813 lines
52 KiB
TeX
813 lines
52 KiB
TeX
\documentclass[journal=jpclcd,manuscript=letter,layout=traditional]{achemso}
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\usepackage{graphicx,dcolumn,bm,xcolor,microtype,hyperref,multirow,amsmath,amssymb,amsfonts,physics,float,lscape,soul,rotating,longtable}
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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{\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}[4]{{#1}\,$^{#2}$#3$_{#4}$}
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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{\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}{exCI}
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\newcommand{\FCI}{FCI}
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% basis
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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{\AVPZ}{\emph{aug}-cc-pV5Z}
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\newcommand{\DAVPZ}{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{\pis}{\pi^\star}
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\newcommand{\si}{\sigma}
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\newcommand{\sis}{\sigma^\star}
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\newcommand{\SI}{Supporting Information}
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\renewcommand\floatpagefraction{.99}
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\renewcommand\topfraction{.99}
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\renewcommand\textfraction{.01}
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\title{Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?\\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]{Laboratoire de Chimie et Physique Quantiques, Universit\'e de Toulouse, CNRS, UPS, France}
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\author{Denis Jacquemin}
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\email{Denis.Jacquemin@univ-nantes.fr}
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\affiliation[UN, Nantes]{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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\begin{document}
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\clearpage
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\section{Vertical energies}
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Below is a list of vertical transition energies obtained for a set of compounds described elsewhere. \cite{Loo18a,Loo20a}. These transition energies, obtained
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on CC3/{\AVTZ} geometries, have been computed with the {\AVTZ} basis set and within the frozen-core approximation. Note that the CC2, ADC(2) and CC3 data are already available in these
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previous works, and are reproduced below for the sake of completeness. To identify the ES with the different approaches considered here, we used the usual strategies, \textit{i.e.}, relative energies,
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spatial and spin symmetries, symmetries and weights of the underlying molecular orbitals, and oscillator strengths. This allows unambiguous assignments for the vast majority of the
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states. There are however some state/method combinations for which strong mixing between ES of the same symmetry makes such assignments difficult. These challenging
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cases are nonetheless statistically irrelevant.
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\renewcommand*{\arraystretch}{.65}
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\LTcapwidth=\textwidth
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\begin{footnotesize}
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\begin{longtable}{p{3.5cm}p{3.3cm}c|cccc}
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\caption{Comparisons between the TBE (see Refs.~\citenum{Loo18a} and \citenum{Loo20a} for details and geometries) and the vertical excitation energies obtained with CC2, CC3, ADC(2), and ADC(3).
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All the values have been obtained with the \emph{aug}-cc-pVTZ basis set and within the frozen-core approximation.
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We have removed from this training set all excited states with a dominant double excitation character.
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F, R and V stand for fluorescence, Rydberg and valence states, respectively.
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} \label{Table-SI-1}\\
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\hline
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Compound & State & TBE & CC2 & CC3 &ADC(2)& ADC(3) \\
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\hline
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\endfirsthead
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\hline
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Compound & State & TBE & CC2 & CC3 &ADC(2)& ADC(3) \\
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\hline
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\endhead
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\hline \multicolumn{7}{r}{{Continued on next page}} \\
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\endfoot
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\hline
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\endlastfoot
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Acetaldehyde &$^1A'' (\Val;n \ra \pis)$ &4.31 &4.41 &4.31 &4.24 &4.29 \\%
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&$^3A'' (\Val;n \ra \pis)$ &3.97 &3.98 &3.95 &3.83 &3.89 \\%
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Acetone &$^1A_2 (\Val; n \ra \pis)$ & 4.47 &4.55 &4.48 &4.37 &4.50\\
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&$^1B_2 (\Ryd; n \ra 3s)$ & 6.46 &5.91 &6.43 &5.87 &6.91\\
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&$^1A_2 (\Ryd; n \ra 3p)$ & 7.47 &6.84 &7.45 &6.81 &7.90\\
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&$^1A_1 (\Ryd; n \ra 3p)$ & 7.51 &6.89 &7.48 &6.85 &7.92\\
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&$^1B_2 (\Ryd; n \ra 3p)$ & 7.62 &7.02 &7.59 &6.99 &8.01\\
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&$^3A_2 (\Val; n \ra \pis)$ & 4.13 &4.16 &4.15 &4.00 &4.12\\
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&$^3A_1 (\Val; \pi \ra \pis)$ & 6.25 &6.50 &6.28 &6.37 &6.01\\
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Acetylene &$^1\Sigma_u^- (\Val;\pi \ra \pis)$ &7.10 &7.26 &7.09 &7.24 &6.72 \\%
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&$^1\Delta_u (\Val;\pi \ra \pis)$ &7.44 &7.59 &7.42 &7.56 &7.06 \\%
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&$^3\Sigma_u^+ (\Val;\pi \ra \pis)$ &5.53 &5.76 &5.50 &5.75 &5.24 \\%
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&$^3\Delta_u (\Val;\pi \ra \pis)$ &6.40 &6.60 &6.40 &6.57 &6.06 \\%
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&$^3\Sigma_u^- (\Val;\pi \ra \pis)$ &7.08 &7.29 &7.07 &7.27 &6.72 \\%
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&$^1A_u [\Fl] (\Val;\pi \ra \pis)$ &3.64 &3.94 &3.64 &3.78 &2.85 \\%
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&$^1A_2 [\Fl] (\Val;\pi \ra \pis)$ &3.85 &4.11 &3.84 &3.99 &3.08 \\%
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Acrolein &$^1A'' (\Val; n \ra \pis)$ & 3.78 &3.85 &3.74 &3.68 &3.76\\
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&$^1A' (\Val; \pi \ra \pis)$ & 6.69 &6.80 &6.65 &6.74 &6.51\\
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&$^1A' (\Ryd; n \ra 3s)$ & 7.08 &6.40 &7.07 &6.35 &7.57\\
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&$^3A'' (\Val; n \ra \pis)$ & 3.51 &3.49 &3.46 &3.33 &3.45\\
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&$^3A' (\Val; \pi \ra \pis)$ & 3.94 &4.06 &3.94 &4.05 &3.66\\
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&$^3A' (\Val; \pi \ra \pis)$ & 6.18 &6.37 &6.19 &6.31 &5.86\\
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Ammonia &$^1A_2 (\Ryd;n \ra 3s)$ &6.59 &6.39 &6.57 &6.40 &6.63 \\%
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&$^1E (\Ryd;n \ra 3p)$ &8.16 &7.85 &8.15 &7.87 &8.21 \\%
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&$^1A_1 (\Ryd;n \ra 3p)$ &9.33 &9.05 &9.32 &9.05 &9.38 \\%
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&$^1A_2 (\Ryd;n \ra 4s)$ &9.96 &9.65 &9.95 &9.67 &10.00 \\%
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&$^3A_2 (\Ryd;n \ra 3s)$ &6.31 &6.14 &6.29 &6.16 &6.31 \\%
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Carbon monoxyde &$^1\Pi (\Val;n \ra \pis)$ & 8.49 &8.64 &8.49 &8.69 &8.24 \\%
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&$^1\Sigma^- (\Val;\pi \ra \pis)$ & 9.92 &10.30 &9.99 &10.03 &9.73 \\%
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&$^1\Delta (\Val;\pi \ra \pis)$ &10.06 &10.60 &10.12 &10.30 &9.82 \\%
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&$^1\Sigma^+ (\Ryd)$ &10.95 &11.11 &10.94 &11.32 &10.79 \\%
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&$^1\Sigma^+ (\Ryd)$ &11.52 &11.63 &11.49 &11.83 &11.33 \\%
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&$^1\Pi (\Ryd)$ &11.72 &11.83 &11.69 &12.03 &11.56 \\%
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&$^3\Pi (\Val;n \ra \pis)$ & 6.28 &6.42 &6.30 &6.45 &5.97 \\%
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&$^3\Sigma^+ (\Val;\pi \ra \pis)$ & 8.45 &8.72 &8.45 &8.54 &8.21 \\%
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&$^3\Delta (\Val;\pi \ra \pis)$ & 9.27 &9.56 &9.30 &9.33 &9.03 \\%
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&$^3\Sigma^- (\Val;\pi \ra \pis)$ & 9.80 &10.27 &9.82 &10.01 &9.53 \\%
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&$^3\Sigma^+ (\Ryd)$ & 10.47 &10.60 &10.45 &10.83 &10.29 \\%
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Benzene &$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.06 &5.26 &5.09 &5.27 &5.01\\
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&$^1B_{1u} (\Val; \pi \ra \pis)$ & 6.45 &6.48 &6.44 &6.45 &6.24\\
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&$^1E_{1g} (\Ryd; \pi \ra 3s)$ & 6.52 &6.47 &6.52 &6.52 &6.38\\
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&$^1A_{2u} (\Ryd; \pi \ra 3p)$ & 7.08 &7.00 &7.08 &7.06 &6.92\\
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&$^1E_{2u} (\Ryd; \pi \ra 3p)$ & 7.15 &7.06 &7.15 &7.12 &7.00\\
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&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.16 &4.37 &4.18 &4.37 &3.94\\
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&$^3E_{1u}(\Val; \pi \ra \pis)$ & 4.85 &5.08 &4.86 &5.07 &4.60\\
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&$^3B_{2u} (\Val; \pi \ra \pis)$ & 5.81 &5.89 &5.81 &5.87 &5.51\\
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Butadiene &$^1B_u (\Val; \pi \ra \pis)$ & 6.22 &6.16 &6.22 &6.12 &6.02\\
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&$^1B_g (\Ryd; \pi \ra 3s)$ & 6.33 &6.26 &6.33 &6.31 &6.12\\
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&$^1A_g (\Val; \pi \ra \pis)$ & 6.50 &7.09 &6.67 &7.14 &5.86\\
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&$^1A_u (\Ryd; \pi \ra 3p)$ & 6.64 &6.57 &6.64 &6.63 &6.44\\
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&$^1A_u (\Ryd; \pi \ra 3p)$ & 6.80 &6.70 &6.80 &6.76 &6.59\\
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&$^1B_u (\Ryd; \pi \ra 3p)$ & 7.68 &7.63 &7.68 &7.48 &7.46\\
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&$^3B_u (\Val; \pi \ra \pis)$ & 3.36 &3.45 &3.36 &3.46 &3.09\\
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&$^3A_g (\Val; \pi \ra \pis)$ & 5.20 &5.30 &5.20 &5.27 &4.94\\
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&$^3B_g (\Ryd; \pi \ra 3s)$ & 6.29 &6.21 &6.28 &6.27 &6.06\\
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Cyanoacetylene&$^1\Sigma^- (\Val; \pi \ra \pis)$ & 5.80 &6.03 &5.80 &5.99 &5.37\\
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&$^1\Delta (\Val; \pi \ra \pis)$ & 6.07 &6.30 &6.08 &6.25 &5.64\\
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&$^3\Sigma^+ (\Val; \pi \ra \pis)$ & 4.44 &4.80 &4.45 &4.77 &4.11\\
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&$^3\Delta (\Val; \pi \ra \pis)$ & 5.21 &5.50 &5.22 &5.46 &4.80\\
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&$^1A'' [\Fl] (\Val; \pi \ra \pis)$ & 3.54 &3.79 &3.54 &3.73 &2.78\\
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Cyanoformaldehyde &$^1A'' (\Val; n \ra \pis)$ & 3.81 &3.97 &3.83 &3.83 &3.77\\
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&$^1A'' (\Val; \pi \ra \pis)$ & 6.46 &6.74 &6.42 &6.73 &6.07\\
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&$^3A'' (\Val; n \ra \pis)$ & 3.44 &3.51 &3.46 &3.37 &3.38\\
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&$^3A' (\Val; \pi \ra \pis)$ & 5.01 &5.34 &5.01 &5.27 &4.63\\
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Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 6.39 &6.72 &6.39 &6.67 &5.88\\
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& $^1\Delta_u (\Val; \pi \ra \pis)$ & 6.66 &7.02 &6.66 &6.95 &6.16\\
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& $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.91 &5.35 &4.90 &5.31 &4.49\\
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& $^1\Sigma_u^- [\Fl] (\Val; \pi \ra \pis)$ & 5.05 &5.48 &5.06 &5.39 &4.32\\
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Cyclopentadiene&$^1B_2 (\Val; \pi \ra \pis)$ & 5.56 &5.52 &5.54 &5.49 &5.35\\
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&$^1A_2 (\Ryd; \pi \ra 3s)$ & 5.78 &5.66 &5.77 &5.71 &5.63\\
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&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.41 &6.26 &6.40 &6.31 &6.25\\
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&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.46 &6.30 &6.45 &6.35 &6.30\\
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&$^1B_2 (\Ryd; \pi \ra 3p)$ & 6.56 &6.42 &6.56 &6.48 &6.41\\
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&$^3B_2 (\Val; \pi \ra \pis)$ & 3.31 &3.42 &3.32 &3.42 &3.05\\
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&$^3A_1 (\Val; \pi \ra \pis)$ & 5.11 &5.36 &5.12 &5.23 &4.86\\
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&$^3A_2 (\Ryd; \pi \ra 3s)$ & 5.73 &5.62 &5.73 &5.67 &5.57\\
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&$^3B_1 (\Ryd; \pi \ra 3p)$ & 6.36 &6.22 &6.36 &6.27 &6.20\\
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Cyclopropene &$^1B_1 (\Val;\sigma \ra \pis)$ &6.68 &6.73 &6.68 &6.75 &6.56 \\%
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&$^1B_2 (\Val;\pi \ra \pis)$ &6.79 &6.78 &6.73 &6.86 &6.56 \\%
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&$^3B_2 (\Val;\pi \ra \pis)$ &4.38 &4.46 &4.34 &4.45 &4.09 \\%
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&$^3B_1 (\Val;\sigma \ra \pis)$ &6.45 &6.44 &6.40 &6.45 &6.26 \\%
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Cyclopropenone&$^1B_1 (\Val; n \ra \pis)$ & 4.26 &4.01 &4.21 &3.88 &4.66\\
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&$^1A_2 (\Val; n \ra \pis)$ & 5.55 &5.65 &5.57 &5.47 &5.61\\
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&$^1B_2 (\Ryd; n \ra 3s)$ & 6.34 &5.84 &6.32 &5.79 &6.64\\
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&$^1B_2 (\Val; \pi \ra \pis$) & 6.54 &6.46 &6.54 &6.33 &6.83\\
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&$^1B_2 (\Ryd; n \ra 3p)$ & 6.98 &6.56 &6.96 &6.43 &7.33\\
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&$^1A_1 (\Ryd; n \ra 3p)$ & 7.02 &6.47 &7.00 &6.41 &7.36\\
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&$^1A_1 (\Val; \pi \ra \pis)$ & 8.28 &8.28 &8.28 &8.10 &8.17\\
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&$^3B_1 (\Val; n \ra \pis)$ & 3.93 &3.73 &3.91 &3.62 &4.28\\
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&$^3B_2 (\Val; \pi \ra \pis)$ & 4.88 &4.99 &4.89 &4.90 &4.80\\
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&$^3A_2 (\Val; n \ra \pis)$ & 5.35 &5.45 &5.37 &5.28 &5.36\\
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&$^3A_1 (\Val; \pi \ra \pis)$ & 6.79 &6.42 &6.83 &6.84 &6.63\\
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Cyclopropenethione&$^1A_2 (\Val; n \ra \pis)$ & 3.41 &3.53 &3.43 &3.38 &3.46\\
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&$^1B_1 (\Val; n \ra \pis)$ & 3.45 &3.50 &3.43 &3.37 &3.82\\
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&$^1B_2 (\Val; \pi \ra \pis)$ & 4.60 &4.91 &4.64 &4.72 &4.72\\
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&$^1B_2 (\Ryd; n \ra 3s)$ & 5.34 &5.22 &5.34 &5.17 &5.41\\
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&$^1A_1 (\Val; \pi \ra \pis)$ & 5.46 &5.59 &5.49 &5.36 &5.36\\
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&$^1B_2 (\Ryd; n \ra 3p)$ & 5.92 &5.82 &5.93 &5.77 &6.02\\
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&$^3A_2 (\Val; n \ra \pis)$ & 3.28 &3.37 &3.30 &3.23 &3.30\\
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&$^3B_1 (\Val; n \ra \pis)$ & 3.32 &3.38 &3.31 &3.26 &3.65\\
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&$^3B_2 (\Val; \pi \ra \pis)$ & 4.01 &4.24 &4.02 &4.12 &3.96\\
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&$^3A_1 (\Val; \pi \ra \pis)$ & 4.01 &4.16 &4.03 &4.04 &3.83\\
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Diacetylene &$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 5.33 &5.51 &5.34 &5.49 &4.95 \\
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&$^1\Delta_u (\Val; \pi \ra \pis)$ & 5.61 &5.76 &5.61 &5.72 &5.22 \\
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&$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.10 &4.39 &4.08 &4.37 &3.79 \\
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&$^3\Delta_u (\Val; \pi \ra \pis)$ & 4.78 &5.03 &4.80 &5.01 &4.43 \\
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Diazomethane &$^1A_2 (\Val;\pi \ra \pis)$ &3.14 &3.37 &3.07 &3.34 &2.74 \\%
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&$^1B_1 (\Ryd;\pi \ra 3s)$ &5.54 &5.53 &5.45 &5.63 &5.23 \\%
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&$^1A_1 (\Val;\pi \ra \pis)$ &5.90 &6.00 &5.84 &5.97 &5.48 \\%
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&$^3A_2 (\Val;\pi \ra \pis)$ &2.79 &3.08 &2.83 &3.01 &2.44 \\%
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&$^3A_1 (\Val;\pi \ra \pis)$ &4.05 &4.25 &4.03 &4.20 &3.64 \\%
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&$^3B_1 (\Ryd;\pi \ra 3s)$ &5.35 &5.40 &5.31 &5.50 &5.08 \\%
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&$^3A_1 (\Ryd;\pi \ra 3p)$ &6.82 &7.04 &6.80 &7.09 &6.36 \\%
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&$^1A'' [\Fl] (\Val;\pi \ra \pis)$ &0.71 &0.90 &0.68 &0.81 &0.24 \\%
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Dinitrogen &$^1\Pi_g (\Val;n \ra \pis)$ &9.34 &9.44 &9.34 &9.48 &9.16 \\%
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&$^1\Sigma_u^- (\Val;\pi \ra \pis)$ &9.88 &10.32 &9.88 &10.26 &9.33 \\%
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&$^1\Delta_u (\Val;\pi \ra \pis)$ &10.29 &10.86 &10.29 &10.79 &9.74 \\%
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&$^1\Sigma_g^+ (\Ryd)$ &12.98 &12.83 &13.01 &12.99 &13.01 \\%
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&$^1\Pi_u (\Ryd)$ &13.03 &13.15 &13.22 &13.32 &12.98 \\%
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&$^1\Sigma_u^+ (\Ryd)$ &13.09 &12.89 &13.12 &13.07 &13.09 \\%
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&$^1\Pi_u (\Ryd)$ &13.46 &13.96 &13.49 &14.00 &13.40 \\%
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&$^3\Sigma_u^+ (\Val;\pi \ra \pis)$ &7.70 &8.19 &7.68 &8.15 &7.25 \\%
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&$^3\Pi_g (\Val;n \ra \pis)$ &8.01 &8.19 &8.04 &8.20 &7.77 \\%
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&$^3\Delta_u (\Val;\pi \ra \pis)$ &8.87 &9.30 &8.87 &9.25 &8.36 \\%
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&$^3\Sigma_u^- (\Val;\pi \ra \pis)$ &9.66 &10.29 &9.68 &10.23 &9.14 \\%
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Ethylene &$^1B_{3u} (\Ryd;\pi \ra 3s)$ &7.39 &7.29 &7.35 &7.34 &7.17 \\%
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&$^1B_{1u} (\Val;\pi \ra \pis)$ &7.93 &7.92 &7.91 &7.91 &7.69 \\%
|
|
&$^1B_{1g} (\Ryd;\pi \ra 3p)$ &8.08 &7.95 &8.03 &7.99 &7.84 \\%
|
|
&$^3B_{1u} (\Val;\pi \ra \pis)$ &4.54 &4.59 &4.53 &4.59 &4.28 \\%
|
|
&$^3B_{3u} (\Ryd;\pi \ra 3s)$ &7.23 &7.19 &7.24 &7.23 &7.05 \\%
|
|
&$^3B_{1g} (\Ryd;\pi \ra 3p)$ &7.98 &7.91 &7.98 &7.95 &7.80 \\%
|
|
Formaldehyde &$^1A_2 (\Val; n \ra \pis)$ &3.98 &4.07 &3.97 &3.92 &3.90 \\%
|
|
&$^1B_2 (\Ryd;n \ra 3s)$ &7.23 &6.56 &7.18 &6.50 &7.62 \\%
|
|
&$^1B_2 (\Ryd;n \ra 3p)$ &8.13 &7.57 &8.07 &7.53 &8.45 \\%
|
|
&$^1A_1 (\Ryd;n \ra 3p)$ &8.23 &7.52 &8.18 &7.47 &8.61 \\%
|
|
&$^1A_2 (\Ryd;n \ra 3p)$ &8.67 &8.04 &8.64 &7.99 &9.02 \\%
|
|
&$^1B_1 (\Val;\sigma \ra \pis)$ &9.22 &9.32 &9.19 &9.17 &9.17 \\%
|
|
&$^1A_1 (\Val;\pi \ra \pis)$ &9.43 &9.54 &9.48 &9.46 &9.05 \\%
|
|
&$^3A_2 (\Val;n \ra \pis)$ &3.58 &3.59 &3.57 &3.46 &3.48 \\%
|
|
&$^3A_1 (\Val;\pi \ra \pis)$ &6.06 &6.30 &6.05 &6.20 &5.71 \\%
|
|
&$^3B_2 (\Ryd;n \ra 3s)$ &7.06 &6.44 &7.03 &6.39 &7.44 \\%
|
|
&$^3B_2 (\Ryd;n \ra 3p)$ &7.94 &7.45 &7.92 &7.41 &8.23 \\%
|
|
&$^3A_1 (\Ryd;n \ra 3p)$ &8.10 &7.44 &8.08 &7.40 &8.46 \\%
|
|
&$^3B_1 (\Ryd;n \ra 3d)$ &8.42 &8.52 &8.41 &8.39 &8.32 \\%
|
|
&$^1A^" [\Fl] (\Val;n \ra \pis)$ &2.80 &2.97 &2.84 &2.71 &2.77 \\%
|
|
Formamide &$^1A'' (\Val;n \ra \pis)$ &5.65 &5.69 &5.66 &5.45 &5.75 \\%
|
|
&$^3A'' (\Val;n \ra \pis)$ &5.38 &5.36 &5.38 &5.15 &5.42 \\%
|
|
&$^3A' (\Val;\pi \ra \pis)$ &5.81 &5.99 &5.82 &5.88 &5.63 \\%
|
|
Furan &$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.09 &6.06 &6.08 &6.12 &5.95\\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 6.37 &6.45 &6.34 &6.47 &6.15\\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.56 &6.77 &6.58 &6.76 &6.48\\
|
|
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.64 &6.59 &6.63 &6.64 &6.49\\
|
|
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.81 &6.75 &6.80 &6.82 &6.67\\
|
|
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 7.24 &7.25 &7.23 &7.29 &7.09 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.20 &4.43 &4.22 &4.41 &3.91 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.46 &5.66 &5.48 &5.59 &5.23 \\
|
|
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 6.02 &6.01 &6.02 &6.08 &5.89 \\
|
|
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 6.59 &6.55 &6.59 &6.61 &6.45 \\
|
|
Glyoxal &$^1A_u (\Val; n \ra \pis)$ & 2.88 &2.91 &2.88 &2.83 &2.83 \\
|
|
&$^1B_g (\Val; n \ra \pis)$ & 4.24 &4.44 &4.27 &4.27 &4.23 \\
|
|
&$^1B_g (\Val; n \ra \pis)$ & 6.57 &6.51 &6.58 &6.50 &6.80 \\
|
|
&$^1B_u (\Ryd; n \ra 3p)$ & 7.71 &7.16 &7.67 &7.18 &7.86 \\
|
|
&$^3A_u (\Val; n \ra \pis)$ & 2.49 &2.47 &2.49 &2.39 &2.40 \\
|
|
&$^3B_g (\Val; n \ra \pis)$ & 3.89 &3.96 &3.90 &3.82 &3.85 \\
|
|
&$^3B_u (\Val; \pi \ra \pis)$ & 5.15 &5.42 &5.17 &5.33 &4.83 \\
|
|
&$^3A_g (\Val; \pi \ra \pis)$ & 6.30 &6.56 &6.30 &6.45 &5.93 \\
|
|
Hydrogen chloride & $^1\Pi (\mathrm{CT})$ &7.84 &7.96 &7.84 &7.97 &7.79 \\%
|
|
Hydrogen sulfide &$^1A_2 (\Ryd;n \ra 4p)$ &6.18 &6.35 &6.19 &6.37 &6.05 \\%
|
|
&$^1B_1 (\Ryd;n \ra 4s)$ &6.24 &6.30 &6.24 &6.34 &6.18 \\%
|
|
&$^3A_2 (\Ryd;n \ra 4p)$ &5.81 &5.91 &5.82 &5.91 &5.67 \\%
|
|
&$^3B_1 (\Ryd;n \ra 4s)$ &5.88 &5.94 &5.88 &5.96 &5.81 \\%
|
|
Imidazole &$^1A'' (\Ryd; \pi \ra 3s)$ & 5.71 &5.69 &5.71 &5.75 &5.61 \\
|
|
&$^1A' (\Val; \pi \ra \pis)$ & 6.41 &6.51 &6.41 &6.50 &6.31 \\
|
|
&$^1A'' (\Val; n \ra \pis)$ & 6.50 &6.47 &6.50 &6.51 &6.39 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 4.73 &4.94 &4.75 &4.92 &4.47 \\
|
|
&$^3A'' (\Ryd; \pi \ra 3s)$ & 5.66 &5.66 &5.67 &5.72 &5.57 \\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 5.74 &5.94 &5.74 &5.93 &5.49 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 6.31 &6.36 &6.33 &6.31 &6.26 \\
|
|
Isobutene &$^1B_1 (\Ryd; \pi \ra 3s)$ & 6.46 &6.37 &6.45 &6.43 &6.33 \\
|
|
&$^1A_1 (\Ryd; \pi \ra 3p)$ & 7.01 &6.95 &7.00 &6.97 &6.82 \\
|
|
&$^3A_1 (\Val; (\pi \ra \pis)$ & 4.53 &4.62 &4.53 &4.62 &4.30 \\
|
|
Ketene &$^1A_2 (\Val;\pi \ra \pis)$ &3.86 &4.17 &3.88 &4.11 &3.67 \\%
|
|
&$^1B_1 (\Ryd;n \ra 3s)$ &6.01 &5.94 &5.96 &6.03 &5.87 \\%
|
|
&$^1A_2 (\Ryd;\pi \ra 3p)$ &7.18 &7.09 &7.16 &7.18 &7.07 \\%
|
|
&$^3A_2 (\Val;n \ra \pis)$ &3.77 &3.98 &3.78 &3.92 &3.56 \\%
|
|
&$^3A_1 (\Val;\pi \ra \pis)$ &5.61 &5.72 &5.61 &5.67 &5.39 \\%
|
|
&$^3B_1 (\Ryd;n \ra 3s)$ &5.79 &5.77 &5.76 &5.85 &5.67 \\%
|
|
&$^3A_2 (\Ryd;\pi \ra 3p)$ &7.12 &7.06 &7.12 &7.15 &7.03 \\%
|
|
&$^1A^" [\Fl] (\Val;\pi \ra \pis)$ &1.00 &1.26 &1.00 &1.19 &0.67 \\%
|
|
Methanimine &$^1A^" (\Val; n \ra \pis)$ &5.23 &5.32 &5.20 &5.29 &5.05 \\%
|
|
&$^3A^" (\Val; n \ra \pis)$ &4.65 &4.65 &4.61 &4.61 &4.44 \\%
|
|
Methylenecyclopropene& $^1B_2 (\Val; \pi \ra \pis)$ & 4.28 &4.51 &4.31 &4.46 &4.18 \\
|
|
&$^1B_1 (\Ryd; \pi \ra 3s)$ & 5.44 &5.35 &5.44 &5.38 &5.26 \\
|
|
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 5.96 &5.85 &5.95 &5.87 &5.78 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 3.49 &3.64 &3.50 &3.61 &3.30\\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.74 &4.81 &4.74 &4.80 &4.51\\
|
|
Nitrosomethane&$^1A'' (\Val;n \ra \pis)$ &1.96 &1.98 &1.96 &1.88 &1.72 \\%
|
|
&$^1A' (\Ryd;n \ra 3s/3p)$ &6.40 &5.84 &6.31 &5.86 &6.48 \\%
|
|
&$^3A'' (\Val;n \ra \pis)$ &1.16 &1.12 &1.14 &1.03 &0.84 \\%
|
|
&$^3A' (\Val;\pi \ra \pis)$ &5.60 &5.74 &5.51 &5.75 &5.04 \\%
|
|
&$^1A'' [\Fl] (\Val;n \ra \pis)$ &1.67 &1.68 &1.69 &1.55 &1.40 \\%
|
|
Propynal & $^1A'' (\Val; n \ra \pis)$ & 3.80 &3.96 &3.82 &3.78 &3.81\\
|
|
&$^1A'' (\Val; \pi \ra \pis)$ & 5.54 &5.71 &5.51 &5.73 &5.20\\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 3.47 &3.53 &3.49 &3.38 &3.45\\
|
|
&$^3A' (\Val; \pi \ra \pis)$ & 4.47 &4.71 &4.43 &4.67 &4.10\\
|
|
Pyrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 4.15 &4.14 &4.14 &4.17 &4.13\\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 4.98 &4.86 &4.97 &4.88 &5.21\\
|
|
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.02 &5.14 &5.03 &5.47 &4.88\\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.71 &5.86 &5.71 &5.87 &5.67\\
|
|
&$^1A_{g} (\Ryd; n \ra 3s)$ & 6.65 &6.20 &6.66 &6.30 &6.96\\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.74 &6.67 &6.73 &6.67 &7.00\\
|
|
&$^1B_{1u} (\Val; \pi \ra \pis)$ & 6.88 &6.89 &6.86 &6.88 &6.66\\
|
|
&$^1B_{1g} (\Ryd; \pi \ra 3s)$ & 7.21 &7.21 &7.20 &7.27 &7.18\\
|
|
&$^1B_{2u} (\Ryd; n \ra 3p)$ & 7.24 &6.74 &7.25 & &\\
|
|
&$^1B_{1u} (\Ryd; n \ra 3p)$ & 7.44 &7.03 &7.45 & &\\
|
|
&$^3B_{3u} (\Val; n \ra \pis)$ & 3.59 &3.60 &3.59 &3.62 &3.52\\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.35 &4.60 &4.39 &4.57 &4.05\\
|
|
&$^3B_{2u} (\Val; (\pi \ra \pis)$ & 4.39 &4.57 &4.40 &4.59 &4.10 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 4.93 &4.82 &4.93 &4.84 &5.15 \\
|
|
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.08 &5.19 &5.08 & &\\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.28 &5.59 &5.29 & &\\
|
|
Pyridazine &$^1B_1 (\Val; n \ra \pis)$ & 3.83 &3.78 &3.83 &3.79 &3.86 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 4.37 &4.26 &4.37 &4.27 &4.60 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.26 &5.43 &5.29 &5.44 &5.18 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.72 &5.79 &5.74 &5.81 &5.74 \\
|
|
&$^1B_2 (\Ryd; n \ra 3s)$ & 6.17 &5.59 &6.17 &5.69 &6.67 \\
|
|
&$^1B_1 (\Val; n \ra \pis)$ & 6.37 &6.33 &6.37 &6.35 &6.62 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 6.75 &6.86 &6.74 &6.85 & \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 3.19 &3.18 &3.19 &3.19 &3.12 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 4.11 &4.01 &4.11 &4.02 &4.22 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.82 &5.07 &4.83 &5.06 &4.46 \\
|
|
Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 4.95 &4.99 &4.96 &4.98 &4.99 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.14 &5.32 &5.17 &5.33 &5.08 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.40 &5.28 &5.40 &5.27 &5.70 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.62 &6.21 &6.63 &6.31 &7.17 \\
|
|
&$^1A_1 (\Ryd; n \ra 3s)$ & 6.76 &6.68 &6.76 &6.65 &6.39 \\
|
|
&$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.82 &6.79 &6.81 &6.83 &6.65 \\
|
|
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 7.39 &7.34 &7.38 &7.38 &7.21 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 7.39 &7.45 &7.39 &7.48 &7.27 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.30 &4.53 &4.33 &4.53 &4.06 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 4.46 &4.48 &4.46 &4.47 &4.43 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.79 &4.98 &4.79 &4.98 &4.49 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.04 &5.29 &5.05 &5.28 &4.75 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 5.36 &5.24 &5.35 &5.23 &5.62 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 6.24 &6.39 &6.25 &6.35 &5.98 \\
|
|
Pyrimidine &$^1B_1 (\Val; n \ra \pis)$ & 4.44 &4.41 &4.44 &4.37 &4.54 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 4.85 &4.77 &4.86 &4.73 &5.06 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.38 &5.54 &5.41 &5.52 &5.33 \\
|
|
&$^1A_2 (\Val; n \ra \pis)$ & 5.92 &5.96 &5.93 &5.93 &6.08 \\
|
|
&$^1B_1 (\Val; n \ra \pis)$ & 6.26 &6.25 &6.26 &6.22 &6.52 \\
|
|
&$^1B_2 (\Ryd; n \ra 3s)$ & 6.70 &6.20 &6.72 &6.25 &7.11 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.88 &6.84 &6.87 &6.83 &6.52 \\
|
|
&$^3B_1 (\Val; n \ra \pis)$ & 4.09 &4.07 &4.10 &4.05 &4.12 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 4.66 &4.60 &4.66 &4.58 &4.73 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.96 &5.17 &4.96 &5.14 &4.63 \\
|
|
Pyrrole &$^1A_2 (\Ryd; \pi \ra 3s)$ & 5.24 &5.23 &5.24 &5.30 &5.14 \\
|
|
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.00 &5.91 &5.98 &5.94 &5.89 \\
|
|
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.00 &5.96 &6.01 &6.03 &5.91 \\
|
|
&$^1B_2 (\Val; (\pi \ra \pis)$ & 6.26 &6.30 &6.25 &6.35 &6.11 \\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.30 &6.47 &6.32 &6.47 &6.29 \\
|
|
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 6.83 &6.89 &6.83 &6.91 &6.69 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.51 &4.72 &4.53 &4.71 &4.26 \\
|
|
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 5.21 &5.20 &5.21 &5.27 &5.11 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.45 &5.66 &5.46 &5.62 &5.23 \\
|
|
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 5.91 &5.86 &5.92 &5.89 &5.84 \\
|
|
Streptocyanine &$^1B_2 (\Val;\pi \ra \pis)$ &7.13 &7.20 &7.13 &7.00 &7.16 \\%
|
|
&$^3B_2 (\Val;\pi \ra \pis)$ & 5.47 &5.60 &5.48 &5.55 &5.33 \\%
|
|
Tetrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 2.47 &2.38 &2.46 &2.42 &2.42 \\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 3.69 &3.53 &3.67 &3.58 &3.87 \\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 4.93 &5.02 &4.91 &5.04 &4.97 \\
|
|
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.21 &5.31 &5.23 &5.31 &5.08 \\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.45 &5.64 &5.46 &5.68 &5.13 \\
|
|
&$^1A_{u} (\Val; n \ra \pis)$ & 5.53 &5.56 &5.52 &5.59 &5.49 \\
|
|
&$^1B_{2g} (\Val; n \ra \pis)$ & 6.12 &6.18 &6.13 &6.21 &6.50 \\
|
|
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.91 &6.95 &6.92 &6.97 &6.59 \\
|
|
&$^3B_{3u} (\Val; n \ra \pis)$ & 1.85 &1.81 &1.85 &1.85 &1.74 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 3.45 &3.31 &3.44 &3.35 &3.54 \\
|
|
&$^3B_{1g} (\Val; n \ra \pis)$ & 4.20 &4.27 &4.20 &4.27 &4.06 \\
|
|
&$^3B_{2u} (\Val; \pi \ra \pis)$ & 4.52 &4.77 &4.52 &4.76 &4.06 \\
|
|
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.04 &5.15 &5.05 &5.16 &4.86 \\
|
|
&$^3A_{u} (\Val; n \ra \pis)$ & 5.11 &5.13 &5.11 &5.16 &5.07 \\
|
|
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.42 &5.70 &5.42 &5.67 &5.06 \\
|
|
Thioacetone &$^1A_2 (\Val; n \ra \pis)$ & 2.53 &2.63 &2.55 &2.47 &2.50 \\
|
|
&$^1B_2 (\Ryd; n \ra 4s)$ & 5.56 &5.50 &5.55 &5.47 &5.65\\
|
|
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.88 &6.09 &5.90 &5.87 &5.53 \\
|
|
&$^1B_2 (\Ryd; n \ra 4p)$ & 6.51 &6.44 &6.51 &6.43 &6.53 \\
|
|
&$^1A_1 (\Ryd; n \ra 4p)$ & 6.61 &6.53 &6.61 &6.48 &6.64 \\
|
|
&$^3A_2 (\Val; n \ra \pis)$ & 2.33 &2.33 &2.34 &2.20 &2.26 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 3.45 &3.59 &3.46 &3.52 &3.17 \\
|
|
Thioformaldehyde&$^1A_2 (\Val;n \ra \pis)$ &2.22 &2.34 &2.23 &2.24 &2.05 \\%
|
|
&$^1B_2 (\Ryd;n \ra 4s)$ &5.96 &5.82 &5.91 &5.80 &5.94 \\%
|
|
&$^1A_1 (\Val;\pi \ra \pis)$ &6.38 &6.71 &6.48 &6.57 &5.98 \\%
|
|
&$^3A_2 (\Val;n \ra \pis)$ &1.94 &1.94 &1.94 &1.86 &1.77 \\%
|
|
&$^3A_1 (\Val;\pi \ra \pis)$ & 3.43 &3.48 &3.38 &3.45 &3.07 \\%
|
|
&$^3B_2 (\Ryd;n \ra 4s)$ &5.72 &5.64 &5.72 &5.62 &5.71 \\%
|
|
&$^1A_2 [\Fl] (\Val;n \ra \pis)$ &1.95 &2.09 &1.97 &1.92 &1.80 \\%
|
|
Thiophene &$^1A_1 (\Val; \pi \ra \pis)$ & 5.64 &5.75 &5.65 &5.72 &5.61 \\
|
|
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.98 &6.07 &5.96 &6.07 &5.79 \\
|
|
&$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.14 &6.07 &6.14 &6.15 &6.03 \\
|
|
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.14 &6.15 &6.14 &6.24 &6.02 \\
|
|
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.21 &6.35 &6.25 &6.35 &6.14 \\
|
|
&$^1B_1 (\Ryd; \pi \ra 3s)$ & 6.49 &6.48 &6.50 &6.51 &6.43 \\
|
|
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 7.29 &7.26 &7.29 &7.34 &7.18 \\
|
|
&$^3B_2 (\Val; \pi \ra \pis)$ & 3.92 &4.12 &3.94 &4.11 &3.65 \\
|
|
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.76 &4.91 &4.77 &4.86 &4.56 \\
|
|
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 5.93 &6.00 &5.95 &6.09 &5.83 \\
|
|
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 6.08 &6.03 &6.09 &6.11 &5.97 \\
|
|
Thiopropynal &$^1A'' (\Val; n \ra \pis)$ & 2.03 &2.20 &2.05 &2.08 &1.86 \\
|
|
&$^3A'' (\Val; n \ra \pis)$ & 1.80 &1.84 &1.81 &1.74 &1.63 \\
|
|
Triazine &$^1A_1'' (\Val; n \ra \pis)$ & 4.72 &4.64 &4.73 &4.58 &4.83 \\
|
|
&$^1A_2'' (\Val; n \ra \pis)$ & 4.75 &4.75 &4.74 &4.69 &4.99 \\
|
|
&$^1E'' (\Val; n \ra \pis)$ & 4.78 &4.72 &4.78 &4.66 &4.95 \\
|
|
&$^1A_2' (\Val; \pi \ra \pis)$ & 5.75 &5.89 &5.78 &5.83 &5.78 \\
|
|
&$^1A_1' (\Val; \pi \ra \pis)$ & 7.24 &7.32 &7.24 &7.18 &6.78 \\
|
|
&$^1E' (\Ryd; n \ra 3s)$ & 7.32 &6.87 &7.35 &6.89 &7.68 \\
|
|
&$^1E'' (\Val; n \ra \pis)$ & 7.78 &7.71 &7.79 & &\\
|
|
&$^1E' (\Val; \pi \ra \pis)$ & 7.94 &7.63 &7.92 &7.65 &7.88 \\
|
|
&$^3A_2'' (\Val; n \ra \pis)$ & 4.33 &4.32 &4.33 &4.29 &4.35 \\
|
|
&$^3E'' (\Val; n \ra \pis)$ & 4.51 &4.46 &4.51 &4.42 &4.59 \\
|
|
&$^3A_1'' (\Val; n \ra \pis)$ & 4.73 &4.65 &4.75 &4.59 &4.53 \\
|
|
&$^3A_1' (\Val; \pi \ra \pis)$ & 4.85 &5.12 &4.88 &5.10 &4.97 \\
|
|
&$^3E' (\Val; \pi \ra \pis)$ & 5.59 &5.88 &5.61 &5.82 &5.32 \\
|
|
&$^3A_2' (\Val; (\pi \ra \pis)$ & 6.62 &6.76 &6.63 &6.63 &6.27 \\
|
|
Water & $^1B_1 (\Ryd; n \ra 3s)$ &7.62 &7.23 &7.65 &7.18 &7.84 \\%
|
|
& $^1A_2 (\Ryd; n \ra 3p)$ &9.41 &8.89 &9.43 &8.84 &9.63 \\%
|
|
& $^1A_1 (\Ryd; n \ra 3s)$ &9.99 &9.58 &10.00 &9.52 &10.22 \\%
|
|
& $^3B_1 (\Ryd; n \ra 3s)$ &7.25 &6.91 &7.28 &6.86 &7.41 \\%
|
|
& $^3A_2 (\Ryd; n \ra 3p)$ &9.24 &8.77 &9.26 &8.72 &9.43 \\%
|
|
& $^3A_1 (\Ryd; n \ra 3s)$ &9.54 &9.20 &9.56 &9.15 &9.70 \\%
|
|
\end{longtable}
|
|
\end{footnotesize}
|
|
|
|
\begin{figure}
|
|
\includegraphics[width=\linewidth,viewport=2cm 22cm 19cm 27.5cm,clip]{Fig-S1.pdf}%DJ to T2: NE PAS CHANGER
|
|
\caption{Histograms of the errors (in eV) obtained with ADC(2), ADC(2.5), and ADC(3) taking the TBE/\emph{aug}-cc-pVTZ values of Refs.~\citenum{Loo18a} and \citenum{Loo20a} as reference (as in Fig.~1 in the main text).
|
|
``Count'' refers to the number of transitions in each group. Note the difference of scaling in the vertical axes.}
|
|
\label{Fig-1}
|
|
\end{figure}
|
|
|
|
\clearpage
|
|
|
|
\section{0-0 energies}
|
|
|
|
For the 0-0 energies, we used the (EOM-)CCSD/\emph{def2}-TZVPP geometries available in the Supporting Information of Ref.~\citenum{Loo19a}. We reproduce below the experimental values together with the literature references and the ZPVE
|
|
corrections (mostly determined at the B3LYP/6-31+G(d) level, see Ref. \citenum{Loo19a} for details). Two ``large'' (10 non-hydrogen atoms) molecules have been added to the original
|
|
set: \emph{p}-diisocyano-benzene and tetrafluorobenzene. The geometries are given below in the same format as in Ref.~\citenum{Loo19a}.
|
|
|
|
%
|
|
% Table-S-2
|
|
%
|
|
\renewcommand*{\arraystretch}{.65}
|
|
\LTcapwidth=\textwidth
|
|
\begin{footnotesize}
|
|
\begin{longtable}{ll|cccc}
|
|
\caption{Experimental 0-0 energies and symmetries for the set of 0-0 energies. The experimental 0-0 energies are reported in both cm$^{-1}$ (the unit used in most experimental works) and
|
|
eV. The ZPVE are also indicated in eV in the rightmost column.
|
|
} \label{Table-SI-2}\\
|
|
\hline
|
|
& & \multicolumn{3}{c}{Experimental reference} &\\
|
|
Molecule & State & cm$^{-1}$ & eV & Ref. & $\Delta^{\mathrm{ZPVE}}$\\
|
|
\hline
|
|
\endfirsthead
|
|
\hline
|
|
& & \multicolumn{3}{c}{Experimental reference}& \\
|
|
Molecule & State & cm$^{-1}$ & eV & Ref. & $\Delta^{\mathrm{ZPVE}}$\\
|
|
\hline
|
|
\endhead
|
|
\hline \multicolumn{6}{r}{{Continued on next page}} \\
|
|
\endfoot
|
|
\hline
|
|
\begin{scriptsize}
|
|
$^a$ in nm; $^b$ "best estimate"
|
|
\end{scriptsize}
|
|
\endlastfoot
|
|
Acetaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) &29769 &3.691 &\citenum{Liu95} &-0.070 \\
|
|
Acetone &$^1A_2$ ($n \rightarrow \pi^\star$) &30435 &3.773 &\citenum{Bab83} &-0.058 \\
|
|
Acetyl cyanide &$^1A^{''}$ ($n \rightarrow \pi^\star$) &27511 &3.411 &\citenum{Yoo99} &-0.053 \\
|
|
Acetylene &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &42197.7 &5.232 &\citenum{Her66} &-0.077 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) &54116 &6.710 &\citenum{Foo73} &-0.136 \\
|
|
Acrolein &$^1A^{''}$ ($n \rightarrow \pi^\star$) &25858.1 &3.206 &\citenum{Hol63} &-0.089 \\
|
|
Aniline &$^1A^{''}$ ($\pi \rightarrow \pi^\star$) &34029 &4.219 &\citenum{Sin96} &-0.191 \\
|
|
Benzene &$^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &38086.7 &4.722 &\citenum{Chr98} &-0.162 \\
|
|
Benzonitrile &$^1B_1$ ($\pi \rightarrow \pi^\star$) &36513 &4.527 &\citenum{Bor07d} &-0.145 \\
|
|
Benzoquinone &$^1B_{1g}$ ($n \rightarrow \pi^\star$) &20045 &2.485 &\citenum{Ter79} &-0.080 \\
|
|
CCl$_2$ &$^1B_1$ &17256.9 &2.140 &\citenum{Ric08} &0.010 \\
|
|
CClF &$^1A^{''}$ &25277.8 &3.134 &\citenum{Kar93} &-0.001 \\
|
|
CF$_2$ &$^1B_1$ &37226 &4.615 &\citenum{Mat67} &-0.008 \\
|
|
Cyanoacetylene &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &38484.9 &4.772 &\citenum{Job66a} &-0.118 \\
|
|
&$^1\Delta$ ($\pi \rightarrow \pi^\star$) &44221 &5.483 &\citenum{Job66b} &-0.119 \\
|
|
Cyanoformaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) &26283.37 &3.259 &\citenum{Kar91b} &-0.063 \\
|
|
Cyanogen &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &45399.85 &5.629 &\citenum{Fis72} &-0.086 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) & &5.96 &\citenum{Hal97} &-0.078 \\
|
|
2-Cyclopenten-1-one &$^1A^{''}$ ($n \rightarrow \pi^\star$) &27210 &3.374 &\citenum{Che98c} &-0.096 \\
|
|
Diacetylene &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &34912.37 &4.329 &\citenum{Har77} &-0.125 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) &40845 &5.064 &\citenum{Ban92} &-0.192 \\
|
|
\emph{p}-Dicyano-benzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &35120 &4.354 &\citenum{Fuj92} &-0.140 \\%N
|
|
\emph{p}-Diethynylbenzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &34255 &4.247 &\citenum{Ste03} &-0.134 \\%N
|
|
\emph{p}-Difluoro-benzene&$^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &36838 &4.567 &\citenum{Kni88} &-0.160 \\
|
|
Difluorodiazirine &$^1B_1$ ($n \rightarrow \pi^\star$) &28374.21 &3.518 &\citenum{Sie90} &-0.072 \\
|
|
2,6-Difluoro-pyridine & $^1B_2$ ($\pi \rightarrow \pi^\star$) &37820 &4.689 &\citenum{Nib03} &-0.149 \\
|
|
\emph{p}-Diisocyano-benzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &35566 &4.410 &\citenum{Meh15} &-0.137 \\
|
|
Fluoro-benzene &$^1B_2$ ($\pi \rightarrow \pi^\star$) &37813 &4.688 &\citenum{But07} &-0.161 \\
|
|
Formaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &28188.02 &3.495 &\citenum{Clo83} &-0.085 \\
|
|
Formic acid &$^1A^{''}$ ($n \rightarrow \pi^\star$) &37413.39 &4.639 &\citenum{Bea01} &-0.096 \\
|
|
Formylchloride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &32760 &4.062 &\citenum{Din99} &-0.069 \\
|
|
Formylfluoride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &37491.7 &4.648 &\citenum{Cra97} &-0.063 \\
|
|
Glyoxal &$^1A_u$ ($n \rightarrow \pi^\star$) &21973.43 &2.724 &\citenum{Pad67} &-0.060 \\
|
|
H$_2$C$_3$ &$^1A_2$ ($\pi \rightarrow \pi^\star$) &13677 &1.696 &\citenum{Sta12} &-0.059 \\
|
|
HCN &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &52256.4 &6.479 &\citenum{Her66} &-0.120 \\
|
|
HCP &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &34769.9 &4.311 &\citenum{Her66} &-0.087 \\
|
|
HNO &$^1A^{''}$ ($n \rightarrow \pi^\star$) &13154.4 &1.631 &\citenum{Her66} &-0.029 \\
|
|
HPO &$^1A^{''}$ ($n \rightarrow \pi^\star$) &19032.78 &2.360 &\citenum{Tac02} &-0.043 \\
|
|
HPS &$^1A^{''}$ ($\sigma \rightarrow \pi^\star$) &12291.4 &1.524 &\citenum{Gri13b} &-0.019 \\
|
|
HSiF &$^1A^{''}$ &23260.021 &2.884 &\citenum{Har95} &-0.037 \\
|
|
\emph{cis}-Hydroquinone & $^1A_1$ ($\pi \rightarrow \pi^\star$) &33534.782 &4.158 &\citenum{Hum93} &-0.156 \\%N
|
|
\emph{trans}-Hydroquinone& $^1B_u$ ($\pi \rightarrow \pi^\star$) &33500.054 &4.153 &\citenum{Hum93} &-0.159 \\%N
|
|
Isocyanogen &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &42523 &5.272 &\citenum{Lyn07} &-0.077 \\
|
|
Nitrosomethane &$^1A^{''}$ ($n \rightarrow \pi^\star$) &14408 &1.786 &\citenum{Ern78} &-0.026 \\
|
|
Nitrosylcyanide &$^1A^{''}$ ($n \rightarrow \pi^\star$) &11339.9 &1.406 &\citenum{Dix85} &0.004 \\
|
|
Oxalyl fluoride &$^1A_u$ ($n \rightarrow \pi^\star$) &32445 &4.023 &\citenum{Liv79} &-0.104 \\
|
|
Phenylacetylene &$^1B_2$ ($\pi \rightarrow \pi^\star$) &35877.18 &4.448 &\citenum{Rib99} &-0.158 \\
|
|
Phosgene &$^1A_2$ ($n \rightarrow \pi^\star$) &32730 &4.058 &\citenum{Gid62} &-0.089 \\
|
|
Propynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &26162.94 &3.244 &\citenum{Bra74} &-0.092 \\
|
|
4H-pyran-4-one & $^1A^2$ ($n \rightarrow \pi^\star$) &28360 &3.516 &\citenum{Gor93} &-0.122 \\
|
|
Pyrazine &$^1B_{3u}$ ($n \rightarrow \pi^\star$) &30875.78 &3.828 &\citenum{Sie89} &-0.209 \\
|
|
Pyrimidine &$^1B_1$ ($n \rightarrow p$) &31188 &3.867 &\citenum{Fis03b} &-0.174 \\
|
|
Selenoformaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &13635 &1.691 &\citenum{Clo87} &-0.062 \\
|
|
SiCl$_2$ &$^1B_1$ &30013.5 &3.721 &\citenum{Kar93b} &-0.015 \\
|
|
Silylidene &$^1A_2$ (Ryd) &15132.97 &1.876 &\citenum{Smi03} &0.009 \\
|
|
&$^1B_2$ (Ryd) &29312.88 &3.634 &\citenum{Har97} &0.018 \\
|
|
Tetrafluorobenzene & $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &36555 &4.532 &\citenum{Oku86} &-0.136 \\
|
|
Tetrazine &$^1B_{3u}$ ($n \rightarrow \pi^\star$) &18128.07 &2.248 &\citenum{Ker97} &-0.093 \\
|
|
Thioacetaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) & &2.22 &\citenum{Jud83} &-0.064 \\
|
|
Thioacetone &$^1A_2$ ($n \rightarrow \pi^\star$) & &2.33 &\citenum{Jud83} &-0.047 \\
|
|
Thioacrolein &$^1A^{''}$ ($n \rightarrow \pi^\star$) &15124.6 &1.875 &\citenum{Jud84b} &-0.050 \\
|
|
Thiocarbonyllbromide &$^1A_2$ ($n \rightarrow \pi^\star$) &17992 &2.231 &\citenum{Sim87} &-0.033 \\
|
|
Thiocarbonylchlorofluoride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &21657.4 &2.685 &\citenum{Sub74} &-0.032 \\
|
|
&$^2A^{'}$ ($\pi \rightarrow \pi^\star$) &35277 &4.374 &\citenum{Clo80} &-0.066 \\
|
|
Thiocarbonylfluoride &$^1A_2$ ($n \rightarrow \pi^\star$) &23477.1 &2.911 &\citenum{Mou70} &-0.034 \\
|
|
Thioformaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &16395.6 &2.033 &\citenum{Clo83} &-0.066 \\
|
|
Thioformylchloride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &18792 &2.330 &\citenum{Jud85b} &-0.054 \\
|
|
Thiophosgene &$^1A_2$ ($n \rightarrow \pi^\star$) &18712.2 &2.320 &\citenum{Fuj07} &-0.030 \\
|
|
& $^2A_1$ ($\pi \rightarrow \pi^\star$) &34277.32 &4.250 &\citenum{Fuj07} &-0.069 \\
|
|
Thiopropynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &14656.4 &1.817 &\citenum{Jud84c} &-0.048 \\
|
|
Trifluoronitrosomethane &$^1A^{''}$ ($n \rightarrow \pi^\star$) &13929.7 &1.727 &\citenum{Dye87} &-0.017 \\
|
|
Acetaldehyde &$^3A^{''}$ ($n \rightarrow \pi^\star$) &27240 &3.377& \citenum{Mou85} &-0.074\\
|
|
Acrolein &$^3 A^{''}$ ($n \rightarrow \pi^\star$) &24247.3 &3.006& \citenum{Hla13} &-0.109\\
|
|
Benzaldehyde &$^3 A^{''}$ ($n \rightarrow \pi^\star$) &25183 &3.122& \citenum{Ohm88} &-0.111\\
|
|
Benzoquinone &$^3B_{1g}$ ($n \rightarrow \pi^\star$) &18370 &2.278& \citenum{Koy71} &-0.075\\
|
|
CHCl &$^3 A^{''}$ &2163.28 &0.268& \citenum{Tao08b} &0.007\\
|
|
Cyanogen &$^3\Sigma_u^+$ ($\pi \rightarrow \pi^\star$) &33289.9 &4.127& \citenum{Cal63} &-0.110\\
|
|
4-Cyclopentene-1,3-dione &$^3B_1$ ($n \rightarrow \pi^\star$) &20540 &2.547& \citenum{Spr09} &-0.074\\
|
|
2-Cyclopenten-1-one &$^3A^{''}$ ($n \rightarrow \pi^\star$) &25956.29 &3.218& \citenum{Pil07} &-0.111\\
|
|
Formaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &25194.34 &3.124& \citenum{Clo83} &-0.092\\
|
|
Glyoxal & $^3A_u$ ($n \rightarrow \pi^\star$) &19199 &2.380& \citenum{Ott99c} &-0.056\\
|
|
H$_2$C$_3$ &$^3B_1$ ($\pi \rightarrow \pi^\star$) &10354 &1.284& \citenum{Sta12} &-0.066\\
|
|
Oxalyl Chloride &$^3A_u$ ($n \rightarrow \pi^\star$) &410.02$^a$ &3.024& \citenum{Yos96} &-0.085\\
|
|
Ozone &$^3A_2$ &9553.021 &1.184& \citenum{Bou98} &-0.061\\
|
|
Propynal &$^3A^{''}$ ($n \rightarrow \pi^\star$) &24127.1 &2.991& \citenum{Bir73} &-0.106\\
|
|
4H-pyran-4-one &$^3A^2$ ($n \rightarrow \pi^\star$) &27291.5 &3.384& \citenum{Hof08} &-0.134\\
|
|
4H-pyran-4-thione &$^3A^2$ ($n \rightarrow \pi^\star$) &16846.4 &2.089& \citenum{Rut02} &-0.097\\
|
|
Pyrazine &$^3B_{3u}$ ($n \rightarrow \pi^\star$) &26820.3 &3.325& \citenum{Ott95} &-0.177\\
|
|
Pyrimidine &$^3 B_1$ ($n \rightarrow \pi^\star$) &28534.0 &3.538& \citenum{Ott93} &-0.176\\
|
|
Selenoformaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &12171.0 &1.509& \citenum{Jud88} &-0.071\\
|
|
SiF$_2$ &$^3 B_1$ &26319.5 &3.263& \citenum{Kar95} &-0.002\\
|
|
SO$_2$ &$^3 B_1$ &25765.737 &3.195& \citenum{Hua00} &-0.055\\
|
|
Tetrazine &$^3B_{3u}$ ($n \rightarrow \pi^\star$) &13608.0 &1.687& \citenum{Liv71} &-0.061\\
|
|
Thioacetaldehyde &$^3A^{''}$ ($n \rightarrow \pi^\star$) &16293.8 &2.020& \citenum{Jud87} &-0.060\\
|
|
Thioacetone &$^3A_2$ ($n \rightarrow \pi^\star$) &17327.8 &2.148& \citenum{Mou91} &-0.045\\
|
|
Thioacrolein &$^3A^{''}$ ($n \rightarrow \pi^\star$) &14036.2 &1.740& \citenum{Jud84b} &-0.070\\
|
|
Thioformaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &14507.39 &1.799& \citenum{Clo83} &-0.080\\
|
|
Thioformylchloride &$^3A^{''}$ ($n \rightarrow \pi^\star$) &17233.9 &2.137& \citenum{Jud85b} &-0.050\\
|
|
Thiophosgene &$^3A_2$ ($n \rightarrow \pi^\star$) &17493.788 &2.169& \citenum{Fuj06} &-0.035\\
|
|
Thiopropynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &13257.4 &1.644& \citenum{Jud84c} &-0.064\\
|
|
Triazine &$^3E^{"}$ ($n \rightarrow \pi^\star$) &335$^{a,b}$ &3.701& \citenum{Oht83} &-0.148\\
|
|
\end{longtable}
|
|
\end{footnotesize}
|
|
|
|
|
|
Cartesian coordinates (in \AA) obtained at the (EOM-)CCSD/\emph{def2}-TZVPP level of theory for the two additional compounds.
|
|
The notations of the excited states refer to the ground-state point group symmetry.
|
|
|
|
\subsubsection{\emph{p}-Diisocyano-benzene}
|
|
|
|
\begin{singlespace}
|
|
|
|
Ground state
|
|
\begin{verbatim}
|
|
C 0.000000 1.210459 0.692565
|
|
C 0.000000 1.210459 -0.692565
|
|
C 0.000000 0.000000 1.377022
|
|
C 0.000000 0.000000 -1.377022
|
|
C 0.000000 -1.210459 0.692565
|
|
C 0.000000 -1.210459 -0.692565
|
|
C 0.000000 0.000000 3.932314
|
|
C 0.000000 0.000000 -3.932314
|
|
N 0.000000 0.000000 2.763434
|
|
N 0.000000 0.000000 -2.763434
|
|
H 0.000000 2.135125 1.244480
|
|
H 0.000000 2.135125 -1.244480
|
|
H 0.000000 -2.135125 1.244480
|
|
H 0.000000 -2.135125 -1.244480
|
|
\end{verbatim}
|
|
|
|
Excited state [$^1B_{2u}$ ($\pi \rightarrow \pi^\star$)]
|
|
\begin{verbatim}
|
|
C 0.000000 1.238754 0.709424
|
|
C 0.000000 1.238754 -0.709424
|
|
C 0.000000 -0.000000 1.404087
|
|
C 0.000000 -0.000000 -1.404087
|
|
C 0.000000 -1.238754 0.709424
|
|
C 0.000000 -1.238754 -0.709424
|
|
C 0.000000 -0.000000 3.944346
|
|
C 0.000000 -0.000000 -3.944346
|
|
N 0.000000 -0.000000 2.771103
|
|
N 0.000000 -0.000000 -2.771103
|
|
H 0.000000 2.159635 1.265112
|
|
H 0.000000 2.159635 -1.265112
|
|
H 0.000000 -2.159635 1.265112
|
|
H 0.000000 -2.159635 -1.265112
|
|
\end{verbatim}
|
|
|
|
|
|
|
|
\subsubsection{Tetrafluorobenzene}
|
|
|
|
Ground state
|
|
\begin{verbatim}
|
|
C 0.000000 1.190995 0.692100
|
|
C 0.000000 1.190995 -0.692100
|
|
C 0.000000 0.000000 -1.393333
|
|
C 0.000000 -1.190995 -0.692100
|
|
C 0.000000 -1.190995 0.692100
|
|
C 0.000000 0.000000 1.393333
|
|
F 0.000000 2.348323 -1.348963
|
|
F 0.000000 2.348323 1.348963
|
|
F 0.000000 -2.348323 1.348963
|
|
F 0.000000 -2.348323 -1.348963
|
|
H 0.000000 0.000000 -2.469482
|
|
H 0.000000 0.000000 2.469482
|
|
\end{verbatim}
|
|
|
|
Excited state [$^1B_{2u}$ ($\pi \rightarrow \pi^\star$)]
|
|
\begin{verbatim}
|
|
C 1.178195 0.707583 0.063424
|
|
C 1.178195 -0.707583 0.063424
|
|
C 0.000000 -1.473594 0.163267
|
|
C -1.178195 -0.707583 0.063424
|
|
C -1.178195 0.707583 0.063424
|
|
C 0.000000 1.473594 0.163267
|
|
F 2.339183 -1.319369 -0.118329
|
|
F 2.339183 1.319369 -0.118329
|
|
F -2.339183 1.319369 -0.118329
|
|
F -2.339183 -1.319369 -0.118329
|
|
H 0.000000 -2.523792 0.389226
|
|
H 0.000000 2.523792 0.389226
|
|
\end{verbatim}
|
|
|
|
\end{singlespace}
|
|
|
|
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\clearpage
|
|
%
|
|
% Table-S-2
|
|
%
|
|
\renewcommand*{\arraystretch}{.65}
|
|
\LTcapwidth=\textwidth
|
|
\begin{footnotesize}
|
|
\begin{longtable}{ll|cccc}
|
|
\caption{0-0 energies computed with ADC(2), ADC(3), CC2, and CC3. All values are in eV, and they have been obtained on the basis of the corresponding \emph{aug}-cc-pVTZ frozen-core adiabatic energies
|
|
determined on the (EOM-)CCSD/\emph{def2}-TZVPP geometries. The ZPVE corrections are listed above.} \label{Table-SI-3}\\
|
|
\hline
|
|
Molecule & State & ADC(2) & ADC(3) & CC2 & CC3 \\
|
|
\hline
|
|
\endfirsthead
|
|
\hline
|
|
Molecule & State & ADC(2) & ADC(3) & CC2 & CC3 \\
|
|
\hline
|
|
\endhead
|
|
\hline \multicolumn{6}{r}{{Continued on next page}} \\
|
|
\endfoot
|
|
\hline
|
|
\endlastfoot
|
|
Acetaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.455 &3.830 &3.671 &3.663 \\
|
|
Acetone &$^1A_2$ ($n \rightarrow \pi^\star$) &3.430 &4.007 &3.671 &3.733 \\
|
|
Acetyl cyanide &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.136 &3.607 &3.348 &3.381 \\
|
|
Acetylene &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &5.323 &4.753 &5.322 &5.163 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) &6.797 &6.247 &6.808 &6.627 \\
|
|
Acrolein &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.040 &3.445 &3.254 &3.229 \\
|
|
Aniline &$^1A^{''}$ ($\pi \rightarrow \pi^\star$) &4.264 &4.165 &4.261 &4.169 \\
|
|
Benzene &$^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.930 &4.684 &4.904 &4.709 \\
|
|
Benzonitrile &$^1B_1$ ($\pi \rightarrow \pi^\star$) &4.735 &4.494 &4.711 &4.526 \\
|
|
Benzoquinone &$^1B_{1g}$ ($n \rightarrow \pi^\star$) &2.310 &2.788 &2.443 &2.502 \\
|
|
CCl$_2$ &$^1B_1$ &2.066 &1.986 &2.180 &2.232 \\
|
|
CClF &$^1A^{''}$ &3.048 &2.978 &3.170 &3.198 \\
|
|
CF$_2$ &$^1B_1$ &4.504 &4.474 &4.632 &4.642 \\
|
|
Cyanoacetylene &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &4.815 &4.323 &4.780 &4.693 \\
|
|
&$^1\Delta$ ($\pi \rightarrow \pi^\star$) &5.483 &5.060 &5.480 &5.413 \\
|
|
Cyanoformaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.133 &3.371 &3.309 &3.270 \\
|
|
Cyanogen &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &5.721 &5.212 &5.696 &5.595 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) &6.051 &5.529 &6.045 &5.907 \\
|
|
2-Cyclopenten-1-one &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.065 &3.734 &3.275 &3.355 \\
|
|
Diacetylene &$^1\Sigma_u^-$ ($\pi \rightarrow \pi^\star$) &4.268 &3.927 &4.237 &4.243 \\
|
|
&$^1\Delta_u$ ($\pi \rightarrow \pi^\star$) &4.966 &4.613 &4.958 &4.935 \\
|
|
\emph{p}-Dicyano-benzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.546 &4.308 &4.522 &4.351 \\
|
|
\emph{p}-Diethynylbenzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.455 &4.220 &4.434 &4.265 \\
|
|
\emph{p}-Difluoro-benzene&$^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.631 &4.519 &4.741 &4.525 \\
|
|
Difluorodiazirine &$^1B_1$ ($n \rightarrow \pi^\star$) &3.488 &3.304 &3.477 &3.501 \\
|
|
2,6-Difluoro-pyridine & $^1B_2$ ($\pi \rightarrow \pi^\star$) &4.744 &4.647 &4.758 &4.644 \\
|
|
\emph{p}-Diisocyano-benzene& $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.606 &4.372 &4.590 &4.407 \\
|
|
Fluoro-benzene &$^1B_2$ ($\pi \rightarrow \pi^\star$) &4.841 &4.648 &4.831 &4.664 \\
|
|
Formaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &3.365 &3.548 &3.541 &3.482 \\
|
|
Formic acid &$^1A^{''}$ ($n \rightarrow \pi^\star$) &4.308 &4.886 &4.563 &4.588 \\
|
|
Formylchloride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.839 &4.219 &4.075 &4.047 \\
|
|
Formylfluoride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &4.410 &4.820 &4.661 &4.611 \\
|
|
Glyoxal &$^1A_u$ ($n \rightarrow \pi^\star$) &2.662 &2.733 &2.727 &2.726 \\
|
|
H$_2$C$_3$ &$^1A_2$ ($\pi \rightarrow \pi^\star$) &1.952 &1.418 &1.930 &1.713 \\
|
|
HCN &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &6.760 &5.963 &6.681 &6.409 \\
|
|
HCP &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &4.458 &3.794 &4.432 &4.250 \\
|
|
HNO &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.555 &1.403 &1.600 &1.637 \\
|
|
HPO &$^1A^{''}$ ($n \rightarrow \pi^\star$) &2.087 &2.291 &2.242 &2.277 \\
|
|
HPS &$^1A^{''}$ ($\sigma \rightarrow \pi^\star$) &1.460 &1.250 &1.522 &1.426 \\
|
|
HSiF &$^1A^{''}$ &2.923 &2.684 &2.955 &2.886 \\
|
|
\emph{cis}-Hydroquinone & $^1A_1$ ($\pi \rightarrow \pi^\star$) &4.119 &4.103 &4.125 &4.092 \\
|
|
\emph{trans}-Hydroquinone& $^1B_u$ ($\pi \rightarrow \pi^\star$) &4.111 &4.097 &4.127 &4.085 \\
|
|
Isocyanogen &$^1\Sigma^-$ ($\pi \rightarrow \pi^\star$) &5.209 &5.168 &5.405 &5.108 \\
|
|
Nitrosomethane &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.666 &1.569 &1.749 &1.781 \\
|
|
Nitrosylcyanide &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.441 &1.165 &1.417 &1.446 \\
|
|
Oxalyl fluoride &$^1A_u$ ($n \rightarrow \pi^\star$) &3.758 &4.209 &3.928 &3.988 \\
|
|
Phenylacetylene &$^1B_2$ ($\pi \rightarrow \pi^\star$) &4.652 &4.409 &4.628 &4.445 \\
|
|
Phosgene &$^1A_2$ ($n \rightarrow \pi^\star$) &3.727 &4.394 &3.956 &4.039 \\
|
|
Propynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &3.039 &3.430 &3.251 &3.241 \\
|
|
4H-pyran-4-one & $^1A^2$ ($n \rightarrow \pi^\star$) &3.168 &3.971 &3.422 &3.487 \\
|
|
Pyrazine &$^1B_{3u}$ ($n \rightarrow \pi^\star$) &3.827 &3.797 &3.795 &3.799 \\
|
|
Pyrimidine &$^1B_1$ ($n \rightarrow p$) &3.717 &3.909 &3.770 &3.818 \\
|
|
Selenoformaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &1.659 &1.625 &1.812 &1.708 \\
|
|
SiCl$_2$ &$^1B_1$ &3.749 &3.541 &3.794 &3.697 \\
|
|
Silylidene &$^1A_2$ (Ryd) &2.127 &1.557 &2.089 &1.850 \\
|
|
&$^1B_2$ (Ryd) &3.692 &3.224 &3.633 &3.579 \\
|
|
Tetrafluorobenzene & $^1B_{2u}$ ($\pi \rightarrow \pi^\star$) &4.532 &4.501 &4.553 &4.487 \\
|
|
Tetrazine &$^1B_{3u}$ ($n \rightarrow \pi^\star$) &2.207 &2.185 &2.177 &2.246 \\
|
|
Thioacetaldehyde &$^1A^{''}$ ($n \rightarrow \pi^\star$) &2.145 &2.169 &2.300 &2.204 \\
|
|
Thioacetone &$^1A_2$ ($n \rightarrow \pi^\star$) &2.171 &2.361 &2.358 &2.298 \\
|
|
Thioacrolein &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.913 &1.828 &2.062 &1.923 \\
|
|
Thiocarbonyllbromide &$^1A_2$ ($n \rightarrow \pi^\star$) &2.114 &2.237 &2.284 &2.233 \\
|
|
Thiocarbonylchlorofluoride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &2.582 &2.640 &2.756 &2.618 \\
|
|
&$^2A^{'}$ ($\pi \rightarrow \pi^\star$) &4.112 &4.007 &4.542 &4.324 \\
|
|
Thiocarbonylfluoride &$^1A_2$ ($n \rightarrow \pi^\star$) &2.889 &2.825 &3.029 &2.815 \\
|
|
Thioformaldehyde &$^1A_2$ ($n \rightarrow \pi^\star$) &2.042 &1.911 &2.154 &2.038 \\
|
|
Thioformylchloride &$^1A^{''}$ ($n \rightarrow \pi^\star$) &2.282 &2.277 &2.448 &2.337 \\
|
|
Thiophosgene &$^1A_2$ ($n \rightarrow \pi^\star$) &2.240 &2.368 &2.425 &2.349 \\
|
|
& $^2A_1$ ($\pi \rightarrow \pi^\star$) &3.948 &3.878 &4.411 &4.229 \\
|
|
Thiopropynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.845 &1.715 &1.971 &1.849 \\
|
|
Trifluoronitrosomethane &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.666 &1.470 &1.717 &1.739 \\
|
|
Acetaldehyde &$^3A^{''}$ ($n \rightarrow \pi^\star$) &3.037 &3.429 &3.214 &3.308 \\
|
|
Acrolein &$^3 A^{''}$ ($n \rightarrow \pi^\star$) &2.664 &3.172 &2.849 &2.946 \\
|
|
Benzaldehyde &$^3 A^{''}$ ($n \rightarrow \pi^\star$) &2.711 &3.333 &2.900 &3.050 \\
|
|
Benzoquinone &$^3B_{1g}$ ($n \rightarrow \pi^\star$) &2.161 &2.522 &2.229 &2.351 \\
|
|
CHCl &$^3 A^{''}$ &0.091 &0.010 &0.190 &0.270 \\
|
|
Cyanogen &$^3\Sigma_u^+$ ($\pi \rightarrow \pi^\star$) &4.329 &3.790 &4.263 &4.006 \\
|
|
4-Cyclopentene-1,3-dione &$^3B_1$ ($n \rightarrow \pi^\star$) &2.219 &2.765 &2.297 &2.499 \\
|
|
2-Cyclopenten-1-one &$^3A^{''}$ ($n \rightarrow \pi^\star$) &2.767 &3.549 &2.960 &3.137 \\
|
|
Formaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &2.878 &3.092 &3.012 &3.067 \\
|
|
Glyoxal & $^3A_u$ ($n \rightarrow \pi^\star$) &2.247 &2.320 &2.308 &2.360 \\
|
|
H$_2$C$_3$ &$^3B_1$ ($\pi \rightarrow \pi^\star$) &1.395 &1.115 &1.378 &1.308 \\
|
|
Oxalyl Chloride &$^3A_u$ ($n \rightarrow \pi^\star$) &2.663 &3.238 &2.808 &3.004 \\
|
|
Ozone &$^3A_2$ &1.377 &0.459 &1.051 &1.164 \\
|
|
Propynal &$^3A^{''}$ ($n \rightarrow \pi^\star$) &2.628 &3.104 &2.804 &2.922 \\
|
|
4H-pyran-4-one &$^3A^2$ ($n \rightarrow \pi^\star$) &2.892 &3.770 &3.122 &3.293 \\
|
|
4H-pyran-4-thione &$^3A^2$ ($n \rightarrow \pi^\star$) &1.934 &2.117 &2.095 &2.044 \\
|
|
Pyrazine &$^3B_{3u}$ ($n \rightarrow \pi^\star$) &3.333 &3.242 &3.312 &3.301 \\
|
|
Pyrimidine &$^3 B_1$ ($n \rightarrow \pi^\star$) &3.389 &3.527 &3.432 &3.486 \\
|
|
Selenoformaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &1.340 &1.403 &1.461 &1.475 \\
|
|
SiF$_2$ &$^3 B_1$ &2.932 &3.019 &2.992 &3.176 \\
|
|
SO$_2$ &$^3 B_1$ &2.774 &2.829 &2.804 &2.925 \\
|
|
Tetrazine &$^3B_{3u}$ ($n \rightarrow \pi^\star$) &1.666 &1.543 &1.642 &1.673 \\
|
|
Thioacetaldehyde &$^3A^{''}$ ($n \rightarrow \pi^\star$) &1.855 &1.941 &1.977 &1.986 \\
|
|
Thioacetone &$^3A_2$ ($n \rightarrow \pi^\star$) &1.923 &2.149 &2.075 &2.108 \\
|
|
Thioacrolein &$^3A^{''}$ ($n \rightarrow \pi^\star$) &1.624 &1.628 &1.742 &1.712 \\
|
|
Thioformaldehyde &$^3A_2$ ($n \rightarrow \pi^\star$) &1.675 &1.646 &1.761 &1.763 \\
|
|
Thioformylchloride &$^3A^{''}$ ($n \rightarrow \pi^\star$) &1.980 &2.050 &2.117 &2.115 \\
|
|
Thiophosgene &$^3A_2$ ($n \rightarrow \pi^\star$) &1.960 &2.158 &2.117 &2.141 \\
|
|
Thiopropynal &$^1A^{''}$ ($n \rightarrow \pi^\star$) &1.515 &1.501 &1.613 &1.613 \\
|
|
Triazine &$^3E^{"}$ ($n \rightarrow \pi^\star$) &3.451 &3.730 &3.530 &3.643 \\
|
|
\end{longtable}
|
|
\end{footnotesize}
|
|
|
|
\clearpage
|
|
|
|
\bibliography{biblio-new}
|
|
|
|
|
|
|
|
\end{document}
|
|
|