764 lines
40 KiB
TeX
764 lines
40 KiB
TeX
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\documentclass[journal=jctcce,manuscript=article,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{\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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\title{A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks\\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{Anthony Scemama}
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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{Aymeric Blondel}
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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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\author{Yann Garniron}
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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{Michel Caffarel}
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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{Basis set and frozen-core effects}
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\subsection{Water, ammonia and hydrogen chloride}
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\begin{sidewaystable}[htp]
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\caption{\small CC3 vertical transition energies of water (top), ammonia (center), and hydrogen chloride (bottom) using various atomic basis sets.
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FC stands for frozen core (large frozen core for the latter compound). All values are in eV.}
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\label{Table-wat-bs}
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\begin{small}
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\begin{tabular}{l|ccccccccccc}
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\hline
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& {\AVDZ} & {\AVTZ} & {\DAVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & \multicolumn{2}{c}{\TAVQZ} & {\AVPZ} & {\DAVPZ} \\
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& FC & FC &FC & FC & Full & FC & Full & FC & Full & Full & Full\\
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\hline
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& \multicolumn{11}{c}{Water} \\
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\hline
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$^1B_1 (n \rightarrow 3s)$ &7.51 &7.60&7.60 &7.65 &7.66 &7.65 &7.66 &7.64 &7.66 &7.67 &7.67 \\
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$^1A_2 (n \rightarrow 3p)$ &9.29 &9.38&9.37 &9.43 &9.43 &9.42 &9.42 &9.42 &9.42 &9.44 &9.44 \\
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$^1A_1 (n \rightarrow 3s)$ &9.92 &9.97&9.89 &10.00 &10.00 &9.94 &9.94 &9.93 &9.94 &10.00 &9.95 \\
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$^3B_1 (n \rightarrow 3s)$ &7.13 &7.23&7.23 &7.28 &7.29 &7.28 &7.29 &7.28 &7.29 &7.31 &7.31 \\
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$^3A_2 (n \rightarrow 3p)$ &9.12 &9.22&9.30 &9.26 &9.27 &9.26 &9.26 &9.26 &9.26 &9.28 &9.28 \\
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$^3A_1 (n \rightarrow 3s)$ &9.47 &9.52&9.52 &9.56 &9.56 &9.56 &9.56 &9.56 &9.56 &9.57 &9.57 \\
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\hline
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& \multicolumn{11}{c}{Ammonia} \\
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\hline
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$^1A_2 (n \rightarrow 3s)$ &6.46 & 6.57&6.57 &6.61 &6.61 &6.61 &6.61 &6.61 &6.61 &6.63 &6.63 \\
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$^1E (n \rightarrow 3p)$ &8.06 & 8.15&8.12 &8.18 &8.18 &8.16 &8.16 &8.16 &8.16 &8.18 &8.17 \\
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$^1A_1 (n \rightarrow 3p)$ &9.66 & 9.32&8.56 &9.11 &9.11 &8.61 &8.61 &8.60 &8.60 &8.91 &8.62 \\
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$^1A_2 (n \rightarrow 4s)$ &10.40& 9.95&9.12 &9.77 &9.77 &9.16 &9.17 &9.15 &9.16 &9.61 &9.18 \\
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$^3A_2 (n \rightarrow 3s)$ &6.18 & 6.29&6.29 &6.33 &6.34 &6.33 &6.34 &6.33 &6.34 &6.35 &6.35 \\
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\hline
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& \multicolumn{11}{c}{Hydrogen chloride} \\
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\hline
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$^1\Pi (\mathrm{CT})$ &7.82 & 7.84 & 7.83 &7.89 &7.87 &7.88 &7.87 &7.88 &7.87 &7.87 &7.87\\
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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{Dinitrogen and carbon monoxide}
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\begin{sidewaystable}[htp]
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\caption{\small CC3 vertical transition energies of dinitrogen (top) and carbon monoxide (bottom) using various atomic basis sets.
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See caption of Table \ref{Table-wat-bs} for more details.}
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\label{Table-n2co-bs}
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\begin{small}
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\begin{tabular}{l|cccccccccc}
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\hline
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& {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & \multicolumn{2}{c}{\TAVQZ} & {\AVPZ} & {\DAVPZ} \\
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& FC & FC & FC & Full & FC & Full & FC & Full & Full & Full\\
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\hline
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& \multicolumn{10}{c}{Dinitrogen} \\
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\hline
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$^1\Pi_g (\mathrm{V}; n \rightarrow \pi^\star)$ &9.44 &9.34 &9.33 &9.32 &9.33 &9.32 &9.33 &9.32 &9.32 &9.32 \\%B2G-B3G
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$^1\Sigma_u^- (\mathrm{V}; \pi \rightarrow \pi^\star)$ &10.06 &9.88 &9.87 &9.87 &9.87 &9.87 &9.87 &9.87 &9.86 &9.86 \\%AU
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$^1\Delta_u (\mathrm{V}; \pi \rightarrow \pi^\star)$ &10.43 &10.29 &10.27 &10.27 &10.27 &10.27 &10.27 &10.27 &10.27 &10.27 \\%B1U/AU
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$^1\Sigma_g^+ (\mathrm{R}; n \rightarrow \sigma^\star)$ &13.23 &13.01 &12.90 &12.91 &12.27 &12.28 &12.27 &12.28 &12.77 &12.31 \\%AG
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$^1\Pi_u (\mathrm{R})$ &13.28 &13.22 &13.17 &13.16 &12.89 &12.90 &12.89 &12.90 &13.08 &12.92 \\%B2U-B3U
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$^1\Sigma_u^+ (\mathrm{R}; n \rightarrow \sigma^\star)$ &13.14 &13.12 &13.09 &13.10 &12.94 &12.96 &12.94 &12.96 &13.06 &12.98 \\%B1IU
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$^1\Pi_u (\mathrm{R})$ &13.64 &13.49 &13.42 &13.40 &13.34 &13.31 &13.34 &13.31 &13.34 &13.30 \\%B2U-B3U
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$^3\Sigma_u^+ (\mathrm{V}; \pi \rightarrow \pi^\star)$ &7.67 &7.68 &7.71 &7.70 &7.71 &7.70 &7.71 &7.70 &7.71 &7.71 \\%B1IU
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$^3\Pi_g (\mathrm{V}; n \rightarrow \pi^\star)$ &8.07 &8.04 &8.04 &8.03 &8.04 &8.03 &8.04 &8.03 &8.04 &8.04 \\%B2G-B3G
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$^3\Delta_u (\mathrm{V}; \pi \rightarrow \pi^\star)$ &8.97 &8.87 &8.87 &8.86 &8.87 &8.86 &8.87 &8.86 &8.87 &8.87 \\%B1U/AU
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$^3\Sigma_u^- (\mathrm{V}; \pi \rightarrow \pi^\star)$ &9.78 &9.68 &9.68 &9.67 &9.68 &9.67 &9.68 &9.67 &9.67 &9.67 \\%AU
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\hline
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& \multicolumn{10}{c}{Carbon monoxide} \\
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\hline
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$^1\Pi (\mathrm{V}; n \rightarrow \pi^\star)$ &8.57 &8.49 &8.47 &8.46 &8.47 &8.45 &8.47 &8.45 &8.45 &8.45 \\%B1/B2
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$^1\Sigma^- (\mathrm{V}; \pi \rightarrow \pi^\star)$ &10.12 &9.99 &9.99 &9.98 &9.99 &9.98 &9.99 &9.98 &9.98 &9.98 \\%A2
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$^1\Delta (\mathrm{V}; \pi \rightarrow \pi^\star)$ &10.23 &10.12 &10.12 &10.11 &10.12 &10.11 &10.11 &10.11 &10.11 &10.11 \\%A1/A2
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$^1\Sigma^+ (\mathrm{R})$ &10.92 &10.94 &10.90 &10.91 &10.72 &10.72 &10.72 &10.72 &10.85 &10.74 \\%A1
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$^1\Sigma^+ (\mathrm{R})$ &11.48 &11.49 &11.46 &11.47 &11.33 &11.34 &11.33 &11.34 &11.42 &11.35 \\%A1
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$^1\Pi (\mathrm{R})$ &11.74 &11.69 &11.63 &11.64 &11.46 &11.46 &11.46 &11.46 &11.57 &11.48 \\%B1/B2
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$^3\Pi (\mathrm{V}; n \rightarrow \pi^\star)$ &6.31 &6.30 &6.30 &6.29 &6.30 &6.29 &6.30 &6.29 &6.29 &6.29 \\%B1/B2
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$^3\Sigma^+ (\mathrm{V}; \pi \rightarrow \pi^\star)$ &8.45 &8.45 &8.48 &8.47 &8.48 &8.47 &8.48 &8.47 &8.48 &8.48 \\%A1
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$^3\Delta (\mathrm{V}; \pi \rightarrow \pi^\star)$ &9.37 &9.30 &9.31 &9.30 &9.31 &9.30 &9.31 &9.30 &9.30 &9.30 \\%A1/A2
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$^3\Sigma^- (\mathrm{V}; \pi \rightarrow \pi^\star)$ &9.89 &9.82 &9.82 &9.81 &9.81 &9.81 &9.82 &9.81 &9.81 &9.81 \\%A2
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$^3\Sigma^- (\mathrm{R})$ &10.39 &10.45 &10.44 &10.45 &10.33 &10.33 &10.33 &10.34 &10.42 &10.35 \\%A1
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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{Acetylene and ethylene}
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies determined of acetylene (top) and ethylene (bottom) using various atomic basis sets.
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See caption of Table \ref{Table-wat-bs} for more details.}
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\label{Table-acetethy-bs}
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\begin{small}
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\begin{tabular}{l|ccccccc}
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\hline
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& {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & {\AVPZ} \\
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& FC & FC & FC & Full & FC & Full & Full \\
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\hline
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& \multicolumn{7}{c}{Acetylene} \\
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\hline
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$^1\Sigma_u^- (\pi \rightarrow \pi^\star)$ &7.21&7.09 &7.09 &7.09 &7.09 &7.09 &7.09 \\
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$^1\Delta_u (\pi \rightarrow \pi^\star)$ &7.51&7.42 &7.41 &7.42 &7.41 &7.42 &7.42 \\
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$^3\Sigma_u^+ (\pi \rightarrow \pi^\star)$ &5.48&5.50 &5.53 &5.52 &5.53 &5.52 &5.53 \\
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$^3\Delta_u (\pi \rightarrow \pi^\star)$ &6.46&6.40 &6.40 &6.40 &6.40 &6.40 &6.40 \\
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$^3\Sigma_u^- (\pi \rightarrow \pi^\star)$ &7.13&7.07 &7.07 &7.07 &7.07 &7.07 &7.08 \\
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$^1A_u [\mathrm{F}] (\pi \rightarrow \pi^\star)$ &3.70&3.64 &3.63 &3.63 &3.63 &3.63 &3.63 \\
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$^1A_2 [\mathrm{F}] (\pi \rightarrow \pi^\star)$ &3.92&3.84 &3.83 &3.84 &3.84 &3.84 &3.84 \\
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\hline
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& \multicolumn{7}{c}{Ethylene} \\
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\hline
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$^1B_{3u} (\pi \rightarrow 3s)$ &7.29&7.35 &7.38 &7.39 &7.37 &7.38 &7.39 \\
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$^1B_{1u} (\pi \rightarrow \pi^\star)$ &7.94&7.91 &7.90 &7.91 &7.90 &7.93 &7.91 \\
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$^1B_{1g} (\pi \rightarrow 3p)$ &7.97&8.03 &8.04 &8.05 &8.03 &8.04 &8.05 \\
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$^3B_{1u} (\pi \rightarrow \pi^\star)$ &4.53&4.53 &4.54 &4.53 &4.54 &4.53 &4.53 \\
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$^3B_{3u} (\pi \rightarrow 3s)$ &7.17&7.24 &7.27 &7.28 &7.26 &7.28 &7.29 \\
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$^3B_{1g} (\pi \rightarrow 3p)$ &7.93&7.98 &8.00 &8.00 &7.99 &7.99 &8.01 \\
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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{Formaldehyde, methanimine and thioformaldehyde}
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies determined of formaldehyde (top), methanimine (center), and thioformaldehyde (bottom) using various atomic basis sets.
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See caption of Table \ref{Table-wat-bs} for more details.}
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\label{Table-forma-bs}
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\begin{small}
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\begin{tabular}{l|ccccccc}
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\hline
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& {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & {\AVPZ} \\
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& FC & FC & FC & Full & FC & Full & Full \\
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\hline
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& \multicolumn{7}{c}{Formaldehyde} \\
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\hline
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$^1A_2 (n \rightarrow \pi^\star)$ &4.00&3.97& 3.97& 3.96& 3.97 & 3.96 & 3.96 \\
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$^1B_2 (n \rightarrow 3s)$ &7.05&7.18& 7.23& 7.23& 7.22 & 7.23 & 7.25 \\
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$^1B_2 (n \rightarrow 3p)$ &8.02&8.07& 8.10& 8.11& 8.05 & 8.06 & 8.10 \\
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$^1A_1 (n \rightarrow 3p)$ &8.08&8.18& 8.22& 8.23& 8.20 & 8.20 & 8.23 \\
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$^1A_2 (n \rightarrow 3p)$ &8.65&8.64& 8.60& 8.61& & 8.61 & 8.54 \\
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$^1B_1 (\sigma \rightarrow \pi^\star)$ &9.31&9.19& 9.19& 9.18& 9.19 & 9.18 & 9.18 \\
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$^1A_1 (\pi \rightarrow \pi^\star)$ &9.59&9.48& 9.46& 9.46& 9.30 & 9.31 & 9.43 \\
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|
|
$^3A_2 (n \rightarrow \pi^\star)$ &3.58&3.57& 3.58& 3.57& 3.58 & 3.57 & 3.57 \\
|
||
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &6.09&6.05& 6.06& 6.06& 6.07 & 6.06 & 6.06 \\
|
||
|
|
$^3B_2 (n \rightarrow 3s)$ &6.91&7.03& 7.08& 7.09& 7.08 & 7.09 & 7.11 \\
|
||
|
|
$^3B_2 (n \rightarrow 3p)$ &7.84&7.92& 7.95& 7.96& 7.91 & 7.96 & 7.95 \\
|
||
|
|
$^3A_1 (n \rightarrow 3p)$ &7.97&8.08& 8.12& 8.12& 8.10 & 8.11 & 8.13 \\
|
||
|
|
$^3B_1 (n \rightarrow 3d)$ &8.48&8.41& 8.42& 8.41& 8.42 & 8.41 & 8.41 \\
|
||
|
|
$^1A^" [\mathrm{F}] (n \rightarrow \pi^\star)$ &2.87&2.84& 2.85& 2.84& 2.85 & 2.84 & 2.84 \\
|
||
|
|
\hline
|
||
|
|
& \multicolumn{7}{c}{Methanimine} \\
|
||
|
|
\hline
|
||
|
|
$^1A^"(n \rightarrow \pi^\star)$ &5.26&5.20& 5.20& 5.18& 5.20 & 5.18 & 5.18 \\
|
||
|
|
$^3A^" (n \rightarrow \pi^\star)$ &4.63&4.61& 4.62& 4.60& 4.62 & 4.60 & 4.60 \\
|
||
|
|
\hline
|
||
|
|
& \multicolumn{7}{c}{Thioformaldehyde} \\
|
||
|
|
\hline
|
||
|
|
$^1A_2 (n \rightarrow \pi^\star)$ &2.27&2.23& 2.23& 2.21& 2.23& 2.21 & 2.21 \\
|
||
|
|
$^1B_2 (n \rightarrow 4s)$ &5.80&5.91& 5.95& 5.95& 5.95& 5.94 & 5.96 \\
|
||
|
|
$^1A_1 (\pi \rightarrow \pi^\star)$ &6.62&6.48& 6.46& 6.45& 6.45& 6.45 & 6.43 \\
|
||
|
|
$^3A_2 (n \rightarrow \pi^\star)$ &1.97&1.94& 1.95& 1.94& 1.95& 1.94 & \\
|
||
|
|
$^3A_1 (\pi \rightarrow \pi^\star)$ &3.43&3.38& 3.40& 3.39& 3.40& 3.39 & 3.39 \\
|
||
|
|
$^3B_2 (n \rightarrow 4s)$ &5.64&5.72& 5.75& 5.75& 5.75& 5.74 & \\
|
||
|
|
$^1A_2 [\mathrm{F}] (n \rightarrow \pi^\star)$ &2.00&1.97& 1.98& 1.96& 1.97& 1.96 & 1.95 \\
|
||
|
|
\hline
|
||
|
|
\end{tabular}
|
||
|
|
\end{small}
|
||
|
|
\end{table}
|
||
|
|
\clearpage
|
||
|
|
|
||
|
|
\subsection{Larger compounds}
|
||
|
|
|
||
|
|
\begin{table}[htp]
|
||
|
|
\caption{\small CC3 vertical transition energies determined of six compounds incorporating three non-hydrogen atoms.
|
||
|
|
See caption of Table \ref{Table-wat-bs} for more details.}
|
||
|
|
\label{Table-3at-bs}
|
||
|
|
\begin{small}
|
||
|
|
\begin{tabular}{ll|ccccc}
|
||
|
|
\hline
|
||
|
|
&& {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & {\DAVQZ} \\
|
||
|
|
Molecule state && FC & FC & FC & Full & Full \\
|
||
|
|
\hline
|
||
|
|
Acetaldehyde &$^1A''(n \rightarrow \pi^\star)$ &4.34 &4.31 &4.32& & \\
|
||
|
|
&$^3A''(n \rightarrow \pi^\star)$ &3.96 &3.95 &3.97& & \\
|
||
|
|
\hline
|
||
|
|
Cyclopropene &$^1B_1 (\sigma \rightarrow \pi^\star)$ &6.72 &6.68 &6.68 &6.68\\
|
||
|
|
&$^1B_2 (\pi \rightarrow \pi^\star)$ &6.77 &6.73 &6.73 &6.73\\
|
||
|
|
&$^3B_2 (\pi \rightarrow \pi^\star)$ &4.34 &4.34 &4.35 &4.34\\
|
||
|
|
&$^3B_1 (\sigma \rightarrow \pi^\star)$ &6.43 &6.40 &6.41 &6.40\\
|
||
|
|
\hline%
|
||
|
|
Diazomethane &$^1A_2 (\pi \rightarrow \pi^\star)$ &3.10 &3.07 &3.07 &3.06 &3.06 \\
|
||
|
|
&$^1B_1 (\pi \rightarrow 3s)$ &5.32 &5.45 &5.49 &5.51 &5.50 \\
|
||
|
|
&$^1A_1 (\pi \rightarrow \pi^\star)$ &5.80 &5.84 &5.85 &5.85 &5.83 \\
|
||
|
|
&$^3A_2 (\pi \rightarrow \pi^\star)$ &2.84 &2.83 &2.82 &2.82 & \\
|
||
|
|
&$^3A_1 (\pi \rightarrow \pi^\star)$ &4.05 &4.03 &4.04 &4.03 &4.03 \\
|
||
|
|
&$^3B_1 (\pi \rightarrow 3s)$ &5.17 &5.31 &5.35 &5.37 &5.36 \\
|
||
|
|
&$^3A_1 (\pi \rightarrow 3p)$ &6.83 &6.80 &6.81 &6.80 &6.70 \\
|
||
|
|
&$^1A'' [\mathrm{F}] (\pi \rightarrow \pi^\star)$ &0.68 &0.68 &0.68 &0.67 & \\
|
||
|
|
\hline
|
||
|
|
Formamide &$^1A'' (n \rightarrow \pi^\star)$ &5.71 &5.66 & &\\
|
||
|
|
&$^1A' (n \rightarrow 3s)$ &6.65 &6.74 & &\\
|
||
|
|
&$^1A' (\pi \rightarrow \pi^\star)$$^a$ &7.63 &7.62 & &\\
|
||
|
|
&$^1A' (n \rightarrow 3p)$$^a$ &7.31 &7.40 & &\\
|
||
|
|
&$^3A'' (n \rightarrow \pi^\star)$ &5.42 &5.38 & &\\
|
||
|
|
&$^3A' (\pi \rightarrow \pi^\star)$ &5.83 &5.82 &5.83 &\\
|
||
|
|
\hline
|
||
|
|
Ketene &$^1A_2 (\pi \rightarrow \pi^\star)$ &3.89 &3.88 &3.88 &3.88 &3.88 \\
|
||
|
|
&$^1B_1 (n \rightarrow 3s)$ &5.83 &5.96 &6.00 &6.01 &6.01 \\
|
||
|
|
&$^1A_2 (\pi \rightarrow 3p)$ &7.05 &7.16 &7.19 &7.20 &7.17 \\
|
||
|
|
&$^3A_2 (n \rightarrow \pi^\star)$ &3.79 &3.78 &3.79 &3.78 &3.78 \\
|
||
|
|
&$^3A_1 (\pi \rightarrow \pi^\star)$ &5.62 &5.61 &5.62 &5.60 &5.60 \\
|
||
|
|
&$^3B_1 (n \rightarrow 3s)$ &5.63 &5.76 &5.81 &5.82 &5.82 \\
|
||
|
|
&$^3A_2 (\pi \rightarrow 3p)$ &7.01 &7.12 &7.15 &7.16 &7.14 \\
|
||
|
|
&$^1A'' [\mathrm{F}] (\pi \rightarrow \pi^\star)$ &1.00 &1.00 &1.00 &1.00 & \\
|
||
|
|
\hline
|
||
|
|
Nitrosomethane&$^1A'' (n \rightarrow \pi^\star)$ &2.00 &1.96 &1.96 &1.96\\
|
||
|
|
&$^1A' (n,n \rightarrow \pi^\star,\pi^\star)$ &5.75 &5.76 &5.74 &5.73\\
|
||
|
|
&$^1A' (n \rightarrow 3s/3p)$ &6.20 &6.31 &6.35 &6.36\\
|
||
|
|
&$^3A'' (n \rightarrow \pi^\star)$ &1.13 &1.14 &1.15 &1.14\\
|
||
|
|
&$^3A' (\pi \rightarrow \pi^\star)$ &5.54 &5.51 &5.52 &5.52\\
|
||
|
|
&$^1A'' [\mathrm{F}] (n \rightarrow \pi^\star)$ &1.70 &1.69 & & \\
|
||
|
|
|
||
|
|
\hline
|
||
|
|
Streptocyanine-C1&$^1B_2 (\pi \rightarrow \pi^\star)$ &7.14 &7.13 &7.13 &7.12\\
|
||
|
|
& $^3B_2 (\pi \rightarrow \pi^\star)$ &5.48 &5.48 &5.49 &5.48\\
|
||
|
|
\hline
|
||
|
|
\end{tabular}
|
||
|
|
\end{small}
|
||
|
|
\begin{flushleft}
|
||
|
|
\begin{footnotesize}
|
||
|
|
$^a${Strong state mixing.}
|
||
|
|
\end{footnotesize}
|
||
|
|
\end{flushleft}
|
||
|
|
\end{table}
|
||
|
|
|
||
|
|
\clearpage
|
||
|
|
|
||
|
|
\section{Geometries}
|
||
|
|
|
||
|
|
Below are given 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{Acetaldehyde}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C -0.00234503 0.00000000 0.87125063
|
||
|
|
C -1.75847785 0.00000000 -1.34973671
|
||
|
|
O 2.27947397 0.00000000 0.71968028
|
||
|
|
H -0.92904537 0.00000000 2.73929404
|
||
|
|
H -2.97955463 1.66046488 -1.25209463
|
||
|
|
H -2.97955463 -1.66046488 -1.25209463
|
||
|
|
H -0.70043433 0.00000000 -3.11066412
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Acetylene}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 1.14048351
|
||
|
|
C 0.00000000 0.00000000 -1.14048351
|
||
|
|
H 0.00000000 0.00000000 3.14009043
|
||
|
|
H 0.00000000 0.00000000 -3.14009043
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\emph{Trans} excited state ($^1A_u$ state in the $C_{2h}$ point group)
|
||
|
|
\begin{verbatim}
|
||
|
|
C 1.29567779 0.00000000 -0.01846047
|
||
|
|
C -1.29567779 0.00000000 0.01846047
|
||
|
|
H 2.41938674 0.00000000 1.70881682
|
||
|
|
H -2.41938674 0.00000000 -1.70881682
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\emph{Cis} excited state ($^1A_2$ state in the $C_{2v}$ point group)
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 1.26834508 -0.11726146
|
||
|
|
C 0.00000000 -1.26834508 -0.11726146
|
||
|
|
H 0.00000000 2.67282325 1.39629264
|
||
|
|
H 0.00000000 -2.67282325 1.39629264
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Ammonia}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
N 0.12804615 -0.00000000 0.00000000
|
||
|
|
H -0.59303935 0.88580079 -1.53425197
|
||
|
|
H -0.59303935 -1.77160157 -0.00000000
|
||
|
|
H -0.59303935 0.88580079 1.53425197
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Carbon monoxide}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -1.24942055
|
||
|
|
O 0.00000000 0.00000000 0.89266692
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Cyclopropene}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -1.66820880
|
||
|
|
C 0.00000000 1.22523906 0.90681419
|
||
|
|
C 0.00000000 -1.22523906 0.90681419
|
||
|
|
H 1.72255446 0.00000000 -2.77881149
|
||
|
|
H -1.72255446 0.00000000 -2.77881149
|
||
|
|
H 0.00000000 2.97844519 1.92076771
|
||
|
|
H 0.00000000 -2.97844519 1.92076771
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
|
||
|
|
\subsection{Diazomethane}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -2.30830005
|
||
|
|
N 0.00000000 0.00000000 0.14457890
|
||
|
|
N 0.00000000 0.00000000 2.29923216
|
||
|
|
H 0.00000000 1.79875201 -3.24272317
|
||
|
|
H 0.00000000 -1.79875201 -3.24272317
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Excited state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 1.80206107 0.00000000 -1.03389466
|
||
|
|
N -0.01743713 0.00000000 0.84742344
|
||
|
|
N -2.25203764 0.00000000 0.54034983
|
||
|
|
H 3.74280590 0.00000000 -0.44375913
|
||
|
|
H 1.20115546 0.00000000 -2.98380249
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Dinitrogen}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
N 0.00000000 0.00000000 1.04008632
|
||
|
|
N 0.00000000 0.00000000 -1.04008632
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Ethylene}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 1.26026583 0.00000000
|
||
|
|
C 0.00000000 -1.26026583 0.00000000
|
||
|
|
H 0.00000000 2.32345976 1.74287672
|
||
|
|
H 0.00000000 -2.32345976 1.74287672
|
||
|
|
H 0.00000000 2.32345976 -1.74287672
|
||
|
|
H 0.00000000 -2.32345976 -1.74287672
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Formaldehyde}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -1.13947666
|
||
|
|
O 0.00000000 0.00000000 1.14402883
|
||
|
|
H 0.00000000 1.76627623 -2.23398653
|
||
|
|
H 0.00000000 -1.76627623 -2.23398653
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Excited state
|
||
|
|
\begin{verbatim}
|
||
|
|
C -0.09942705 0.00000000 1.27071070
|
||
|
|
O 0.01987299 0.00000000 -1.23280536
|
||
|
|
H 0.42778855 1.76729629 2.18470884
|
||
|
|
H 0.42778855 -1.76729629 2.18470884
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Formamide}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00183118 0.00000000 0.79313299
|
||
|
|
O 2.26817156 0.00000000 0.43918824
|
||
|
|
N -1.76886033 0.00000000 -1.06219243
|
||
|
|
H -0.84133459 0.00000000 2.68872485
|
||
|
|
H -1.21254414 0.00000000 -2.87596907
|
||
|
|
H -3.61627502 0.00000000 -0.65031317
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Hydrogen chloride}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
Cl 0.00000000 0.00000000 -0.02489783
|
||
|
|
H 0.00000000 0.00000000 2.38483140
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Ketene}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -2.44810151
|
||
|
|
C 0.00000000 0.00000000 0.03498545
|
||
|
|
O 0.00000000 0.00000000 2.23663914
|
||
|
|
H 0.00000000 1.77432079 -3.43705988
|
||
|
|
H 0.00000000 -1.77432079 -3.43705988
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Excited state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 2.04306304 0.00000000 -0.93056721
|
||
|
|
C 0.00400918 0.00000000 0.83531393
|
||
|
|
O -2.23710378 0.00000000 0.46984584
|
||
|
|
H 1.63603518 0.00000000 -2.93687368
|
||
|
|
H 3.96212800 0.00000000 -0.26649149
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Methanimine}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.10696646 0.00000000 1.11091130
|
||
|
|
N 0.10764012 0.00000000 -1.29677742
|
||
|
|
H -1.59140953 0.00000000 2.27296652
|
||
|
|
H 1.90475160 0.00000000 2.09393982
|
||
|
|
H -1.69956184 0.00000000 -1.96217482
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\clearpage
|
||
|
|
|
||
|
|
\subsection{Nitrosomethane}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C -1.78426612 0.00000000 -1.07224050
|
||
|
|
N -0.00541753 0.00000000 1.08060391
|
||
|
|
O 2.18814985 0.00000000 0.43452135
|
||
|
|
H -0.77343975 0.00000000 -2.86415606
|
||
|
|
H -2.97471478 1.66801808 -0.86424584
|
||
|
|
H -2.97471478 -1.66801808 -0.86424584
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Excited state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 1.86306273 0.00000000 -1.06035094
|
||
|
|
N 0.00638693 0.00000000 1.02546010
|
||
|
|
O -2.26923072 0.00000000 0.47699489
|
||
|
|
H 3.72600129 0.00000000 -0.21094854
|
||
|
|
H 1.58491147 1.68964774 -2.20977225
|
||
|
|
H 1.58491147 -1.68964774 -2.20977225
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\subsection{Streptocyanine-C1}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 0.80488833
|
||
|
|
N 0.00000000 2.19423463 -0.33580561
|
||
|
|
N 0.00000000 -2.19423463 -0.33580561
|
||
|
|
H 0.00000000 0.00000000 2.84436959
|
||
|
|
H 0.00000000 2.36978315 -2.23371976
|
||
|
|
H 0.00000000 -2.36978315 -2.23371976
|
||
|
|
H 0.00000000 3.79412648 0.69399206
|
||
|
|
H 0.00000000 -3.79412648 0.69399206
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
|
||
|
|
\subsection{Thioformaldehyde}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Ground state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -2.08677304
|
||
|
|
S 0.00000000 0.00000000 0.97251194
|
||
|
|
H 0.00000000 1.73657773 -3.17013507
|
||
|
|
H 0.00000000 -1.73657773 -3.17013507
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\clearpage
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
Excited state
|
||
|
|
\begin{verbatim}
|
||
|
|
C 0.00000000 0.00000000 -2.20256705
|
||
|
|
S 0.00000000 0.00000000 1.02717172
|
||
|
|
H 0.00000000 1.76634191 -3.21909384
|
||
|
|
H 0.00000000 -1.76634191 -3.21909384
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
|
||
|
|
\subsection{Water}
|
||
|
|
|
||
|
|
\begin{singlespace}
|
||
|
|
\begin{verbatim}
|
||
|
|
O 0.00000000 0.00000000 -0.13209669
|
||
|
|
H 0.00000000 1.43152878 0.97970006
|
||
|
|
H 0.00000000 -1.43152878 0.97970006
|
||
|
|
\end{verbatim}
|
||
|
|
\end{singlespace}
|
||
|
|
|
||
|
|
\clearpage
|
||
|
|
|
||
|
|
\section{Benchmark}
|
||
|
|
|
||
|
|
|
||
|
|
\clearpage
|
||
|
|
\begin{landscape}
|
||
|
|
\renewcommand*{\arraystretch}{.55}
|
||
|
|
\LTcapwidth=\textwidth
|
||
|
|
\begin{footnotesize}
|
||
|
|
\begin{longtable}{p{2.73cm}p{3.3cm}p{.55cm}|p{.75cm}p{.55cm}p{.95cm}p{.9cm}p{.9cm}p{1.6cm}p{.55cm}p{1.1cm}p{1.2cm}p{1.0cm}p{1.0 cm}}
|
||
|
|
\caption{Comparisons between TBE obtained at the {\AVTZ} basis set in the frozen-core approximation (see Table 6) and the results obtained with various
|
||
|
|
computational approaches, using the same basis set and approximation.
|
||
|
|
STEOM stands for STEOM-CCSD and CC(3) for CCSDR(3).} \label{Table-benchmark}\\
|
||
|
|
\hline
|
||
|
|
Compound & State & TBE & CIS(D) & CC2 & STEOM & CCSD & CC(3) &CCSDT-3& CC3& CCSDT& CCSDTQ&ADC(2)& ADC(3) \\
|
||
|
|
\hline
|
||
|
|
\endfirsthead
|
||
|
|
\hline
|
||
|
|
Compound & State & TBE & CIS(D) & CC2 & STEOM & CCSD & CC(3) &CCSDT-3& CC3& CCSDT& CCSDTQ&ADC(2)& ADC(3) \\
|
||
|
|
\hline
|
||
|
|
\endhead
|
||
|
|
\hline \multicolumn{13}{r}{{Continued on next page}} \\
|
||
|
|
\endfoot
|
||
|
|
\hline
|
||
|
|
\endlastfoot
|
||
|
|
Acetaldehyde &$^1A''(\mathrm{V};n \rightarrow \pi^\star)$ &4.31 &4.36 &4.41 &4.25 &4.36 &4.31 &4.32 &4.31 &4.29 & &4.24 &4.29 \\
|
||
|
|
&$^3A''(\mathrm{V};n \rightarrow \pi^\star)$ &3.97 &3.96 &3.98 &3.95 &3.95 & & &3.95 &3.94$^a$& &3.83 &3.89 \\
|
||
|
|
Acetylene &$^1\Sigma_u^- (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.10 & 7.28 &7.26 &7.08 &7.15 &7.09 &7.09 &7.09 &7.09 &7.09$^b$&7.24 &6.72 \\
|
||
|
|
&$^1\Delta_u (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.44 & 7.62 &7.59 &7.42 &7.48 &7.43 &7.42 &7.42 &7.43 &7.43$^b$&7.56 &7.06 \\
|
||
|
|
&$^3\Sigma_u^+ (\mathrm{V};\pi \rightarrow \pi^\star)$ &5.53 & 5.79 &5.76 &5.20 &5.45 & & &5.50 &5.51 &5.52$^b$&5.75 &5.24 \\
|
||
|
|
&$^3\Delta_u (\mathrm{V};\pi \rightarrow \pi^\star)$ &6.40 & 6.62 &6.60 &6.13 &6.41 & & &6.40 &6.39 &6.39$^b$&6.57 &6.06 \\
|
||
|
|
&$^3\Sigma_u^- (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.08 & 7.31 &7.29 &6.84 &7.12 & & &7.07 &7.08$^a$&7.08$^c$&7.27 &6.72 \\
|
||
|
|
&$^1A_u [\mathrm{F}] (\mathrm{V};\pi \rightarrow \pi^\star)$ &3.64 & 3.85 &3.94 &3.65 &3.70 &3.66 &3.64 &3.64 &3.66 &3.64$^b$&3.78 &2.85 \\
|
||
|
|
&$^1A_2 [\mathrm{F}] (\mathrm{V};\pi \rightarrow \pi^\star)$ &3.85 & 4.06 &4.11 &3.85 &3.92 &3.85 &3.84 &3.84 &3.86 &3.85$^b$&3.99 &3.08 \\
|
||
|
|
Ammonia &$^1A_2 (\mathrm{R};n \rightarrow 3s)$ &6.59 &6.37 &6.39 &6.55 &6.60 &6.57 &6.58 &6.57 &6.57 &6.59 &6.40 &6.63 \\
|
||
|
|
&$^1E (\mathrm{R};n \rightarrow 3p)$ &8.16 &7.86 &7.85 &8.14 &8.15 &8.15 &8.15 &8.15 &8.14 &8.16$^b$&7.87 &8.21 \\
|
||
|
|
&$^1A_1 (\mathrm{R};n \rightarrow 3p)$ &9.33 &9.04 &9.05 &9.33 &9.33 &9.32 &9.32 &9.32 &9.31 &9.34$^b$&9.05 &9.38 \\
|
||
|
|
&$^1A_2 (\mathrm{R};n \rightarrow 4s)$ &9.96 &9.59 &9.65 &9.98 &9.95 &9.94 &9.95 &9.95 &9.94 &9.96$^b$&9.67 &10.00 \\
|
||
|
|
&$^3A_2 (\mathrm{R};n \rightarrow 3s)$ &6.31 &6.18 &6.14 &6.31 &6.30 & & &6.29 &6.29 &6.30 &6.16 &6.31 \\
|
||
|
|
Carbon monoxyde &$^1\Pi (\mathrm{V};n \rightarrow \pi^\star)$ & 8.49 &8.78 &8.64 &8.55 &8.59 &8.52 &8.51 &8.49 &8.57 &8.48 &8.69 &8.24 \\
|
||
|
|
&$^1\Sigma^- (\mathrm{V};\pi \rightarrow \pi^\star)$ & 9.92 &10.13 &10.30 &9.90 &9.99 &9.98 &9.98 &9.99 &10.06 &9.93 &10.03 &9.73 \\
|
||
|
|
&$^1\Delta (\mathrm{V};\pi \rightarrow \pi^\star)$ &10.06 &10.41 &10.60 &10.07 &10.12 &10.12 &10.11 &10.12 &10.18 &10.07$^b$&10.30 &9.82 \\
|
||
|
|
&$^1\Sigma^+ (\mathrm{R})$ &10.95 &11.48 &11.11 &11.14 &11.22 &10.99 &11.02 &10.94 &10.94 &10.98 &11.32 &10.79 \\
|
||
|
|
&$^1\Sigma^+ (\mathrm{R})$ &11.52 &11.71 &11.63 &11.75 &11.75 &11.53 &11.55 &11.49 &11.52 &11.52 &11.83 &11.33 \\
|
||
|
|
&$^1\Pi (\mathrm{R})$ &11.72 &12.06 &11.83 &12.00 &11.96 &11.73 &11.76 &11.69 &11.77 &11.73$^b$&12.03 &11.56 \\
|
||
|
|
&$^3\Pi (\mathrm{V};n \rightarrow \pi^\star)$ & 6.28 &6.51 &6.42 &6.32 &6.36 & & &6.30 &6.30 &6.28 &6.45 &5.97 \\
|
||
|
|
&$^3\Sigma^+ (\mathrm{V};\pi \rightarrow \pi^\star)$ & 8.45 &8.63 &8.72 &8.37 &8.34 & & &8.45 &8.43 &8.43$^b$&8.54 &8.21 \\
|
||
|
|
&$^3\Delta (\mathrm{V};\pi \rightarrow \pi^\star)$ & 9.27 &9.44 &9.56 &9.21 &9.23 & & &9.30 &9.33 &9.26 &9.33 &9.03 \\
|
||
|
|
&$^3\Sigma^- (\mathrm{V};\pi \rightarrow \pi^\star)$ & 9.80 &10.10 &10.27 &9.83 &9.81 & & &9.82 & & &10.01 &9.53 \\
|
||
|
|
&$^3\Sigma^+ (\mathrm{R})$ & 10.47 &10.98 &10.60 &10.73 &10.71 & & &10.45 &10.42 &10.50$^b$&10.83 &10.29 \\
|
||
|
|
Cyclopropene &$^1B_1 (\mathrm{V};\sigma \rightarrow \pi^\star)$ &6.68 &6.90 &6.73 & &6.76 &6.68 &6.70 &6.68 &6.68 & &6.75 &6.56 \\
|
||
|
|
&$^1B_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &6.79 &6.90 &6.78 &6.94 &6.86 &6.73 &6.76 &6.73 &6.75 & &6.86 &6.56 \\
|
||
|
|
&$^3B_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &4.38 &4.55 &4.46 &4.36 &4.30 & & &4.34 &4.35$^a$& &4.45 &4.09 \\
|
||
|
|
&$^3B_1 (\mathrm{V};\sigma \rightarrow \pi^\star)$ &6.45 &6.49 &6.44 &6.57 &6.46 & & &6.40 &6.40$^a$& &6.45 &6.26 \\
|
||
|
|
Diazomethane &$^1A_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &3.14 &3.55 &3.37 &3.20 &3.19 &3.12 &3.10 &3.07 &3.07 & &3.34 &2.74 \\
|
||
|
|
&$^1B_1 (\mathrm{R};\pi \rightarrow 3s)$ &5.54 &5.65 &5.53 &5.57 &5.57 &5.48 &5.47 &5.45 &5.48 & &5.63 &5.23 \\
|
||
|
|
&$^1A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &5.90 &6.03 &6.00 &5.75 &5.94 &5.87 &5.86 &5.84 &5.86 & &5.97 &5.48 \\
|
||
|
|
&$^3A_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &2.79 &3.21 &3.08 &2.85 &3.19 & & &2.83 &2.82 & &3.01 &2.44 \\
|
||
|
|
&$^3A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &4.05 &4.28 &4.25 &3.91 &3.95 & & &4.03 &4.02 & &4.20 &3.64 \\
|
||
|
|
&$^3B_1 (\mathrm{R};\pi \rightarrow 3s)$ &5.35 &5.53 &5.53 &5.43 &5.42 & & &5.31 &5.34 & &5.50 &5.08 \\
|
||
|
|
&$^3A_1 (\mathrm{R};\pi \rightarrow 3p)$ &6.82 &7.37 &7.04 & &6.85 & & &6.80 &6.80$^a$& &7.09 &6.36 \\
|
||
|
|
&$^1A'' [\mathrm{F}] (\mathrm{V};\pi \rightarrow \pi^\star)$ &0.71 &1.06 &0.90 &0.88 &0.81 &0.73 &0.70 &0.68 &0.67 & &0.81 &0.24 \\
|
||
|
|
Dinitrogen &$^1\Pi_g (\mathrm{V};n \rightarrow \pi^\star)$ &9.34 &9.66 &9.44 &9.37 &9.41 &9.36 &9.35 &9.34 &9.33 &9.32 &9.48 &9.16 \\
|
||
|
|
&$^1\Sigma_u^- (\mathrm{V};\pi \rightarrow \pi^\star)$ &9.88 &10.31 &10.32 &10.09 &10.00 &9.90 &9.89 &9.88 &9.89 &9.88 &10.26 &9.33 \\
|
||
|
|
&$^1\Delta_u (\mathrm{V};\pi \rightarrow \pi^\star)$ &10.29 &10.85 &10.86 &10.56 &10.44 &10.33 &10.31 &10.29 &10.30 &10.29$^b$&10.79 &9.74 \\
|
||
|
|
&$^1\Sigma_g^+ (\mathrm{R})$ &12.98 &13.67 &12.83 &13.13 &13.15 &13.04 &13.06 &13.01 &13.00 &12.98$^b$&12.99 &13.01 \\
|
||
|
|
&$^1\Pi_u (\mathrm{R})$ &13.03 &13.64 &13.15 &13.43 &13.43 &13.28 &13.27 &13.22 &13.14 &13.09 &13.32 &12.98 \\
|
||
|
|
&$^1\Sigma_u^+ (\mathrm{R})$ &13.09 &13.75 &12.89 &13.22 &13.26 &13.14 &13.16 &13.12 &13.12 &13.10$^b$&13.07 &13.09 \\
|
||
|
|
&$^1\Pi_u (\mathrm{R})$ &13.46 &14.52 &13.96 &13.73 &13.67 &13.52 & &13.49 &13.45 &13.42 &14.00 &13.40 \\
|
||
|
|
&$^3\Sigma_u^+ (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.70 &8.20 &8.19 &7.70 &7.66 & & &7.68 &7.69 &7.70 &8.15 &7.25 \\
|
||
|
|
&$^3\Pi_g (\mathrm{V};n \rightarrow \pi^\star)$ &8.01 &8.33 &8.19 &8.16 &8.09 & & &8.04 &8.03 &8.02 &8.20 &7.77 \\
|
||
|
|
&$^3\Delta_u (\mathrm{V};\pi \rightarrow \pi^\star)$ &8.87 &9.30 &9.30 &8.94 &8.91 & & &8.87 &8.87 &8.87 &9.25 &8.36 \\
|
||
|
|
&$^3\Sigma_u^- (\mathrm{V};\pi \rightarrow \pi^\star)$ &9.66 &10.29 &10.29 &9.90 &9.83 & & &9.68 &9.68 &9.66 &10.23 &9.14 \\
|
||
|
|
Ethylene &$^1B_{3u} (\mathrm{R};\pi \rightarrow 3s)$ &7.40 &7.35 &7.29 &7.42 &7.42 &7.35 &7.36 &7.35 &7.37 &7.38$^b$&7.34 &7.17 \\
|
||
|
|
&$^1B_{1u} (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.91 &7.95 &7.92 & &8.02 &7.89 &7.92 &7.91 &7.92 &7.91$^b$&7.91 &7.69 \\
|
||
|
|
&$^1B_{1g} (\mathrm{R};\pi \rightarrow 3p)$ &8.07 &8.01 &7.95 &8.10 &8.08 &8.02 &8.03 &8.03 &8.04 &8.05$^b$&7.99 &7.84 \\
|
||
|
|
&$^3B_{1u} (\mathrm{V};\pi \rightarrow \pi^\star)$ &4.54 &4.62 &4.59 &4.36 &4.46 & & &4.53 &4.53 &4.53$^b$&4.59 &4.28 \\
|
||
|
|
&$^3B_{3u} (\mathrm{R};\pi \rightarrow 3s)$ &7.23 &7.26 &7.19 &7.31 &7.29 & & &7.24 &7.25 &7.25$^b$&7.23 &7.05 \\
|
||
|
|
&$^3B_{1g} (\mathrm{R};\pi \rightarrow 3p)$ &7.98 &7.97 &7.91 &8.08 &8.03 & & &7.98 &7.99 &7.99$^b$&7.95 &7.80 \\
|
||
|
|
Formaldehyde &$^1A_2 (\mathrm{V}; n \rightarrow \pi^\star)$ &3.98 &4.04 &4.07 &3.91 &4.01 &3.97 &3.98 &3.97 &3.95 &3.96$^b$&3.92 &3.90 \\
|
||
|
|
&$^1B_2 (\mathrm{R};n \rightarrow 3s)$ &7.23 &6.64 &6.56 &7.19 &7.23 &7.18 &7.21 &7.18 &7.16 &7.21$^b$&6.50 &7.62 \\
|
||
|
|
&$^1B_2 (\mathrm{R};n \rightarrow 3p)$ &8.13 &7.56 &7.57 &8.05 &8.12 &8.08 &8.11 &8.07 &8.07 &8.11$^b$&7.53 &8.45 \\
|
||
|
|
&$^1A_1 (\mathrm{R};n \rightarrow 3p)$ &8.23 &8.16 &7.52 &8.18 &8.21 &8.17 &8.21 &8.18 &8.16 &8.21$^b$&7.47 &8.61 \\
|
||
|
|
&$^1A_2 (\mathrm{R};n \rightarrow 3p)$ &8.67 &8.04 &8.04 &8.68 &8.65 &8.63 &8.66 &8.64 &8.61 &8.66$^b$&7.99 &9.02 \\
|
||
|
|
&$^1B_1 (\mathrm{V};\sigma \rightarrow \pi^\star)$ &9.22 &9.38 &9.32 &9.08 &9.28 &9.20 &9.20 &9.19 &9.17 &9.18$^b$&9.17 &9.17 \\
|
||
|
|
&$^1A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &9.43 &9.08 &9.54 & &9.67 &9.51 &9.51 &9.48 &9.49 &9.44$^b$&9.46 &9.05 \\
|
||
|
|
&$^3A_2 (\mathrm{V};n \rightarrow \pi^\star)$ &3.58 &3.58 &3.59 &3.54 &3.56 & & &3.57 &3.56 &3.57$^b$&3.46 &3.48 \\
|
||
|
|
&$^3A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &6.06 &6.27 &6.30 &5.89 &5.97 & & &6.05 &6.05 &6.06$^b$&6.20 &5.71 \\
|
||
|
|
&$^3B_2 (\mathrm{R};n \rightarrow 3s)$ &7.06 &6.66 &6.44 &7.07 &7.08 & & &7.03 &7.02 &7.07$^b$&6.39 &7.44 \\
|
||
|
|
&$^3B_2 (\mathrm{R};n \rightarrow 3p)$ &7.94 &7.52 &7.45 &7.98 &7.94 & & &7.92 &7.90 &7.94$^b$&7.41 &8.23 \\
|
||
|
|
&$^3A_1 (\mathrm{R};n \rightarrow 3p)$ &8.10 &7.68 &7.44 &8.15 &8.09 & & &8.08 &8.06 &8.11$^b$&7.40 &8.46 \\
|
||
|
|
&$^3B_1 (\mathrm{R};n \rightarrow 3d)$ &8.42 &8.57 &8.52 &8.36 &8.43 & & &8.41 &8.40 &8.41$^b$&8.39 &8.32 \\
|
||
|
|
&$^1A^" [\mathrm{F}] (\mathrm{V};n \rightarrow \pi^\star)$ &2.80 &2.90 &2.97 &2.81 &2.93 &2.86 &2.86 &2.84 &2.82 &2.84$^b$&2.71 &2.77 \\
|
||
|
|
Formamide &$^1A'' \mathrm{V};(n \rightarrow \pi^\star)$ &\hl{xxx} &5.58 &5.69 &5.72 &5.69 &5.66 &5.67 &5.66 &\hl{xxx} & &5.45 &5.75 \\
|
||
|
|
&$^1A' (\mathrm{R};n \rightarrow 3s)$ &\hl{xxx} &6.82$^c$&6.31$^c$&6.94 &6.99 &6.83 &6.83 &6.74 &\hl{xxx} & &6.26$^c$&7.20 \\
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&$^1A' (\mathrm{V};\pi \rightarrow \pi^\star)$ &\hl{xxx} &6.84$^c$&7.55$^c$& &7.55$^c$&7.44 &7.68$^c$&7.62$^c$&\hl{xxx} & &7.39$^c$&7.80$^c$\\
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&$^1A' (\mathrm{R};n \rightarrow 3p)$ &\hl{xxx} &6.89$^c$&6.89$^c$& &7.78$^c$&7.65 &7.46$^c$&7.40$^c$&\hl{xxx} & &6.83$^c$&8.12$^c$\\
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&$^3A'' (\mathrm{V};n \rightarrow \pi^\star)$ &\hl{xxx} &5.31 &5.36 &5.29 &5.36 & & &5.38 &\hl{xxx} & &5.15 &5.42 \\
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&$^3A' (\mathrm{V};\pi \rightarrow \pi^\star)$ &\hl{xxx} &6.07 &5.99 &5.74 &5.77 & & &5.82 &\hl{xxx} & &5.88 &5.63 \\
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Hydrogen chloride & $^1\Pi (\mathrm{CT})$ &7.84 &7.98 &7.96 &7.91 &7.91 &7.84 &7.85 &7.84 &7.83 &7.84 &7.97 &7.79 \\
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Ketene &$^1A_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &3.86 &4.18 &4.17 &3.84 &3.97 &3.92 &3.90 &3.88 &3.87 & &4.11 &3.67 \\
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&$^1B_1 (\mathrm{R};n \rightarrow 3s)$ &6.01 &6.09 &5.94 &6.08 &6.09 &5.99 &5.99 &5.96 &5.99 & &6.03 &5.87 \\
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&$^1A_2 (\mathrm{R};\pi \rightarrow 3p)$ &7.18 &7.25 &7.09 &7.29 &7.29 &7.19 &7.20 &7.16 &7.20 & &7.18 &7.07 \\
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&$^3A_2 (\mathrm{V};n \rightarrow \pi^\star)$ &3.77 &4.00 &3.98 &3.82 &3.83 & & &3.78 &3.78 & &3.92 &3.56 \\
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&$^3A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &5.61 &5.79 &5.72 &5.53 &5.55 & & &5.61 &5.60 & &5.67 &5.39 \\
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&$^3B_1 (\mathrm{R};n \rightarrow 3s)$ &5.79 &5.94 &5.77 &5.91 &5.89 & & &5.76 &5.80 & &5.85 &5.67 \\
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&$^3A_2 (\mathrm{R};\pi \rightarrow 3p)$ &7.12 &7.24 &7.06 &7.32 &7.25 & & &7.12 &7.17 & &7.15 &7.03 \\
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&$^1A^" [\mathrm{F}] (\mathrm{V};\pi \rightarrow \pi^\star)$ &1.00 &1.28 &1.26 &1.03 &1.13 &1.06 &1.03 &1.00 &1.00 & &1.19 &0.67 \\
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Methanimine &$^1A^"(\mathrm{V}; n \rightarrow \pi^\star)$ &5.23 &5.38 &5.32 &5.20 &5.28 &5.20 &5.22 &5.20 &5.19 & &5.29 &5.05 \\
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&$^3A^" (\mathrm{V}; n \rightarrow \pi^\star)$ &4.65 &4.71 &4.65 &4.62 &4.63 & & &4.61 &4.61 & &4.61 &4.44 \\
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Nitrosomethane&$^1A'' (\mathrm{V};n \rightarrow \pi^\star)$ &1.96 &2.03 &1.98 &1.80 &1.98 &1.96 &1.96 &1.96 &1.95 & &1.88 &1.72 \\
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&$^1A' (\mathrm{V};n,n \rightarrow \pi^\star,\pi^\star)$ &4.72 & & & & & &6.02 &5.76 &5.29 & & &3.00 \\
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&$^1A' (\mathrm{R};n \rightarrow 3s/3p)$ &6.37 &5.89 &5.84 &6.51 &6.43 &6.33 &6.38 &6.31 &6.30 & &5.86 &6.48 \\
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&$^3A'' (\mathrm{V};n \rightarrow \pi^\star)$ &1.16 &1.18 &1.12 &0.99 &1.11 & & &1.14 &1.13 & &1.03 &0.84 \\
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&$^3A' (\mathrm{V};\pi \rightarrow \pi^\star)$ &5.60 &5.89 &5.74 &5.04 &5.43 & & &5.51 &5.51$^a$& &5.75 &5.04 \\
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&$^1A'' [\mathrm{F}] (\mathrm{V};n \rightarrow \pi^\star)$ &\hl{xxx} &1.73 &1.68 &1.49 &1.68 &1.67 &1.67 &1.69 &\hl{xxx} & &1.55 &1.40 \\
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Streptocyanine &$^1B_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ &7.13 &6.99 &7.20 &6.76 &7.24 &7.12 &7.16 &7.13 &7.11 & &7.00 &7.16 \\
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& $^3B_2 (\mathrm{V};\pi \rightarrow \pi^\star)$ & 5.47 &5.61 &5.60 &5.40 &5.45 & & &5.48 &5.47 & &5.55 &5.33 \\
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Thioformaldehyde&$^1A_2 (\mathrm{V};n \rightarrow \pi^\star)$ &2.22 &2.30 &2.34 &2.17 &2.29 &2.22 &2.24 &2.23 &2.21 &2.22$^b$&2.24 &2.05 \\
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&$^1B_2 (\mathrm{R};n \rightarrow 4s)$ &5.96 &5.87 &5.82 &5.92 &5.97 &5.90 &5.94 &5.91 &5.89 &5.91$^b$&5.80 &5.94 \\
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&$^1A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ &6.38 &6.65 &6.71 &6.48 &6.63 &6.50 &6.51 &6.48 &6.47 &6.38$^b$&6.57 &5.98 \\
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&$^3A_2 (\mathrm{V};n \rightarrow \pi^\star)$ &1.94 &1.94 &1.94 &1.91 &1.95 & & &1.94 &1.93 &1.93$^b$&1.86 &1.77 \\
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&$^3A_1 (\mathrm{V};\pi \rightarrow \pi^\star)$ & 3.43 &3.49 &3.48 &3.18 &3.28 & & &3.38 &3.38 &3.39$^b$&3.45 &3.07 \\
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&$^3B_2 (\mathrm{R};n \rightarrow 4s)$ &5.72 &5.78 &5.64 &5.71 &5.76 & & &5.72 &5.71 &5.73$^b$&5.62 &5.71 \\
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&$^1A_2 [\mathrm{F}] (\mathrm{V};n \rightarrow \pi^\star)$ &1.95 &2.00 &2.09 &1.92 &2.05 &1.97 &1.98 &1.97 &1.98 &1.96$^b$&1.92 &1.80 \\
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Water & $^1B_1 (\mathrm{R}; n \rightarrow 3s)$ &7.62 &7.17 &7.23 &7.56 &7.60 &7.60 &7.61 &7.65 &7.65 &7.62 &7.18 &7.84 \\
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& $^1A_2 (\mathrm{R}; n \rightarrow 3p)$ &9.41 &8.92 &8.89 &9.37 &9.36 &9.38 &9.38 &9.43 &9.42 &9.40 &8.84 &9.63 \\
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& $^1A_1 (\mathrm{R}; n \rightarrow 3s)$ &9.99 &9.52 &9.58 &9.92 &9.96 &9.96 &9.97 &10.00 &9.98 &9.98 &9.52 &10.22 \\
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& $^3B_1 (\mathrm{R}; n \rightarrow 3s)$ &7.25 &6.92 &6.91 &7.24 &7.20 & & &7.28 &7.28 &7.24 &6.86 &7.41 \\
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& $^3A_2 (\mathrm{R}; n \rightarrow 3p)$ &9.24 &8.91 &8.77 &9.21 &9.20 & & &9.26 &9.25 &9.23 &8.72 &9.43 \\
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& $^3A_1 (\mathrm{R}; n \rightarrow 3s)$ &9.54 &9.30 &9.20 &9.51 &9.49 & & &9.56 &9.54 &9.53 &9.15 &9.70 \\
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\end{longtable}
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\end{footnotesize}
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\begin{flushleft}\begin{footnotesize}\begin{singlespace}
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$^a${{\CCSDT}/{\AVDZ} value corrected with the difference between {\CC{3}}/{\AVTZ} and {\CC{3}}/{\AVDZ} values;}
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$^b${{\CCSDTQ}/{\AVDZ} value corrected with the difference between {\CCSDT}/{\AVTZ} and {\CCSDT}/{\AVDZ} values;}
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$^c${{\CCSDTQ}/{\AVDZ} value corrected with the difference between {\CC{3}}/{\AVTZ} and {\CC{3}}/{\AVDZ} values;}
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$^d${Strong state mixing.}
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\end{singlespace}\end{footnotesize}\end{flushleft}
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\end{landscape}
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\end{document}
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