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\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
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acetone.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Acetone & $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 4.57$ ^ a $ ,4.48$ ^ b $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 s ) $ & 6.81$ ^ c $ \\
& $ ^ 1 A _ 2 ( \Ryd ; n \ra 3 p ) $ & 7.65$ ^ b $ \\
& $ ^ 1 A _ 1 ( \Ryd ; n \ra 3 p ) $ & 7.75$ ^ d $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 p ) $ & 7.91$ ^ c $ \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 4.20$ ^ a $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.28$ ^ e $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (6e,5o) active space including valence $ \pi $ , $ n _ \text { O } $ , $ \si _ \text { CO } $ and $ \si ^ * _ \text { CO } $ orbitals.
$ ^ b $ Using reference (6e,6o) active space including valence $ \pi $ , $ n _ \text { O } $ , $ \si _ \text { CO } $ , $ \si ^ * _ \text { CO } $ and $ 3 p _ x $ orbitals.
$ ^ c $ Using reference (6e,7o) active space including valence $ \pi $ , $ n _ \text { O } $ , $ \si _ \text { CO } $ , $ \si ^ * _ \text { CO } $ , 3s and $ 3 p _ z $ orbitals.
$ ^ d $ Using reference (6e,6o) active space including valence $ \pi $ , $ n _ \text { O } $ , $ \si _ \text { CO } $ , $ \si ^ * _ \text { CO } $ and $ 3 p _ y $ orbitals.
$ ^ e $ Using reference (4e,4o) active space including valence $ \pi $ , $ \si _ \text { CO } $ and $ \si ^ * _ \text { CO } $ orbitals.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of acrolein.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Acrolein & $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 3.76$ ^ a $ ,3.73$ ^ b $ \\
& $ ^ 1 A' ( \Val ; \pi \ra \pis ) $ & 6.67$ ^ a $ \\
& $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 7.16$ ^ { a,c } $ ,7.57$ ^ { b,c } $ \\
& $ ^ 1 A' ( \Ryd ; n \ra 3 s ) $ & 7.05$ ^ a $ \\
& $ ^ 3 A'' ( \Val ; n \ra \pis ) $ & 3.46$ ^ a $ ,3.44$ ^ b $ \\
& $ ^ 3 A' ( \Val ; \pi \ra \pis ) $ & 3.95$ ^ a $ \\
& $ ^ 3 A' ( \Val ; \pi \ra \pis ) $ & 6.23$ ^ a $ \\
& $ ^ 3 A'' ( \Val ; n \ra \pis ) $ & 6.83$ ^ { a,d } $ ,7.06$ ^ { b,d } $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (12e,12o) active space including valence $ \pi $ , $ \si _ \text { CC } $ , $ \si _ \text { CO } $ , $ \si ^ * _ \text { CC } $ , $ \si ^ * _ \text { CO } $ , $ n _ \text { O } $ and 3s orbitals.
$ ^ b $ Using reference (12e,13o) active space including valence $ \pi $ , $ \si _ \text { CC } $ , $ \si _ \text { CO } $ , $ \si ^ * _ \text { CC } $ , $ \si ^ * _ \text { CO } $ , $ n _ \text { O } $ , 3s and $ 3 p _ z $ orbitals.
$ ^ c $ Substantial Rydberg and doubly-excited character.
$ ^ d $ Substantial doubly-excited character.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of benzene.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Benzene & $ ^ 1 B _ { 2 u } ( \Val ; \pi \ra \pis ) $ & 5.32$ ^ a $ ,5.32$ ^ b $ \\
& $ ^ 1 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 6.01$ ^ a $ ,6.43$ ^ b $ \\
& $ ^ 1 E _ { 1 g } ( \Ryd ; \pi \ra 3 s ) $ & 6.75$ ^ c $ \\
& $ ^ 1 A _ { 2 u } ( \Ryd ; \pi \ra 3 p ) $ & 7.40$ ^ d $ \\
& $ ^ 1 E _ { 2 u } ( \Ryd ; \pi \ra 3 p ) $ & 7.45$ ^ d $ \\
& $ ^ 3 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 4.44$ ^ a $ ,4.32$ ^ b $ \\
& $ ^ 3 E _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 4.99$ ^ a $ ,4.92$ ^ b $ \\
& $ ^ 3 B _ { 2 u } ( \Val ; \pi \ra \pis ) $ & 5.30$ ^ a $ ,5.51$ ^ b $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
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$ ^ a $ Using reference (6e,6o) active space including valence $ \pi $ orbitals.
$ ^ b $ Using reference (6e,9o) active space including valence $ \pi $ and three $ 3 p _ z $ orbitals.
$ ^ c $ Using reference (6e,7o) active space including valence $ \pi $ and 3s orbitals.
$ ^ d $ Using reference (6e,8o) active space including valence $ \pi $ , $ 3 p _ x $ and $ 3 p _ y $ orbitals.
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\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of butadiene.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Butadiene & $ ^ 1 B _ u ( \Val ; \pi \ra \pis ) $ & 6.04$ ^ a $ ,6.73$ ^ b $ ,6.68$ ^ c $ \\
& $ ^ 1 B _ g ( \Ryd ; \pi \ra 3 s ) $ & 6.44$ ^ d $ \\
& $ ^ 1 A _ g ( \Val ; \pi \ra \pis ) $ & 6.70$ ^ a $ \\
& $ ^ 1 A _ u ( \Ryd ; \pi \ra 3 p ) $ & 6.84$ ^ e $ \\
& $ ^ 1 A _ u ( \Ryd ; \pi \ra 3 p ) $ & 7.01$ ^ e $ \\
& $ ^ 1 B _ u ( \Ryd ; \pi \ra 3 p ) $ & 6.99$ ^ b $ ,7.45$ ^ c $ \\
& $ ^ 3 B _ u ( \Val ; \pi \ra \pis ) $ & 3.40$ ^ a $ \\
& $ ^ 3 A _ g ( \Val ; \pi \ra \pis ) $ & 5.30$ ^ a $ \\
& $ ^ 3 B _ g ( \Ryd ; \pi \ra 3 s ) $ & 6.38$ ^ d $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (10e,10o) active space including valence $ \pi $ , $ \si _ \text { CC } $ and $ \si ^ * _ \text { CC } $ orbitals.
$ ^ b $ Using reference (10e,11o) active space including valence $ \pi $ , $ \si _ \text { CC } $ , $ \si ^ * _ \text { CC } $ and $ 3 p _ z $ orbitals.
$ ^ c $ Using reference (4e,8o) active space including valence $ \pi $ and four $ 3 p _ z $ .
$ ^ d $ Using reference (10e,11o) active space including valence $ \pi $ , $ \si _ \text { CC } $ , $ \si ^ * _ \text { CC } $ and 3s orbitals.
$ ^ e $ Using reference (10e,12o) active space including valence $ \pi $ , $ \si _ \text { CC } $ , $ \si ^ * _ \text { CC } $ , $ 3 p _ x $ and $ 3 p _ y $ orbitals.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoacetylene.}
\begin { tabularx} { \textwidth } { XXX}
\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 \\
& $ ^ 1 \Delta ( \Val ; \pi \ra \pis ) $ & 6.10 \\
& $ ^ 3 \Sigma ^ + ( \Val ; \pi \ra \pis ) $ & 4.45 \\
& $ ^ 3 \Delta ( \Val ; \pi \ra \pis ) $ & 5.19 \\
& $ ^ 1 A'' [ \mathrm { F } ] ( \Val ; \pi \ra \pis ) $ & 3.50 \\
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\hline
\end { tabularx}
\begin { flushleft}
\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}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoformaldehyde.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Cyanoformaldehyde & $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 3.98$ ^ a $ \\
& $ ^ 1 A'' ( \Val ; \pi \ra \pis ) $ & 6.44$ ^ a $ \\
& $ ^ 3 A'' ( \Val ; n \ra \pis ) $ & 3.58$ ^ a $ \\
& $ ^ 3 A' ( \Val ; \pi \ra \pis ) $ & 5.35$ ^ b $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (8e,7o) active space including valence $ \pi $ and $ n _ \text { O } $ orbitals.
$ ^ b $ Using reference (6e,6o) active space including valence $ \pi $ orbitals.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanogen.}
\begin { tabularx} { \textwidth } { XXX}
\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 \\
& $ ^ 1 \Delta _ u ( \Val ; \pi \ra \pis ) $ & 6.66 \\
& $ ^ 3 \Sigma _ u ^ + ( \Val ; \pi \ra \pis ) $ & 4.88 \\
& $ ^ 1 \Sigma _ u ^ - [ \mathrm { F } ] ( \Val ; \pi \ra \pis ) $ & 4.97 \\
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\hline
\end { tabularx}
\begin { flushleft}
\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}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopentadiene.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
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Cyclopentadiene & $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.96$ ^ a $ ,4.92$ ^ b $ ,5.65$ ^ c $ \\
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& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 5.92$ ^ d $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.42$ ^ e $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.59$ ^ d $ \\
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& $ ^ 1 B _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.58$ ^ b $ ,6.60$ ^ c $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.75$ ^ { a,f } $ \\
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& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 3.41$ ^ a $ \\
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& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.30$ ^ a $ \\
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& $ ^ 3 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 5.73$ ^ g $ \\
& $ ^ 3 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.40$ ^ e $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (4e,4o) active space including valence $ \pi $ orbitals.
$ ^ b $ Using reference (4e,5o) active space including valence $ \pi $ and $ 3 p _ x $ orbitals.
$ ^ c $ Using reference (4e,8o) active space including valence $ \pi $ and four $ 3 p _ x $ orbitals.
$ ^ d $ Using reference (4e,6o) active space including valence $ \pi $ , 3s and $ 3 p _ z $ orbitals.
$ ^ e $ Using reference (4e,5o) active space including valence $ \pi $ and $ 3 p _ y $ orbitals.
$ ^ f $ Strong double-excitation character.
$ ^ g $ Using reference (4e,5o) active space including valence $ \pi $ and 3s orbitals.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenone.}
\begin { tabularx} { \textwidth } { XXX}
\hline
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Molecule & State & NEVPT2$ ^ a $ \\
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\hline
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Cyclopropenone & $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 4.04 \\
& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 5.85 \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 s ) $ & 6.51 \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis $ ) & 6.82 \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 p ) $ & 7.07 \\
& $ ^ 1 A _ 1 ( \Ryd ; n \ra 3 p ) $ & 7.28 \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 8.19 \\
& $ ^ 3 B _ 1 ( \Val ; n \ra \pis ) $ & 3.51 \\
& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 5.10 \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 5.60 \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 7.16 \\
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\hline
\end { tabularx}
\begin { flushleft}
\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}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenethione.}
\begin { tabularx} { \textwidth } { XXX}
\hline
Molecule & State & NEVPT2 \\
\hline
Cyclopropenethione & $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 3.52$ ^ a $ \\
& $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 3.50$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.77$ ^ b $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 s ) $ & 5.35$ ^ b $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.54$ ^ c $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 p ) $ & 5.99$ ^ b $ \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 3.38$ ^ a $ \\
& $ ^ 3 B _ 1 ( \Val ; n \ra \pis ) $ & 3.40$ ^ a $ \\
& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.21$ ^ c $ ,4.17$ ^ b $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 4.13$ ^ c $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (6e,5o) active space.
$ ^ b $ Using reference (6e,7o) active space.
$ ^ c $ Using reference (4e,4o) active space.
\end { footnotesize}
\end { flushleft}
\end { table}
\begin { table}
\caption { NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of diacetylene.}
\begin { tabularx} { \textwidth } { XXX}
\hline
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Molecule & State & NEVPT2$ ^ a $ \\
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\hline
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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 \\
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\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
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$ ^ a $ All calculations using a full valence $ \pi $ active space of (8e,8o).
2019-12-04 15:41:30 +01:00
\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 & $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 6.28$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 5.92$ ^ b $ ,6.20$ ^ { c,d } $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.77$ ^ { b,e } $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.71$ ^ f $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.99$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 7.01$ ^ { c,d } $ \\
& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.42$ ^ b $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.60$ ^ b $ \\
& $ ^ 3 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 6.08$ ^ g $ \\
& $ ^ 3 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.68$ ^ f $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
$ ^ a $ Using reference (6e,7o) active space including valence $ \pi $ , 3s and $ 3 p _ z $ orbitals.
$ ^ b $ Using reference (6e,5o) active space including valence $ \pi $ orbitals.
$ ^ c $ Using reference (6e,6o) active space including valence $ \pi $ and $ 3 p _ x $ orbitals.
$ ^ d $ Increasing the $ \pi $ $ 3 p _ 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 $ 3 p _ 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 & $ ^ 1 A _ u ( \Val ; n \ra \pis ) $ & 2.90$ ^ a $ \\
& $ ^ 1 B _ g ( \Val ; n \ra \pis ) $ & 4.31$ ^ a $ ,4.30$ ^ b $ \\
& $ ^ 1 A _ g ( \Val ; n,n \ra \pis , \pis ) $ & 5.52$ ^ a $ \\
& $ ^ 1 B _ g ( \Val ; n \ra \pis ) $ & 6.91$ ^ { a,c } $ ,6.64$ ^ { b,c } $ \\
& $ ^ 1 B _ u ( \Ryd ; n \ra 3 p ) $ & 7.84$ ^ d $ \\
& $ ^ 3 A _ u ( \Val ; n \ra \pis ) $ & 2.49$ ^ a $ \\
& $ ^ 3 B _ g ( \Val ; n \ra \pis ) $ & 3.99$ ^ a $ \\
& $ ^ 3 B _ u ( \Val ; \pi \ra \pis ) $ & 5.17$ ^ a $ \\
& $ ^ 3 A _ g ( \Val ; \pi \ra \pis ) $ & 6.33$ ^ a $ \\
\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
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$ ^ 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 $ 3 p _ z $ orbitals.
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$ ^ c $ Non-negligible doubly-excited and Rydberg character.
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$ ^ 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 $ 3 p _ x $ orbitals.
2019-12-04 15:41:30 +01:00
\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 & $ ^ 1 A'' ( \Ryd ; \pi \ra 3 s ) $ & 5.97$ ^ a $ ,5.93$ ^ b $ \\
& $ ^ 1 A' ( \Val ; \pi \ra \pis ) $ & 6.86$ ^ c $ ,6.81$ ^ d $ ,6.73$ ^ e $ \\
& $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 6.97$ ^ f $ ,6.96$ ^ b $ \\
& $ ^ 1 A' ( \Ryd ; \pi \ra 3 p ) $ & 7.08$ ^ d $ ,7.00$ ^ e $ \\
& $ ^ 3 A' ( \Val ; \pi \ra \pis ) $ & 4.98$ ^ c $ ,4.86$ ^ e $ \\
& $ ^ 3 A'' ( \Ryd ; \pi \ra 3 s ) $ & 5.93$ ^ a $ ,5.91$ ^ b $ \\
& $ ^ 3 A' ( \Val ; \pi \ra \pis ) $ & 6.09$ ^ c $ ,5.91$ ^ e $ \\
& $ ^ 3 A'' ( \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 $ 3 p _ z $ orbitals.
$ ^ e $ Using reference (6e,9o) active space including valence $ \pi $ and four $ 3 p _ 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 $ 3 p _ 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 & $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 s ) $ & 6.63$ ^ a $ \\
& $ ^ 1 A _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 7.20$ ^ b $ \\
& $ ^ 3 A _ 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 $ 3 p _ 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& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.37$ ^ a $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 s ) $ & 5.51$ ^ b $ ,5.49$ ^ c $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.00$ ^ c $ \\
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& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.33$ ^ d $ ,6.36$ ^ e $ \\
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& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 3.66$ ^ a $ \\
& $ ^ 3 A _ 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 & $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 3.95$ ^ a $ \\
& $ ^ 1 A'' ( \Val ; \pi \ra \pis ) $ & 5.50$ ^ a $ \\
& $ ^ 3 A'' ( \Val ; n \ra \pis ) $ & 3.59$ ^ a $ \\
& $ ^ 3 A' ( \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 & $ ^ 1 B _ { 3 u } ( \Val ; n \ra \pis ) $ & 4.17$ ^ a $ \\
& $ ^ 1 A _ { u } ( \Val ; n \ra \pis ) $ & 4.77$ ^ a $ \\
& $ ^ 1 B _ { 2 u } ( \Val ; \pi \ra \pis ) $ & 5.32$ ^ b $ ,5.37$ ^ c $ \\
& $ ^ 1 B _ { 2 g } ( \Val ; n \ra \pis ) $ & 5.88$ ^ a $ \\
& $ ^ 1 A _ { g } ( \Ryd ; n \ra 3 s ) $ & 6.70$ ^ d $ \\
& $ ^ 1 B _ { 1 g } ( \Val ; n \ra \pis ) $ & 6.75$ ^ a $ \\
& $ ^ 1 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 6.38$ ^ b $ ,6.31$ ^ e $ ,6.81$ ^ f $ \\
& $ ^ 1 B _ { 1 g } ( \Ryd ; \pi \ra 3 s ) $ & 7.33$ ^ g $ \\
& $ ^ 1 B _ { 2 u } ( \Ryd ; n \ra 3 p ) $ & 7.25$ ^ c $ \\
& $ ^ 1 B _ { 1 u } ( \Ryd ; n \ra 3 p ) $ & 7.42$ ^ e $ \\
& $ ^ 1 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 7.29$ ^ b $ ,6.96$ ^ e $ ,8.25$ ^ f $ \\
& $ ^ 3 B _ { 3 u } ( \Val ; n \ra \pis ) $ & 3.56$ ^ a $ \\
& $ ^ 3 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 4.68$ ^ b $ ,4.57$ ^ f $ \\
& $ ^ 3 B _ { 2 u } ( \Val ; ( \pi \ra \pis ) $ & 4.42$ ^ b $ \\
& $ ^ 3 A _ { u } ( \Val ; n \ra \pis ) $ & 4.75$ ^ a $ \\
& $ ^ 3 B _ { 2 g } ( \Val ; n \ra \pis ) $ & 5.21$ ^ a $ \\
& $ ^ 3 B _ { 1 u } ( \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 $ 3 p _ 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 $ 3 p _ z $ orbitals.
$ ^ f $ Using reference (6e,9o) active space including valence $ \pi $ and three $ 3 p _ 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 & $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 3.80$ ^ a $ \\
& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 4.40$ ^ a $ \\
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& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.58$ ^ b $ \\
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& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 5.88$ ^ a $ \\
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& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 s ) $ & 6.21$ ^ c $ \\
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& $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 6.64$ ^ a $ \\
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& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 7.82$ ^ b $ ,7.19$ ^ d $ ,7.10$ ^ e $ \\
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& $ ^ 3 B _ 1 ( \Val ; n \ra \pis ) $ & 3.13$ ^ a $ \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 4.14$ ^ a $ \\
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& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.65$ ^ b $ ,4.55$ ^ d $ ,4.49$ ^ e $ \\
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& $ ^ 3 A _ 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.
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$ ^ d $ Using reference (6e,9o) active space including valence $ \pi $ , $ n _ \text { N } $ and three $ 3 p _ x $ orbitals.
2019-12-04 15:41:30 +01:00
$ ^ e $ Using reference (6e,12o) active space including valence $ \pi $ , $ n _ \text { N } $ and six $ 3 p _ 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
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Pyridine & $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 5.17$ ^ a $ ,5.15$ ^ b $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 5.44$ ^ c $ ,5.31$ ^ d $ \\
& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 5.32$ ^ a $ ,5.29$ ^ e $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.69$ ^ c $ \\
& $ ^ 1 A _ 1 ( \Ryd ; n \ra 3 s ) $ & 6.99$ ^ e $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 6.96$ ^ f $ ,6.86$ ^ e $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 8.61$ ^ a $ ,7.83$ ^ d $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 7.57$ ^ g $ ,7.45$ ^ b $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.97$ ^ c $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 4.60$ ^ c $ \\
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& $ ^ 3 B _ 1 ( \Val ; n \ra \pis ) $ & 4.58$ ^ a $ \\
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& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.90$ ^ c $ ,4.88$ ^ d $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.19$ ^ c $ \\
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& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 5.33$ ^ a $ \\
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& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 7.00$ ^ c $ ,6.29$ ^ d $ \\
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\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 $ 3 p _ y $ orbitals.
$ ^ c $ Using reference (6e,6o) active space including valence $ \pi $ orbitals.
2019-12-04 20:33:17 +01:00
$ ^ d $ Using reference (6e,10o) active space including valence $ \pi $ and four $ 3 p _ x $ orbitals.
2019-12-04 15:41:30 +01:00
$ ^ 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 $ 3 p _ 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 & $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 4.55$ ^ a $ \\
& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 4.84$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 5.71$ ^ b $ ,5.57$ ^ d $ ,5.53$ ^ e $ \\
& $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 6.02$ ^ a $ \\
& $ ^ 1 B _ 1 ( \Val ; n \ra \pis ) $ & 6.40$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 3 s ) $ & 6.77$ ^ c $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 7.47$ ^ b $ ,7.11$ ^ e $ \\
& $ ^ 3 B _ 1 ( \Val ; n \ra \pis ) $ & 4.17$ ^ a $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 4.84$ ^ b $ ,4.67$ ^ e $ \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 4.72$ ^ a $ \\
& $ ^ 3 B _ 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 $ 3 p _ x $ orbitals.
$ ^ e $ Using reference (6e,11o) active space including valence $ \pi $ and five $ 3 p _ 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 & $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 5.51$ ^ a $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.32$ ^ b $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.44$ ^ c $ \\
& $ ^ 1 B _ 2 ( \Val ; ( \pi \ra \pis ) $ & 6.48$ ^ { e,f } $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.53$ ^ d $ \\
& $ ^ 1 B _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.50$ ^ d $ ,6.62$ ^ e $ \\
& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.74$ ^ d $ \\
& $ ^ 3 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 5.49$ ^ a $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.56$ ^ d $ \\
& $ ^ 3 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 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 $ 3 p _ y $ orbitals.
$ ^ c $ Using reference (6e,7o) active space including valence $ \pi $ , 3s and $ 3 p _ z $ orbitals.
$ ^ d $ Using reference (6e,5o) active space including valence $ \pi $ orbitals.
$ ^ e $ Using reference (6e,6o) active space including valence $ \pi $ and $ 3 p _ x $ orbitals.
$ ^ f $ Increasing the $ \pi $ $ 3 p _ 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 & $ ^ 1 B _ { 3 u } ( \Val ; n \ra \pis ) $ & 2.35$ ^ a $ \\
& $ ^ 1 A _ { u } ( \Val ; n \ra \pis ) $ & 3.58$ ^ a $ \\
& $ ^ 1 A _ { g } ( \Val ; n,n \ra \pis , \pis ) $ & 4.61$ ^ a $ \\
& $ ^ 1 B _ { 1 g } ( \Val ; n \ra \pis ) $ & 4.95$ ^ a $ \\
& $ ^ 1 B _ { 2 u } ( \Val ; \pi \ra \pis ) $ & 5.56$ ^ b $ \\
& $ ^ 1 B _ { 2 g } ( \Val ; n \ra \pis ) $ & 5.63$ ^ a $ \\
& $ ^ 1 A _ { u } ( \Val ; n \ra \pis ) $ & 5.62$ ^ a $ \\
& $ ^ 1 B _ { 3 g } ( \Val ; n,n \ra \pis , \pis ) $ & 6.15$ ^ a $ \\
& $ ^ 1 B _ { 2 g } ( \Val ; n \ra \pis ) $ & 6.13$ ^ a $ \\
& $ ^ 1 B _ { 1 g } ( \Val ; n \ra \pis ) $ & 6.76$ ^ a $ \\
& $ ^ 3 B _ { 3 u } ( \Val ; n \ra \pis ) $ & 1.73$ ^ a $ \\
& $ ^ 3 A _ { u } ( \Val ; n \ra \pis ) $ & 3.36$ ^ a $ \\
& $ ^ 3 B _ { 1 g } ( \Val ; n \ra \pis ) $ & 4.24$ ^ a $ \\
& $ ^ 3 B _ { 1 u } ( \Val ; \pi \ra \pis ) $ & 4.80$ ^ b $ ,4.70$ ^ a $ \\
& $ ^ 3 B _ { 2 u } ( \Val ; \pi \ra \pis ) $ & 4.58$ ^ b $ \\
& $ ^ 3 B _ { 2 g } ( \Val ; n \ra \pis ) $ & 5.27$ ^ a $ \\
& $ ^ 3 A _ { u } ( \Val ; n \ra \pis ) $ & 5.13$ ^ a $ \\
& $ ^ 3 B _ { 3 g } ( \Val ; n,n \ra \pis , \pis ) $ & 5.51$ ^ a $ \\
& $ ^ 3 B _ { 1 u } ( \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 $ 3 p _ 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 & $ ^ 1 A _ 2 ( \Val ; n \ra \pis ) $ & 2.55$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 4 s ) $ & 5.72$ ^ b $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 6.09$ ^ c $ ,6.24$ ^ d $ \\
& $ ^ 1 B _ 2 ( \Ryd ; n \ra 4 p ) $ & 6.62$ ^ b $ \\
& $ ^ 1 A _ 1 ( \Ryd ; n \ra 4 p ) $ & 6.52$ ^ d $ \\
& $ ^ 3 A _ 2 ( \Val ; n \ra \pis ) $ & 2.32$ ^ a $ \\
& $ ^ 3 A _ 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 $ 4 p _ 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 $ 4 p _ 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 & $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 5.84$ ^ a $ \\
& $ ^ 1 B _ 2 ( \Val ; \pi \ra \pis ) $ & 5.64$ ^ a $ ,5.54$ ^ b $ ,6.10$ ^ c $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 6.20$ ^ d $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 6.19$ ^ e $ \\
& $ ^ 1 A _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 6.40$ ^ e $ ,6.52$ ^ f $ \\
& $ ^ 1 B _ 1 ( \Ryd ; \pi \ra 3 s ) $ & 6.73$ ^ d $ , 6.71$ ^ f $ \\
& $ ^ 1 B _ 2 ( \Ryd ; \pi \ra 3 p ) $ & 77.42$ ^ b $ ,7.25$ ^ c $ \\
& $ ^ 1 A _ 1 ( \Val ; \pi \ra \pis ) $ & 7.39$ ^ { a,h } $ \\
& $ ^ 3 B _ 2 ( \Val ; \pi \ra \pis ) $ & 4.13$ ^ a $ \\
& $ ^ 3 A _ 1 ( \Val ; \pi \ra \pis ) $ & 4.84$ ^ a $ \\
& $ ^ 3 B _ 1 ( \Ryd ; \pi \ra 3 p ) $ & 5.98$ ^ e $ \\
& $ ^ 3 A _ 2 ( \Ryd ; \pi \ra 3 s ) $ & 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 $ 3 p _ x $ orbitals.
$ ^ c $ Using reference (6e,7o) active space including valence $ \pi $ and two $ 3 p _ 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 $ 3 p _ y $ orbitals.
$ ^ f $ Using reference (6e,7o) active space including valence $ \pi $ , 3s and $ 3 p _ y $ orbitals.
$ ^ g $ Using reference (6e,8o) active space including valence $ \pi $ , 3s, $ 3 p _ y $ and $ 3 p _ 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
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Molecule & State & NEVPT2$ ^ a $ \\
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\hline
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Thiopropynal & $ ^ 1 A'' ( \Val ; n \ra \pis ) $ & 2.05 \\
& $ ^ 3 A'' ( \Val ; n \ra \pis ) $ & 1.81 \\
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\hline
\end { tabularx}
\begin { flushleft}
\begin { footnotesize}
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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}
\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 & $ ^ 1 A _ 1 '' ( \Val ; n \ra \pis ) $ & 4.61$ ^ a $ \\
& $ ^ 1 A _ 2 '' ( \Val ; n \ra \pis ) $ & 4.89$ ^ a $ \\
& $ ^ 1 E'' ( \Val ; n \ra \pis ) $ & 4.88$ ^ a $ \\
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& $ ^ 1 A _ 2 ' ( \Val ; \pi \ra \pis ) $ & 6.10$ ^ b $ ,6.15$ ^ c $ ,5.95$ ^ d $ \\
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& $ ^ 1 A _ 1 ' ( \Val ; \pi \ra \pis ) $ & 7.06$ ^ b $ ,7.30$ ^ d $ \\
& $ ^ 1 E' ( \Ryd ; n \ra 3 s ) $ & 7.45$ ^ c $ \\
& $ ^ 1 E'' ( \Val ; n \ra \pis ) $ & 7.98$ ^ a $ \\
& $ ^ 1 E' ( \Val ; \pi \ra \pis ) $ & 7.74$ ^ b $ ,8.34$ ^ d $ \\
& $ ^ 3 A _ 2 '' ( \Val ; n \ra \pis ) $ & 4.51$ ^ a $ \\
& $ ^ 3 E'' ( \Val ; n \ra \pis ) $ & 4.61$ ^ a $ \\
& $ ^ 3 A _ 1 '' ( \Val ; n \ra \pis ) $ & 4.71$ ^ a $ \\
& $ ^ 3 A _ 1 ' ( \Val ; \pi \ra \pis ) $ & 5.20$ ^ b $ ,5.05$ ^ d $ \\
& $ ^ 3 E' ( \Val ; \pi \ra \pis ) $ & 5.83$ ^ b $ ,5.73$ ^ d $ \\
& $ ^ 3 A _ 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 $ 3 p _ x $ orbitals.
\end { footnotesize}
\end { flushleft}
\end { table}
\end { document}