\documentclass[journal=jctcce,manuscript=article,layout=traditional]{achemso} \usepackage{graphicx,dcolumn,bm,xcolor,microtype,hyperref,multirow,amsmath,amssymb,amsfonts,physics,float,lscape,soul,rotating,longtable} \usepackage[version=4]{mhchem} \newcommand{\alert}[1]{\textcolor{red}{#1}} \newcommand{\mc}{\multicolumn} \newcommand{\mcc}[1]{\multicolumn{1}{c}{#1}} \newcommand{\mr}{\multirow} \newcommand{\EFCI}{E_\text{FCI}} \newcommand{\EexCI}{E_\text{exCI}} \newcommand{\EsCI}{E_\text{sCI}} \newcommand{\EPT}{E_\text{PT2}} \newcommand{\PsisCI}{\Psi_\text{sCI}} \newcommand{\Ndet}{N_\text{det}} \newcommand{\ex}[6]{$^{#1}#2_{#3}^{#4}(#5 \rightarrow #6)$} \newcommand{\pis}{\pi^\star} \newcommand{\si}{\sigma} \newcommand{\sis}{\sigma^\star} % methods \newcommand{\TDDFT}{TD-DFT} \newcommand{\CASSCF}{CASSCF} \newcommand{\CASPT}{CASPT2} \newcommand{\ADC}[1]{ADC(#1)} \newcommand{\CC}[1]{CC#1} \newcommand{\CCSD}{CCSD} \newcommand{\EOMCCSD}{EOM-CCSD} \newcommand{\CCSDT}{CCSDT} \newcommand{\CCSDTQ}{CCSDTQ} \newcommand{\CI}{CI} \newcommand{\sCI}{sCI} \newcommand{\exCI}{exFCI} \newcommand{\FCI}{FCI} % basis \newcommand{\Pop}{6-31+G(d)} \newcommand{\AVDZ}{\emph{aug}-cc-pVDZ} \newcommand{\AVTZ}{\emph{aug}-cc-pVTZ} \newcommand{\DAVTZ}{d-\emph{aug}-cc-pVTZ} \newcommand{\AVQZ}{\emph{aug}-cc-pVQZ} \newcommand{\DAVQZ}{d-\emph{aug}-cc-pVQZ} \newcommand{\TAVQZ}{t-\emph{aug}-cc-pVQZ} \newcommand{\AVFZ}{\emph{aug}-cc-pV5Z} \newcommand{\DAVFZ}{d-\emph{aug}-cc-pV5Z} % units \newcommand{\IneV}[1]{#1 eV} \newcommand{\InAU}[1]{#1 a.u.} \newcommand{\SI}{Supporting Information} \setcounter{table}{0} \setcounter{figure}{0} \setcounter{page}{1} \setcounter{equation}{0} \renewcommand{\thepage}{S\arabic{page}} \renewcommand{\thefigure}{S\arabic{figure}} \renewcommand{\theequation}{S\arabic{equation}} \renewcommand{\thetable}{S\arabic{table}} \renewcommand{\thesection}{S\arabic{section}} \renewcommand\floatpagefraction{.99} \renewcommand\topfraction{.99} \renewcommand\bottomfraction{.99} \renewcommand\textfraction{.01} % addresses \newcommand{\LCPQ}{Laboratoire de Chimie et Physique Quantiques, Universit\'e de Toulouse, CNRS, UPS, France} \newcommand{\CEISAM}{Laboratoire CEISAM - UMR CNRS 6230, Universit\'e de Nantes, 2 Rue de la Houssini\`ere, BP 92208, 44322 Nantes Cedex 3, France} \newcommand{\Pisa}{Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Moruzzi 3, 56124 Pisa, Italy} \title{Highly-Accurate Reference Excitation Energies and Benchmarks: Medium Size Molecules\\Supporting Information} \author{Pierre-Fran{\c c}ois Loos} \email{loos@irsamc.ups-tlse.fr} \affiliation[LCPQ, Toulouse]{\LCPQ} \author{Filippo Lipparini} \affiliation[DC, Pisa]{\Pisa} \email{filippo.lipparini@unipi.it} \author{Martial Boggio-Pasqua} \affiliation[LCPQ, Toulouse]{\LCPQ} \author{Anthony Scemama} \affiliation[LCPQ, Toulouse]{\LCPQ} \author{Denis Jacquemin} \email{Denis.Jacquemin@univ-nantes.fr} \affiliation[UN, Nantes]{\CEISAM} \begin{document} \clearpage \section{Basis set and frozen-core effects} \subsection{CC3} \subsubsection{Cyanoacetylene, cyanogen, and diacetylene} \begin{table}[htp] \caption{\small CC3 vertical transition energies of cyanoacetylene, cyanogen, and diacetylene using various atomic basis sets. FC stands for frozen core. All values are in eV.} \label{Table-S1} \begin{small} \begin{tabular}{l|cccccccc} \hline & {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} & \multicolumn{2}{c}{\DAVQZ} & {\AVFZ} \\ & FC & FC &FC & FC & Full & FC & Full & FC \\ \hline & \multicolumn{8}{c}{Cyanoacetylene} \\ \hline $^1\Sigma^-$ &6.02 &5.92 &5.80 &5.79 &5.79 &5.79 &5.79 &5.79 \\ $^1\Delta$ &6.29 &6.17 &6.08 &6.06 &6.07 &6.06 &6.07 &6.06 \\ $^3\Sigma^+$ &4.44 &4.43 &4.45 &4.46 &4.46 &4.46 &4.46 &4.47 \\ $^3\Delta$ &5.35 &5.28 &5.22 &5.22 &5.21 &5.22 &5.21 &5.22 \\ \hline & \multicolumn{8}{c}{Cyanogen} \\ \hline $^1\Sigma_u^-$ &6.62 &6.52 &6.39 &6.38 &6.38 &6.38 &6.38 &6.38 \\ $^1\Delta_u$ &6.88 &6.77 &6.66 &6.64 &6.65 &6.64 &6.65 &6.64 \\ $^3\Sigma_u^+$ &4.92 &4.89 &4.90 &4.91 &4.91 &4.91 &4.91 &4.92 \\ $^1\Sigma_u^-$[F] &5.27 &5.19 &5.06 &5.05 &5.05 &5.05 &5.05 &5.04 \\ \hline & \multicolumn{8}{c}{Diacetylene} \\ \hline $^1\Sigma_u^-$ &5.57 &5.44 &5.34 &5.33 &5.34 &5.33 &5.34 &5.33 \\ $^1\Delta_u$ &5.83 &5.69 &5.61 &5.60 &5.60 &5.60 &5.60 &5.60 \\ $^3\Sigma_u^+$ &4.07 &4.06 &4.08 &4.10 &4.09 &4.10 &4.09 &4.11 \\ $^3\Delta_u$ &4.93 &4.86 &4.80 &4.80 &4.80 &4.80 &4.80 &4.80 \\ \hline \end{tabular} \end{small} \end{table} \clearpage \subsubsection{Cyclopropenone, cyclopropenethione, and methylenecyclopropene} \begin{table}[htp] \caption{\small CC3 vertical transition energies of cyclopropenone, cyclopropenethione, and methylenecyclopropene using various atomic basis sets. FC stands for frozen core. All values are in eV.} \label{Table-S2} \begin{small} \begin{tabular}{l|ccccccc} \hline & {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} & {\AVFZ} \ \\ & FC & FC &FC & FC & Full & FC & FC \\ \hline & \multicolumn{7}{c}{Cyclopropenone} \\ \hline $^1B_1 (n \rightarrow \pi^\star)$ &4.32 &4.22 &4.21 &4.23 &4.22& 4.23 & 4.23\\% 4.23 en 5Z $^1A_2 (n \rightarrow \pi^\star)$ &5.68 &5.59 &5.57 &5.58 &5.57& 5.58 & 5.58\\% 5.58 en 5Z $^1B_2 (n \rightarrow 3s)$ &6.39 &6.21 &6.32 &6.37 &6.38& 6.36 & \hl{xxx}\\% $^1B_2 (\pi \rightarrow \pi^\star)$ &6.70 &6.56 &6.54 &6.56 &6.56& 6.56 & \hl{xxx}\\% $^1B_2 (n \rightarrow 3p)$ &6.92 &6.88 &6.96 &6.99 &7.00& 6.96 & \hl{xxx}\\% $^1A_1 (n \rightarrow 3p)$ &7.00 &6.88 &7.00 &7.05 &7.06& 7.03 & 7.06\\%To be looked at 7.06 en 5Z $^1A_1 (\pi \rightarrow \pi^\star)$ &8.51 &8.32 &8.28 &8.28 &8.28& 8.22 & 8.26\\%To be looked at 8.26 en 5Z $^3B_1 (n \rightarrow \pi^\star)$ &4.02 &3.90 &3.91 &3.93 &3.92& 3.93 & \hl{xxx}\\% N043, ~3.94, proche $^3B_2 (\pi \rightarrow \pi^\star)$ &4.92 &4.90 &4.89 &4.91 &4.90& 4.91 & \hl{xxx} \\% $^3A_2 (n \rightarrow \pi^\star)$ &5.48 &5.38 &5.37 &5.39 &5.37& 5.39 & \hl{xxx}\\% $^3A_1 (\pi \rightarrow \pi^\star)$ &6.89 &6.79 &6.83 &6.84 &6.83& 6.84 & 6.85\\% 6.85 en 57 \hline & \multicolumn{7}{c}{Cyclopropenethione} \\ \hline $^1A_2 (n \rightarrow \pi^\star)$ &3.46 &3.47 &3.43 &3.44 &3.42& 3.44 \\ $^1B_1 (n \rightarrow \pi^\star)$ &3.45 &3.42 &3.43 &3.45 &3.43& 3.45 \\ $^1B_2 (\pi \rightarrow \pi^\star)$ &4.67 &4.66 &4.64 &4.66 &4.64& 4.66 \\ $^1B_2 (n \rightarrow 3s)$ &5.26 &5.23 &5.34 &5.39 &5.39& 5.38 \\ $^1A_1 (\pi \rightarrow \pi^\star)$ &5.53 &5.52 &5.49 &5.49 &5.48& 5.49 \\ $^1B_2 (n \rightarrow 3p)$ &5.83 &5.86 &5.93 &5.95 &5.95& 5.91 \\%$^a$, mais les autres aussi !! $^3A_2 (n \rightarrow \pi^\star)$ &3.33 &3.34 &3.31 &3.31 &3.29& 3.31 \\ $^3B_1 (n \rightarrow \pi^\star)$ &3.34 &3.30 &3.31 &3.34 &3.32& 3.34 \\ $^3B_2 (\pi \rightarrow \pi^\star)$ &4.01 &4.03 &4.02 &4.04 &4.03& 4.04 \\ $^3A_1 (\pi \rightarrow \pi^\star)$ &4.06 &4.09 &4.03 &4.04 &4.02& 4.04 \\ \hline & \multicolumn{7}{c}{Methylenecyclopropene} \\ \hline $^1B_2 (\pi \rightarrow \pi^\star)$ &4.38 &4.32 &4.31 &4.31 &4.31& 4.31 \\ $^1B_1 (\pi \rightarrow \sigma^\star)$ &5.65 &5.35 &5.44 &5.47 &5.48& 5.46\\ $^1A_2 (\pi \rightarrow 3p)$ &5.97 &5.86 &5.95 &5.98 &5.99& 5.96\\ $^1A_1 (\pi \rightarrow \pi^\star)$ &6.17 &6.15 &6.13 &6.09 &6.10& 5.98\\%<= Stong mixing $^3B_2 (\pi \rightarrow \pi^\star)$ &3.50 &3.49 &3.50 &3.50 &3.50& 3.50\\ $^3A_1 (\pi \rightarrow \pi^\star)$ &4.74 &4.74 &4.74 &4.75 &4.74& 4.74\\ \hline \end{tabular} \begin{flushleft} %$^a${Significant mixing.} \end{flushleft} \end{small} \end{table} \clearpage \subsubsection{Acrolein, butadiene, and glyoxal} \begin{table}[htp] \caption{\small CC3 vertical transition energies of acrolein, butadiene, and glyoxal using various atomic basis sets. FC stands for frozen core. All values are in eV.} \label{Table-S3} \begin{small} \begin{tabular}{l|cccccc} \hline & {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} \\ & FC & FC &FC & FC & Full & FC \\ \hline & \multicolumn{6}{c}{Acrolein} \\ \hline $^1A'' (n \rightarrow \pi^\star)$ &3.83 &3.77 &3.74 &3.75 &3.74\\ $^1A' (\pi \rightarrow \pi^\star)$ &6.83 &6.67 &6.65 &6.65 &6.65\\ $^1A'' (n \rightarrow \pi^\star)$ &6.94 &6.75 &6.75 &6.77 &6.76\\ $^1A' (n \rightarrow 3s)$ &7.22 &6.99 &7.07 &7.11 &7.11\\ $^3A'' (n \rightarrow \pi^\star)$ &3.55 &3.47 &3.46 &3.47 &3.46\\ $^3A' (\pi \rightarrow \pi^\star)$ &3.94 &3.95 &3.94 &3.95 &3.94\\ $^3A' (\pi \rightarrow \pi^\star)$ &6.25 &6.22 &6.19 &6.20 &6.19\\ $^3A'' (\pi \rightarrow 3s)$ &6.81 &6.60 &6.61 &6.63 &6.62\\ \hline & \multicolumn{6}{c}{Butadiene} \\ \hline $^1B_u (\pi \rightarrow \pi^\star)$ &6.41 &6.25 &6.22 &6.21 &6.22\\ $^1B_g (\pi \rightarrow 3s)$ &6.53 &6.26 &6.33 &6.35 &6.36\\ $^1A_g (\pi \rightarrow \pi^\star)$ &6.73 &6.68 &6.67 &6.67 &6.67& 6.67\\ $^1A_u (\pi \rightarrow 3p)$ &6.87 &6.57 &6.64 &6.66 &6.67\\ $^1A_u (\pi \rightarrow 3p)$ &6.93 &6.73 &6.80 &6.82 &6.83\\ $^1B_u (\pi \rightarrow 3p)$ &7.98 &7.86 &7.68 &7.54 &7.55\\ $^3B_u (\pi \rightarrow \pi^\star)$ &3.35 &3.36 &3.36 &3.37 &3.36\\ $^3A_g (\pi \rightarrow \pi^\star)$ &5.22 &5.21 &5.20 &5.21 &5.20\\ $^3B_g (\pi \rightarrow 3s)$ &6.46 &6.20 &6.28 &6.30 &6.31\\ \hline & \multicolumn{6}{c}{Glyoxal} \\ \hline $^1A_u (n \rightarrow \pi^\star)$ &2.94 &2.90 &2.88 &2.88 &2.87& 2.88\\ $^1B_g (n \rightarrow \pi^\star)$ &4.34 &4.30 &4.27 &4.27 &4.27& 4.27\\ $^1A_g (n,n \rightarrow \pi^\star,\pi^\star)$&6.74 &6.70 &6.76 &6.76 &6.74& 6.76\\ $^1B_g (n \rightarrow \pi^\star)$ &6.81 &6.59 &6.58 &6.59 &6.58& 6.58\\ $^1B_u (n \rightarrow3p)$ &7.72 &7.55 &7.67 &7.72 &7.73& 7.72\\ $^3A_u (n \rightarrow \pi^\star)$ &2.55 &2.49 &2.49 &2.49 &2.49& 2.49\\ $^3B_g (n \rightarrow \pi^\star)$ &3.97 &3.91 &3.90 &3.91 &3.90& 3.91\\ $^3B_u (\pi \rightarrow \pi^\star)$ &5.22 &5.20 &5.17 &5.18 &5.17& 5.18\\ $^3A_g (\pi \rightarrow \pi^\star)$ &6.35 &6.34 &6.30 &6.31 &6.30& 6.31\\ \hline \end{tabular} \end{small} \end{table} \clearpage \subsubsection{Acetone, cyanoformaldehyde, isobutene, propynal, thioacetone, and thiopropynal} \begin{table}[htp] \caption{\small CC3 vertical transition energies of acetone, cyanoformaldehyde, isobutene, propynal, thioacetone, and thiopropynal using various atomic basis sets. FC stands for frozen core. All values are in eV.} \label{Table-S4} \begin{small} \begin{tabular}{l|cccccc} \hline & {\Pop} & {\AVDZ} & {\AVTZ} & \multicolumn{2}{c}{\AVQZ} &{\DAVQZ} \\ & FC & FC &FC & FC & Full & FC\\ \hline & \multicolumn{5}{c}{Acetone} \\ \hline $^1A_2 (n \rightarrow \pi^\star)$ &4.55 &4.50 &4.48 &4.49 &4.48\\ $^1B_2 (n \rightarrow 3s)$ &6.65 &6.31 &6.43 &6.48 &6.49\\ $^1A_2 (n \rightarrow 3p)$ &7.83 &7.37 &7.45 &7.48 &7.49\\ $^1A_1 (n \rightarrow 3p)$ &7.81 &7.39 &7.48 &7.52 &7.53\\ $^1B_2 (n \rightarrow 3p)$ &7.87 &7.56 &7.59 &7.60 &7.61\\ $^3A_2 (n \rightarrow \pi^\star)$ &4.21 &4.16 &4.15 &4.17 &4.16\\ $^3A_1 (\pi \rightarrow \pi^\star)$ &6.32 &6.31 &6.28 &6.30 &6.28\\ \hline & \multicolumn{5}{c}{Cyanoformaldehyde} \\ \hline $^1A'' (n \rightarrow \pi^\star)$ &3.91 &3.86 &3.83 &3.84 &3.83 &3.84\\ $^1A'' (\pi \rightarrow \pi^\star)$ &6.64 &6.51 &6.42 &6.41 &6.41 &6.41\\ $^3A'' (n \rightarrow \pi^\star)$ &3.53 &3.47 &3.46 &3.47 &3.46 &3.47\\ $^3A' (\pi \rightarrow \pi^\star)$ &5.07 &5.03 &5.01 &5.02 &5.01 &5.02\\ \hline & \multicolumn{5}{c}{Isobutene} \\ \hline $^1B_1 (\pi \rightarrow 3s)$ &6.77 &6.39 &6.45 &6.47 &\\ $^1A_1 (\pi \rightarrow 3p)$ &7.16 &7.00 &7.00 &6.99 &\\ $^3A_1 (\pi \rightarrow \pi^\star)$ &4.52 &4.54 &4.53 &4.54 &\\ \hline & \multicolumn{5}{c}{Propynal} \\ \hline $^1A'' (n \rightarrow \pi^\star)$ &3.90 &3.85 &3.82 &3.83 &3.82 &3.83\\ $^1A'' (\pi \rightarrow \pi^\star)$ &5.69 &5.59 &5.51 &5.50 &5.50 &5.50\\ $^3A'' (n \rightarrow \pi^\star)$ &3.56 &3.50 &3.49 &3.50 &3.49 &\hl{xxx}\\ $^3A' (\pi \rightarrow \pi^\star)$ &4.46 &4.40 &4.43 &4.44 &4.43 &4.44\\ \hline & \multicolumn{5}{c}{Thioacetone} \\ \hline $^1A_2 (n \rightarrow \pi^\star)$ &2.58 &2.59 &2.55 &2.56 &\\ $^1B_2 (n \rightarrow 4s)$ &5.65 &5.44 &5.55 &5.60 &\\ $^1A_1 (\pi \rightarrow \pi^\star)$ &6.09 &5.97 &5.90 &5.88 &\\ $^1A_1 (n \rightarrow 4p)$ &6.95 &6.54 &6.61 &6.64 &\\ $^1B_2 (n \rightarrow 4p)$ &6.59 &6.45 &6.51 &6.52 &\\ $^3A_2 (n \rightarrow \pi^\star)$ &2.36 &2.36 &2.34 &2.35 &\\ $^3A_1 (\pi \rightarrow \pi^\star)$ s&3.45 &3.51 &3.46 &3.47 &\\ \hline & \multicolumn{5}{c}{Thiopropynal} \\ \hline $^1A'' (n \rightarrow \pi^\star)$ &2.09 &2.09 &2.05 &2.06 &2.04\\ $^3A'' (n \rightarrow \pi^\star)$ &1.84 &1.83 &1.81 &1.82 &\hl{xxx}\\ \hline \end{tabular} \end{small} \end{table} \clearpage \subsection{Multi-reference results} \subsubsection{Cyanoacetylene, cyanogen, and diacetylene} \begin{table}[htp] \caption{\small Vertical transition energies of cyanoacetylene, cyanogen, and diacetylene using various atomic basis sets and multi-reference methods. All values are in eV and have been obtained with within the FC approximation. The CASPT2 calculations are performed with a level shift of 0.3 and a IPEA of 0.25. Pop, AVDZ, AVTZ, and AVQZ respectively stand for {\Pop}, {\AVDZ}, {\AVTZ}, and {\AVQZ}. } \label{Table-S1b} \begin{footnotesize} \begin{tabular}{l|cccccccccccc} \hline & \multicolumn{4}{c}{CASPT2(8,8)} & \multicolumn{4}{c}{PC-NEVPT2(8,8)} & \multicolumn{4}{c}{SC-NEVPT2(8,8)} \\ & Pop &AVDZ & AVTZ & AVQZ & Pop &AVDZ & AVTZ & AVQZ& Pop &AVDZ & AVTZ & AVQZ \\ \hline & \multicolumn{12}{c}{Cyanoacetylene} \\ \hline $^1\Sigma^-$ & & 6.00 & 5.86 & & & 5.93 & 5.78 & & & 5.98 & 5.83 & \\ $^1\Delta$ & & 6.26 & 6.13 & & & 6.22 & 6.10 & & & 6.27 & 6.14 & \\ $^3\Sigma^+$ & & 4.47 & 4.45 & & & 4.46 & 4.45 & & & 4.51 & 4.49 & \\ $^3\Delta$ & & 5.30 & 5.21 & & & 5.28 & 5.19 & & & 5.31 & 5.23 & \\ \hline & \multicolumn{12}{c}{Cyanogen} \\ \hline $^1\Sigma_u^-$ & 6.63 & 6.56 & 6.40 & 6.37 & 6.56 & 6.49 & 6.32 & 6.29 & 6.61 & 6.54 & 6.37 & 6.34 \\ $^1\Delta_u$ & 6.93 & 6.84 & 6.70 & 6.66 & 6.91 & 6.81 & 6.66 & 6.63 & 6.95 & 6.86 & 6.71 & 6.68 \\ $^3\Sigma_u^+$ & 4.91 & 4.89 & 4.86 & 4.86 & 4.92 & 4.91 & 4.88 & 4.89 & 4.96 & 4.95 & 4.92 & 4.93 \\ $^1\Sigma_u^-$[F] & & 5.23 & 5.07 & & & 5.14 & 4.97 & & & 5.17 & 5.01 & \\ \hline & \multicolumn{12}{c}{Diacetylene} \\ \hline $^1\Sigma_u^-$ & & 5.56 & 5.43 & & & 5.47 & 5.33 & & & 5.53 & 5.39 & \\ $^1\Delta_u$ & & 5.80 & 5.68 & & & 5.73 & 5.61 & & & 5.78 & 5.67 & \\ $^3\Sigma_u^+$ & & 4.12 & 4.11 & & & 4.09 & 4.08 & & & 4.14 & 4.13 & \\ $^3\Delta_u$ & & 4.89 & 4.81 & & & 4.86 & 4.78 & & & 4.90 & 4.82 & \\ \hline \end{tabular} \end{footnotesize} \end{table} \clearpage \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{Acetone} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 0.18807702 C 0.00000000 2.42007545 -1.31764698 C 0.00000000 -2.42007545 -1.31764698 O 0.00000000 0.00000000 2.48269094 H 0.00000000 4.03690733 -0.05185132 H 0.00000000 -4.03690733 -0.05185132 H 1.66061256 2.48420530 -2.53995285 H -1.66061256 2.48420530 -2.53995285 H 1.66061256 -2.48420530 -2.53995285 H -1.66061256 -2.48420530 -2.53995285 \end{verbatim} \end{singlespace} \subsection{Acrolein} \begin{singlespace} \begin{verbatim} C -1.11645072 -0.68348783 0.00000000 C 1.20647847 0.83714564 0.00000000 C 3.46831059 -0.28872636 0.00000000 O -3.23666415 0.19187203 0.00000000 H -0.80613858 -2.74747338 0.00000000 H 0.98699813 2.86613511 0.00000000 H 5.20930864 0.77443560 0.00000000 H 3.60951559 -2.33000749 0.00000000 \end{verbatim} \end{singlespace} \subsection{Butadiene} \begin{singlespace} \begin{verbatim} C 1.14656244 0.00000000 0.75468820 C -1.14656244 0.00000000 -0.75468820 C 3.48132647 0.00000000 -0.22482805 C -3.48132647 0.00000000 0.22482805 H 0.90770978 0.00000000 2.78883925 H -0.90770978 0.00000000 -2.78883925 H 3.77525814 0.00000000 -2.24895470 H -3.77525814 0.00000000 2.24895470 H 5.13664967 0.00000000 0.96861890 H -5.13664967 0.00000000 -0.96861890 \end{verbatim} \end{singlespace} \subsection{Cyanoacetylene} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 -3.59120182 C 0.00000000 0.00000000 -1.30693904 C 0.00000000 0.00000000 1.28880240 N 0.00000000 0.00000000 3.48692211 H 0.00000000 0.00000000 -5.59619886 \end{verbatim} \end{singlespace} \subsection{Cyanoformaldehyde} \begin{singlespace} \begin{verbatim} C -0.91561483 0.00000000 -1.22522833 C -0.01092219 0.00000000 1.39523175 N 0.64170259 0.00000000 3.48820325 O 0.50833684 0.00000000 -3.00337867 H -2.97202213 0.00000000 -1.42565674 \end{verbatim} \end{singlespace} \subsection{Cyanogen} \begin{singlespace} Ground state \begin{verbatim} C 0.00000000 0.00000000 1.30401924 C 0.00000000 0.00000000 -1.30401924 N 0.00000000 0.00000000 3.49784121 N 0.00000000 0.00000000 -3.49784121 \end{verbatim} \end{singlespace} \begin{singlespace} \noindent Lowest excited state \begin{verbatim} C 0.00000000 0.00000000 1.22784115 C 0.00000000 0.00000000 -1.22784115 N 0.00000000 0.00000000 3.56462559 N 0.00000000 0.00000000 -3.56462559 \end{verbatim} \end{singlespace} \subsection{Cyclopentadiene} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 -2.33113051 C 0.00000000 2.22209092 -0.56871188 C 0.00000000 -2.22209092 -0.56871188 C 0.00000000 1.38514451 1.83772922 C 0.00000000 -1.38514451 1.83772922 H 1.66130504 0.00000000 -3.56414299 H -1.66130504 0.00000000 -3.56414299 H 0.00000000 4.16550405 -1.18116624 H 0.00000000 -4.16550405 -1.18116624 H 0.00000000 2.54514584 3.51352303 H 0.00000000 -2.54514584 3.51352303 \end{verbatim} \end{singlespace} \subsection{Cyclopropenone} \begin{singlespace} \begin{verbatim} C 0.00000000 1.27491826 -1.86930519 C 0.00000000 -1.27491826 -1.86930519 C 0.00000000 0.00000000 0.51814554 O 0.00000000 0.00000000 2.79326776 H 0.00000000 2.92791371 -3.05679837 H 0.00000000 -2.92791371 -3.05679837 \end{verbatim} \end{singlespace} \subsection{Cyclopropenethione} \begin{singlespace} \begin{verbatim} C 0.00000000 1.26230744 -2.86571925 C 0.00000000 -1.26230744 -2.86571925 C 0.00000000 0.00000000 -0.49233236 S 0.00000000 0.00000000 2.57821680 H 0.00000000 2.97773331 -3.95114059 H 0.00000000 -2.97773331 -3.95114059 \end{verbatim} \end{singlespace} \subsection{Diacetylene} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 1.29447700 C 0.00000000 0.00000000 -1.29447700 C 0.00000000 0.00000000 3.58448429 C 0.00000000 0.00000000 -3.58448429 H 0.00000000 0.00000000 5.58943003 H 0.00000000 0.00000000 -5.58943003 \end{verbatim} \end{singlespace} \subsection{Furan} \begin{singlespace} \begin{verbatim} C 0.00000000 2.06365826 -0.60051250 C 0.00000000 -2.06365826 -0.60051250 C 0.00000000 1.35348578 1.86336416 C 0.00000000 -1.35348578 1.86336416 O 0.00000000 0.00000000 -2.13945332 H 0.00000000 3.86337287 -1.53765695 H 0.00000000 -3.86337287 -1.53765695 H 0.00000000 2.59168789 3.47168051 H 0.00000000 -2.59168789 3.47168051 \end{verbatim} \end{singlespace} \subsection{Glyoxal} \begin{singlespace} \begin{verbatim} C 1.21360282 0.75840215 0.00000000 C -1.21360282 -0.75840215 0.00000000 O 3.25581408 -0.26453186 0.00000000 O -3.25581408 0.26453186 0.00000000 H 0.96135276 2.81883243 0.00000000 H -0.96135276 -2.81883243 0.00000000 \end{verbatim} \end{singlespace} \subsection{Imidazole} \begin{singlespace} \begin{verbatim} C 0.41662795 2.06006259 0.00000000 C -1.52618386 -1.62343163 0.00000000 C 1.04160471 -1.93007427 0.00000000 N -1.90345764 0.94914956 0.00000000 N 2.24215443 0.38083431 0.00000000 H 0.65501634 4.07748278 0.00000000 H -3.57500545 1.84103166 0.00000000 H -3.06363894 -2.94559167 0.00000000 H 2.08673940 -3.67001102 0.00000000 \end{verbatim} \end{singlespace} \subsection{Isobutene} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 2.70790758 C 0.00000000 0.00000000 0.18431282 C 0.00000000 2.39894572 -1.32482735 C 0.00000000 -2.39894572 -1.32482735 H 0.00000000 1.74848405 3.76691310 H 0.00000000 -1.74848405 3.76691310 H 0.00000000 4.05897160 -0.10582007 H 0.00000000 -4.05897160 -0.10582007 H 1.66026992 2.48337908 -2.55086178 H -1.66026992 2.48337908 -2.55086178 H 1.66026992 -2.48337908 -2.55086178 H -1.66026992 -2.48337908 -2.55086178 \end{verbatim} \end{singlespace} \subsection{Methylenecyclopropene} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 0.53512883 C 0.00000000 0.00000000 3.04739824 C 0.00000000 1.25042956 -1.88571561 C 0.00000000 -1.25042956 -1.88571561 H 0.00000000 2.96887531 -2.96270271 H 0.00000000 -2.96887531 -2.96270271 H 0.00000000 1.75335023 4.08608382 H 0.00000000 -1.75335023 4.08608382 \end{verbatim} \end{singlespace} \subsection{Propynal} \begin{singlespace} \begin{verbatim} C -0.78051115 0.00000000 -1.38900384 C -0.17873562 0.00000000 1.27825868 C 0.23763714 0.00000000 3.52644798 O 0.80143996 0.00000000 -3.04628328 H -2.80713069 0.00000000 -1.82768750 H 0.64026209 0.00000000 5.48853193 \end{verbatim} \end{singlespace} \subsection{Pyrrole} \begin{singlespace} \begin{verbatim} C 0.00000000 2.11924634 0.62676569 C 0.00000000 -2.11924634 0.62676569 C 0.00000000 1.34568862 -1.85506908 C 0.00000000 -1.34568862 -1.85506908 N 0.00000000 0.00000000 2.10934391 H 0.00000000 0.00000000 4.00257355 H 0.00000000 3.97648410 1.44830201 H 0.00000000 -3.97648410 1.44830201 H 0.00000000 2.56726559 -3.47837232 H 0.00000000 -2.56726559 -3.47837232 \end{verbatim} \end{singlespace} \subsection{Thioacetone} \begin{singlespace} \begin{verbatim} C 0.00000000 0.00000000 0.68476030 C 0.00000000 2.38541696 2.20685096 C 0.00000000 -2.38541696 2.20685096 S 0.00000000 0.00000000 -2.39920303 H 0.00000000 4.04609254 1.00090614 H 0.00000000 -4.04609254 1.00090614 H 1.65894780 2.42602225 3.43712000 H -1.65894780 2.42602225 3.43712000 H 1.65894780 -2.42602225 3.43712000 H -1.65894780 -2.42602225 3.43712000 \end{verbatim} \end{singlespace} \subsection{Thiophene} \begin{singlespace} \begin{verbatim} C 0.00000000 2.33342542 -0.09858421 C 0.00000000 -2.33342542 -0.09858421 C 0.00000000 1.34371718 -2.48297725 C 0.00000000 -1.34371718 -2.48297725 S 0.00000000 0.00000000 2.17250692 H 0.00000000 4.29028016 0.44577296 H 0.00000000 -4.29028016 0.44577296 H 0.00000000 2.48760051 -4.16768392 H 0.00000000 -2.48760051 -4.16768392 \end{verbatim} \end{singlespace} \subsection{Thiopropynal} \begin{singlespace} \begin{verbatim} C -0.00382924 0.00000000 -1.25249909 C -2.27832423 0.00000000 0.15152736 C -4.26309583 0.00000000 1.29548793 S 2.81920288 0.00000000 -0.00828974 H -0.23056990 0.00000000 -3.28862183 H -5.97712967 0.00000000 2.33206931 \end{verbatim} \end{singlespace} \clearpage \section{Benchmark} \end{document}