56 &3.50 &3.84& &3.51 &3.56 &3.43 &3.37 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 4.60 &5.06 &4.91 &4.98& &4.69 &4.73 &4.64 &4.72 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3s)$ & 5.34 &5.24 &5.22 &5.41& 5.45 &5.34 &5.38 &5.34 &5.17 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.46 &5.47 &5.59 &5.55& &5.48 &5.52 &5.49 &5.36 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3p)$ & 5.92 &5.93 &5.82 &6.03& 6.05 &5.93 &5.97 &5.93 &5.77 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 3.28 &3.34 &3.37 &3.34& 3.23 & & &3.30 &3.23 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 3.32 &3.55 &3.38 &3.69& 3.55 & & &3.31 &3.26 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.01 &4.62 &4.24 &4.16& 4.05 & & &4.02 &4.12 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.01 &4.12 &4.16 &3.97& 3.87 & & &4.03 &4.04 \\
|
|
Diacetylene &$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 5.33 &5.62 &5.51 &5.41& 5.37 &5.37 &5.35 &5.34 &5.49 \\
|
|
&$^1\Delta_u (\Val; \pi \ra \pis)$ & 5.61 &5.86 &5.76 &5.67& 5.64 &5.64 &5.62 &5.61 &5.72 \\
|
|
&$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.10 &4.48 &4.39 &4.01& 4.05 & & &4.08 &4.37 \\
|
|
&$^3\Delta_u (\Val; \pi \ra \pis)$ & 4.78 &5.14 &5.03 &4.82& 4.87 & & &4.80 &5.01 \\
|
|
Furan &$^1A_2 (\mathrm{R}; \pi \ra 3s)$ & 6.09 &6.16 &6.06 &6.17& 6.15 &6.10 &6.09 &6.08 &6.12 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 6.37 &6.59 &6.45 &6.51& 6.45 &6.38 &6.37 &6.34 &6.47 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.56 &7.01 &6.77 &6.85& &6.68 &6.65 &6.58 &6.76 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.64 &6.67 &6.59 &6.71& 6.70 &6.65 &6.64 &6.63 &6.64 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3p)$ & 6.81 &6.84 &6.75 &6.89& 6.93 &6.82 &6.81 &6.80 &6.82 \\
|
|
&$^1B_2 (\mathrm{R}; \pi \ra 3p)$ & 7.24 &7.34 &7.25 &7.32& 7.35 &7.25 & &7.23 &7.29 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.20 &4.51 &4.43 &4.15& 4.17 & & &4.22 &4.41 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.46 &5.69 &5.66 &5.47& 5.61 & & &5.48 &5.59 \\
|
|
&$^3A_2 (\mathrm{R}; \pi \ra 3s)$ & 6.02 &6.13 &6.01 &6.11& 6.20 & & &6.02 &6.08 \\
|
|
&$^3B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.59 &6.64 &6.55 &6.66& 6.73 & & &6.59 &6.61 \\
|
|
Glyoxal &$^1A_u (\Val; n \ra \pis)$ & 2.88 &3.01 &2.91 &3.01& 2.86 &2.92 &2.91 &2.88 &2.83 \\
|
|
&$^1B_g (\Val; n \ra \pis)$ & 4.24 &4.46 &4.44 &4.42& 4.32 &4.32 &4.30 &4.27 &4.27 \\
|
|
&$^1A_g (\Val; n,n \ra \pis,\pis)$ & 5.61 & & & & & &7.26 &6.76 & \\
|
|
&$^1B_g (\Val; n \ra \pis)$ & 6.57 &7.01 &6.51 &7.12& &6.75 &6.73 &6.58 &6.50 \\
|
|
&$^1B_u (\mathrm{R}; n \ra 3p)$ & 7.71 &7.25 &7.16 &7.84& 7.94 &7.71 &7.74 &7.67 &7.18 \\
|
|
&$^3A_u (\Val; n \ra \pis)$ & 2.49 &2.59 &2.47 &2.56& 2.44 & & &2.49 &2.39 \\
|
|
&$^3B_g (\Val; n \ra \pis)$ & 3.89 &4.00 &3.96 &3.96& 3.88 & & &3.90 &3.82 \\
|
|
&$^3B_u (\Val; \pi \ra \pis)$ & 5.15 &5.47 &5.42 &5.10& 4.92 & & &5.17 &5.33 \\
|
|
&$^3A_g (\Val; \pi \ra \pis)$ & 6.30 &6.54 &6.56 &6.23& 6.13 & & &6.30 &6.45 \\
|
|
Imidazole &$^1A'' (\mathrm{R}; \pi \ra 3s)$ & 5.71 &5.81 &5.69 &5.80& 5.91 &5.73 &5.72 &5.71 &5.75 \\
|
|
&$^1A' (\Val; \pi \ra \pis)$ & 6.41 &6.73 &6.51 &6.59& 6.76 &6.47 &6.46 &6.41 &6.50 \\
|
|
&$^1A'' (\Val; n \ra \pis)$ & 6.50 &6.52 &6.47 &6.58& 6.66 &6.53 &6.51 &6.50 &6.51 \\
|
|
&$^1A' (\mathrm{R}; \pi \ra 3p)$ & \emph{6.83} &7.40 &6.41 &7.02& 6.92 &6.93 &6.91 &6.87 & \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 4.73 &5.04 &4.94 &4.68& 4.66 & & &4.75 &4.92 \\
|
|
&$^3A'' (\mathrm{R}; \pi \ra 3s)$ & 5.66 &5.80 &5.66 &5.77& 5.87 & & &5.67 &5.72 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 5.74 &6.06 &5.94 &5.77& 5.60 & & &5.74 &5.93 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 6.31 &6.47 &6.36 &6.40& 6.28 & & &6.33 &6.31 \\
|
|
Isobutene &$^1B_1 (\mathrm{R}; \pi \ra 3s)$ & 6.46 &6.46 &6.37 &6.54& 6.59 &6.46 &6.47 &6.45 &6.43 \\
|
|
&$^1A_1 (\mathrm{R}; \pi \ra 3p)$ & 7.01 &7.01 &6.95 &7.09& 7.11 &7.00 &7.01 &7.00 &6.97 \\
|
|
&$^3A_1 (\Val; (\pi \ra \pis)$ & 4.53 &4.68 &4.62 &4.48& 4.22 & & &4.53 &4.62 \\
|
|
Methylenecyclopropene& $^1B_2 (\Val; \pi \ra \pis)$ & 4.28 &4.72 &4.51 &4.58& 4.76 &4.35 &4.38 &4.31 &4.46 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3s)$ & 5.44 &5.43 &5.35 &5.48& 5.45 &5.44 &5.45 &5.44 &5.38 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3p)$ & 5.96 &5.94 &5.85 &6.00& 6.01 &5.96 &5.97 &5.95 &5.87 \\
|
|
&$^1A_1(\Val; \pi \ra \pis)$ & \emph{6.12} &6.14 &6.09 &6.18& 6.21 &6.12 &6.14 &6.13 &6.09 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 3.49 &3.94 &3.64 &3.57& 3.67 & & &3.50 &3.61 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.74 &4.86 &4.81 &4.69& 4.78 & & &4.74 &4.80 \\
|
|
Propynal & $^1A'' (\Val; n \ra \pis)$ & 3.80 &3.95 &3.96 &3.84& 3.82 &3.86 &3.85 &3.82 &3.78 \\
|
|
&$^1A'' (\Val; \pi \ra \pis)$ & 5.54 &5.95 &5.71 &5.69& 5.72 &5.57 &5.55 &5.51 &5.73 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 3.47 &3.55 &3.53 &3.53& 3.40 & & &3.49 &3.38 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 4.47 &4.81 &4.71 &4.40& 4.38 & & &4.43 &4.67 \\
|
|
Pyrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 4.15 &4.37 &4.14 &4.32& 4.10 &4.21 &4.20 &4.14 &4.17 \\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 4.98 &4.91 &4.86 &5.23& 5.04 &5.04 &5.06 &4.97 &4.88 \\
|
|
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.02 &5.26 &5.14 &5.15& 4.83 &5.09 &5.06 &5.03 &5.17 \\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.71 &6.22 &5.86 &6.00& 5.71 &5.84 &5.80 &5.71 &5.87 \\
|
|
&$^1A_{g} (\mathrm{R}; n \ra 3s)$ & 6.65 &6.20 &6.20 &6.83& 6.86 &6.71 &6.74 &6.66 &6.30 \\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.74 &7.31 &6.67 &7.14& 7.33 &6.85 &6.87 &6.73 &6.67 \\
|
|
&$^1B_{1u} (\Val; \pi \ra \pis)$ & 6.88 &7.13 &6.89 &6.96& &6.90 &6.88 &6.86 &6.88 \\
|
|
&$^1B_{1g} (\mathrm{R}; \pi \ra 3s)$ & 7.21 &7.31 &7.21 &7.26& &7.22 &7.21 &7.20 &7.27 \\
|
|
&$^1B_{2u} (\mathrm{R}; n \ra 3p)$ & 7.24 &7.30 &6.74 &7.44& 7.49 &7.31 &7.35 &7.25 & \\
|
|
&$^1B_{1u} (\mathrm{R}; n \ra 3p)$ & 7.44 &7.19 &7.03 &7.60& &7.50 &7.52 &7.45 & \\
|
|
&$^1B_{1u} (\Val; \pi \ra \pis)$ & \emph{7.98} &7.85 &7.87 &8.20& &7.98 &8.02 &7.94 & \\
|
|
&$^3B_{3u} (\Val; n \ra \pis)$ & 3.59 &3.84 &3.60 &3.70& 3.48 & & &3.59 &3.62 \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.35 &4.76 &4.60 &4.19& 3.93 & & &4.39 &4.57 \\
|
|
&$^3B_{2u} (\Val; (\pi \ra \pis)$ & 4.39 &4.67 &4.57 &4.40& 4.32 & & &4.40 &4.59 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 4.93 &4.93 &4.82 &5.16& 4.97 & & &4.93 &4.84 \\
|
|
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.08 &5.41 &5.17 &5.21& 4.89 & & &5.08 & \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.28 &5.59 &5.59 &5.35& 5.21 & & &5.29 & \\
|
|
Pyridazine &$^1B_1 (\Val; n \ra \pis)$ & 3.83 &4.12 &3.78 &4.03& 3.76 &3.91 &3.89 &3.83 &3.79 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 4.37 &4.84 &4.26 &4.65& 4.44 &4.46 &4.47 &4.37 &4.27 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.26 &5.51 &5.43 &5.43& &5.36 &5.32 &5.29 &5.44 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.72 &5.62 &5.79 &6.01& 5.76 &5.84 &5.82 &5.74 &5.81 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3s)$ & 6.17 &5.83 &5.59 &6.42& 6.45 &6.27 &6.31 &6.17 &5.69 \\
|
|
&$^1B_1 (\Val; n \ra \pis)$ & 6.37 &6.39 &6.33 &6.67& 6.47 &6.46 &6.47 &6.37 &6.35 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 6.75 & &6.86 &6.88& &6.81 &6.77 &6.74 &6.85 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 3.19 &3.50 &3.18 &3.30& 3.06 & & &3.19 &3.19 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 4.11 &4.64 &4.01 &4.31& 4.13 & & &4.11 &4.02 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & \emph{4.34} &4.75 &4.61 &4.17& 3.89 & & &4.38 &4.60 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.82 &5.18 &5.07 &4.86& 4.78 & & &4.83 &5.06 \\
|
|
Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 4.95 &5.22 &4.99 &5.17& 4.94 &5.04 &5.03 &4.96 &4.98 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.14 &5.40 &5.32 &5.29& 5.03 &5.23 &5.20 &5.17 &5.33 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.40 &5.33 &5.28 &5.64& 5.45 &5.46 &5.48 &5.40 &5.27 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.62 &6.84 &6.24 &6.96& 6.98 &6.67 &6.65 &6.63 &6.31 \\
|
|
&$^1A_1 (\mathrm{R}; n \ra 3s)$ & 6.76 &6.38 &6.68 &6.71& &6.83 &6.86 &6.76 &6.65 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3s)$ & 6.82 &6.88 &6.79 &6.87& 6.94 &6.83 &6.83 &6.81 &6.83 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & \emph{7.40} &7.56 &7.37 &7.55& &7.40 & &7.38 &6.87 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3p)$ & 7.38 &7.42 &7.34 &7.43& 7.49 &7.40 &7.40 &7.38 &7.38 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 7.39 &7.56 &7.45 &7.59& &7.44 &7.47 &7.39 &7.48 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.30 &4.66 &4.53 &4.15& 3.93 & & &4.33 &4.53 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 4.46 &4.72 &4.48 &4.59& 4.41 & & &4.46 &4.47 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.79 &5.08 &4.98 &4.83& 4.78 & & &4.79 &4.98 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.04 &5.33 &5.29 &5.11& 5.03 & & &5.05 &5.28 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 5.36 &5.36 &5.24 &5.58& 5.39 & & &5.35 &5.23 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 6.24 &6.40 &6.39 &6.26& 6.25 & & &6.25 &6.35 \\
|
|
Pyrimidine &$^1B_1 (\Val; n \ra \pis)$ & 4.44 &4.57 &4.41 &4.66& 4.36 &4.51 &4.51 &4.44 &4.37 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 4.85 &4.97 &4.77 &5.07& 4.81 &4.92 &4.94 &4.86 &4.73 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.38 &5.58 &5.54 &5.53& 5.15 &5.47 &5.44 &5.41 &5.52 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.92 &6.06 &5.96 &6.20& 5.91 &6.03 &6.02 &5.93 &5.93 \\
|
|
&$^1B_1 (\Val; n \ra \pis)$ & 6.26 &7.22 &6.25 &6.54& 6.26 &6.34 &6.36 &6.26 &6.22 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 3s)$ & 6.70 &6.23 &6.20 &6.88& 6.90 &6.77 &6.81 &6.72 &6.25 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.88 &7.07 &6.84 &6.97& &6.91 &6.89 &6.87 &6.83 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 4.09 &4.31 &4.07 &4.25& 4.02 & & &4.10 &4.05 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & \emph{4.51} &4.91 &4.77 &4.39& 4.11 & & &4.55 &4.76 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 4.66 &5.01 &4.60 &4.83& 4.63 & & &4.66 &4.58 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.96 &5.23 &5.17 &4.99& 4.88 & & &4.96 &5.14 \\
|
|
Pyrrole &$^1A_2 (\mathrm{R}; \pi \ra 3s)$ & 5.24 &5.34 &5.23 &5.34& 5.36 &5.28 &5.26 &5.24 &5.30 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.00 &6.04 &5.91 &6.04& 6.08 &6.01 &6.00 &5.98 &5.94 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3p)$ & 6.00 &6.04 &5.96 &6.09& 6.15 &6.04 &6.03 &6.01 &6.03 \\
|
|
&$^1B_2 (\Val; (\pi \ra \pis)$ & 6.26 &6.62 &6.30 &6.35& 6.44 &6.28 &6.27 &6.25 &6.35 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.30 &6.64 &6.47 &6.51& &6.39 &6.36 &6.32 &6.47 \\
|
|
&$^1B_2 (\mathrm{R}; \pi \ra 3p)$ & 6.83 &7.00 &6.89 &6.93& &6.85 &6.85 &6.83 &6.91 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.51 &4.81 &4.72 &4.45& 4.15 & & &4.53 &4.71 \\
|
|
&$^3A_2 (\mathrm{R}; \pi \ra 3s)$ & 5.21 &5.33 &5.20 &5.30& 5.41 & & &5.21 &5.27 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.45 &5.70 &5.66 &5.49& 5.12 & & &5.46 &5.62 \\
|
|
&$^3B_1 (\mathrm{R}; \pi \ra 3p)$ & 5.91 &6.01 &5.86 &5.97& 6.06 & & &5.92 &5.89 \\
|
|
Tetrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 2.47 &2.67 &2.38 &2.64& 2.36 &2.54 &2.52 &2.46 &2.42 \\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 3.69 &3.93 &3.53 &3.96& 3.73 &3.77 &3.78 &3.67 &3.58 \\
|
|
&$^1A_{g} (\Val; n,n \ra \pis, \pis)$ & \emph{4.61} & & & & & &6.77 &6.21 & \\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 4.93 &5.58 &5.02 &5.26& 4.90 &5.09 &5.03 &4.91 &5.04 \\
|
|
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.21 &5.40 &5.31 &5.37& 4.92 &5.31 &5.26 &5.23 &5.31 \\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.45 &6.09 &5.64 &5.84& 5.49 &5.64 &5.57 &5.46 &5.68 \\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 5.53 &5.64 &5.56 &5.77& 5.50 &5.63 & &5.52 &5.59 \\
|
|
&$^1B_{3g} (\Val; n,n \ra \pis, \pis)$ & \emph{6.15} & & & & & & &7.62 & \\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 6.12 &6.08 &6.18 &6.66& &6.34 &6.32 &6.13 &6.21 \\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.91 &6.39 &6.95 &7.32& &7.04 &7.05 &6.92 &6.97 \\
|
|
&$^3B_{3u} (\Val; n \ra \pis)$ & 1.85 &2.13 &1.81 &1.96& 1.70 & & &1.85 &1.85 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 3.45 &4.00 &3.31 &3.66& 3.47 & & &3.44 &3.35 \\
|
|
&$^3B_{1g} (\Val; n \ra \pis)$ & 4.20 &4.46 &4.27 &4.31& 3.96 & & &4.20 &4.27 \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & \emph{4.49} &4.96 &4.81 &4.27& 3.90 & & &4.54 &4.80 \\
|
|
&$^3B_{2u} (\Val; \pi \ra \pis)$ & 4.52 &4.87 &4.77 &4.53& 4.43 & & &4.52 &4.76 \\
|
|
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.04 &5.47 &5.15 &5.23& 4.91 & & &5.05 &5.16 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 5.11 &5.74 &5.13 &5.28& 5.04 & & &5.11 &5.16 \\
|
|
&$^3B_{3g} (\Val; n,n \ra \pis, \pis)$ & \emph{5.51} & & & & & & &7.35 & \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.42 &5.74 &5.70 &5.52& 5.43 & & &5.42 &5.67 \\
|
|
Thioacetone &$^1A_2 (\Val; n \ra \pis)$ & 2.53 &2.55 &2.63 &2.63& 2.47 &2.55 &2.57 &2.55 &2.47 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 4s)$ & 5.56 &5.59 &5.50 &5.67& 5.72 &5.57 &5.61 &5.55 &5.47 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.88 &6.01 &6.09 &6.01& &5.90 &5.93 &5.90 &5.87 \\
|
|
&$^1B_2 (\mathrm{R}; n \ra 4p)$ & 6.51 &6.54 &6.44 &6.59& 6.62 &6.52 &6.54 &6.51 &6.43 \\
|
|
&$^1A_1 (\mathrm{R}; n \ra 4p)$ & 6.61 &6.52 &6.53 &6.71& 6.76 &6.62 &6.66 &6.61 &6.48 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 2.33 &2.30 &2.33 &2.35& 2.25 & & &2.34 &2.20 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 3.45 &3.60 &3.59 &3.66& 3.22 & & &3.46 &3.52 \\
|
|
Thiophene &$^1A_1 (\Val; \pi \ra \pis)$ & 5.64 &5.77 &5.75 &5.78& &5.69 &5.69 &5.65 &5.72 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.98 &6.24 &6.07 &6.12& &6.00 &5.99 &5.96 &6.07 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3s)$ & 6.14 &6.18 &6.07 &6.22& 6.18 &6.17 &6.15 &6.14 &6.15 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3p)$ & 6.14 &6.44 &6.15 &6.31& 6.23 &6.20 &6.18 &6.14 &6.24 \\
|
|
&$^1A_2 (\mathrm{R}; \pi \ra 3p)$ & 6.21 &6.42 &6.35 &6.32& 6.16 &6.28 &6.28 &6.25 &6.35 \\
|
|
&$^1B_1 (\mathrm{R}; \pi \ra 3s)$ & 6.49 &6.49 &6.48 &6.56& 6.52 &6.52 &6.52 &6.50 &6.51 \\
|
|
&$^1B_2 (\mathrm{R}; \pi \ra 3p)$ & 7.29 &7.37 &7.26 &7.38& 7.35 &7.33 &7.31 &7.29 &7.34 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & \emph{7.31} &7.68 &7.48 &7.57& &7.46 &7.42 &7.35 &7.51 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 3.92 &4.22 &4.12 &3.85& 3.70 & & &3.94 &4.11 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.76 &5.02 &4.91 &4.77& 4.71 & & &4.77 &4.86 \\
|
|
&$^3B_1 (\mathrm{R}; \pi \ra 3p)$ & 5.93 &6.28 &6.00 &6.12& 6.16 & & &5.95 &6.09 \\
|
|
&$^3A_2 (\mathrm{R}; \pi \ra 3s)$ & 6.08 &6.17 &6.03 &6.16& 6.24 & & &6.09 &6.11 \\
|
|
Thiopropynal &$^1A'' (\Val; n \ra \pis)$ & 2.03 &2.14 &2.20 &2.15& 2.06 &2.07 &2.08 &2.05 &2.08 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 1.80 &1.83 &1.84 &1.83& 1.79 & & &1.81 &1.74 \\
|
|
Triazine &$^1A_1'' (\Val; n \ra \pis)$ & 4.72 &4.59 &4.64 &4.92& 4.62 &4.77 &4.80 &4.73 &4.58 \\
|
|
&$^1A_2'' (\Val; n \ra \pis)$ & 4.75 &4.86 &4.75 &4.99& 4.76 &4.82 &4.82 &4.74 &4.69 \\
|
|
&$^1E'' (\Val; n \ra \pis)$ & 4.78 &4.84 &4.72 &4.99& 4.74 &4.84 &4.86 &4.78 &4.66 \\
|
|
&$^1A_2' (\Val; \pi \ra \pis)$ & 5.75 &5.83 &5.89 &5.91& 5.45 &5.85 &5.82 &5.78 &5.83 \\
|
|
&$^1A_1' (\Val; \pi \ra \pis)$ & 7.24 &7.39 &7.32 &7.34& &7.28 &7.27 &7.24 &7.18 \\
|
|
&$^1E' (\mathrm{R}; n \ra 3s)$ & 7.32 &7.83 &6.87 &7.45& &7.37 &7.41 &7.35 &6.89 \\
|
|
&$^1E'' (\Val; n \ra \pis)$ & 7.78 & &7.71 &8.13& &7.96 & &7.79 & \\
|
|
&$^1E' (\Val; \pi \ra \pis)$ & 7.94 &7.84 &7.63 &8.14& &7.95 & &7.92 &7.65 \\
|
|
&$^3A_2'' (\Val; n \ra \pis)$ & 4.33 &4.52 &4.32 &4.51& 4.32 & & &4.33 &4.29 \\
|
|
&$^3E'' (\Val; n \ra \pis)$ & 4.51 &4.71 &4.46 &4.67& 4.47 & & &4.51 &4.42 \\
|
|
&$^3A_1'' (\Val; n \ra \pis)$ & 4.73 &4.65 &4.65 &4.91& 4.43 & & &4.75 &4.59 \\
|
|
&$^3A_1' (\Val; \pi \ra \pis)$ & 4.85 &5.27 &5.12 &4.74& 4.69 & & &4.88 &5.10 \\
|
|
&$^3E' (\Val; \pi \ra \pis)$ & 5.59 &5.91 &5.88 &5.70& 5.61 & & &5.61 &5.82 \\
|
|
&$^3A_2' (\Val; (\pi \ra \pis)$ & 6.62 &6.71 &6.76 &6.59& 6.60 & & &6.63 &6.63 \\
|
|
\end{longtable}
|
|
\end{footnotesize}
|
|
\end{landscape}
|
|
|
|
\clearpage
|
|
|
|
\subsection{Statistical analysis}
|
|
|
|
\begin{table}[htp]
|
|
\caption{MSE (in eV) obtained for various subsets of transition energies.}
|
|
\label{Table-SI-b2}
|
|
\begin{tabular}{lcccccc}
|
|
\hline
|
|
Method & Singlet & Triplet & Valence & Rydberg & $n\rightarrow\pi^\star$ & $\pi\rightarrow\pi^\star$ \\
|
|
\hline
|
|
CIS(D) &0.10 &0.24 &0.24 &-0.05 &0.19 &0.28 \\
|
|
{\AD} &-0.04 &0.07 &0.06 &-0.13 &-0.04 &0.14 \\
|
|
{\CCD} &-0.03 &0.11 &0.10 &-0.17 &0.01 &0.17 \\
|
|
{\STEOM} &0.06 &-0.06 &-0.04 &0.12 &-0.02 &-0.06 \\
|
|
{\CCSD} &0.15 &0.05 &0.12 &0.09 &0.19 &0.07 \\
|
|
CCSDR(3) &0.05 & &0.07 &0.02 &0.08 &0.06 \\
|
|
CCSDT-3 &0.05 & &0.06 &0.03 &0.08 &0.04 \\
|
|
{\CCT} &0.00 &0.01 &0.01 &0.00 &0.00 &0.01 \\
|
|
NEVPT2 &0.10 &0.08 &0.08 &0.12 &0.05 &0.11 \\
|
|
\hline
|
|
\end{tabular}
|
|
\end{table}
|
|
|
|
|
|
\clearpage
|
|
|
|
\section{Geometries}
|
|
|
|
Below, we provide the cartesian coordinates of the compounds investigated in this study.
|
|
These are provided in atomic units (bohr) and they have been obtained at the \CC{3}(full)/{\AVTZ} level of theory.
|
|
|
|
\subsection{Acetone}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 0.18807702
|
|
C 0.00000000 2.42007545 -1.31764698
|
|
C 0.00000000 -2.42007545 -1.31764698
|
|
O 0.00000000 0.00000000 2.48269094
|
|
H 0.00000000 4.03690733 -0.05185132
|
|
H 0.00000000 -4.03690733 -0.05185132
|
|
H 1.66061256 2.48420530 -2.53995285
|
|
H -1.66061256 2.48420530 -2.53995285
|
|
H 1.66061256 -2.48420530 -2.53995285
|
|
H -1.66061256 -2.48420530 -2.53995285
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Acrolein}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C -1.11645072 -0.68348783 0.00000000
|
|
C 1.20647847 0.83714564 0.00000000
|
|
C 3.46831059 -0.28872636 0.00000000
|
|
O -3.23666415 0.19187203 0.00000000
|
|
H -0.80613858 -2.74747338 0.00000000
|
|
H 0.98699813 2.86613511 0.00000000
|
|
H 5.20930864 0.77443560 0.00000000
|
|
H 3.60951559 -2.33000749 0.00000000
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\clearpage
|
|
|
|
\subsection{Benzene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 2.63144965 0.00000000
|
|
C -2.27890225 1.31572483 0.00000000
|
|
C -2.27890225 -1.31572483 0.00000000
|
|
C 0.00000000 -2.63144965 0.00000000
|
|
C 2.27890225 -1.31572483 0.00000000
|
|
C 2.27890225 1.31572483 0.00000000
|
|
H -4.04725813 2.33668557 0.00000000
|
|
H -4.04725813 -2.33668557 0.00000000
|
|
H -0.00000000 -4.67337115 0.00000000
|
|
H 4.04725813 -2.33668557 0.00000000
|
|
H 4.04725813 2.33668557 0.00000000
|
|
H 0.00000000 4.67337115 0.00000000
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Butadiene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 1.14656244 0.00000000 0.75468820
|
|
C -1.14656244 0.00000000 -0.75468820
|
|
C 3.48132647 0.00000000 -0.22482805
|
|
C -3.48132647 0.00000000 0.22482805
|
|
H 0.90770978 0.00000000 2.78883925
|
|
H -0.90770978 0.00000000 -2.78883925
|
|
H 3.77525814 0.00000000 -2.24895470
|
|
H -3.77525814 0.00000000 2.24895470
|
|
H 5.13664967 0.00000000 0.96861890
|
|
H -5.13664967 0.00000000 -0.96861890
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Cyanoacetylene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 -3.59120182
|
|
C 0.00000000 0.00000000 -1.30693904
|
|
C 0.00000000 0.00000000 1.28880240
|
|
N 0.00000000 0.00000000 3.48692211
|
|
H 0.00000000 0.00000000 -5.59619886
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\clearpage
|
|
|
|
\begin{singlespace}
|
|
\noindent Lowest excited state
|
|
\begin{verbatim}
|
|
C 1.99411175 0.00000000 2.81781077
|
|
C -0.07304269 0.00000000 1.33125774
|
|
C -0.63630126 0.00000000 -1.14556678
|
|
N -1.39755756 0.00000000 -3.26154643
|
|
H 1.90749857 0.00000000 4.87279180
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Cyanoformaldehyde}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C -0.91561483 0.00000000 -1.22522833
|
|
C -0.01092219 0.00000000 1.39523175
|
|
N 0.64170259 0.00000000 3.48820325
|
|
O 0.50833684 0.00000000 -3.00337867
|
|
H -2.97202213 0.00000000 -1.42565674
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Cyanogen}
|
|
|
|
\begin{singlespace}
|
|
Ground state
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 1.30401924
|
|
C 0.00000000 0.00000000 -1.30401924
|
|
N 0.00000000 0.00000000 3.49784121
|
|
N 0.00000000 0.00000000 -3.49784121
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\begin{singlespace}
|
|
\noindent Lowest excited state
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 1.22784115
|
|
C 0.00000000 0.00000000 -1.22784115
|
|
N 0.00000000 0.00000000 3.56462559
|
|
N 0.00000000 0.00000000 -3.56462559
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\clearpage
|
|
|
|
|
|
\subsection{Cyclopentadiene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 -2.33113051
|
|
C 0.00000000 2.22209092 -0.56871188
|
|
C 0.00000000 -2.22209092 -0.56871188
|
|
C 0.00000000 1.38514451 1.83772922
|
|
C 0.00000000 -1.38514451 1.83772922
|
|
H 1.66130504 0.00000000 -3.56414299
|
|
H -1.66130504 0.00000000 -3.56414299
|
|
H 0.00000000 4.16550405 -1.18116624
|
|
H 0.00000000 -4.16550405 -1.18116624
|
|
H 0.00000000 2.54514584 3.51352303
|
|
H 0.00000000 -2.54514584 3.51352303
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Cyclopropenone}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 1.27491826 -1.86930519
|
|
C 0.00000000 -1.27491826 -1.86930519
|
|
C 0.00000000 0.00000000 0.51814554
|
|
O 0.00000000 0.00000000 2.79326776
|
|
H 0.00000000 2.92791371 -3.05679837
|
|
H 0.00000000 -2.92791371 -3.05679837
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Cyclopropenethione}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 1.26230744 -2.86571925
|
|
C 0.00000000 -1.26230744 -2.86571925
|
|
C 0.00000000 0.00000000 -0.49233236
|
|
S 0.00000000 0.00000000 2.57821680
|
|
H 0.00000000 2.97773331 -3.95114059
|
|
H 0.00000000 -2.97773331 -3.95114059
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\clearpage
|
|
|
|
\subsection{Diacetylene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 1.29447700
|
|
C 0.00000000 0.00000000 -1.29447700
|
|
C 0.00000000 0.00000000 3.58448429
|
|
C 0.00000000 0.00000000 -3.58448429
|
|
H 0.00000000 0.00000000 5.58943003
|
|
H 0.00000000 0.00000000 -5.58943003
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Furan}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 2.06365826 -0.60051250
|
|
C 0.00000000 -2.06365826 -0.60051250
|
|
C 0.00000000 1.35348578 1.86336416
|
|
C 0.00000000 -1.35348578 1.86336416
|
|
O 0.00000000 0.00000000 -2.13945332
|
|
H 0.00000000 3.86337287 -1.53765695
|
|
H 0.00000000 -3.86337287 -1.53765695
|
|
H 0.00000000 2.59168789 3.47168051
|
|
H 0.00000000 -2.59168789 3.47168051
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Glyoxal}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 1.21360282 0.75840215 0.00000000
|
|
C -1.21360282 -0.75840215 0.00000000
|
|
O 3.25581408 -0.26453186 0.00000000
|
|
O -3.25581408 0.26453186 0.00000000
|
|
H 0.96135276 2.81883243 0.00000000
|
|
H -0.96135276 -2.81883243 0.00000000
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\clearpage
|
|
|
|
|
|
\subsection{Imidazole}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.41662795 2.06006259 0.00000000
|
|
C -1.52618386 -1.62343163 0.00000000
|
|
C 1.04160471 -1.93007427 0.00000000
|
|
N -1.90345764 0.94914956 0.00000000
|
|
N 2.24215443 0.38083431 0.00000000
|
|
H 0.65501634 4.07748278 0.00000000
|
|
H -3.57500545 1.84103166 0.00000000
|
|
H -3.06363894 -2.94559167 0.00000000
|
|
H 2.08673940 -3.67001102 0.00000000
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Isobutene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 2.70790758
|
|
C 0.00000000 0.00000000 0.18431282
|
|
C 0.00000000 2.39894572 -1.32482735
|
|
C 0.00000000 -2.39894572 -1.32482735
|
|
H 0.00000000 1.74848405 3.76691310
|
|
H 0.00000000 -1.74848405 3.76691310
|
|
H 0.00000000 4.05897160 -0.10582007
|
|
H 0.00000000 -4.05897160 -0.10582007
|
|
H 1.66026992 2.48337908 -2.55086178
|
|
H -1.66026992 2.48337908 -2.55086178
|
|
H 1.66026992 -2.48337908 -2.55086178
|
|
H -1.66026992 -2.48337908 -2.55086178
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Methylenecyclopropene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 0.53512883
|
|
C 0.00000000 0.00000000 3.04739824
|
|
C 0.00000000 1.25042956 -1.88571561
|
|
C 0.00000000 -1.25042956 -1.88571561
|
|
H 0.00000000 2.96887531 -2.96270271
|
|
H 0.00000000 -2.96887531 -2.96270271
|
|
H 0.00000000 1.75335023 4.08608382
|
|
H 0.00000000 -1.75335023 4.08608382
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Propynal}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C -0.78051115 0.00000000 -1.38900384
|
|
C -0.17873562 0.00000000 1.27825868
|
|
C 0.23763714 0.00000000 3.52644798
|
|
O 0.80143996 0.00000000 -3.04628328
|
|
H -2.80713069 0.00000000 -1.82768750
|
|
H 0.64026209 0.00000000 5.48853193
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Pyrazine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 2.13188686 1.31510863
|
|
C 0.00000000 -2.13188686 1.31510863
|
|
C 0.00000000 2.13188686 -1.31510863
|
|
C 0.00000000 -2.13188686 -1.31510863
|
|
N 0.00000000 0.00000000 2.66620111
|
|
N 0.00000000 0.00000000 -2.66620111
|
|
H 0.00000000 3.88751412 2.35234226
|
|
H 0.00000000 -3.88751412 2.35234226
|
|
H 0.00000000 3.88751412 -2.35234226
|
|
H 0.00000000 -3.88751412 -2.35234226
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Pyridazine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 1.30150855 -2.31552865
|
|
C 0.00000000 -1.30150855 -2.31552865
|
|
C 0.00000000 2.49271907 0.03513416
|
|
C 0.00000000 -2.49271907 0.03513416
|
|
N 0.00000000 1.26228251 2.23104685
|
|
N 0.00000000 -1.26228251 2.23104685
|
|
H 0.00000000 4.52804172 0.19299731
|
|
H 0.00000000 -4.52804172 0.19299731
|
|
H 0.00000000 2.39011496 -4.03967703
|
|
H 0.00000000 -2.39011496 -4.03967703
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Pyridine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 -2.66451139
|
|
C 0.00000000 2.25494985 -1.32069889
|
|
C 0.00000000 -2.25494985 -1.32069889
|
|
C 0.00000000 2.15398594 1.30669632
|
|
C 0.00000000 -2.15398594 1.30669632
|
|
N 0.00000000 0.00000000 2.62778932
|
|
H 0.00000000 0.00000000 -4.70641516
|
|
H 0.00000000 4.05768507 -2.27625442
|
|
H 0.00000000 -4.05768507 -2.27625442
|
|
H 0.00000000 3.88059079 2.40341581
|
|
H 0.00000000 -3.88059079 2.40341581
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Pyrimidine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 2.41518350
|
|
C 0.00000000 -0.00000000 -2.60410885
|
|
C 0.00000000 2.23272561 -1.22869402
|
|
C 0.00000000 -2.23272561 -1.22869402
|
|
N 0.00000000 2.26214196 1.29619742
|
|
N 0.00000000 -2.26214196 1.29619742
|
|
H 0.00000000 0.00000000 4.45780256
|
|
H 0.00000000 0.00000000 -4.64120942
|
|
H 0.00000000 4.05149341 -2.16351748
|
|
H 0.00000000 -4.05149341 -2.16351748
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Pyrrole}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 2.11924634 0.62676569
|
|
C 0.00000000 -2.11924634 0.62676569
|
|
C 0.00000000 1.34568862 -1.85506908
|
|
C 0.00000000 -1.34568862 -1.85506908
|
|
N 0.00000000 0.00000000 2.10934391
|
|
H 0.00000000 0.00000000 4.00257355
|
|
H 0.00000000 3.97648410 1.44830201
|
|
H 0.00000000 -3.97648410 1.44830201
|
|
H 0.00000000 2.56726559 -3.47837232
|
|
H 0.00000000 -2.56726559 -3.47837232
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Tetrazine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 2.38208164
|
|
C 0.00000000 0.00000000 -2.38208164
|
|
N 2.25673244 0.00000000 1.24973261
|
|
N -2.25673244 0.00000000 1.24973261
|
|
N 2.25673244 0.00000000 -1.24973261
|
|
N -2.25673244 0.00000000 -1.24973261
|
|
H 0.00000000 0.00000000 4.41850901
|
|
H 0.00000000 0.00000000 -4.41850901
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Thioacetone}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 0.00000000 0.68476030
|
|
C 0.00000000 2.38541696 2.20685096
|
|
C 0.00000000 -2.38541696 2.20685096
|
|
S 0.00000000 0.00000000 -2.39920303
|
|
H 0.00000000 4.04609254 1.00090614
|
|
H 0.00000000 -4.04609254 1.00090614
|
|
H 1.65894780 2.42602225 3.43712000
|
|
H -1.65894780 2.42602225 3.43712000
|
|
H 1.65894780 -2.42602225 3.43712000
|
|
H -1.65894780 -2.42602225 3.43712000
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Thiophene}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 2.33342542 -0.09858421
|
|
C 0.00000000 -2.33342542 -0.09858421
|
|
C 0.00000000 1.34371718 -2.48297725
|
|
C 0.00000000 -1.34371718 -2.48297725
|
|
S 0.00000000 0.00000000 2.17250692
|
|
H 0.00000000 4.29028016 0.44577296
|
|
H 0.00000000 -4.29028016 0.44577296
|
|
H 0.00000000 2.48760051 -4.16768392
|
|
H 0.00000000 -2.48760051 -4.16768392
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
\subsection{Thiopropynal}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C -0.00382924 0.00000000 -1.25249909
|
|
C -2.27832423 0.00000000 0.15152736
|
|
C -4.26309583 0.00000000 1.29548793
|
|
S 2.81920288 0.00000000 -0.00828974
|
|
H -0.23056990 0.00000000 -3.28862183
|
|
H -5.97712967 0.00000000 2.33206931
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\subsection{Triazine}
|
|
|
|
\begin{singlespace}
|
|
\begin{verbatim}
|
|
C 0.00000000 -2.11414732 -1.22060353
|
|
C 0.00000000 0.00000000 2.44120705
|
|
C 0.00000000 2.11414732 -1.22060353
|
|
N 0.00000000 -2.24624733 1.29687150
|
|
N 0.00000000 2.24624733 1.29687150
|
|
N 0.00000000 0.00000000 -2.59374300
|
|
H 0.00000000 3.88296710 -2.24183210
|
|
H 0.00000000 -3.88296710 -2.24183210
|
|
H 0.00000000 0.00000000 4.48366420
|
|
\end{verbatim}
|
|
\end{singlespace}
|
|
|
|
|
|
\clearpage
|
|
|
|
|
|
|
|
\end{document}
|
|
|