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@ -640,7 +640,7 @@ Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 5.17$^a$,5.15$^b$ \\
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$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
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$^b$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and $3p_y$ orbitals.
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$^c$Using reference (6e,6o) active space including valence $\pi$ orbitals.
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$^d$Using reference (6e,10o) active space including valence $\pi$and four $3p_x$ orbitals.
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$^d$Using reference (6e,10o) active space including valence $\pi$ and four $3p_x$ orbitals.
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$^e$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
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$^d$Using reference (6e,8o) active space including valence $\pi$ and 3s orbitals.
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$^g$Using reference (6e,7o) active space including valence $\pi$ and $3p_y$ orbitals.
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@ -814,16 +814,16 @@ $^h$Strong double-excitation character.
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thiopropynal.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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Molecule & State & NEVPT2$^a$ \\
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\hline
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Thiopropynal &$^1A'' (\Val; n \ra \pis)$ & 2.05$^a$ \\
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&$^3A'' (\Val; n \ra \pis)$ & 1.81$^a$ \\
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Thiopropynal &$^1A'' (\Val; n \ra \pis)$ & 2.05 \\
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&$^3A'' (\Val; n \ra \pis)$ & 1.81 \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
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$^a$All calculations using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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@ -838,7 +838,7 @@ Molecule & State & NEVPT2 \\
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Triazine &$^1A_1'' (\Val; n \ra \pis)$ & 4.61$^a$ \\
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&$^1A_2'' (\Val; n \ra \pis)$ & 4.89$^a$ \\
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&$^1E'' (\Val; n \ra \pis)$ & 4.88$^a$ \\
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&$^1A_2' (\Val; \pi \ra \pis)$ & 6.10$^v$,6.15$^c$,5.95$^d$ \\
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&$^1A_2' (\Val; \pi \ra \pis)$ & 6.10$^b$,6.15$^c$,5.95$^d$ \\
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&$^1A_1' (\Val; \pi \ra \pis)$ & 7.06$^b$,7.30$^d$ \\
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&$^1E' (\Ryd; n \ra 3s)$ & 7.45$^c$ \\
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&$^1E'' (\Val; n \ra \pis)$ & 7.98$^a$ \\
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@ -1,5 +1,5 @@
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\documentclass[journal=jctcce,manuscript=article]{achemso}
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\usepackage{graphicx,dcolumn,bm,xcolor,microtype,hyperref,multirow,amsmath,amssymb,amsfonts,physics,float,lscape,soul,rotating,longtable}
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\usepackage{graphicx,dcolumn,bm,xcolor,microtype,hyperref,multirow,amsmath,amssymb,amsfonts,physics,float,lscape,soul,rotating,longtable,tabularx}
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\usepackage[version=4]{mhchem}
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@ -450,7 +450,7 @@ $^3B_{2u} (\pi \rightarrow \pi^\star)$ &6.06 &5.86 &5.81 &5.81\\
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\clearpage
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\begin{table}[htp]
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\caption{\small CC3 vertical transition energies of tetrazine using various atomic basis sets.
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\caption{\small CC3 vertical transition energies of pyrazine and tetrazine using various atomic basis sets.
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FC stands for frozen core. All values are in eV.}
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\label{Table-S8}
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\begin{small}
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@ -609,7 +609,7 @@ $^3A_2' (\pi \rightarrow \pi^\star)$ & 6.85 &6.69 &6.63 &6.62\\
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\clearpage
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\section{Multi-reference results}
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\section{Multiconfigurational results}
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\subsection{Basis set effects}
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@ -653,9 +653,769 @@ $^3\Delta_u$ & & 4.89 & 4.81 & & & 4.86 & 4.78 & & & 4.90 & 4.82 & \\
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\subsection{Active Spaces}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acetone.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Acetone &$^1A_2 (\Val; n \ra \pis)$ &4.57$^a$,4.48$^b$ \\
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&$^1B_2 (\Ryd; n \ra 3s)$ &6.81$^c$ \\
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&$^1A_2 (\Ryd; n \ra 3p)$ &7.65$^b$ \\
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&$^1A_1 (\Ryd; n \ra 3p)$ &7.75$^d$ \\
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&$^1B_2 (\Ryd; n \ra 3p)$ &7.91$^c$ \\
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&$^3A_2 (\Val; n \ra \pis)$ &4.20$^a$ \\
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&$^3A_1 (\Val; \pi \ra \pis)$ &6.28$^e$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (6e,5o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
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$^b$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $3p_x$ orbitals.
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$^c$Using reference (6e,7o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$, 3s and $3p_z$ orbitals.
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$^d$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $3p_y$ orbitals.
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$^e$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acrolein.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Acrolein &$^1A'' (\Val; n \ra \pis)$ &3.76$^a$,3.73$^b$ \\
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&$^1A' (\Val; \pi \ra \pis)$ &6.67$^a$ \\
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&$^1A'' (\Val; n \ra \pis)$ &7.16$^{a,c}$,7.57$^{b,c}$ \\
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&$^1A' (\Ryd; n \ra 3s)$ &7.05$^a$ \\
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&$^3A'' (\Val; n \ra \pis)$ &3.46$^a$,3.44$^b$ \\
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&$^3A' (\Val; \pi \ra \pis)$ &3.95$^a$ \\
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&$^3A' (\Val; \pi \ra \pis)$ &6.23$^a$ \\
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&$^3A'' (\Val; n \ra \pis)$ &6.83$^{a,d}$,7.06$^{b,d}$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (12e,12o) active space including valence $\pi$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$, $n_\text{O}$ and 3s orbitals.
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$^b$Using reference (12e,13o) active space including valence $\pi$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$, $n_\text{O}$, 3s and $3p_z$ orbitals.
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$^c$Substantial Rydberg and doubly-excited character.
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$^d$Substantial doubly-excited character.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of benzene.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Benzene &$^1B_{2u} (\Val; \pi \ra \pis)$ &5.32$^a$,5.32$^b$ \\
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&$^1B_{1u} (\Val; \pi \ra \pis)$ &6.01$^a$,6.43$^b$ \\
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&$^1E_{1g} (\Ryd; \pi \ra 3s)$ &6.75$^c$ \\
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&$^1A_{2u} (\Ryd; \pi \ra 3p)$ &7.40$^d$\\
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&$^1E_{2u} (\Ryd; \pi \ra 3p)$ &7.45$^d$ \\
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&$^3B_{1u} (\Val; \pi \ra \pis)$ &4.44$^a$,4.32$^b$\\
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&$^3E_{1u}(\Val; \pi \ra \pis)$ &4.99$^a$,4.92$^b$\\
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&$^3B_{2u} (\Val; \pi \ra \pis)$ &5.30$^a$,5.51$^b$\\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (6e,6o) active space including valence $\pi$ orbitals.
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$^b$Using reference (6e,9o) active space including valence $\pi$ and three $3p_z$ orbitals.
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$^c$Using reference (6e,7o) active space including valence $\pi$ and 3s orbitals.
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$^d$Using reference (6e,8o) active space including valence $\pi$, $3p_x$ and $3p_y$ orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of butadiene.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Butadiene &$^1B_u (\Val; \pi \ra \pis)$ &6.04$^a$,6.73$^b$,6.68$^c$ \\
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&$^1B_g (\Ryd; \pi \ra 3s)$ &6.44$^d$ \\
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&$^1A_g (\Val; \pi \ra \pis)$ &6.70$^a$ \\
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&$^1A_u (\Ryd; \pi \ra 3p)$ &6.84$^e$ \\
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&$^1A_u (\Ryd; \pi \ra 3p)$ &7.01$^e$ \\
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&$^1B_u (\Ryd; \pi \ra 3p)$ &6.99$^b$,7.45$^c$ \\
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&$^3B_u (\Val; \pi \ra \pis)$ &3.40$^a$ \\
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&$^3A_g (\Val; \pi \ra \pis)$ &5.30$^a$ \\
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&$^3B_g (\Ryd; \pi \ra 3s)$ &6.38$^d$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (10e,10o) active space including valence $\pi$, $\si_\text{CC}$ and $\si^*_\text{CC}$ orbitals.
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$^b$Using reference (10e,11o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3p_z$ orbitals.
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$^c$Using reference (4e,8o) active space including valence $\pi$ and four $3p_z$.
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$^d$Using reference (10e,11o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and 3s orbitals.
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$^e$Using reference (10e,12o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$, $3p_x$ and $3p_y$ orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoacetylene.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2$^a$ \\
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\hline
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Cyanoacetylene &$^1\Sigma^- (\Val; \pi \ra \pis)$ & 5.78 \\
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&$^1\Delta (\Val; \pi \ra \pis)$ & 6.10 \\
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&$^3\Sigma^+ (\Val; \pi \ra \pis)$ & 4.45 \\
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&$^3\Delta (\Val; \pi \ra \pis)$ & 5.19 \\
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&$^1A'' [\mathrm{F}] (\Val; \pi \ra \pis)$ & 3.50 \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoformaldehyde.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Cyanoformaldehyde &$^1A'' (\Val; n \ra \pis)$ &3.98$^a$ \\
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&$^1A'' (\Val; \pi \ra \pis)$ & 6.44$^a$ \\
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&$^3A'' (\Val; n \ra \pis)$ & 3.58$^a$ \\
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&$^3A' (\Val; \pi \ra \pis)$ & 5.35$^b$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$ Using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
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$^b$ Using reference (6e,6o) active space including valence $\pi$ orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanogen.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2$^a$ \\
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\hline
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Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 6.32 \\
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& $^1\Delta_u (\Val; \pi \ra \pis)$ & 6.66 \\
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& $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.88 \\
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& $^1\Sigma_u^- [\mathrm{F}] (\Val; \pi \ra \pis)$ & 4.97 \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopentadiene.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Cyclopentadiene &$^1B_2 (\Val; \pi \ra \pis)$ &4.96$^a$,4.92$^b$,5.65$^c$ \\
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&$^1A_2 (\Ryd; \pi \ra 3s)$ &5.92$^d$ \\
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&$^1B_1 (\Ryd; \pi \ra 3p)$ &6.42$^e$ \\
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&$^1A_2 (\Ryd; \pi \ra 3p)$ &6.59$^d$ \\
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&$^1B_2 (\Ryd; \pi \ra 3p)$ &6.58$^b$,6.60$^c$ \\
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&$^1A_1 (\Val; \pi \ra \pis)$ &6.75$^{a,f}$ \\
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&$^3B_2 (\Val; \pi \ra \pis)$ &3.41$^a$ \\
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&$^3A_1 (\Val; \pi \ra \pis)$ &5.30$^a$ \\
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&$^3A_2 (\Ryd; \pi \ra 3s)$ &5.73$^g$ \\
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&$^3B_1 (\Ryd; \pi \ra 3p)$ &6.40$^e$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (4e,4o) active space including valence $\pi$ orbitals.
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$^b$Using reference (4e,5o) active space including valence $\pi$ and $3p_x$ orbitals.
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$^c$Using reference (4e,8o) active space including valence $\pi$ and four $3p_x$ orbitals.
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$^d$Using reference (4e,6o) active space including valence $\pi$, 3s and $3p_z$ orbitals.
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$^e$Using reference (4e,5o) active space including valence $\pi$ and $3p_y$ orbitals.
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$^f$Strong double-excitation character.
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$^g$Using reference (4e,5o) active space including valence $\pi$ and 3s orbitals.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenone.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2$^a$ \\
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\hline
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Cyclopropenone &$^1B_1 (\Val; n \ra \pis)$ & 4.04 \\
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&$^1A_2 (\Val; n \ra \pis)$ & 5.85 \\
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&$^1B_2 (\Ryd; n \ra 3s)$ & 6.51 \\
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&$^1B_2 (\Val; \pi \ra \pis$) & 6.82 \\
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&$^1B_2 (\Ryd; n \ra 3p)$ & 7.07 \\
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&$^1A_1 (\Ryd; n \ra 3p)$ & 7.28 \\
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&$^1A_1 (\Val; \pi \ra \pis)$ & 8.19 \\
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&$^3B_1 (\Val; n \ra \pis)$ & 3.51 \\
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&$^3B_2 (\Val; \pi \ra \pis)$ & 5.10 \\
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&$^3A_2 (\Val; n \ra \pis)$ & 5.60 \\
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&$^3A_1 (\Val; \pi \ra \pis)$ & 7.16 \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$All calculation using reference (6e,7o) active space averaging with the ground state for each irreducible representation.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenethione.}
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\begin{tabularx}{\textwidth}{XXX}
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\hline
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Molecule & State & NEVPT2 \\
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\hline
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Cyclopropenethione &$^1A_2 (\Val; n \ra \pis)$ &3.52$^a$ \\
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&$^1B_1 (\Val; n \ra \pis)$ &3.50$^a$ \\
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&$^1B_2 (\Val; \pi \ra \pis)$ &4.77$^b$ \\
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&$^1B_2 (\Ryd; n \ra 3s)$ &5.35$^b$ \\
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&$^1A_1 (\Val; \pi \ra \pis)$ &5.54$^c$ \\
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&$^1B_2 (\Ryd; n \ra 3p)$ &5.99$^b$ \\
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&$^3A_2 (\Val; n \ra \pis)$ &3.38$^a$ \\
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&$^3B_1 (\Val; n \ra \pis)$ &3.40$^a$ \\
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&$^3B_2 (\Val; \pi \ra \pis)$ &4.21$^c$,4.17$^b$ \\
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&$^3A_1 (\Val; \pi \ra \pis)$ &4.13$^c$ \\
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\hline
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\end{tabularx}
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\begin{flushleft}
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\begin{footnotesize}
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$^a$Using reference (6e,5o) active space.
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$^b$Using reference (6e,7o) active space.
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$^c$Using reference (4e,4o) active space.
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\end{footnotesize}
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\end{flushleft}
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\end{table}
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\begin{table}
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\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of diacetylene.}
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\begin{tabularx}{\textwidth}{XXX}
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||||
\hline
|
||||
Molecule & State & NEVPT2$^a$ \\
|
||||
\hline
|
||||
Diacetylene &$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 5.33 \\
|
||||
&$^1\Delta_u (\Val; \pi \ra \pis)$ & 5.61 \\
|
||||
&$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.08 \\
|
||||
&$^3\Delta_u (\Val; \pi \ra \pis)$ & 4.78 \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of furan.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Furan &$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.28$^a$ \\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.92$^b$,6.20$^{c,d}$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.77$^{b,e}$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.71$^f$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.99$^a$ \\
|
||||
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 7.01$^{c,d}$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.42$^b$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.60$^b$ \\
|
||||
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 6.08$^g$ \\
|
||||
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 6.68$^f$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (6e,7o) active space including valence $\pi$, 3s and $3p_z$ orbitals.
|
||||
$^b$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
||||
$^d$Increasing the $\pi$ $3p_x$ active space leads to strong mixing in the zeroth-order wavefunction requiring QD-NEVPT2 (see Pastore et al., Chem. Phys. Lett. 2006, 426, 445--451).
|
||||
$^e$Strong double-excitation character.
|
||||
$^f$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
||||
$^g$Using reference (4e,5o) active space including valence $\pi$ and 3s orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of glyoxal.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Glyoxal &$^1A_u (\Val; n \ra \pis)$ & 2.90$^a$ \\
|
||||
&$^1B_g (\Val; n \ra \pis)$ & 4.31$^a$,4.30$^b$ \\
|
||||
&$^1A_g (\Val; n,n \ra \pis,\pis)$ & 5.52$^a$ \\
|
||||
&$^1B_g (\Val; n \ra \pis)$ & 6.91$^{a,c}$,6.64$^{b,c}$ \\
|
||||
&$^1B_u (\Ryd; n \ra 3p)$ & 7.84$^d$ \\
|
||||
&$^3A_u (\Val; n \ra \pis)$ & 2.49$^a$ \\
|
||||
&$^3B_g (\Val; n \ra \pis)$ & 3.99$^a$ \\
|
||||
&$^3B_u (\Val; \pi \ra \pis)$ & 5.17$^a$ \\
|
||||
&$^3A_g (\Val; \pi \ra \pis)$ & 6.33$^a$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (14e,12o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$ and $\si^*_\text{CO}$ orbitals.
|
||||
$^b$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_z$ orbitals.
|
||||
$^c$Non-negligible doubly-excited and Rydberg character.
|
||||
$^d$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of imidazole.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Imidazole &$^1A'' (\Ryd; \pi \ra 3s)$ &5.97$^a$,5.93$^b$ \\
|
||||
&$^1A' (\Val; \pi \ra \pis)$ &6.86$^c$,6.81$^d$,6.73$^e$ \\
|
||||
&$^1A'' (\Val; n \ra \pis)$ &6.97$^f$,6.96$^b$ \\
|
||||
&$^1A' (\Ryd; \pi \ra 3p)$ &7.08$^d$,7.00$^e$ \\
|
||||
&$^3A' (\Val; \pi \ra \pis)$ &4.98$^c$,4.86$^e$ \\
|
||||
&$^3A'' (\Ryd; \pi \ra 3s)$ &5.93$^a$,5.91$^b$ \\
|
||||
&$^3A' (\Val; \pi \ra \pis)$ &6.09$^c$,5.91$^e$ \\
|
||||
&$^3A'' (\Val; n \ra \pis)$ &6.49$^f$,6.48$^b$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (6e,6o) active space including valence $\pi$ and 3s orbitals.
|
||||
$^b$Using reference (8e,7o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^c$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
||||
$^d$Using reference (6e,6o) active space including valence $\pi$ and one $3p_z$ orbitals.
|
||||
$^e$Using reference (6e,9o) active space including valence $\pi$ and four $3p_z$ orbitals.
|
||||
$^f$Using reference (8e,6o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^g$Using reference (8e,9o) active space including valence $\pi$, $n_\text{N}$, two $3p_z$ and 3s orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of isobutene.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Isobutene &$^1B_1 (\Ryd; \pi \ra 3s)$ &6.63$^a$ \\
|
||||
&$^1A_1 (\Ryd; \pi \ra 3p)$ &7.20$^b$ \\
|
||||
&$^3A_1 (\Val; (\pi \ra \pis)$ &4.61$^c$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (4e,5o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and 3s orbitals.
|
||||
$^b$Using reference (4e,5o) active space including valence $\pi$, $\si_\text{CC}$, $\si^*_\text{CC}$ and $3p_x$ orbitals.
|
||||
$^c$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CC}$ and $\si^*_\text{CC}$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of methylenecyclopropene.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Methylenecyclopropene& $^1B_2 (\Val; \pi \ra \pis)$ &4.37$^a$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3s)$ &5.51$^b$,5.49$^c$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3p)$ &6.00$^c$ \\
|
||||
&$^1A_1(\Val; \pi \ra \pis)$ &6.33$^d$,6.36$^e$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ &3.66$^a$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ &4.87$^d$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (4e,4o) active space.
|
||||
$^b$Using reference (6e,6o) active space.
|
||||
$^c$Using reference (4e,5o) active space.
|
||||
$^d$Using reference (4e,6o) active space.
|
||||
$^e$Using reference (4e,7o) active space.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of propynal.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Propynal & $^1A'' (\Val; n \ra \pis)$ &3.95$^a$ \\
|
||||
&$^1A'' (\Val; \pi \ra \pis)$ & 5.50$^a$ \\
|
||||
&$^3A'' (\Val; n \ra \pis)$ & 3.59$^a$ \\
|
||||
&$^3A' (\Val; \pi \ra \pis)$ & 4.63$^b$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrazine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Pyrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 4.17$^a$ \\
|
||||
&$^1A_{u} (\Val; n \ra \pis)$ & 4.77$^a$ \\
|
||||
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.32$^b$,5.37$^c$ \\
|
||||
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.88$^a$ \\
|
||||
&$^1A_{g} (\Ryd; n \ra 3s)$ & 6.70$^d$\\
|
||||
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.75$^a$ \\
|
||||
&$^1B_{1u} (\Val; \pi \ra \pis)$ & 6.38$^b$,6.31$^e$,6.81$^f$ \\
|
||||
&$^1B_{1g} (\Ryd; \pi \ra 3s)$ & 7.33$^g$ \\
|
||||
&$^1B_{2u} (\Ryd; n \ra 3p)$ & 7.25$^c$ \\
|
||||
&$^1B_{1u} (\Ryd; n \ra 3p)$ & 7.42$^e$ \\
|
||||
&$^1B_{1u} (\Val; \pi \ra \pis)$ & 7.29$^b$,6.96$^e$,8.25$^f$\\
|
||||
&$^3B_{3u} (\Val; n \ra \pis)$ & 3.56$^a$ \\
|
||||
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.68$^b$,4.57$^f$ \\
|
||||
&$^3B_{2u} (\Val; (\pi \ra \pis)$ & 4.42$^b$ \\
|
||||
&$^3A_{u} (\Val; n \ra \pis)$ & 4.75$^a$ \\
|
||||
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.21$^a$ \\
|
||||
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.43$^b$,5.35$^f$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3p_y$ orbitals.
|
||||
$^d$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^e$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and $3p_z$ orbitals.
|
||||
$^f$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyridazine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Pyridazine &$^1B_1 (\Val; n \ra \pis)$ & 3.80$^a$ \\
|
||||
&$^1A_2 (\Val; n \ra \pis)$ & 4.40$^a$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 5.58$^b$ \\
|
||||
&$^1A_2 (\Val; n \ra \pis)$ & 5.88$^a$ \\
|
||||
&$^1B_2 (\Ryd; n \ra 3s)$ & 6.21$^c$ \\
|
||||
&$^1B_1 (\Val; n \ra \pis)$ & 6.64$^a$ \\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 7.82$^b$,7.19$^d$,7.10$^e$ \\
|
||||
&$^3B_1 (\Val; n \ra \pis)$ & 3.13$^a$ \\
|
||||
&$^3A_2 (\Val; n \ra \pis)$ & 4.14$^a$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.65$^b$,4.55$^d$,4.49$^e$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.94$^a$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^d$Using reference (6e,9o) active space including valence $\pi$, $n_\text{N}$ and three $3p_x$ orbitals.
|
||||
$^e$Using reference (6e,12o) active space including valence $\pi$, $n_\text{N}$ and six $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyridine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 5.17$^a$,5.15$^b$ \\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.44$^c$,5.31$^d$ \\
|
||||
&$^1A_2 (\Val; n \ra \pis)$ & 5.32$^a$,5.29$^e$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.69$^c$ \\
|
||||
&$^1A_1 (\Ryd; n \ra 3s)$ & 6.99$^e$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.96$^f$,6.86$^e$\\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 8.61$^a$,7.83$^d$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 7.57$^g$,7.45$^b$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.97$^c$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.60$^c$ \\
|
||||
&$^3B_1 (\Val; n \ra \pis)$ & 4.58$^a$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.90$^c$,4.88$^d$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.19$^c$ \\
|
||||
&$^3A_2 (\Val; n \ra \pis)$ & 5.33$^a$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 7.00$^c$,6.29$^d$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (8e,7o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^b$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and $3p_y$ orbitals.
|
||||
$^c$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^d$Using reference (6e,10o) active space including valence $\pi$ and four $3p_x$ orbitals.
|
||||
$^e$Using reference (8e,8o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^d$Using reference (6e,8o) active space including valence $\pi$ and 3s orbitals.
|
||||
$^g$Using reference (6e,7o) active space including valence $\pi$ and $3p_y$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrimidine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Pyrimidine &$^1B_1 (\Val; n \ra \pis)$ & 4.55$^a$ \\
|
||||
&$^1A_2 (\Val; n \ra \pis)$ & 4.84$^a$ \\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.71$^b$,5.57$^d$,5.53$^e$ \\
|
||||
&$^1A_2 (\Val; n \ra \pis)$ & 6.02$^a$ \\
|
||||
&$^1B_1 (\Val; n \ra \pis)$ & 6.40$^a$ \\
|
||||
&$^1B_2 (\Ryd; n \ra 3s)$ & 6.77$^c$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 7.47$^b$,7.11$^e$ \\
|
||||
&$^3B_1 (\Val; n \ra \pis)$ & 4.17$^a$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.84$^b$,4.67$^e$ \\
|
||||
&$^3A_2 (\Val; n \ra \pis)$ & 4.72$^a$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 5.08$^b$,5.01$^e$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^d$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
||||
$^e$Using reference (6e,11o) active space including valence $\pi$ and five $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of pyrrole.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Pyrrole &$^1A_2 (\Ryd; \pi \ra 3s)$ & 5.51$^a$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.32$^b$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.44$^c$ \\
|
||||
&$^1B_2 (\Val; (\pi \ra \pis)$ & 6.48$^{e,f}$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.53$^d$ \\
|
||||
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 6.50$^d$,6.62$^e$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.74$^d$ \\
|
||||
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 5.49$^a$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 5.56$^d$ \\
|
||||
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 6.28$^b$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (6e,6o) active space including valence $\pi$ and 3s orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
||||
$^c$Using reference (6e,7o) active space including valence $\pi$, 3s and $3p_z$ orbitals.
|
||||
$^d$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
||||
$^e$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
||||
$^f$Increasing the $\pi$ $3p_x$ active space leads to strong mixing in the zeroth-order wavefunction requiring a multi-state treatment (see Roos et al., J. Chem. Phys. 2002, 116, 7526--7536).
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of tetrazine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Tetrazine &$^1B_{3u} (\Val; n \ra \pis)$ & 2.35$^a$ \\
|
||||
&$^1A_{u} (\Val; n \ra \pis)$ & 3.58$^a$ \\
|
||||
&$^1A_{g} (\Val; n,n \ra \pis, \pis)$ & 4.61$^a$ \\
|
||||
&$^1B_{1g} (\Val; n \ra \pis)$ & 4.95$^a$ \\
|
||||
&$^1B_{2u} (\Val; \pi \ra \pis)$ & 5.56$^b$ \\
|
||||
&$^1B_{2g} (\Val; n \ra \pis)$ & 5.63$^a$ \\
|
||||
&$^1A_{u} (\Val; n \ra \pis)$ & 5.62$^a$ \\
|
||||
&$^1B_{3g} (\Val; n,n \ra \pis, \pis)$ & 6.15$^a$ \\
|
||||
&$^1B_{2g} (\Val; n \ra \pis)$ & 6.13$^a$ \\
|
||||
&$^1B_{1g} (\Val; n \ra \pis)$ & 6.76$^a$ \\
|
||||
&$^3B_{3u} (\Val; n \ra \pis)$ & 1.73$^a$ \\
|
||||
&$^3A_{u} (\Val; n \ra \pis)$ & 3.36$^a$ \\
|
||||
&$^3B_{1g} (\Val; n \ra \pis)$ & 4.24$^a$ \\
|
||||
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 4.80$^b$,4.70$^a$ \\
|
||||
&$^3B_{2u} (\Val; \pi \ra \pis)$ & 4.58$^b$ \\
|
||||
&$^3B_{2g} (\Val; n \ra \pis)$ & 5.27$^a$ \\
|
||||
&$^3A_{u} (\Val; n \ra \pis)$ & 5.13$^a$ \\
|
||||
&$^3B_{3g} (\Val; n,n \ra \pis, \pis)$ & 5.51$^a$ \\
|
||||
&$^3B_{1u} (\Val; \pi \ra \pis)$ & 5.64$^b$,5.56$^c$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (14e,10o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thioacetone.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Thioacetone &$^1A_2 (\Val; n \ra \pis)$ & 2.55$^a$ \\
|
||||
&$^1B_2 (\Ryd; n \ra 4s)$ & 5.72$^b$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 6.09$^c$,6.24$^d$ \\
|
||||
&$^1B_2 (\Ryd; n \ra 4p)$ & 6.62$^b$ \\
|
||||
&$^1A_1 (\Ryd; n \ra 4p)$ & 6.52$^d$ \\
|
||||
&$^3A_2 (\Val; n \ra \pis)$ & 2.32$^a$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 3.48$^c$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (6e,5o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
||||
$^b$Using reference (6e,7o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$, 4s and $4p_z$ orbitals.
|
||||
$^c$Using reference (4e,4o) active space including valence $\pi$, $\si_\text{CO}$ and $\si^*_\text{CO}$ orbitals.
|
||||
$^d$Using reference (6e,6o) active space including valence $\pi$, $n_\text{O}$, $\si_\text{CO}$, $\si^*_\text{CO}$ and $4p_y$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thiophene.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Thiophene &$^1A_1 (\Val; \pi \ra \pis)$ & 5.84$^a$ \\
|
||||
&$^1B_2 (\Val; \pi \ra \pis)$ & 5.64$^a$,5.54$^b$,6.10$^c$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.20$^d$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3p)$ & 6.19$^e$ \\
|
||||
&$^1A_2 (\Ryd; \pi \ra 3p)$ & 6.40$^e$,6.52$^f$ \\
|
||||
&$^1B_1 (\Ryd; \pi \ra 3s)$ & 6.73$^d$, 6.71$^f$ \\
|
||||
&$^1B_2 (\Ryd; \pi \ra 3p)$ & 77.42$^b$,7.25$^c$ \\
|
||||
&$^1A_1 (\Val; \pi \ra \pis)$ & 7.39$^{a,h}$ \\
|
||||
&$^3B_2 (\Val; \pi \ra \pis)$ & 4.13$^a$ \\
|
||||
&$^3A_1 (\Val; \pi \ra \pis)$ & 4.84$^a$ \\
|
||||
&$^3B_1 (\Ryd; \pi \ra 3p)$ & 5.98$^e$ \\
|
||||
&$^3A_2 (\Ryd; \pi \ra 3s)$ & 6.14$^d$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (6e,5o) active space including valence $\pi$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
|
||||
$^c$Using reference (6e,7o) active space including valence $\pi$ and two $3p_x$ orbitals.
|
||||
$^d$Using reference (6e,6o) active space including valence $\pi$ and 3s orbitals.
|
||||
$^e$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
|
||||
$^f$Using reference (6e,7o) active space including valence $\pi$, 3s and $3p_y$ orbitals.
|
||||
$^g$Using reference (6e,8o) active space including valence $\pi$, 3s, $3p_y$ and $3p_z$ orbitals.
|
||||
$^h$Strong double-excitation character.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of thiopropynal.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2$^a$ \\
|
||||
\hline
|
||||
Thiopropynal &$^1A'' (\Val; n \ra \pis)$ & 2.05 \\
|
||||
&$^3A'' (\Val; n \ra \pis)$ & 1.81 \\
|
||||
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$All calculations using reference (8e,7o) active space including valence $\pi$ and $n_\text{O}$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\begin{table}
|
||||
\caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of triazine.}
|
||||
\begin{tabularx}{\textwidth}{XXX}
|
||||
\hline
|
||||
Molecule & State & NEVPT2 \\
|
||||
\hline
|
||||
Triazine &$^1A_1'' (\Val; n \ra \pis)$ & 4.61$^a$ \\
|
||||
&$^1A_2'' (\Val; n \ra \pis)$ & 4.89$^a$ \\
|
||||
&$^1E'' (\Val; n \ra \pis)$ & 4.88$^a$ \\
|
||||
&$^1A_2' (\Val; \pi \ra \pis)$ & 6.10$^b$,6.15$^c$,5.95$^d$ \\
|
||||
&$^1A_1' (\Val; \pi \ra \pis)$ & 7.06$^b$,7.30$^d$ \\
|
||||
&$^1E' (\Ryd; n \ra 3s)$ & 7.45$^c$ \\
|
||||
&$^1E'' (\Val; n \ra \pis)$ & 7.98$^a$ \\
|
||||
&$^1E' (\Val; \pi \ra \pis)$ & 7.74$^b$,8.34$^d$ \\
|
||||
&$^3A_2'' (\Val; n \ra \pis)$ & 4.51$^a$ \\
|
||||
&$^3E'' (\Val; n \ra \pis)$ & 4.61$^a$ \\
|
||||
&$^3A_1'' (\Val; n \ra \pis)$ & 4.71$^a$ \\
|
||||
&$^3A_1' (\Val; \pi \ra \pis)$ & 5.20$^b$,5.05$^d$ \\
|
||||
&$^3E' (\Val; \pi \ra \pis)$ & 5.83$^b$,5.73$^d$ \\
|
||||
&$^3A_2' (\Val; (\pi \ra \pis)$ & 5.83$^b$,6.36$^d$ \\
|
||||
\hline
|
||||
\end{tabularx}
|
||||
\begin{flushleft}
|
||||
\begin{footnotesize}
|
||||
$^a$Using reference (12e,9o) active space including valence $\pi$ and $n_\text{N}$ orbitals.
|
||||
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
|
||||
$^c$Using reference (12e,10o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals.
|
||||
$^d$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
|
||||
\end{footnotesize}
|
||||
\end{flushleft}
|
||||
\end{table}
|
||||
|
||||
|
||||
\clearpage
|
||||
|
||||
\section{sCI results}
|
||||
\section{Selected CI results}
|
||||
|
||||
\begin{landscape}
|
||||
\begin{footnotesize}
|
||||
@ -824,7 +1584,7 @@ Thiopropynal & $^1A'' (\Val; n \ra \pis)$ & $15\,782\,429$ & $2.07$ & $2.0
|
||||
\LTcapwidth=\textwidth
|
||||
\begin{footnotesize}
|
||||
\begin{longtable}{p{3.73cm}p{3.6cm}p{.55cm}|p{1.2cm}p{1.2cm}p{1.2cm}p{1.2cm}p{1.2cm}p{1.6cm}p{1.2cm}p{1.2cm}}\\
|
||||
\caption{Comparisons between the TBE/{\AVTZ} benchmark (see Table 11) and the results obtained with various computational
|
||||
\caption{Comparisons between the TBE(FC)/{\AVTZ} benchmark (see Table 11) and the results obtained with various computational
|
||||
approaches using the same basis set. STEOM stands for STEOM-CCSD and CC(3) for CCSDR(3).} \label{Table-SI-b1}\\
|
||||
\hline
|
||||
Compound & State & TBE & CIS(D) & CC2 & CCSD & STEOM & CC(3) &CCSDT-3& CC3& ADC(2) \\
|
||||
@ -1082,10 +1842,10 @@ Triazine &$^1A_1'' (\Val; n \ra \pis)$ & 4.72 &4.59 &4.64 &4.92& 4.62 &4.
|
||||
|
||||
\clearpage
|
||||
|
||||
\subsection{MSE determined for the subsets}
|
||||
\subsection{Statistical analysis}
|
||||
|
||||
\begin{table}[htp]
|
||||
\caption{MSE in eV obtained for various subsets of transition energies.}
|
||||
\caption{MSE (in eV) obtained for various subsets of transition energies.}
|
||||
\label{Table-SI-b2}
|
||||
\begin{tabular}{lcccccc}
|
||||
\hline
|
||||
|
||||
Loading…
Reference in New Issue
Block a user