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Pierre-Francois Loos 2022-03-21 16:27:40 +01:00
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\documentclass[aip,jcp,reprint,noshowkeys,superscriptaddress]{revtex4-1}
\usepackage{graphicx,dcolumn,bm,xcolor,microtype,multirow,amscd,amsmath,amssymb,amsfonts,physics,wrapfig,txfonts,siunitx,longtable}
\usepackage{graphicx,dcolumn,bm,xcolor,microtype,multirow,amscd,amsmath,amssymb,amsfonts,physics,wrapfig,txfonts,siunitx,longtable,pifont}
\usepackage[version=4]{mhchem}
%\usepackage{natbib}
%\bibliographystyle{achemso}
@ -65,6 +65,11 @@
]{hyperref}
\urlstyle{same}
\newcommand{\cmark}{\ding{51}}%
\newcommand{\xmark}{\ding{55}}%
\newcommand{\Y}{\textbf{\textcolor{green}{\cmark}}}
\newcommand{\N}{\textbf{\textcolor{red}{\xmark}}}
\begin{document}
% addresses
@ -85,9 +90,9 @@
% Abstract
\begin{abstract}
The present study assesses the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states.
Based on 284 vertical transition energies of various natures extracted from the QUEST database, we show that CASPT3 provides a significant improvement compared to its second-order counterpart, CASPT2. %, with a reduction of the mean absolute from X.XX to X.XX eV.
As already reported, we have also observed that the accuracy of CASPT3 is much less sensitive to the infamous ionization-potential-electron-affinity (IPEA) shift.
Based on 284 vertical transition energies of various natures extracted from the QUEST database, we assess the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states.
When one applies the infamous ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of 0.11 eV.
However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespectively of the type of the transitions, with a small reduction of the mean absolute errors to 0.09 eV when the IPEA shift is switched off
%\bigskip
%\begin{center}
% \boxed{\includegraphics[width=0.4\linewidth]{TOC}}
@ -185,18 +190,7 @@ deviation of the errors (SDE), as well as largest positive and negative deviatio
\label{sec:res}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%% FIGURE 2 %%%
\begin{figure}
\includegraphics[width=\linewidth]{PT2_vs_PT3.pdf}
\caption{Histograms of the errors (in \si{\eV}) obtained for CASPT2 and CASPT3 with and without IPEA shift.
\label{fig:PT2_vs_PT3}}
\end{figure}
%%% %%% %%% %%%
A detailed discussion of each individual molecule can be found in Ref.~\onlinecite{Sarka_2022} where we also report relevant values from the literature.
Here, we focus on global trends.
The exhaustive list of CASPT2 and CASPT3 transitions can be found in Table \ref{tab:BigTab} and are represented in Fig.~\ref{fig:PT2_vs_PT3}.
%%% TABLE I %%%
\begin{longtable*}{cllccccccccc}
\caption{Vertical excitation energies (in \si{\eV}) computed with various multi-reference methods.
The reference TBEs of the QUEST database, their percentage of single excitations $\%T_1$ involved in the transition (computed at the CC3 level), their nature
@ -220,302 +214,311 @@ TBEs listed as ``safe'' are assumed to be chemically accurate (\ie, absolute err
\endfoot
\hline\hline
\endlastfoot
1 &Acetaldehyde &$^1A''(n,\pis)$ &V &91.3 &4.31 &Y &4.62 &4.35 &4.13 &4.44 &4.41\\
2 & &$^3A''(n,\pis)$ &V &97.9 &3.97 &Y &4.28 &3.94 &3.71 &4.06 &4.03\\
3 &Acetone &$^1A_2(n,\pis)$ &V &91.1 &4.47 &Y &4.77 &4.44 &4.19 &4.57 &4.55\\
4 & &$^1B_2(n,3s)$ &R &90.5 &6.46 &Y &5.50 &6.46 &6.35 &6.64 &6.67\\
5 & &$^1A_2(n,3p)$ &R &90.9 &7.47 &Y &7.46 &7.80 &7.55 &7.76 &7.68\\
6 & &$^1A_1(n,3p)$ &R &90.6 &7.51 &Y &7.03 &7.67 &7.46 &7.76 &7.75\\
7 & &$^1B_2(n,3p)$ &R &91.2 &7.62 &Y &6.44 &7.56 &7.47 &7.73 &7.76\\
8 & &$^3A_2(n,\pis)$ &V &97.8 &4.13 &Y &4.47 &4.13 &3.89 &4.27 &4.24\\
9 & &$^3A_1(\pi,\pis)$ &V &98.7 &6.25 &Y &6.22 &6.24 &6.07 &6.26 &6.22\\
10 &Acrolein &$^1A''(n,\pis)$ &V &87.6 &3.78 &Y &3.48 &3.58 &3.46 &3.66 &3.66\\
11 & &$^1A'(\pi,\pis)$ &V &91.2 &6.69 &Y &8.84 &6.93 &6.28 &7.18 &7.05\\
12 & &$^1A''(n,\pis)$ &V &79.4 &6.72 &N &6.76 &6.79 &6.34 &6.88 &6.80\\
13 & &$^1A'(n,3s)$ &R &89.4 &7.08 &Y &7.20 &7.21 &6.98 &7.20 &7.16\\
14 & &$^1A'(\pi,\pis)$ &V &75.0 &7.87 &Y &7.01 &8.10 &7.75 &8.02 &7.95\\
15 & &$^3A''(n,\pis)$ &V &97.0 &3.51 &Y &3.25 &3.28 &3.15 &3.39 &3.40\\
16 & &$^3A'(\pi,\pis)$ &V &98.6 &3.94 &Y &3.89 &4.01 &3.78 &3.96 &3.91\\
17 & &$^3A'(\pi,\pis)$ &V &98.4 &6.18 &Y &5.89 &6.20 &5.93 &6.10 &6.02\\
18 & &$^3A''(n,\pis)$ &V &92.7 &6.54 &N &6.67 &6.65 &6.21 &6.74 &6.66\\
19 &Benzene &$^1B_{2u}(\pi,\pis)$ &V &86.3 &5.06 &Y &4.98 &5.14 &4.66 &5.09 &5.01\\
20 & &$^1B_{1u}(\pi,\pis)$ &V &92.9 &6.45 &Y &7.27 &6.65 &6.23 &6.67 &6.58\\
21 & &$^1E_{1g}(\pi,3s)$ &R &92.8 &6.52 &Y &5.90 &6.70 &6.57 &6.56 &6.51\\
22 & &$^1A_{2u}(\pi,3p)$ &R &93.4 &7.08 &Y &6.14 &7.21 &7.07 &7.07 &7.02\\
23 & &$^1E_{2u}(\pi,3p)$ &R &92.8 &7.15 &Y &6.21 &7.26 &7.12 &7.13 &7.08\\
24 & &$^1E_{2g}(\pi,\pis)$ &V &73.0 &8.28 &Y &8.10 &8.31 &7.82 &8.26 &8.16\\
25 & &$^1A_{1g}(\text{double})$ &V &n.d. &10.55 &N &11.44 &10.24 &9.33 & &\\
26 & &$^3B_{1u}(\pi,\pis)$ &V &98.6 &4.16 &Y &3.85 &4.22 &3.92 &4.14 &4.08\\
27 & &$^3E_{1u}(\pi,\pis)$ &V &97.1 &4.85 &Y &4.85 &4.89 &4.51 &4.87 &4.80\\
28 & &$^3B_{2u}(\pi,\pis)$ &V &98.1 &5.81 &Y &6.75 &5.85 &5.40 &5.90 &5.81\\
29 &Butadiene &$^1B_u(\pi,\pis)$ &V &93.3 &6.22 &Y &6.65 &6.76 &6.52 &6.72 &6.65\\
30 & &$^1B_g(\pi,3s)$ &R &94.1 &6.33 &Y &5.94 &6.49 &6.32 &6.43 &6.38\\
31 & &$^1A_g(\pi,\pis)$ &V &75.1 &6.50 &Y &6.99 &6.74 &6.30 &6.73 &6.66\\
32 & &$^1A_u(\pi,3p)$ &R &94.1 &6.64 &Y &5.95 &6.74 &6.64 &6.70 &6.67\\
33 & &$^1A_u(\pi,3p)$ &R &94.1 &6.80 &Y &6.12 &6.95 &6.84 &6.90 &6.86\\
34 & &$^1B_u(\pi,3p)$ &R &93.8 &7.68 &Y &7.93 &7.60 &7.30 &7.62 &7.54\\
35 & &$^3B_u(\pi,\pis)$ &V &98.4 &3.36 &Y &3.55 &3.40 &3.19 &3.40 &3.35\\
36 & &$^3A_g(\pi,\pis)$ &V &98.7 &5.20 &Y &5.52 &5.32 &4.93 &5.29 &5.19\\
37 & &$^3B_g(\pi,3s)$ &R &97.9 &6.29 &Y &5.89 &6.44 &6.27 &6.38 &6.33\\
38 &Carbon Trimer &$^1\Delta_g(\text{double})$ &R &1.0 &5.22 &Y &4.98 &5.08 &4.85 &5.20 &5.19\\
39 & &$^1\Sigma^+_g(\text{double})$ &R &1.0 &5.91 &Y &5.84 &5.82 &5.58 &5.92 &5.89\\
40 &Cyanoacetylene &$^1\Sigma^-(\pi,\pis)$ &V &94.3 &5.80 &Y &6.54 &5.85 &5.47 &5.89 &5.81\\
41 & &$^1\Delta(\pi,\pis)$ &V &94.0 &6.07 &Y &6.80 &6.13 &5.78 &6.17 &6.09\\
42 & &$^3\Sigma^+(\pi,\pis)$ &V &98.5 &4.44 &Y &4.86 &4.45 &4.04 &4.52 &4.45\\
43 & &$^3\Delta(\pi,\pis)$ &V &98.2 &5.21 &Y &5.64 &5.21 &4.86 &5.26 &5.19\\
44 & &$^1A''[F](\pi,\pis)$ &V &93.6 &3.54 &Y &4.30 &3.67 &3.47 &3.64 &3.58\\
45 &Cyanoformaldehyde &$^1A''(n,\pis)$ &V &89.8 &3.81 &Y &4.02 &3.98 &3.67 &3.94 &3.89\\
46 & &$^1A''(\pi,\pis)$ &V &91.9 &6.46 &Y &7.61 &6.79 &6.43 &6.77 &6.67\\
47 & &$^3A''(n,\pis)$ &V &97.6 &3.44 &Y &3.52 &3.46 &3.25 &3.51 &3.50\\
48 & &$^3A'(\pi,\pis)$ &V &98.4 &5.01 &Y &4.98 &5.25 &5.03 &5.16 &5.12\\
49 &Cyanogen &$^1\Sigma_u^-(\pi,\pis)$ &V &94.1 &6.39 &Y &7.14 &6.40 &6.03 &6.46 &6.39\\
50 & &$^1\Delta_u(\pi,\pis)$ &V &93.4 &6.66 &Y &7.46 &6.70 &6.35 &6.75 &6.68\\
51 & &$^3\Sigma_u^+(\pi,\pis)$ &V &98.5 &4.91 &Y &5.28 &4.85 &4.46 &4.95 &4.89\\
52 & &$^1\Sigma_u^-[F](\pi,\pis)$ &V &93.4 &5.05 &Y &5.68 &5.07 &4.75 &5.11 &5.04\\
53 &Cyclopentadiene &$^1B_2(\pi,\pis)$ &V &93.8 &5.56 &Y &6.71 &5.96 &5.62 &6.06 &5.99\\
54 & &$^1A_2(\pi,3s)$ &R &94.0 &5.78 &Y &5.21 &5.88 &5.78 &5.81 &5.77\\
55 & &$^1B_1(\pi,3p)$ &R &94.2 &6.41 &Y &6.08 &6.59 &6.44 &6.47 &6.41\\
56 & &$^1A_2(\pi,3p)$ &R &93.8 &6.46 &Y &5.78 &6.55 &6.46 &6.45 &6.41\\
57 & &$^1B_2(\pi,3p)$ &R &94.2 &6.56 &Y &6.16 &6.72 &6.56 &6.61 &6.54\\
58 & &$^1A_1(\pi,\pis)$ &V &78.9 &6.52 &N &6.49 &6.63 &6.13 &6.59 &6.50\\
59 & &$^3B_2(\pi,\pis)$ &V &98.4 &3.31 &Y &3.26 &3.34 &3.09 &3.31 &3.26\\
60 & &$^3A_1(\pi,\pis)$ &V &98.6 &5.11 &Y &4.92 &5.14 &4.78 &5.10 &5.03\\
61 & &$^3A_2(\pi,3s)$ &R &97.9 &5.73 &Y &5.53 &5.91 &5.74 &5.81 &5.75\\
62 & &$^3B_1(\pi,3p)$ &R &97.9 &6.36 &Y &6.05 &6.56 &6.40 &6.43 &6.37\\
63 &Cyclopropene &$^1B_1(\sig,\pis)$ &V &92.8 &6.68 &Y &7.48 &6.86 &6.58 &6.85 &6.77\\
64 &                   &$^1B_2(\pi,\pis)$ &V &95.1 &6.79 &Y &7.47 &6.89 &6.47 &6.96 &6.87\\
65 &                   &$^3B_2(\pi,\pis)$ &V &98.0 &4.38 &Y &4.60 &4.47 &4.27 &4.46 &4.40\\
66 &                   &$^3B_1(\sig,\pis)$ &V &98.9 &6.45 &Y &7.08 &6.56 &6.32 &6.55 &6.47\\
67 &Cyclopropenone &$^1B_1(n,\pis)$ &V &87.7 &4.26 &Y &4.92 &4.12 &3.75 &4.40 &4.38\\
68 & &$^1A_2(n,\pis)$ &V &91.0 &5.55 &Y &5.64 &5.62 &5.31 &5.67 &5.64\\
69 & &$^1B_2(n,3s)$ &R &90.8 &6.34 &Y &5.68 &6.28 &6.21 &6.41 &6.44\\
70 & &$^1B_2(\pi,\pis)$ &V &86.5 &6.54 &Y &6.40 &6.54 &6.20 &6.63 &6.62\\
71 & &$^1B_2(n,3p)$ &R &91.1 &6.98 &Y &6.35 &6.84 &6.70 &6.99 &7.01\\
72 & &$^1A_1(n,3p)$ &R &91.2 &7.02 &Y &6.84 &7.27 &7.03 &7.26 &7.24\\
73 & &$^1A_1(\pi,\pis)$ &V &90.8 &8.28 &Y &10.42 &8.96 &8.11 &9.21 &9.07\\
74 & &$^3B_1(n,\pis)$ &V &96.0 &3.93 &Y &4.72 &3.65 &3.28 &4.00 &3.98\\
75 & &$^3B_2(\pi,\pis)$ &V &97.9 &4.88 &Y &4.39 &4.76 &4.60 &4.76 &4.74\\
76 & &$^3A_2(n,\pis)$ &V &97.5 &5.35 &Y &5.40 &5.36 &5.06 &5.44 &5.42\\
77 & &$^3A_1(\pi,\pis)$ &V &98.1 &6.79 &Y &6.59 &6.93 &6.61 &6.86 &6.82\\
78 &Cyclopropenethione &$^1A_2(n,\pis)$ &V &89.6 &3.41 &Y &3.44 &3.43 &3.14 &3.46 &3.40\\
79 & &$^1B_1(n,\pis)$ &V &84.8 &3.45 &Y &3.57 &3.45 &3.17 &3.52 &3.46\\
80 & &$^1B_2(\pi,\pis)$ &V &83.0 &4.60 &Y &4.51 &4.64 &4.35 &4.66 &4.61\\
81 & &$^1B_2(n,3s)$ &R &91.8 &5.34 &Y &4.59 &5.25 &5.15 &5.25 &5.22\\
82 & &$^1A_1(\pi,\pis)$ &V &89.0 &5.46 &Y &6.46 &5.84 &5.32 &5.88 &5.75\\
83 & &$^1B_2(n,3p)$ &R &91.3 &5.92 &Y &5.27 &5.93 &5.86 &5.92 &5.90\\
84 & &$^3A_2(n,\pis)$ &V &97.2 &3.28 &Y &3.26 &3.28 &3.00 &3.33 &3.28\\
85 & &$^3B_1(n,\pis)$ &V &94.5 &3.32 &Y &3.51 &3.35 &3.07 &3.42 &3.36\\
86 & &$^3B_2(\pi,\pis)$ &V &96.5 &4.01 &Y &3.80 &3.97 &3.75 &3.99 &3.95\\
87 & &$^3A_1(\pi,\pis)$ &V &98.2 &4.01 &Y &3.83 &4.01 &3.77 &4.00 &3.95\\
88 &Diacetylene &$^1\Sigma_u^-(\pi,\pis)$ &V &94.4 &5.33 &Y &6.13 &5.42 &5.01 &5.45 &5.36\\
89 & &$^1\Delta_u(\pi,\pis)$ &V &94.1 &5.61 &Y &6.39 &5.68 &5.30 &5.72 &5.63\\
90 & &$^3\Sigma_u^+(\pi,\pis)$ &V &98.5 &4.10 &Y &4.54 &4.11 &3.67 &4.17 &4.09\\
91 & &$^3\Delta_u(\pi,\pis)$ &V &98.2 &4.78 &Y &5.28 &4.82 &4.45 &4.86 &4.78\\
92 &Diazomethane &$^1A_2(\pi,\pis)$ &V &90.1 &3.14 &Y &3.27 &3.13 &2.92 &3.09 &3.04\\
93 &                   &$^1B_1(\pi,3s)$ &R &93.8 &5.54 &Y &4.59 &5.50 &5.30 &5.48 &5.45\\
94 &                   &$^1A_1(\pi,\pis)$ &V &91.4 &5.90 &Y &5.65 &6.21 &5.92 &6.18 &6.13\\
95 &                   &$^3A_2(\pi,\pis)$ &V &97.7 &2.79 &Y &3.02 &2.87 &2.67 &2.84 &2.79\\
96 &                   &$^3A_1(\pi,\pis)$ &V &98.6 &4.05 &Y &4.27 &4.10 &3.88 &4.06 &4.01\\
97 &                   &$^3B_1(\pi,3s )$ &R &98.0 &5.35 &Y &4.45 &5.34 &5.15 &5.33 &5.30\\
98 &                   &$^3A_1(\pi,3p)$ &R &98.5 &6.82 &Y &6.34 &7.00 &6.76 &6.96 &6.91\\
99 &                   &$^1A''[F](\pi,\pis)$ &V &87.4 &0.71 &Y &0.72 &0.69 &0.52 &0.66 &0.62\\
100 &Formamide &$^1A''(n,\pis)$ &V &90.8 &5.65 &Y &5.95 &5.66 &5.45 &5.71 &5.67\\
101 & &$^1A'(n,3s)$ &R &88.6 &6.77 &Y &6.17 &6.80 &6.64 &6.82 &6.81\\
102 & &$^1A'(n,3p)$ &R &89.6 &7.38 &N &6.74 &7.45 &7.32 &7.46 &7.46\\
103 & &$^1A'(\pi,\pis)$ &V &89.3 &7.63 &N &8.80 &7.88 &7.13 &7.95 &7.78\\
104 &                   &$^3A''(n,\pis)$ &V &97.7 &5.38 &Y &5.89 &5.36 &5.16 &5.41 &5.37\\
105 &                   &$^3A'(\pi,\pis)$ &V &98.2 &5.81 &Y &6.10 &5.88 &5.62 &5.91 &5.87\\
106 &Furan &$^1A_2(\pi,3s)$ &R &93.8 &6.09 &Y &5.26 &6.16 &6.04 &6.06 &6.02\\
107 & &$^1B_2(\pi,\pis)$ &V &93.0 &6.37 &Y &7.78 &6.59 &6.02 &6.80 &6.71\\
108 & &$^1A_1(\pi,\pis)$ &V &92.4 &6.56 &Y &6.73 &6.66 &6.10 &6.69 &6.62\\
109 & &$^1B_1(\pi,3p)$ &R &93.9 &6.64 &Y &6.07 &6.79 &6.63 &6.65 &6.60\\
110 & &$^1A_2(\pi,3p)$ &R &93.6 &6.81 &Y &5.87 &6.87 &6.77 &6.76 &6.72\\
111 & &$^1B_2(\pi,3p)$ &R &93.5 &7.24 &Y &6.54 &7.11 &6.84 &6.96 &6.88\\
112 & &$^3B_2(\pi,\pis)$ &V &98.4 &4.20 &Y &3.94 &4.26 &4.01 &4.17 &4.12\\
113 & &$^3A_1(\pi,\pis)$ &V &98.1 &5.46 &Y &5.41 &5.50 &5.09 &5.47 &5.40\\
114 & &$^3A_2(\pi,3s)$ &R &97.9 &6.02 &Y &5.57 &6.16 &5.99 &6.05 &5.99\\
115 & &$^3B_1(\pi,3p)$ &R &97.9 &6.59 &Y &6.04 &6.76 &6.60 &6.62 &6.56\\
116 &Glyoxal &$^1A_u(n,\pis)$ &V &91.0 &2.88 &Y &3.42 &2.82 &2.51 &2.97 &2.94\\
117 & &$^1B_g(n,\pis)$ &V &88.3 &4.24 &Y &4.68 &4.21 &3.89 &4.36 &4.31\\
118 & &$^1A_g(\text{double})$ &V &0.5 &5.61 &Y &5.92 &5.37 &5.21 &5.53 &5.55\\
119 & &$^1B_g(n,\pis)$ &V &83.9 &6.57 &Y &7.35 &6.52 &5.98 &6.76 &6.72\\
120 & &$^1B_u(n,3p)$ &R &91.7 &7.71 &Y &7.04 &7.61 &7.34 &7.78 &7.81\\
121 & &$^3A_u(n,\pis)$ &V &97.6 &2.49 &Y &3.06 &2.41 &2.12 &2.57 &2.55\\
122 & &$^3B_g(n,\pis)$ &V &97.4 &3.89 &Y &4.61 &3.90 &3.53 &4.04 &4.01\\
123 & &$^3B_u(\pi,\pis)$ &V &98.5 &5.15 &Y &5.46 &5.14 &4.91 &5.17 &5.14\\
124 & &$^3A_g(\pi,\pis)$ &V &98.8 &6.30 &Y &6.69 &6.32 &6.02 &6.33 &6.27\\
125 &Imidazole &$^1A''(\pi,3s)$ &R &93.0 &5.70 &Y &5.04 &5.88 &5.66 &5.74 &5.68\\
126 & &$^1A'(\pi,3p)$ &R &90.0 &6.41 &Y &6.18 &6.69 &6.45 &6.61 &6.56\\
127 & &$^1A''(\pi,3p)$ &R &93.6 &6.50 &Y &5.43 &6.57 &6.47 &6.47 &6.44\\
128 & &$^1A''(n,\pis)$ &V &89.0 &6.71 &Y &7.13 &6.94 &6.57 &6.92 &6.85\\
129 & &$^1A'(\pi,\pis)$ &V &88.9 &6.86 &Y &6.73 &6.88 &6.46 &6.89 &6.83\\
130 & &$^1A'(n,3s)$ &R &89.0 &7.00 &Y &6.36 &7.10 &6.91 &7.09 &7.07\\
131 & &$^3A'(\pi,\pis)$ &V &98.3 &4.74 &Y &4.55 &4.78 &4.52 &4.73 &4.68\\
132 & &$^3A''(\pi,3s)$ &R &97.6 &5.66 &Y &5.03 &5.86 &5.63 &5.72 &5.66\\
133 & &$^3A'(\pi,\pis)$ &V &97.9 &5.74 &Y &5.69 &5.85 &5.48 &5.80 &5.72\\
134 & &$^3A''(n,\pis)$ &V &97.3 &6.31 &Y &6.58 &6.44 &6.10 &6.43 &6.37\\
135 &Isobutene &$^1B_1(\pi,3s)$ &R &94.1 &6.46 &Y &6.21 &6.74 &6.59 &6.64 &6.57\\
136 & &$^1A_1(\pi,3p)$ &R &94.2 &7.01 &Y &6.90 &7.32 &7.14 &7.24 &7.18\\
137 & &$^3A_1(\pi,\pis)$ &V &98.9 &4.53 &Y &4.66 &4.59 &4.41 &4.58 &4.53\\
138 &Ketene &$^1A_2(\pi,\pis)$ &V &91.0 &3.86 &Y &3.98 &3.92 &3.70 &3.90 &3.85\\
139 &                   &$^1B_1(\pi,3s)$ &R &93.9 &6.01 &Y &5.22 &5.99 &5.79 &6.00 &5.97\\
140 & &$^1A_1(\pi,\pis)$ &V &92.4 &7.25 &Y & & &&&\\
141 &                   &$^1A_2(\pi,3p)$ &R &94.4 &7.18 &Y &6.38 &7.25 &7.05 &7.19 &7.15\\
142 &                   &$^3A_2(\pi,\pis)$ &V &91.0 &3.77 &Y &3.92 &3.81 &3.59 &3.79 &3.74\\
143 &                   &$^3A_1(\pi,\pis)$ &V &98.6 &5.61 &Y &5.79 &5.65 &5.43 &5.63 &5.59\\
144 &                   &$^3B_1(\pi,3s)$ &R &98.1 &5.79 &Y &5.05 &5.79 &5.60 &5.80 &5.77\\
145 &                   &$^3A_2(\pi,3p)$ &R &94.4 &7.12 &Y &6.35 &7.22 &7.01 &7.15 &7.11\\
146 &                   &$^1A''[F](\pi,\pis)$ &V &87.9 &1.00 &Y &0.95 &1.05 &0.88 &1.00 &0.95\\
147 &Methylenecycloprope&ne$^1B_2(\pi,\pis)$ &V &85.4 &4.28 &Y &4.47 &4.40 &4.12 &4.39 &4.33\\
148 & &$^1B_1(\pi,3s)$ &R &93.6 &5.44 &Y &4.92 &5.57 &5.44 &5.46 &5.41\\
149 & &$^1A_2(\pi,3p)$ &R &93.3 &5.96 &Y &5.37 &6.09 &5.97 &5.97 &5.92\\
150 & &$^1A_1(\pi,\pis)$ &V &92.8 &6.12 &N &5.37 &6.26 &6.16 &6.17 &6.13\\
151 & &$^3B_2(\pi,\pis)$ &V &97.2 &3.49 &Y &3.44 &3.57 &3.34 &3.55 &3.49\\
152 & &$^3A_1(\pi,\pis)$ &V &98.6 &4.74 &Y &4.60 &4.82 &4.58 &4.77 &4.72\\
153 &Nitrosomethane &$^1A''(n,\pis)$ &V &93.0 &1.96 &Y &2.12 &1.84 &1.60 &1.94 &1.91\\
154 & &$^1A'(\text{double})$ &V &2.5 &4.76 &Y &4.74 &4.69 &4.67 &4.71 &4.71\\
155 &                   &$^1A'(\text{n.d.})$ &R &90.8 &6.29 &Y &5.87 &6.32 &6.07 &6.34 &6.31\\
156 &                  &$^3A''(n,\pis)$ &V &98.4 &1.16 &Y &1.31 &1.00 &0.75 &1.12 &1.09\\
157 &                   &$^3A'(\pi,\pis)$ &V &98.9 &5.60 &Y &5.52 &5.52 &5.37 &5.54 &5.50\\
158 &                   &$^1A''[F](n,\pis)$ &V &92.7 &1.67 &Y &1.83 &1.55 &1.32 &1.66 &1.62\\
159 &Propynal &$^1A''(n,\pis)$ &V &89.0 &3.80 &Y &4.00 &3.92 &3.64 &3.90 &3.86\\
160 & &$^1A''(\pi,\pis)$ &V &92.9 &5.54 &Y &6.62 &5.82 &5.49 &5.81 &5.72\\
161 & &$^3A''(n,\pis)$ &V &97.4 &3.47 &Y &3.52 &3.48 &3.26 &3.52 &3.50\\
162 & &$^3A'(\pi,\pis)$ &V &98.3 &4.47 &Y &4.69 &4.59 &4.30 &4.54 &4.54\\
163 &Pyrazine &$^1B_{3u}(n,\pis)$ &V &90.1 &4.15 &Y &4.76 &4.09 &3.66 &4.31 &4.30\\
164 & &$^1A_u(n,\pis)$ &V &88.6 &4.98 &Y &5.90 &4.76 &4.26 &5.10 &5.10\\
165 & &$^1B_{2u}(\pi,\pis)$ &V &86.9 &5.02 &Y &4.97 &5.13 &4.65 &5.09 &5.03\\
166 & &$^1B_{2g}(n,\pis)$ &V &85.6 &5.71 &Y &5.80 &5.68 &5.27 &5.73 &5.70\\
167 & &$^1A_g(n,3s)$ &R &91.1 &6.65 &Y &6.69 &6.66 &6.27 &6.81 &6.80\\
168 & &$^1B_{1g}(n,\pis)$ &V &84.2 &6.74 &Y &7.16 &6.61 &6.07 &6.78 &6.76\\
169 & &$^1B_{1u}(\pi,\pis)$ &V &92.8 &6.88 &Y &8.04 &7.14 &6.72 &7.20 &7.12\\
170 & &$^1B_{1g}(\pi,3s)$ &R &93.8 &7.21 &Y &6.73 &7.41 &7.27 &7.24 &7.18\\
171 & &$^1B_{2u}(n,3p)$ &R &90.8 &7.24 &Y &7.49 &7.34 &6.93 &7.43 &7.40\\
172 & &$^1B_{1u}(n,3p)$ &R &91.4 &7.44 &Y &7.83 &7.55 &7.08 &7.64 &7.59\\
173 & &$^1B_{1u}(\pi,\pis)$ &V &90.5 &7.98 &N &9.65 &8.59 &7.96 &8.68 &8.57\\
174 & &$^1A_g(\text{double})$ &V &12.0 &8.04 &N & & &&&\\
175 & &$^1A_g(\pi,\pis)$ &V &71.0 &8.69 &N & & &&&\\
176 & &$^3B_{3u}(n,\pis)$ &V &97.3 &3.59 &Y &4.16 &3.49 &3.08 &3.72 &3.71\\
177 & &$^3B_{1u}(\pi,\pis)$ &V &98.5 &4.35 &Y &3.98 &4.44 &4.15 &4.34 &4.28\\
178 & &$^3B_{2u}(\pi,\pis)$ &V &97.6 &4.39 &Y &4.62 &4.44 &4.09 &4.47 &4.41\\
179 & &$^3A_u(n,\pis)$ &V &96.1 &4.93 &Y &5.85 &4.73 &4.21 &5.07 &5.07\\
180 & &$^3B_{2g}(n,\pis)$ &V &97.0 &5.08 &Y &5.25 &5.04 &4.66 &5.14 &5.11\\
181 & &$^3B_{1u}(\pi,\pis)$ &V &97.0 &5.28 &Y &5.15 &5.29 &4.92 &5.25 &5.19\\
182 &Pyridazine &$^1B_1(n,\pis)$ &V &89.0 &3.83 &Y &4.29 &3.74 &3.36 &3.94 &3.92\\
183 & &$^1A_2(n,\pis)$ &V &86.9 &4.37 &Y &4.83 &4.29 &3.87 &4.49 &4.48\\
184 & &$^1A_1(\pi,\pis)$ &V &85.8 &5.26 &Y &5.12 &5.34 &4.87 &5.30 &5.25\\
185 & &$^1A_2(n,\pis)$ &V &86.2 &5.72 &Y &6.26 &5.73 &5.19 &5.93 &5.89\\
186 & &$^1B_2(n,3s)$ &R &88.5 &6.17 &Y &5.99 &6.18 &5.90 &6.28 &6.27\\
187 & &$^1B_1(n,\pis)$ &V &87.0 &6.37 &Y &7.16 &6.50 &5.94 &6.72 &6.67\\
188 & &$^1B_2(\pi,\pis)$ &V &90.6 &6.75 &Y &7.54 &7.26 &6.82 &7.25 &7.17\\
189 & &$^3B_1(n,\pis)$ &V &97.1 &3.19 &Y &3.60 &3.08 &2.72 &3.29 &3.28\\
190 & &$^3A_2(n,\pis)$ &V &96.1 &4.11 &Y &4.49 &4.01 &3.59 &4.20 &4.18\\
191 & &$^3B_2(\pi,\pis)$ &V &98.5 &4.34 &N &3.92 &4.44 &4.13 &4.30 &4.24\\
192 & &$^3A_1(\pi,\pis)$ &V &97.3 &4.82 &Y &4.93 &4.87 &4.48 &4.89 &4.83\\
193 &Pyridine &$^1B_1(n,\pis)$ &V &88.4 &4.95 &Y &5.43 &5.15 &4.81 &5.18 &5.13\\
194 & &$^1B_2(\pi,\pis)$ &V &86.5 &5.14 &Y &5.03 &5.18 &4.76 &5.15 &5.09\\
195 & &$^1A_2(n,\pis)$ &V &87.9 &5.40 &Y &6.30 &5.46 &5.03 &5.63 &5.59\\
196 & &$^1A_1(\pi,\pis)$ &V &92.1 &6.62 &Y &7.90 &6.92 &6.27 &7.04 &6.93\\
197 & &$^1A_1(n,3s)$ &R &89.7 &6.76 &Y &6.40 &6.90 &6.67 &6.97 &6.96\\
198 & &$^1A_2(\pi,3s)$ &R &93.2 &6.82 &Y &6.60 &7.08 &6.87 &6.88 &6.80\\
199 & &$^1B_1(\pi,3p)$ &R &93.6 &7.38 &Y &7.12 &7.70 &7.51 &7.48 &7.40\\
200 & &$^1A_1(\pi,\pis)$ &V &90.5 &7.39 &Y &9.49 &7.66 &6.63 &7.87 &7.70\\
201 & &$^1B_2(\pi,\pis)$ &V &90.0 &7.40 &N &7.45 &7.92 &7.67 &7.80 &7.73\\
202 & &$^3A_1(\pi,\pis)$ &V &98.5 &4.30 &Y &3.98 &4.40 &4.06 &4.29 &4.22\\
203 & &$^3B_1(n,\pis)$ &V &97.0 &4.46 &Y &4.65 &4.48 &4.21 &4.57 &4.55\\
204 & &$^3B_2(\pi,\pis)$ &V &97.3 &4.79 &Y &4.83 &4.86 &4.53 &4.81 &4.74\\
205 & &$^3A_1(\pi,\pis)$ &V &97.1 &5.04 &Y &5.11 &5.09 &4.63 &5.09 &5.02\\
206 & &$^3A_2(n,\pis)$ &V &95.8 &5.36 &Y &5.94 &5.33 &4.96 &5.53 &5.51\\
207 & &$^3B_2(\pi,\pis)$ &V &97.7 &6.24 &Y &6.93 &6.40 &5.99 &6.43 &6.35\\
208 &Pyrimidine &$^1B_1(n,\pis)$ &V &88.6 &4.44 &Y &4.85 &4.44 &4.07 &4.58 &4.55\\
209 & &$^1A_2(n,\pis)$ &V &88.5 &4.85 &Y &5.52 &4.80 &4.36 &5.02 &5.00\\
210 & &$^1B_2(\pi,\pis)$ &V &86.3 &5.38 &Y &5.28 &5.42 &4.98 &5.41 &5.36\\
211 & &$^1A_2(n,\pis)$ &V &86.7 &5.92 &Y &6.70 &5.92 &5.32 &6.16 &6.10\\
212 & &$^1B_1(n,\pis)$ &V &86.7 &6.26 &Y &7.20 &6.31 &5.65 &6.58 &6.53\\
213 & &$^1B_2(n,3s)$ &R &90.3 &6.70 &Y &6.86 &6.85 &6.50 &6.89 &6.86\\
214 & &$^1A_1(\pi,\pis)$ &V &91.5 &6.88 &Y &7.69 &7.31 &6.94 &7.29 &7.22\\
215 & &$^3B_1(n,\pis)$ &V &96.8 &4.09 &Y &4.45 &4.05 &3.67 &4.20 &4.18\\
216 & &$^3A_1(\pi,\pis)$ &V &98.3 &4.51 &N &4.22 &4.57 &4.25 &4.51 &4.44\\
217 & &$^3A_2(n,\pis)$ &V &96.5 &4.66 &Y &5.20 &4.63 &4.16 &4.81 &4.78\\
218 & &$^3B_2(\pi,\pis)$ &V &97.4 &4.96 &Y &5.10 &5.01 &4.60 &5.03 &4.97\\
219 &Pyrrole &$^1A_2(\pi,3s)$ &R &92.9 &5.24 &Y &4.49 &5.44 &5.23 &5.28 &5.23\\
220 & &$^1B_1(\pi,3p)$ &R &92.4 &6.00 &Y &5.22 &6.26 &6.07 &6.08 &6.02\\
221 & &$^1A_2(\pi,3p)$ &R &93.0 &6.00 &Y &4.89 &6.16 &6.02 &6.01 &5.97\\
222 & &$^1B_2(\pi,\pis)$ &V &92.5 &6.26 &Y &7.73 &6.62 &6.36 &6.45 &6.38\\
223 & &$^1A_1(\pi,\pis)$ &V &86.3 &6.30 &Y &6.47 &6.41 &5.84 &6.43 &6.34\\
224 & &$^1B_2(\pi,3p)$ &R &92.6 &6.83 &Y &5.82 &6.75 &6.11 &6.92 &6.82\\
225 & &$^3B_2(\pi,\pis)$ &V &98.3 &4.51 &Y &4.24 &4.57 &4.30 &4.49 &4.44\\
226 & &$^3A_2(\pi,3s)$ &R &97.6 &5.21 &Y &4.47 &5.41 &5.21 &5.26 &5.20\\
227 & &$^3A_1(\pi,\pis)$ &V &97.8 &5.45 &Y &5.52 &5.50 &5.04 &5.49 &5.40\\
228 & &$^3B_1(\pi,3p)$ &R &97.4 &5.91 &Y &5.18 &6.22 &6.03 &6.04 &5.98\\
229 &Streptocyanine-1 &$^1B_2(\pi,\pis)$ &V &88.7 &7.13 &Y &7.82 &7.17 &6.76 &7.28 &7.21\\
230 &                   &$^3B_2(\pi,\pis)$ &V &98.3 &5.52 &Y &5.86 &5.49 &5.22 &5.54 &5.49\\
231 &Tetrazine &$^1B_{3u}(n,\pis)$ &V &89.8 &2.47 &Y &2.99 &2.31 &1.91 &2.54 &2.53\\
232 & &$^1A_u(n,\pis)$ &V &87.9 &3.69 &Y &4.37 &3.49 &3.00 &3.77 &3.78\\
233 & &$^1A_g(\text{double})$ &V &0.7 &4.61 &N &5.42 &4.69 &4.48 &4.85 &4.87\\
234 & &$^1B_{1g}(n,\pis)$ &V &83.1 &4.93 &Y &5.41 &4.83 &4.33 &5.02 &5.00\\
235 & &$^1B_{2u}(\pi,\pis)$ &V &85.4 &5.21 &Y &5.04 &5.31 &4.84 &5.26 &5.23\\
236 & &$^1B_{2g}(n,\pis)$ &V &81.7 &5.45 &Y &5.43 &5.38 &4.90 &5.42 &5.38\\
237 & &$^1A_u(n,\pis)$ &V &87.7 &5.53 &Y &6.37 &5.51 &4.92 &5.80 &5.80\\
238 & &$^1B_{3g}(\text{double})$ &V &0.7 &6.15 &N &6.59 &5.85 &5.22 &6.20 &6.22\\
239 & &$^1B_{2g}(n,\pis)$ &V &80.2 &6.12 &Y &6.79 &5.96 &5.18 &6.27 &6.28\\
240 & &$^1B_{1g}(n,\pis)$ &V &85.1 &6.91 &Y &7.18 &6.59 &5.89 &6.79 &6.72\\
241 & &$^3B_{3u}(n,\pis)$ &V &97.1 &1.85 &Y &2.38 &1.70 &1.31 &1.94 &1.93\\
242 & &$^3A_u(n,\pis)$ &V &96.3 &3.45 &Y &4.06 &3.26 &2.78 &3.52 &3.52\\
243 & &$^3B_{1g}(n,\pis)$ &V &97.0 &4.20 &Y &4.66 &4.10 &3.62 &4.32 &4.30\\
244 & &$^1B_{1u}(\pi,\pis)$ &V &98.5 &4.49 &N &3.90 &4.55 &4.29 &4.39 &4.34\\
245 & &$^3B_{2u}(\pi,\pis)$ &V &97.5 &4.52 &Y &4.68 &4.55 &4.20 &4.60 &4.55\\
246 & &$^3B_{2g}(n,\pis)$ &V &96.4 &5.04 &Y &5.17 &5.02 &4.53 &5.10 &5.07\\
247 & &$^3A_u(n,\pis)$ &V &96.6 &5.11 &Y &6.12 &5.07 &4.44 &5.41 &5.41\\
248 & &$^3B_{3g}(\text{double})$ &V &5.7 &5.51 &N &6.56 &5.39 &4.86 &5.83 &5.85\\
249 & &$^3B_{1u}(\pi,\pis)$ &V &96.6 &5.42 &Y &5.32 &5.46 &5.08 &5.44 &5.39\\
250 &Thioacetone &$^1A_2(n,\pis)$ &V &88.9 &2.53 &Y &2.72 &2.58 &2.33 &2.60 &2.53\\
251 & &$^1B_2(n,3s)$ &R &91.3 &5.56 &Y &4.80 &5.60 &5.48 &5.64 &5.61\\
252 & &$^1A_1(\pi,\pis)$ &V &90.6 &5.88 &Y &6.94 &6.42 &5.98 &6.40 &6.26\\
253 & &$^1B_2(n,3p)$ &R &92.4 &6.51 &Y &5.57 &6.51 &6.40 &6.53 &6.49\\
254 & &$^1A_1(n,3p)$ &R &91.6 &6.61 &Y &6.24 &6.66 &6.41 &6.59 &6.50\\
255 & &$^3A_2(n,\pis)$ &V &97.4 &2.33 &Y &2.52 &2.34 &2.09 &2.38 &2.31\\
256 & &$^3A_1(\pi,\pis)$ &V &98.7 &3.45 &Y &3.52 &3.48 &3.29 &3.48 &3.43\\
257 &Thiophene &$^1A_1(\pi,\pis)$ &V &87.6 &5.64 &Y &6.11 &5.84 &5.21 &5.89 &5.79\\
258 & &$^1B_2(\pi,\pis)$ &V &91.5 &5.98 &Y &6.94 &6.35 &5.89 &6.44 &6.35\\
259 & &$^1A_2(\pi,3s)$ &R &92.6 &6.14 &Y &5.70 &6.28 &6.07 &6.16 &6.10\\
260 & &$^1B_1(\pi,3p)$ &R &90.1 &6.14 &Y &6.02 &6.21 &5.90 &6.16 &6.10\\
261 & &$^1A_2(\pi,3p)$ &R &91.8 &6.21 &Y &6.05 &6.32 &5.98 &6.28 &6.21\\
262 & &$^1B_1(\pi,3s)$ &R &92.8 &6.49 &Y &5.78 &6.57 &6.28 &6.51 &6.44\\
263 & &$^1B_2(\pi,3p)$ &R &92.4 &7.29 &Y &6.80 &7.29 &7.03 &7.20 &7.13\\
264 & &$^1A_1(\pi,\pis)$ &V &86.5 &7.31 &N &8.29 &7.62 &6.85 &7.71 &7.56\\
265 & &$^3B_2(\pi,\pis)$ &V &98.2 &3.92 &Y &3.68 &3.98 &3.71 &3.90 &3.84\\
266 & &$^3A_1(\pi,\pis)$ &V &97.7 &4.76 &Y &4.97 &4.85 &4.39 &4.87 &4.79\\
267 & &$^3B_1(\pi,3p)$ &R &96.6 &5.93 &Y &5.86 &5.97 &5.64 &5.94 &5.88\\
268 & &$^3A_2(\pi,3s)$ &R &97.5 &6.08 &Y &5.65 &6.22 &6.01 &6.11 &6.04\\
269 &Thiopropynal &$^1A''(n,\pis)$ &V &87.5 &2.03 &Y &2.06 &2.05 &1.84 &2.05 &2.00\\
270 & &$^3A''(n,\pis)$ &V &97.2 &1.80 &Y &1.85 &1.81 &1.60 &1.84 &1.79\\
271 &Triazine &$^1A_1''(n,\pis)$ &V &88.3 &4.72 &Y &5.88 &4.62 &3.90 &5.00 &4.99\\
272 & &$^1A_2''(n,\pis)$ &V &88.3 &4.75 &Y &5.14 &4.77 &4.39 &4.90 &4.87\\
273 & &$^1E''(n,\pis)$ &V &88.3 &4.78 &Y &5.51 &4.76 &4.14 &5.01 &4.98\\
274 & &$^1A_2'(\pi,\pis)$ &V &85.7 &5.75 &Y &5.55 &5.76 &5.32 &5.75 &5.72\\
275 & &$^1A_1'(\pi,\pis)$ &V &90.4 &7.24 &Y &8.20 &7.43 &6.89 &7.50 &7.41\\
276 & &$^1E'(n,3s)$ &R &90.9 &7.32 &Y &7.40 &7.48 &7.15 &7.53 &7.49\\
277 & &$^1E''(n,\pis)$ &V &82.6 &7.78 &Y &8.26 &7.75 &7.04 &7.92 &7.90\\
278 & &$^1E'(\pi,\pis)$ &V &90.0 &7.94 &Y &10.03 &8.65 &7.70 &8.63 &8.72\\
279 & &$^3A_2''(n,\pis)$ &V &96.7 &4.33 &Y &4.74 &4.37 &3.99 &4.51 &4.49\\
280 & &$^3E''(n,\pis)$ &V &96.6 &4.51 &Y &5.14 &4.47 &3.88 &4.71 &4.68\\
281 & &$^3A_1''(n,\pis)$ &V &96.2 &4.73 &Y &5.88 &4.70 &3.94 &5.06 &5.04\\
282 & &$^3A_1'(\pi,\pis)$ &V &98.2 &4.85 &Y &4.46 &4.88 &4.55 &4.81 &4.75\\
283 & &$^3E'(\pi,\pis)$ &V &96.9 &5.59 &Y &5.57 &5.62 &5.20 &5.62 &5.57\\
284 & &$^3A_2'(\pi,\pis)$ &V &97.6 &6.62 &Y &7.70 &6.62 &6.12 &6.76 &6.68\\
1 &Acetaldehyde &$^1A''(n,\pis)$ &V &91.3 &4.31 &\Y &4.62 &4.35 &4.13 &4.44 &4.41\\
2 & &$^3A''(n,\pis)$ &V &97.9 &3.97 &\Y &4.28 &3.94 &3.71 &4.06 &4.03\\
3 &Acetone &$^1A_2(n,\pis)$ &V &91.1 &4.47 &\Y &4.77 &4.44 &4.19 &4.57 &4.55\\
4 & &$^1B_2(n,3s)$ &R &90.5 &6.46 &\Y &5.50 &6.46 &6.35 &6.64 &6.67\\
5 & &$^1A_2(n,3p)$ &R &90.9 &7.47 &\Y &7.46 &7.80 &7.55 &7.76 &7.68\\
6 & &$^1A_1(n,3p)$ &R &90.6 &7.51 &\Y &7.03 &7.67 &7.46 &7.76 &7.75\\
7 & &$^1B_2(n,3p)$ &R &91.2 &7.62 &\Y &6.44 &7.56 &7.47 &7.73 &7.76\\
8 & &$^3A_2(n,\pis)$ &V &97.8 &4.13 &\Y &4.47 &4.13 &3.89 &4.27 &4.24\\
9 & &$^3A_1(\pi,\pis)$ &V &98.7 &6.25 &\Y &6.22 &6.24 &6.07 &6.26 &6.22\\
10 &Acrolein &$^1A''(n,\pis)$ &V &87.6 &3.78 &\Y &3.48 &3.58 &3.46 &3.66 &3.66\\
11 & &$^1A'(\pi,\pis)$ &V &91.2 &6.69 &\Y &8.84 &6.93 &6.28 &7.18 &7.05\\
12 & &$^1A''(n,\pis)$ &V &79.4 &6.72 &\N &6.76 &6.79 &6.34 &6.88 &6.80\\
13 & &$^1A'(n,3s)$ &R &89.4 &7.08 &\Y &7.20 &7.21 &6.98 &7.20 &7.16\\
14 & &$^1A'(\pi,\pis)$ &V &75.0 &7.87 &\Y &7.01 &8.10 &7.75 &8.02 &7.95\\
15 & &$^3A''(n,\pis)$ &V &97.0 &3.51 &\Y &3.25 &3.28 &3.15 &3.39 &3.40\\
16 & &$^3A'(\pi,\pis)$ &V &98.6 &3.94 &\Y &3.89 &4.01 &3.78 &3.96 &3.91\\
17 & &$^3A'(\pi,\pis)$ &V &98.4 &6.18 &\Y &5.89 &6.20 &5.93 &6.10 &6.02\\
18 & &$^3A''(n,\pis)$ &V &92.7 &6.54 &\N &6.67 &6.65 &6.21 &6.74 &6.66\\
19 &Benzene &$^1B_{2u}(\pi,\pis)$ &V &86.3 &5.06 &\Y &4.98 &5.14 &4.66 &5.09 &5.01\\
20 & &$^1B_{1u}(\pi,\pis)$ &V &92.9 &6.45 &\Y &7.27 &6.65 &6.23 &6.67 &6.58\\
21 & &$^1E_{1g}(\pi,3s)$ &R &92.8 &6.52 &\Y &5.90 &6.70 &6.57 &6.56 &6.51\\
22 & &$^1A_{2u}(\pi,3p)$ &R &93.4 &7.08 &\Y &6.14 &7.21 &7.07 &7.07 &7.02\\
23 & &$^1E_{2u}(\pi,3p)$ &R &92.8 &7.15 &\Y &6.21 &7.26 &7.12 &7.13 &7.08\\
24 & &$^1E_{2g}(\pi,\pis)$ &V &73.0 &8.28 &\Y &8.10 &8.31 &7.82 &8.26 &8.16\\
25 & &$^1A_{1g}(\text{double})$ &V &n.d. &10.55 &\N &11.44 &10.24 &9.33 & &\\
26 & &$^3B_{1u}(\pi,\pis)$ &V &98.6 &4.16 &\Y &3.85 &4.22 &3.92 &4.14 &4.08\\
27 & &$^3E_{1u}(\pi,\pis)$ &V &97.1 &4.85 &\Y &4.85 &4.89 &4.51 &4.87 &4.80\\
28 & &$^3B_{2u}(\pi,\pis)$ &V &98.1 &5.81 &\Y &6.75 &5.85 &5.40 &5.90 &5.81\\
29 &Butadiene &$^1B_u(\pi,\pis)$ &V &93.3 &6.22 &\Y &6.65 &6.76 &6.52 &6.72 &6.65\\
30 & &$^1B_g(\pi,3s)$ &R &94.1 &6.33 &\Y &5.94 &6.49 &6.32 &6.43 &6.38\\
31 & &$^1A_g(\pi,\pis)$ &V &75.1 &6.50 &\Y &6.99 &6.74 &6.30 &6.73 &6.66\\
32 & &$^1A_u(\pi,3p)$ &R &94.1 &6.64 &\Y &5.95 &6.74 &6.64 &6.70 &6.67\\
33 & &$^1A_u(\pi,3p)$ &R &94.1 &6.80 &\Y &6.12 &6.95 &6.84 &6.90 &6.86\\
34 & &$^1B_u(\pi,3p)$ &R &93.8 &7.68 &\Y &7.93 &7.60 &7.30 &7.62 &7.54\\
35 & &$^3B_u(\pi,\pis)$ &V &98.4 &3.36 &\Y &3.55 &3.40 &3.19 &3.40 &3.35\\
36 & &$^3A_g(\pi,\pis)$ &V &98.7 &5.20 &\Y &5.52 &5.32 &4.93 &5.29 &5.19\\
37 & &$^3B_g(\pi,3s)$ &R &97.9 &6.29 &\Y &5.89 &6.44 &6.27 &6.38 &6.33\\
38 &Carbon Trimer &$^1\Delta_g(\text{double})$&R &1.0 &5.22 &\Y &4.98 &5.08 &4.85 &5.20 &5.19\\
39 & &$^1\Sigma^+_g(\text{double})$&R&1.0 &5.91 &\Y &5.84 &5.82 &5.58 &5.92 &5.89\\
40 &Cyanoacetylene &$^1\Sigma^-(\pi,\pis)$ &V &94.3 &5.80 &\Y &6.54 &5.85 &5.47 &5.89 &5.81\\
41 & &$^1\Delta(\pi,\pis)$ &V &94.0 &6.07 &\Y &6.80 &6.13 &5.78 &6.17 &6.09\\
42 & &$^3\Sigma^+(\pi,\pis)$ &V &98.5 &4.44 &\Y &4.86 &4.45 &4.04 &4.52 &4.45\\
43 & &$^3\Delta(\pi,\pis)$ &V &98.2 &5.21 &\Y &5.64 &5.21 &4.86 &5.26 &5.19\\
44 & &$^1A''[F](\pi,\pis)$ &V &93.6 &3.54 &\Y &4.30 &3.67 &3.47 &3.64 &3.58\\
45 &Cyanoformaldehyde &$^1A''(n,\pis)$ &V &89.8 &3.81 &\Y &4.02 &3.98 &3.67 &3.94 &3.89\\
46 & &$^1A''(\pi,\pis)$ &V &91.9 &6.46 &\Y &7.61 &6.79 &6.43 &6.77 &6.67\\
47 & &$^3A''(n,\pis)$ &V &97.6 &3.44 &\Y &3.52 &3.46 &3.25 &3.51 &3.50\\
48 & &$^3A'(\pi,\pis)$ &V &98.4 &5.01 &\Y &4.98 &5.25 &5.03 &5.16 &5.12\\
49 &Cyanogen &$^1\Sigma_u^-(\pi,\pis)$ &V &94.1 &6.39 &\Y &7.14 &6.40 &6.03 &6.46 &6.39\\
50 & &$^1\Delta_u(\pi,\pis)$ &V &93.4 &6.66 &\Y &7.46 &6.70 &6.35 &6.75 &6.68\\
51 & &$^3\Sigma_u^+(\pi,\pis)$ &V &98.5 &4.91 &\Y &5.28 &4.85 &4.46 &4.95 &4.89\\
52 & &$^1\Sigma_u^-[F](\pi,\pis)$&V &93.4 &5.05 &\Y &5.68 &5.07 &4.75 &5.11 &5.04\\
53 &Cyclopentadiene &$^1B_2(\pi,\pis)$ &V &93.8 &5.56 &\Y &6.71 &5.96 &5.62 &6.06 &5.99\\
54 & &$^1A_2(\pi,3s)$ &R &94.0 &5.78 &\Y &5.21 &5.88 &5.78 &5.81 &5.77\\
55 & &$^1B_1(\pi,3p)$ &R &94.2 &6.41 &\Y &6.08 &6.59 &6.44 &6.47 &6.41\\
56 & &$^1A_2(\pi,3p)$ &R &93.8 &6.46 &\Y &5.78 &6.55 &6.46 &6.45 &6.41\\
57 & &$^1B_2(\pi,3p)$ &R &94.2 &6.56 &\Y &6.16 &6.72 &6.56 &6.61 &6.54\\
58 & &$^1A_1(\pi,\pis)$ &V &78.9 &6.52 &\N &6.49 &6.63 &6.13 &6.59 &6.50\\
59 & &$^3B_2(\pi,\pis)$ &V &98.4 &3.31 &\Y &3.26 &3.34 &3.09 &3.31 &3.26\\
60 & &$^3A_1(\pi,\pis)$ &V &98.6 &5.11 &\Y &4.92 &5.14 &4.78 &5.10 &5.03\\
61 & &$^3A_2(\pi,3s)$ &R &97.9 &5.73 &\Y &5.53 &5.91 &5.74 &5.81 &5.75\\
62 & &$^3B_1(\pi,3p)$ &R &97.9 &6.36 &\Y &6.05 &6.56 &6.40 &6.43 &6.37\\
63 &Cyclopropene &$^1B_1(\sig,\pis)$ &V &92.8 &6.68 &\Y &7.48 &6.86 &6.58 &6.85 &6.77\\
64 & &$^1B_2(\pi,\pis)$ &V &95.1 &6.79 &\Y &7.47 &6.89 &6.47 &6.96 &6.87\\
65 & &$^3B_2(\pi,\pis)$ &V &98.0 &4.38 &\Y &4.60 &4.47 &4.27 &4.46 &4.40\\
66 & &$^3B_1(\sig,\pis)$ &V &98.9 &6.45 &\Y &7.08 &6.56 &6.32 &6.55 &6.47\\
67 &Cyclopropenone &$^1B_1(n,\pis)$ &V &87.7 &4.26 &\Y &4.92 &4.12 &3.75 &4.40 &4.38\\
68 & &$^1A_2(n,\pis)$ &V &91.0 &5.55 &\Y &5.64 &5.62 &5.31 &5.67 &5.64\\
69 & &$^1B_2(n,3s)$ &R &90.8 &6.34 &\Y &5.68 &6.28 &6.21 &6.41 &6.44\\
70 & &$^1B_2(\pi,\pis)$ &V &86.5 &6.54 &\Y &6.40 &6.54 &6.20 &6.63 &6.62\\
71 & &$^1B_2(n,3p)$ &R &91.1 &6.98 &\Y &6.35 &6.84 &6.70 &6.99 &7.01\\
72 & &$^1A_1(n,3p)$ &R &91.2 &7.02 &\Y &6.84 &7.27 &7.03 &7.26 &7.24\\
73 & &$^1A_1(\pi,\pis)$ &V &90.8 &8.28 &\Y &10.42 &8.96 &8.11 &9.21 &9.07\\
74 & &$^3B_1(n,\pis)$ &V &96.0 &3.93 &\Y &4.72 &3.65 &3.28 &4.00 &3.98\\
75 & &$^3B_2(\pi,\pis)$ &V &97.9 &4.88 &\Y &4.39 &4.76 &4.60 &4.76 &4.74\\
76 & &$^3A_2(n,\pis)$ &V &97.5 &5.35 &\Y &5.40 &5.36 &5.06 &5.44 &5.42\\
77 & &$^3A_1(\pi,\pis)$ &V &98.1 &6.79 &\Y &6.59 &6.93 &6.61 &6.86 &6.82\\
78 &Cyclopropenethione &$^1A_2(n,\pis)$ &V &89.6 &3.41 &\Y &3.44 &3.43 &3.14 &3.46 &3.40\\
79 & &$^1B_1(n,\pis)$ &V &84.8 &3.45 &\Y &3.57 &3.45 &3.17 &3.52 &3.46\\
80 & &$^1B_2(\pi,\pis)$ &V &83.0 &4.60 &\Y &4.51 &4.64 &4.35 &4.66 &4.61\\
81 & &$^1B_2(n,3s)$ &R &91.8 &5.34 &\Y &4.59 &5.25 &5.15 &5.25 &5.22\\
82 & &$^1A_1(\pi,\pis)$ &V &89.0 &5.46 &\Y &6.46 &5.84 &5.32 &5.88 &5.75\\
83 & &$^1B_2(n,3p)$ &R &91.3 &5.92 &\Y &5.27 &5.93 &5.86 &5.92 &5.90\\
84 & &$^3A_2(n,\pis)$ &V &97.2 &3.28 &\Y &3.26 &3.28 &3.00 &3.33 &3.28\\
85 & &$^3B_1(n,\pis)$ &V &94.5 &3.32 &\Y &3.51 &3.35 &3.07 &3.42 &3.36\\
86 & &$^3B_2(\pi,\pis)$ &V &96.5 &4.01 &\Y &3.80 &3.97 &3.75 &3.99 &3.95\\
87 & &$^3A_1(\pi,\pis)$ &V &98.2 &4.01 &\Y &3.83 &4.01 &3.77 &4.00 &3.95\\
88 &Diacetylene &$^1\Sigma_u^-(\pi,\pis)$ &V &94.4 &5.33 &\Y &6.13 &5.42 &5.01 &5.45 &5.36\\
89 & &$^1\Delta_u(\pi,\pis)$ &V &94.1 &5.61 &\Y &6.39 &5.68 &5.30 &5.72 &5.63\\
90 & &$^3\Sigma_u^+(\pi,\pis)$ &V &98.5 &4.10 &\Y &4.54 &4.11 &3.67 &4.17 &4.09\\
91 & &$^3\Delta_u(\pi,\pis)$ &V &98.2 &4.78 &\Y &5.28 &4.82 &4.45 &4.86 &4.78\\
92 &Diazomethane &$^1A_2(\pi,\pis)$ &V &90.1 &3.14 &\Y &3.27 &3.13 &2.92 &3.09 &3.04\\
93 & &$^1B_1(\pi,3s)$ &R &93.8 &5.54 &\Y &4.59 &5.50 &5.30 &5.48 &5.45\\
94 & &$^1A_1(\pi,\pis)$ &V &91.4 &5.90 &\Y &5.65 &6.21 &5.92 &6.18 &6.13\\
95 & &$^3A_2(\pi,\pis)$ &V &97.7 &2.79 &\Y &3.02 &2.87 &2.67 &2.84 &2.79\\
96 & &$^3A_1(\pi,\pis)$ &V &98.6 &4.05 &\Y &4.27 &4.10 &3.88 &4.06 &4.01\\
97 & &$^3B_1(\pi,3s )$ &R &98.0 &5.35 &\Y &4.45 &5.34 &5.15 &5.33 &5.30\\
98 & &$^3A_1(\pi,3p)$ &R &98.5 &6.82 &\Y &6.34 &7.00 &6.76 &6.96 &6.91\\
99 & &$^1A''[F](\pi,\pis)$ &V &87.4 &0.71 &\Y &0.72 &0.69 &0.52 &0.66 &0.62\\
100 &Formamide &$^1A''(n,\pis)$ &V &90.8 &5.65 &\Y &5.95 &5.66 &5.45 &5.71 &5.67\\
101 & &$^1A'(n,3s)$ &R &88.6 &6.77 &\Y &6.17 &6.80 &6.64 &6.82 &6.81\\
102 & &$^1A'(n,3p)$ &R &89.6 &7.38 &\N &6.74 &7.45 &7.32 &7.46 &7.46\\
103 & &$^1A'(\pi,\pis)$ &V &89.3 &7.63 &\N &8.80 &7.88 &7.13 &7.95 &7.78\\
104 & &$^3A''(n,\pis)$ &V &97.7 &5.38 &\Y &5.89 &5.36 &5.16 &5.41 &5.37\\
105 & &$^3A'(\pi,\pis)$ &V &98.2 &5.81 &\Y &6.10 &5.88 &5.62 &5.91 &5.87\\
106 &Furan &$^1A_2(\pi,3s)$ &R &93.8 &6.09 &\Y &5.26 &6.16 &6.04 &6.06 &6.02\\
107 & &$^1B_2(\pi,\pis)$ &V &93.0 &6.37 &\Y &7.78 &6.59 &6.02 &6.80 &6.71\\
108 & &$^1A_1(\pi,\pis)$ &V &92.4 &6.56 &\Y &6.73 &6.66 &6.10 &6.69 &6.62\\
109 & &$^1B_1(\pi,3p)$ &R &93.9 &6.64 &\Y &6.07 &6.79 &6.63 &6.65 &6.60\\
110 & &$^1A_2(\pi,3p)$ &R &93.6 &6.81 &\Y &5.87 &6.87 &6.77 &6.76 &6.72\\
111 & &$^1B_2(\pi,3p)$ &R &93.5 &7.24 &\Y &6.54 &7.11 &6.84 &6.96 &6.88\\
112 & &$^3B_2(\pi,\pis)$ &V &98.4 &4.20 &\Y &3.94 &4.26 &4.01 &4.17 &4.12\\
113 & &$^3A_1(\pi,\pis)$ &V &98.1 &5.46 &\Y &5.41 &5.50 &5.09 &5.47 &5.40\\
114 & &$^3A_2(\pi,3s)$ &R &97.9 &6.02 &\Y &5.57 &6.16 &5.99 &6.05 &5.99\\
115 & &$^3B_1(\pi,3p)$ &R &97.9 &6.59 &\Y &6.04 &6.76 &6.60 &6.62 &6.56\\
116 &Glyoxal &$^1A_u(n,\pis)$ &V &91.0 &2.88 &\Y &3.42 &2.82 &2.51 &2.97 &2.94\\
117 & &$^1B_g(n,\pis)$ &V &88.3 &4.24 &\Y &4.68 &4.21 &3.89 &4.36 &4.31\\
118 & &$^1A_g(\text{double})$ &V &0.5 &5.61 &\Y &5.92 &5.37 &5.21 &5.53 &5.55\\
119 & &$^1B_g(n,\pis)$ &V &83.9 &6.57 &\Y &7.35 &6.52 &5.98 &6.76 &6.72\\
120 & &$^1B_u(n,3p)$ &R &91.7 &7.71 &\Y &7.04 &7.61 &7.34 &7.78 &7.81\\
121 & &$^3A_u(n,\pis)$ &V &97.6 &2.49 &\Y &3.06 &2.41 &2.12 &2.57 &2.55\\
122 & &$^3B_g(n,\pis)$ &V &97.4 &3.89 &\Y &4.61 &3.90 &3.53 &4.04 &4.01\\
123 & &$^3B_u(\pi,\pis)$ &V &98.5 &5.15 &\Y &5.46 &5.14 &4.91 &5.17 &5.14\\
124 & &$^3A_g(\pi,\pis)$ &V &98.8 &6.30 &\Y &6.69 &6.32 &6.02 &6.33 &6.27\\
125 &Imidazole &$^1A''(\pi,3s)$ &R &93.0 &5.70 &\Y &5.04 &5.88 &5.66 &5.74 &5.68\\
126 & &$^1A'(\pi,3p)$ &R &90.0 &6.41 &\Y &6.18 &6.69 &6.45 &6.61 &6.56\\
127 & &$^1A''(\pi,3p)$ &R &93.6 &6.50 &\Y &5.43 &6.57 &6.47 &6.47 &6.44\\
128 & &$^1A''(n,\pis)$ &V &89.0 &6.71 &\Y &7.13 &6.94 &6.57 &6.92 &6.85\\
129 & &$^1A'(\pi,\pis)$ &V &88.9 &6.86 &\Y &6.73 &6.88 &6.46 &6.89 &6.83\\
130 & &$^1A'(n,3s)$ &R &89.0 &7.00 &\Y &6.36 &7.10 &6.91 &7.09 &7.07\\
131 & &$^3A'(\pi,\pis)$ &V &98.3 &4.74 &\Y &4.55 &4.78 &4.52 &4.73 &4.68\\
132 & &$^3A''(\pi,3s)$ &R &97.6 &5.66 &\Y &5.03 &5.86 &5.63 &5.72 &5.66\\
133 & &$^3A'(\pi,\pis)$ &V &97.9 &5.74 &\Y &5.69 &5.85 &5.48 &5.80 &5.72\\
134 & &$^3A''(n,\pis)$ &V &97.3 &6.31 &\Y &6.58 &6.44 &6.10 &6.43 &6.37\\
135 &Isobutene &$^1B_1(\pi,3s)$ &R &94.1 &6.46 &\Y &6.21 &6.74 &6.59 &6.64 &6.57\\
136 & &$^1A_1(\pi,3p)$ &R &94.2 &7.01 &\Y &6.90 &7.32 &7.14 &7.24 &7.18\\
137 & &$^3A_1(\pi,\pis)$ &V &98.9 &4.53 &\Y &4.66 &4.59 &4.41 &4.58 &4.53\\
138 &Ketene &$^1A_2(\pi,\pis)$ &V &91.0 &3.86 &\Y &3.98 &3.92 &3.70 &3.90 &3.85\\
139 & &$^1B_1(\pi,3s)$ &R &93.9 &6.01 &\Y &5.22 &5.99 &5.79 &6.00 &5.97\\
140 & &$^1A_1(\pi,\pis)$ &V &92.4 &7.25 &\Y & & &&&\\
141 & &$^1A_2(\pi,3p)$ &R &94.4 &7.18 &\Y &6.38 &7.25 &7.05 &7.19 &7.15\\
142 & &$^3A_2(\pi,\pis)$ &V &91.0 &3.77 &\Y &3.92 &3.81 &3.59 &3.79 &3.74\\
143 & &$^3A_1(\pi,\pis)$ &V &98.6 &5.61 &\Y &5.79 &5.65 &5.43 &5.63 &5.59\\
144 & &$^3B_1(\pi,3s)$ &R &98.1 &5.79 &\Y &5.05 &5.79 &5.60 &5.80 &5.77\\
145 & &$^3A_2(\pi,3p)$ &R &94.4 &7.12 &\Y &6.35 &7.22 &7.01 &7.15 &7.11\\
146 & &$^1A''[F](\pi,\pis)$ &V &87.9 &1.00 &\Y &0.95 &1.05 &0.88 &1.00 &0.95\\
147 &Methylenecycloprope&ne$^1B_2(\pi,\pis)$ &V &85.4 &4.28 &\Y &4.47 &4.40 &4.12 &4.39 &4.33\\
148 & &$^1B_1(\pi,3s)$ &R &93.6 &5.44 &\Y &4.92 &5.57 &5.44 &5.46 &5.41\\
149 & &$^1A_2(\pi,3p)$ &R &93.3 &5.96 &\Y &5.37 &6.09 &5.97 &5.97 &5.92\\
150 & &$^1A_1(\pi,\pis)$ &V &92.8 &6.12 &\N &5.37 &6.26 &6.16 &6.17 &6.13\\
151 & &$^3B_2(\pi,\pis)$ &V &97.2 &3.49 &\Y &3.44 &3.57 &3.34 &3.55 &3.49\\
152 & &$^3A_1(\pi,\pis)$ &V &98.6 &4.74 &\Y &4.60 &4.82 &4.58 &4.77 &4.72\\
153 &Nitrosomethane &$^1A''(n,\pis)$ &V &93.0 &1.96 &\Y &2.12 &1.84 &1.60 &1.94 &1.91\\
154 & &$^1A'(\text{double})$ &V &2.5 &4.76 &\Y &4.74 &4.69 &4.67 &4.71 &4.71\\
155 & &$^1A'(\text{n.d.})$ &R &90.8 &6.29 &\Y &5.87 &6.32 &6.07 &6.34 &6.31\\
156 & &$^3A''(n,\pis)$ &V &98.4 &1.16 &\Y &1.31 &1.00 &0.75 &1.12 &1.09\\
157 & &$^3A'(\pi,\pis)$ &V &98.9 &5.60 &\Y &5.52 &5.52 &5.37 &5.54 &5.50\\
158 & &$^1A''[F](n,\pis)$ &V &92.7 &1.67 &\Y &1.83 &1.55 &1.32 &1.66 &1.62\\
159 &Propynal &$^1A''(n,\pis)$ &V &89.0 &3.80 &\Y &4.00 &3.92 &3.64 &3.90 &3.86\\
160 & &$^1A''(\pi,\pis)$ &V &92.9 &5.54 &\Y &6.62 &5.82 &5.49 &5.81 &5.72\\
161 & &$^3A''(n,\pis)$ &V &97.4 &3.47 &\Y &3.52 &3.48 &3.26 &3.52 &3.50\\
162 & &$^3A'(\pi,\pis)$ &V &98.3 &4.47 &\Y &4.69 &4.59 &4.30 &4.54 &4.54\\
163 &Pyrazine &$^1B_{3u}(n,\pis)$ &V &90.1 &4.15 &\Y &4.76 &4.09 &3.66 &4.31 &4.30\\
164 & &$^1A_u(n,\pis)$ &V &88.6 &4.98 &\Y &5.90 &4.76 &4.26 &5.10 &5.10\\
165 & &$^1B_{2u}(\pi,\pis)$ &V &86.9 &5.02 &\Y &4.97 &5.13 &4.65 &5.09 &5.03\\
166 & &$^1B_{2g}(n,\pis)$ &V &85.6 &5.71 &\Y &5.80 &5.68 &5.27 &5.73 &5.70\\
167 & &$^1A_g(n,3s)$ &R &91.1 &6.65 &\Y &6.69 &6.66 &6.27 &6.81 &6.80\\
168 & &$^1B_{1g}(n,\pis)$ &V &84.2 &6.74 &\Y &7.16 &6.61 &6.07 &6.78 &6.76\\
169 & &$^1B_{1u}(\pi,\pis)$ &V &92.8 &6.88 &\Y &8.04 &7.14 &6.72 &7.20 &7.12\\
170 & &$^1B_{1g}(\pi,3s)$ &R &93.8 &7.21 &\Y &6.73 &7.41 &7.27 &7.24 &7.18\\
171 & &$^1B_{2u}(n,3p)$ &R &90.8 &7.24 &\Y &7.49 &7.34 &6.93 &7.43 &7.40\\
172 & &$^1B_{1u}(n,3p)$ &R &91.4 &7.44 &\Y &7.83 &7.55 &7.08 &7.64 &7.59\\
173 & &$^1B_{1u}(\pi,\pis)$ &V &90.5 &7.98 &\N &9.65 &8.59 &7.96 &8.68 &8.57\\
174 & &$^1A_g(\text{double})$ &V &12.0 &8.04 &\N & & &&&\\
175 & &$^1A_g(\pi,\pis)$ &V &71.0 &8.69 &\N & & &&&\\
176 & &$^3B_{3u}(n,\pis)$ &V &97.3 &3.59 &\Y &4.16 &3.49 &3.08 &3.72 &3.71\\
177 & &$^3B_{1u}(\pi,\pis)$ &V &98.5 &4.35 &\Y &3.98 &4.44 &4.15 &4.34 &4.28\\
178 & &$^3B_{2u}(\pi,\pis)$ &V &97.6 &4.39 &\Y &4.62 &4.44 &4.09 &4.47 &4.41\\
179 & &$^3A_u(n,\pis)$ &V &96.1 &4.93 &\Y &5.85 &4.73 &4.21 &5.07 &5.07\\
180 & &$^3B_{2g}(n,\pis)$ &V &97.0 &5.08 &\Y &5.25 &5.04 &4.66 &5.14 &5.11\\
181 & &$^3B_{1u}(\pi,\pis)$ &V &97.0 &5.28 &\Y &5.15 &5.29 &4.92 &5.25 &5.19\\
182 &Pyridazine &$^1B_1(n,\pis)$ &V &89.0 &3.83 &\Y &4.29 &3.74 &3.36 &3.94 &3.92\\
183 & &$^1A_2(n,\pis)$ &V &86.9 &4.37 &\Y &4.83 &4.29 &3.87 &4.49 &4.48\\
184 & &$^1A_1(\pi,\pis)$ &V &85.8 &5.26 &\Y &5.12 &5.34 &4.87 &5.30 &5.25\\
185 & &$^1A_2(n,\pis)$ &V &86.2 &5.72 &\Y &6.26 &5.73 &5.19 &5.93 &5.89\\
186 & &$^1B_2(n,3s)$ &R &88.5 &6.17 &\Y &5.99 &6.18 &5.90 &6.28 &6.27\\
187 & &$^1B_1(n,\pis)$ &V &87.0 &6.37 &\Y &7.16 &6.50 &5.94 &6.72 &6.67\\
188 & &$^1B_2(\pi,\pis)$ &V &90.6 &6.75 &\Y &7.54 &7.26 &6.82 &7.25 &7.17\\
189 & &$^3B_1(n,\pis)$ &V &97.1 &3.19 &\Y &3.60 &3.08 &2.72 &3.29 &3.28\\
190 & &$^3A_2(n,\pis)$ &V &96.1 &4.11 &\Y &4.49 &4.01 &3.59 &4.20 &4.18\\
191 & &$^3B_2(\pi,\pis)$ &V &98.5 &4.34 &\N &3.92 &4.44 &4.13 &4.30 &4.24\\
192 & &$^3A_1(\pi,\pis)$ &V &97.3 &4.82 &\Y &4.93 &4.87 &4.48 &4.89 &4.83\\
193 &Pyridine &$^1B_1(n,\pis)$ &V &88.4 &4.95 &\Y &5.43 &5.15 &4.81 &5.18 &5.13\\
194 & &$^1B_2(\pi,\pis)$ &V &86.5 &5.14 &\Y &5.03 &5.18 &4.76 &5.15 &5.09\\
195 & &$^1A_2(n,\pis)$ &V &87.9 &5.40 &\Y &6.30 &5.46 &5.03 &5.63 &5.59\\
196 & &$^1A_1(\pi,\pis)$ &V &92.1 &6.62 &\Y &7.90 &6.92 &6.27 &7.04 &6.93\\
197 & &$^1A_1(n,3s)$ &R &89.7 &6.76 &\Y &6.40 &6.90 &6.67 &6.97 &6.96\\
198 & &$^1A_2(\pi,3s)$ &R &93.2 &6.82 &\Y &6.60 &7.08 &6.87 &6.88 &6.80\\
199 & &$^1B_1(\pi,3p)$ &R &93.6 &7.38 &\Y &7.12 &7.70 &7.51 &7.48 &7.40\\
200 & &$^1A_1(\pi,\pis)$ &V &90.5 &7.39 &\Y &9.49 &7.66 &6.63 &7.87 &7.70\\
201 & &$^1B_2(\pi,\pis)$ &V &90.0 &7.40 &\N &7.45 &7.92 &7.67 &7.80 &7.73\\
202 & &$^3A_1(\pi,\pis)$ &V &98.5 &4.30 &\Y &3.98 &4.40 &4.06 &4.29 &4.22\\
203 & &$^3B_1(n,\pis)$ &V &97.0 &4.46 &\Y &4.65 &4.48 &4.21 &4.57 &4.55\\
204 & &$^3B_2(\pi,\pis)$ &V &97.3 &4.79 &\Y &4.83 &4.86 &4.53 &4.81 &4.74\\
205 & &$^3A_1(\pi,\pis)$ &V &97.1 &5.04 &\Y &5.11 &5.09 &4.63 &5.09 &5.02\\
206 & &$^3A_2(n,\pis)$ &V &95.8 &5.36 &\Y &5.94 &5.33 &4.96 &5.53 &5.51\\
207 & &$^3B_2(\pi,\pis)$ &V &97.7 &6.24 &\Y &6.93 &6.40 &5.99 &6.43 &6.35\\
208 &Pyrimidine &$^1B_1(n,\pis)$ &V &88.6 &4.44 &\Y &4.85 &4.44 &4.07 &4.58 &4.55\\
209 & &$^1A_2(n,\pis)$ &V &88.5 &4.85 &\Y &5.52 &4.80 &4.36 &5.02 &5.00\\
210 & &$^1B_2(\pi,\pis)$ &V &86.3 &5.38 &\Y &5.28 &5.42 &4.98 &5.41 &5.36\\
211 & &$^1A_2(n,\pis)$ &V &86.7 &5.92 &\Y &6.70 &5.92 &5.32 &6.16 &6.10\\
212 & &$^1B_1(n,\pis)$ &V &86.7 &6.26 &\Y &7.20 &6.31 &5.65 &6.58 &6.53\\
213 & &$^1B_2(n,3s)$ &R &90.3 &6.70 &\Y &6.86 &6.85 &6.50 &6.89 &6.86\\
214 & &$^1A_1(\pi,\pis)$ &V &91.5 &6.88 &\Y &7.69 &7.31 &6.94 &7.29 &7.22\\
215 & &$^3B_1(n,\pis)$ &V &96.8 &4.09 &\Y &4.45 &4.05 &3.67 &4.20 &4.18\\
216 & &$^3A_1(\pi,\pis)$ &V &98.3 &4.51 &\N &4.22 &4.57 &4.25 &4.51 &4.44\\
217 & &$^3A_2(n,\pis)$ &V &96.5 &4.66 &\Y &5.20 &4.63 &4.16 &4.81 &4.78\\
218 & &$^3B_2(\pi,\pis)$ &V &97.4 &4.96 &\Y &5.10 &5.01 &4.60 &5.03 &4.97\\
219 &Pyrrole &$^1A_2(\pi,3s)$ &R &92.9 &5.24 &\Y &4.49 &5.44 &5.23 &5.28 &5.23\\
220 & &$^1B_1(\pi,3p)$ &R &92.4 &6.00 &\Y &5.22 &6.26 &6.07 &6.08 &6.02\\
221 & &$^1A_2(\pi,3p)$ &R &93.0 &6.00 &\Y &4.89 &6.16 &6.02 &6.01 &5.97\\
222 & &$^1B_2(\pi,\pis)$ &V &92.5 &6.26 &\Y &7.73 &6.62 &6.36 &6.45 &6.38\\
223 & &$^1A_1(\pi,\pis)$ &V &86.3 &6.30 &\Y &6.47 &6.41 &5.84 &6.43 &6.34\\
224 & &$^1B_2(\pi,3p)$ &R &92.6 &6.83 &\Y &5.82 &6.75 &6.11 &6.92 &6.82\\
225 & &$^3B_2(\pi,\pis)$ &V &98.3 &4.51 &\Y &4.24 &4.57 &4.30 &4.49 &4.44\\
226 & &$^3A_2(\pi,3s)$ &R &97.6 &5.21 &\Y &4.47 &5.41 &5.21 &5.26 &5.20\\
227 & &$^3A_1(\pi,\pis)$ &V &97.8 &5.45 &\Y &5.52 &5.50 &5.04 &5.49 &5.40\\
228 & &$^3B_1(\pi,3p)$ &R &97.4 &5.91 &\Y &5.18 &6.22 &6.03 &6.04 &5.98\\
229 &Streptocyanine-1 &$^1B_2(\pi,\pis)$ &V &88.7 &7.13 &\Y &7.82 &7.17 &6.76 &7.28 &7.21\\
230 & &$^3B_2(\pi,\pis)$ &V &98.3 &5.52 &\Y &5.86 &5.49 &5.22 &5.54 &5.49\\
231 &Tetrazine &$^1B_{3u}(n,\pis)$ &V &89.8 &2.47 &\Y &2.99 &2.31 &1.91 &2.54 &2.53\\
232 & &$^1A_u(n,\pis)$ &V &87.9 &3.69 &\Y &4.37 &3.49 &3.00 &3.77 &3.78\\
233 & &$^1A_g(\text{double})$ &V &0.7 &4.61 &\N &5.42 &4.69 &4.48 &4.85 &4.87\\
234 & &$^1B_{1g}(n,\pis)$ &V &83.1 &4.93 &\Y &5.41 &4.83 &4.33 &5.02 &5.00\\
235 & &$^1B_{2u}(\pi,\pis)$ &V &85.4 &5.21 &\Y &5.04 &5.31 &4.84 &5.26 &5.23\\
236 & &$^1B_{2g}(n,\pis)$ &V &81.7 &5.45 &\Y &5.43 &5.38 &4.90 &5.42 &5.38\\
237 & &$^1A_u(n,\pis)$ &V &87.7 &5.53 &\Y &6.37 &5.51 &4.92 &5.80 &5.80\\
238 & &$^1B_{3g}(\text{double})$ &V &0.7 &6.15 &\N &6.59 &5.85 &5.22 &6.20 &6.22\\
239 & &$^1B_{2g}(n,\pis)$ &V &80.2 &6.12 &\Y &6.79 &5.96 &5.18 &6.27 &6.28\\
240 & &$^1B_{1g}(n,\pis)$ &V &85.1 &6.91 &\Y &7.18 &6.59 &5.89 &6.79 &6.72\\
241 & &$^3B_{3u}(n,\pis)$ &V &97.1 &1.85 &\Y &2.38 &1.70 &1.31 &1.94 &1.93\\
242 & &$^3A_u(n,\pis)$ &V &96.3 &3.45 &\Y &4.06 &3.26 &2.78 &3.52 &3.52\\
243 & &$^3B_{1g}(n,\pis)$ &V &97.0 &4.20 &\Y &4.66 &4.10 &3.62 &4.32 &4.30\\
244 & &$^1B_{1u}(\pi,\pis)$ &V &98.5 &4.49 &\N &3.90 &4.55 &4.29 &4.39 &4.34\\
245 & &$^3B_{2u}(\pi,\pis)$ &V &97.5 &4.52 &\Y &4.68 &4.55 &4.20 &4.60 &4.55\\
246 & &$^3B_{2g}(n,\pis)$ &V &96.4 &5.04 &\Y &5.17 &5.02 &4.53 &5.10 &5.07\\
247 & &$^3A_u(n,\pis)$ &V &96.6 &5.11 &\Y &6.12 &5.07 &4.44 &5.41 &5.41\\
248 & &$^3B_{3g}(\text{double})$ &V &5.7 &5.51 &\N &6.56 &5.39 &4.86 &5.83 &5.85\\
249 & &$^3B_{1u}(\pi,\pis)$ &V &96.6 &5.42 &\Y &5.32 &5.46 &5.08 &5.44 &5.39\\
250 &Thioacetone &$^1A_2(n,\pis)$ &V &88.9 &2.53 &\Y &2.72 &2.58 &2.33 &2.60 &2.53\\
251 & &$^1B_2(n,3s)$ &R &91.3 &5.56 &\Y &4.80 &5.60 &5.48 &5.64 &5.61\\
252 & &$^1A_1(\pi,\pis)$ &V &90.6 &5.88 &\Y &6.94 &6.42 &5.98 &6.40 &6.26\\
253 & &$^1B_2(n,3p)$ &R &92.4 &6.51 &\Y &5.57 &6.51 &6.40 &6.53 &6.49\\
254 & &$^1A_1(n,3p)$ &R &91.6 &6.61 &\Y &6.24 &6.66 &6.41 &6.59 &6.50\\
255 & &$^3A_2(n,\pis)$ &V &97.4 &2.33 &\Y &2.52 &2.34 &2.09 &2.38 &2.31\\
256 & &$^3A_1(\pi,\pis)$ &V &98.7 &3.45 &\Y &3.52 &3.48 &3.29 &3.48 &3.43\\
257 &Thiophene &$^1A_1(\pi,\pis)$ &V &87.6 &5.64 &\Y &6.11 &5.84 &5.21 &5.89 &5.79\\
258 & &$^1B_2(\pi,\pis)$ &V &91.5 &5.98 &\Y &6.94 &6.35 &5.89 &6.44 &6.35\\
259 & &$^1A_2(\pi,3s)$ &R &92.6 &6.14 &\Y &5.70 &6.28 &6.07 &6.16 &6.10\\
260 & &$^1B_1(\pi,3p)$ &R &90.1 &6.14 &\Y &6.02 &6.21 &5.90 &6.16 &6.10\\
261 & &$^1A_2(\pi,3p)$ &R &91.8 &6.21 &\Y &6.05 &6.32 &5.98 &6.28 &6.21\\
262 & &$^1B_1(\pi,3s)$ &R &92.8 &6.49 &\Y &5.78 &6.57 &6.28 &6.51 &6.44\\
263 & &$^1B_2(\pi,3p)$ &R &92.4 &7.29 &\Y &6.80 &7.29 &7.03 &7.20 &7.13\\
264 & &$^1A_1(\pi,\pis)$ &V &86.5 &7.31 &\N &8.29 &7.62 &6.85 &7.71 &7.56\\
265 & &$^3B_2(\pi,\pis)$ &V &98.2 &3.92 &\Y &3.68 &3.98 &3.71 &3.90 &3.84\\
266 & &$^3A_1(\pi,\pis)$ &V &97.7 &4.76 &\Y &4.97 &4.85 &4.39 &4.87 &4.79\\
267 & &$^3B_1(\pi,3p)$ &R &96.6 &5.93 &\Y &5.86 &5.97 &5.64 &5.94 &5.88\\
268 & &$^3A_2(\pi,3s)$ &R &97.5 &6.08 &\Y &5.65 &6.22 &6.01 &6.11 &6.04\\
269 &Thiopropynal &$^1A''(n,\pis)$ &V &87.5 &2.03 &\Y &2.06 &2.05 &1.84 &2.05 &2.00\\
270 & &$^3A''(n,\pis)$ &V &97.2 &1.80 &\Y &1.85 &1.81 &1.60 &1.84 &1.79\\
271 &Triazine &$^1A_1''(n,\pis)$ &V &88.3 &4.72 &\Y &5.88 &4.62 &3.90 &5.00 &4.99\\
272 & &$^1A_2''(n,\pis)$ &V &88.3 &4.75 &\Y &5.14 &4.77 &4.39 &4.90 &4.87\\
273 & &$^1E''(n,\pis)$ &V &88.3 &4.78 &\Y &5.51 &4.76 &4.14 &5.01 &4.98\\
274 & &$^1A_2'(\pi,\pis)$ &V &85.7 &5.75 &\Y &5.55 &5.76 &5.32 &5.75 &5.72\\
275 & &$^1A_1'(\pi,\pis)$ &V &90.4 &7.24 &\Y &8.20 &7.43 &6.89 &7.50 &7.41\\
276 & &$^1E'(n,3s)$ &R &90.9 &7.32 &\Y &7.40 &7.48 &7.15 &7.53 &7.49\\
277 & &$^1E''(n,\pis)$ &V &82.6 &7.78 &\Y &8.26 &7.75 &7.04 &7.92 &7.90\\
278 & &$^1E'(\pi,\pis)$ &V &90.0 &7.94 &\Y &10.03 &8.65 &7.70 &8.63 &8.72\\
279 & &$^3A_2''(n,\pis)$ &V &96.7 &4.33 &\Y &4.74 &4.37 &3.99 &4.51 &4.49\\
280 & &$^3E''(n,\pis)$ &V &96.6 &4.51 &\Y &5.14 &4.47 &3.88 &4.71 &4.68\\
281 & &$^3A_1''(n,\pis)$ &V &96.2 &4.73 &\Y &5.88 &4.70 &3.94 &5.06 &5.04\\
282 & &$^3A_1'(\pi,\pis)$ &V &98.2 &4.85 &\Y &4.46 &4.88 &4.55 &4.81 &4.75\\
283 & &$^3E'(\pi,\pis)$ &V &96.9 &5.59 &\Y &5.57 &5.62 &5.20 &5.62 &5.57\\
284 & &$^3A_2'(\pi,\pis)$ &V &97.6 &6.62 &\Y &7.70 &6.62 &6.12 &6.76 &6.68\\
\end{longtable*}
%%% %%% %%% %%%
%%% FIGURE 2 %%%
\begin{figure}
\includegraphics[width=\linewidth]{PT2_vs_PT3.pdf}
\caption{Histograms of the errors (in \si{\eV}) obtained for CASPT2 and CASPT3 with and without IPEA shift.
\label{fig:PT2_vs_PT3}}
\end{figure}
%%% %%% %%% %%%
%%% TABLE II %%%
\begin{table*}
\caption{Statistical quantities (in eV), considering the 265 ``safe'' TBEs (out of 284) as reference, for various multi-reference methods.
All {error} values are in eV.}
\caption{Statistical quantities (in eV), considering the 265 ``safe'' TBEs (out of 284) as reference, for various multi-reference methods.}
\label{tab:stat}
\begin{ruledtabular}
\begin{tabular}{lccccccc}
\begin{tabular}{lrrrrrrr}
&CASSCF\fnm[1] &CASPT2\fnm[1] &CASPT2\fnm[1] &CASPT3\fnm[1] &CASPT3\fnm[1] &SC-NEVPT2\fnm[2] &PC-NEVPT2\fnm[2]\\
& &(IPEA) &(NOIPEA) &(IPEA) &(NOIPEA)\\
\hline
MSE &$0.11$ &$0.06$ &$-0.26$ &$0,10$ &$0,05$ &$0,13$ &$0,09$\\
MSE &$0.11$ &$0.06$ &$-0.26$ &$0.10$ &$0.05$ &$0.13$ &$0.09$\\
SDE &$0.58$ &$0.14$ &$0.21$ &$0.13$ &$0.13$ &$0.14$ &$0.14$\\
RMSE &$0.61$ &$0.16$ &$0.33$ &$0.17$ &$0.14$ &$0.19$ &$0.17$\\
MAE &$0.48$ &$0.11$ &$0.27$ &$0.11$ &$0.09$ &$0.15$ &$0.13$\\
@ -526,13 +529,15 @@ TBEs listed as ``safe'' are assumed to be chemically accurate (\ie, absolute err
\fnt[1]{Values from the present study.}
\fnt[2]{Values taken from Ref.~\onlinecite{Sarka_2022}.}
\end{table*}
%%% %%% %%% %%%
%%% TABLE II %%%
\begin{table*}
\caption{MAEs determined for several subsets of transitions computed with various multi-reference methods.
\caption{MAEs determined for several subsets of transitions and system sizes computed with various multi-reference methods.
Count is the number of excited states considered in each subset.}
\label{tab:stat_class}
\label{tab:stat_subset}
\begin{ruledtabular}
\begin{tabular}{lcccccccc}
\begin{tabular}{lrrrrrrrr}
Transitions & Count &CASSCF\fnm[1] &CASPT2\fnm[1] &CASPT2\fnm[1] &CASPT3\fnm[1] &CASPT3\fnm[1] &SC-NEVPT2\fnm[2] &PC-NEVPT2\fnm[2]\\
& & &(IPEA) &(NOIPEA) &(IPEA) &(NOIPEA)\\
\hline
@ -543,7 +548,7 @@ TBEs listed as ``safe'' are assumed to be chemically accurate (\ie, absolute err
$n \to \pis$ &78 &0.44 &0.08 &0.44 &0.13 &0.10 &0.12 &0.10\\
$\pi \to \pis$ &119 &0.46 &0.12 &0.27 &0.13 &0.10 &0.18 &0.14\\
Double &9 &0.46 &0.11 &0.22 &0.12 &0.09 &0.14 &0.13\\
1-3 non-H atoms &39 &0.38 &0.07 &0.21 &0.06 &0.05 &0.10 &0.08\\
3 non-H atoms &39 &0.38 &0.07 &0.21 &0.06 &0.05 &0.10 &0.08\\
4 non-H atoms &94 &0.46 &0.11 &0.22 &0.12 &0.09 &0.14 &0.13\\
5-6 non-H atoms &151 &0.51 &0.12 &0.33 &0.12 &0.11 &0.17 &0.15\\
\end{tabular}
@ -551,12 +556,32 @@ TBEs listed as ``safe'' are assumed to be chemically accurate (\ie, absolute err
\fnt[1]{Values from the present study.}
\fnt[2]{Values taken from Ref.~\onlinecite{Sarka_2022}.}
\end{table*}
%%% %%% %%% %%%
A detailed discussion of each individual molecule can be found in Ref.~\onlinecite{Sarka_2022} where we also report relevant values from the literature.
Here, we focus on global trends.
The exhaustive list of CASPT2 and CASPT3 transitions can be found in Table \ref{tab:BigTab} and the distribution of the errors are represented in Fig.~\ref{fig:PT2_vs_PT3}.
Various statistical indictors are given in Table \ref{tab:stat} while MAEs determined for several subsets of transitions (singlet, triplet, valence, Rydberg, $n\to\pis$, $\pi\to\pis$, and double excitations) and system sizes (3 non-H atoms, 4 non-H atoms, and 5-6 non-H atoms) are reported in Table \ref{tab:stat_subset}.
From the different statistical quantities reported in Table \ref{tab:stat}, one can highlight the two following observations.
First, as previously reported, \cite{Werner_1996,Grabarek_2016} CASPT3 vertical excitation energies are much less sensitive to the IPEA shift, which drastically alter the accuracy of CASPT2.
For example, the MAEs of CASPT3(IPEA) and CASPT3(NOIPEA) are amazingly close (\SI{0.11}{} and \SI{0.09}{\eV}), while the MAEs of CASPT2(IPEA) and CASPT2(NOIPEA) are drastically different (\SI{0.27}{} and \SI{0.11}{\eV}).
Importantly, CASPT3 seems to perform slightly better without IPEA shift, which is a great outcome.
Second, CASPT3 (with or without IPEA) has a similar accuracy as CASPT2(IPEA).
All these observations stand for each subset of excitations and irrespectively of the system size (see Table \ref{tab:stat_subset}).
Interestingly, CASPT3(NOIPEA) yields MAEs for each subset that is almost systematically below \SI{0.1}{\eV}, except for the singlet subsets which is polluted by some states showing larger deviations at the CASPT2 and CASPT3 levels.
\titou{Here, discuss difficult case where we have a large (positive) error in CASPT2 and CASPT3.
This is due to the relative small size of the active space and, more precisely, to the lack of direct $\sig$-$\pi$ coupling in the active space which are known to be important in such ionic states. \cite{Garniron_2018}
These errors could be alleviated by using a RAS space.}
%%% TABLE III %%%
\begin{table*}
\caption{CASPT2 and CASPT3 timings (in seconds) for a selection of systems and states.}
\caption{CASPT2 and CASPT3 timings (in seconds) for a selection of systems and transitions.}
\label{tab:timings}
\begin{ruledtabular}
\begin{tabular}{llcccccccc}
System & State &Active &\# electrons &\# basis &\# CAS &\# contracted &\# uncontracted &CPU &CPU\\
System & Transition &Active &\# electrons &\# basis &\# CAS &\# contracted &\# uncontracted &CPU &CPU\\
& &Space & &functions &det. &config. &config. &CASPT2 &CASPT3 \\
\hline
Acetone &$^1A_2(n,\pis)$ &(6e,6o) &32 &322 &104 &$3.86 \times 10^6$ &$1.49 \times 10^8$ &12.50 &33.25\\
@ -566,11 +591,20 @@ TBEs listed as ``safe'' are assumed to be chemically accurate (\ie, absolute err
\end{tabular}
\end{ruledtabular}
\end{table*}
%%% %%% %%% %%%
\titou{Table \ref{tab:timings} reports the evolution of the CPU timings for CASPT2 and CASPT3 as a function of the size of the active space.
It is particularly instructive to study the increase in CPU times as the number of external configuration grows.}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\section{Conclusion}
\label{sec:ccl}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
In the present study, we have benchmarked, using 284 highly-accurate electronic transitions extracted from the QUEST database, \cite{Veril_2021} the third-order multi-reference perturbation theory method, CASPT3, by computing vertical excitation energies with and without IPEA shift.
The two take-home messages are that:
i) CASPT3 transition energies are almost independent of the IPEA shift;
ii) CASPT2(IPEA) and CASPT3 have very similar accuracy.
The global trends are also true for specific sets of excitations and various system size.
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\begin{acknowledgements}

245
Manuscript/sup_CASPT3.tex
View File

@ -1,5 +1,5 @@
\documentclass[aip,jcp,reprint,noshowkeys,superscriptaddress,onecolumn]{revtex4-1}
\usepackage{graphicx,dcolumn,bm,xcolor,microtype,multirow,amscd,amsmath,amssymb,amsfonts,physics,wrapfig,txfonts,siunitx}
\documentclass[aip,jcp,reprint,noshowkeys,onecolumn]{revtex4-1}
\usepackage{graphicx,dcolumn,bm,xcolor,microtype,multirow,amscd,amsmath,amssymb,amsfonts,physics,txfonts,siunitx,float}
\usepackage[version=4]{mhchem}
%\usepackage{natbib}
%\bibliographystyle{achemso}
@ -101,8 +101,12 @@ The state-averaging procedure used is also described in terms of number of state
Note that, for all calculations, the ground state is systematically included in the state averaging
procedure even if it does not belong to the same irreducible representation.
The cartesian coordinates have been extracted from the QUEST database \cite{Veril_2021} and can be downloaded at \url{https://lcpq.github.io/QUESTDB_website}.
\\
\begin{table*}
%------------------------------
\section{Acetaldehyde}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of acetaldehyde.}
\label{tab:acetaldehyde}
\begin{ruledtabular}
@ -116,10 +120,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\end{ruledtabular}
\flushleft
$^a$Reference (6e,5o) active space including valence $\nO$, $\piCO$, $\sigCO$, $\pisCO$ and $\sigsCO$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Acetone}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of acetone.}
\label{tab:acetone}
\begin{ruledtabular}
@ -142,9 +148,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^c$Using reference (6e,6o) active space including valence $\pi$, $\nO$, $\sigCO$, $\sigsCO$ and $3p_y$ orbitals.
$^d$Using reference (6e,5o) active space including valence $\pi$, $\nO$, $\sigCO$ and $\sigsCO$ orbitals.
$^e$Using reference (4e,4o) active space including valence $\pi$, $\sigCO$, $\sigsCO$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Acrolein}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of acrolein.}
\label{tab:acrolein}
\begin{ruledtabular}
@ -170,9 +179,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^d$Using reference (6e,6o) active space including valence $\pi$, $\nO$ and $3s$ orbitals.
$^e$Substantial Rydberg and doubly-excited character.
$^f$Substantial doubly-excited character.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Benzene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of benzene.}
\label{tab:benzene}
\begin{ruledtabular}
@ -197,9 +209,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^c$Using reference (6e,7o) active space including valence $\pi$ and $3s$ orbitals.
$^d$Using reference (6e,8o) active space including valence $\pi$, $3p_x$ and $3p_y$ orbitals.
$^e$Level shift set to \SI{0.4}{\hartree}.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Butadiene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of butadiene.}
\label{tab:butadiene}
\begin{ruledtabular}
@ -224,9 +239,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^c$Using reference (10e,10o) active space including valence $\pi$, $\sigCC$ and $\sigsCC$ orbitals.
$^d$Level shift set to \SI{0.4}{\hartree}.
$^e$Using reference (10e,12o) active space including valence $\pi$, $\sigCC$, $\sigsCC$, $3p_x$ and $3p_y$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Carbon trimer}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of carbon trimer.}
\label{tab:carbon_trimer}
\begin{ruledtabular}
@ -242,9 +260,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^a$All calculations using a full valence (12e,12o) active space.
$^b$Level shift set to \SI{0.4}{\hartree}.
$^c$Level shift set to \SI{0.5}{\hartree}.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyanoacetylene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyanoacetylene.$^a$}
\label{tab:cyanoacetylene}
\begin{ruledtabular}
@ -261,9 +282,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\end{ruledtabular}
\flushleft
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyanoformaldehyde}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyanoformaldehyde.}
\label{tab:cyanoformaldehyde}
\begin{ruledtabular}
@ -280,10 +304,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\flushleft
$^a$Using reference (8e,7o) active space including valence $\pi$ and $\nO$ orbitals.
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyanogen}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyanogen.$^a$}
\label{tab:cyanogen}
\begin{ruledtabular}
@ -299,9 +325,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\end{ruledtabular}
\flushleft
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyclopentadiene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyclopentadiene.}
\label{tab:cyclopentadiene}
\begin{ruledtabular}
@ -328,9 +357,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^d$Using reference (4e,4o) active space including valence $\pi$ orbitals.
$^e$Strong double-excitation character.
$^f$Using reference (4e,5o) active space including valence $\pi$ and $3s$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyclopropene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyclopropene.}
\label{tab:cyclopropene}
\begin{ruledtabular}
@ -346,9 +378,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\end{ruledtabular}
\flushleft
$^a$Reference (8e,8o) active space including valence $\piCC$, $\sigCC$ and $\pisCC$, $\sigsCC$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyclopropenethione}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyclopropenethione.}
\label{tab:cyclopropenethione}
\begin{ruledtabular}
@ -372,9 +407,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
$^a$Using reference (6e,5o) active space including valence $\pi$ and $\nS$.
$^b$Using reference (6e,7o) active space including valence $\pi$, $\nS$, $3s$ and $3p_z$.
$^c$Using reference (4e,4o) active space including valence $\pi$.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Cyclopropenone}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of cyclopropenone.}
\label{tab:cyclopropenone}
\begin{ruledtabular}
@ -398,9 +436,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\flushleft
$^a$Using reference (6e,7o) active space including valence $\pi$, $\nO$, $3s$ and $3p_z$.
$^b$Using reference (6e,7o) active space including valence $\pi$, $\nO$, $3p_x$ and $3p_y$.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Diacetylene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of diacetylene.$^a$}
\label{tab:diacetylene}
\begin{ruledtabular}
@ -416,9 +457,12 @@ $^3A''(n,\pis)$ &(3,2) &(1,1) &4.28$^a$ &3.94$^a$ &3.71$^a$ &4.06$^a$ &4.03$^a$
\end{ruledtabular}
\flushleft
$^a$All calculations using a full valence $\pi$ active space of (8e,8o).
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Diazomethane}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of diazomethane.}
\label{tab:diazomethane}
\begin{ruledtabular}
@ -440,9 +484,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.72$^a$ &0.69$^a$ &0.
$^a$Reference (10e,9o) active space including valence $\pi$, $\sigCN$, $\sigNN$ and $\sigsCN$, $\sigsNN$ orbitals.
$^b$Reference (10e,10o) active space including valence $\pi$, $\sigCN$, $\sigNN$ and $\sigsCN$, $\sigsNN$, Rydberg $3s$ orbitals.
$^c$Reference (10e,10o) active space including valence $\pi$, $\sigCN$, $\sigNN$ and $\sigsCN$, $\sigsNN$, Rydberg $3p$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Formamide}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of formamide.}
\label{tab:formamide}
\begin{ruledtabular}
@ -462,9 +509,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.72$^a$ &0.69$^a$ &0.
$^a$Reference (10e,8o) active space including valence $\pi$, $\nO$, $\sigCN$, $\sigCO$ and $\sigsCN$, $\sigsCO$ orbitals.
$^b$Reference (10e,10o) active space including valence $\pi$, $\nO$, $\sigCN$, $\sigCO$ and $\sigsCN$, $\sigsCO$, Rydberg $3s$ and $3p$ orbitals.
$^c$Reference (8e,7o) active space including valence $\pi$, $\sigCN$, $\sigCO$ and $\sigsCN$, $\sigsCO$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Furan}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of furan.}
\label{tab:furan}
\begin{ruledtabular}
@ -491,9 +541,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.72$^a$ &0.69$^a$ &0.
$^d$Strong double-excitation character.
$^e$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
$^f$Using reference (6e,6o) active space including valence $\pi$ and $3s$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Imidazole}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of imidazole.}
\label{tab:imidazole}
\begin{ruledtabular}
@ -519,9 +572,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.72$^a$ &0.69$^a$ &0.
$^a$Using reference (8e,7o) active space including valence $\pi$, $\nN$ and $3s$ orbitals.
$^b$Using reference (6e,9o) active space including valence $\pi$ and four $3p_z$ orbitals.
$^c$Using reference (8e,10o) active space including valence $\pi$, $\nN$, $3s$ and three $3p$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Isobutene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of isobutene.}
\label{tab:isobutene}
\begin{ruledtabular}
@ -538,9 +594,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.72$^a$ &0.69$^a$ &0.
$^a$Using reference (4e,5o) active space including valence $\pi$, $\sigCC$, $\sigsCC$ and $3s$ orbitals.
$^b$Using reference (4e,5o) active space including valence $\pi$, $\sigCC$, $\sigsCC$ and $3p_x$ orbitals.
$^c$Using reference (4e,4o) active space including valence $\pi$, $\sigCC$ and $\sigsCC$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Ketene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of ketene.}
\label{tab:ketene}
\begin{ruledtabular}
@ -562,9 +621,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.95$^a$ &1.05$^a$ &0.
$^a$Reference (10e,9o) active space including valence $\pi$, $\sigCC$, $\sigCO$ and $\sigsCC$, $\sigsCO$ orbitals.
$^b$Reference (10e,10o) active space including valence $\pi$, $\sigCC$, $\sigCO$ and $\sigsCC$, $\sigsCO$, Rydberg $3s$ orbitals.
$^c$Reference (10e,10o) active space including valence $\pi$, $\sigCC$, $\sigCO$ and $\sigsCC$, $\sigsCO$, Rydberg $3p$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Methylenecyclopropene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of methylenecyclopropene.}
\label{tab:methylenecyclopropene}
\begin{ruledtabular}
@ -586,9 +648,12 @@ $^1A''[F](\pi,\pis)$ &($a'$:6,$a''$:3) &($A'$:1,$A''$:1) &0.95$^a$ &1.05$^a$ &0.
$^c$Using reference (4e,5o) active space including valence $\pi$ and $3p_y$.
$^d$Using reference (4e,7o) active space including valence $\pi$, two $3p_x$ and one $3d_{xz}$.
$^e$Using reference (4e,6o) active space including valence $\pi$, one $3p_x$ and one $3d_{xz}$.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Nitrosomethane}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of nitrosomethane.}
\label{tab:nitrosomethane}
\begin{ruledtabular}
@ -608,9 +673,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^a$Reference (8e,6o) active space including valence $\nO$, $\nN$, $\piNO$, $\sigNO$ and $\sigsNO$, $\pisNO$ orbitals.
$^b$Reference (8e,7o) active space including valence $\nO$, $\nN$, $\piNO$, $\sigNO$ and $\sigsNO$, $\pisNO$, Rydberg 3s orbitals.
$^c$Reference (4e,4o) active space including valence $\piNO$, $\sigNO$ and $\sigsNO$, $\pisNO$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Propynal}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of propynal.}
\label{tab:propynal}
\begin{ruledtabular}
@ -627,9 +695,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
\flushleft
$^a$Using reference (8e,7o) active space including valence $\pi$ and $\nO$ orbitals.
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Pyrazine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of pyrazine.}
\label{tab:pyrazine}
\begin{ruledtabular}
@ -664,9 +735,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^e$Using reference (6e,7o) active space including valence $\pi$ and $3s$ orbitals.
$^f$Using reference (10e,9o) active space including valence $\pi$, $\nN$ and $3p_y$ orbitals.
$^g$Using reference (10e,9o) active space including valence $\pi$, $\nN$ and $3p_z$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Pyridazine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of pyridazine.}
\label{tab:pyridazine}
\begin{ruledtabular}
@ -692,9 +766,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
$^c$Using reference (10e,9o) active space including valence $\pi$, $\nN$ and $3s$ orbitals.
$^d$Using reference (6e,9o) active space including valence $\pi$, $\nN$ and three $3p_x$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Pyridine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of pyridine.}
\label{tab:pyridine}
\begin{ruledtabular}
@ -725,9 +802,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^c$Using reference (8e,8o) active space including valence $\pi$, $\nN$ and $3s$ orbitals.
$^d$Using reference (6e,6o) active space including valence $\pi$ orbitals.
$^e$Using reference (8e,7o) active space including valence $\pi$ and $\nN$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Pyrimidine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of pyrimidine.}
\label{tab:pyrimidine}
\begin{ruledtabular}
@ -753,9 +833,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^b$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
$^c$Using reference (10e,9o) active space including valence $\pi$, $\nN$ and $3s$ orbitals.
$^d$Using reference (6e,6o) active space including valence $\pi$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Pyrrole}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of pyrrole.}
\label{tab:pyrrole}
\begin{ruledtabular}
@ -781,9 +864,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^c$Using reference (6e,7o) active space including valence $\pi$, $3s$ and $3p_z$ orbitals.
$^d$Using reference (6e,6o) active space including valence $\pi$ and $3p_x$ orbitals.
$^e$Using reference (6e,5o) active space including valence $\pi$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Streptocyanine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of streptocyanine.}
\label{tab:streptocyanine}
\begin{ruledtabular}
@ -797,9 +883,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
\end{ruledtabular}
\flushleft
$^a$Reference (8e,7o) active space including valence $\pi$, two $\sigCN$ and two $\sigsCN$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Tetrazine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of tetrazine.}
\label{tab:tetrazine}
\begin{ruledtabular}
@ -833,9 +922,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^b$Using reference (6e,6o) active space including valence $\pi$ orbitals.
$^c$Level shift set to \SI{0.4}{\hartree}.
$^d$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Thioacetone}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of thioacetone.}
\label{tab:thioacetone}
\begin{ruledtabular}
@ -857,9 +949,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^b$Using reference (6e,7o) active space including valence $\pi$, $\nO$, $\sigCO$, $\sigsCO$, $3s$ and $3p_z$ orbitals.
$^c$Using reference (4e,4o) active space including valence $\pi$, $\sigCO$ and $\sigsCO$ orbitals.
$^d$Using reference (6e,6o) active space including valence $\pi$, $\nO$, $\sigCO$, $\sigsCO$ and $3p_y$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Thiophene}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of thiophene.}
\label{tab:thiophene}
\begin{ruledtabular}
@ -888,9 +983,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^d$Using reference (6e,6o) active space including valence $\pi$ and $3p_y$ orbitals.
$^e$Using reference (6e,7o) active space including valence $\pi$, $3s$ and $3p_y$ orbitals.
$^f$Strong double-excitation character.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Thiopropynal}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of thiopropynal.}
\label{tab:thiopropynal}
\begin{ruledtabular}
@ -904,9 +1002,12 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
\end{ruledtabular}
\flushleft
$^a$Using reference (8e,7o) active space including valence $\pi$ and $\nO$ orbitals.
\end{table*}
\end{table}
\begin{table*}
%------------------------------
\section{Triazine}
%------------------------------
\begin{table}[H]
\caption{Vertical transition energies (eV) of triazine.}
\label{tab:triazine}
\begin{ruledtabular}
@ -934,7 +1035,7 @@ $^1A''[F](n,\pis)$ &(4,2) &(1,1) &1.83$^a$ &1.55$^a$ &1.32$^a$ &1.66$^a$ &1.62$^
$^a$Using reference (12e,9o) active space including valence $\pi$ and $\nN$ orbitals.
$^b$Using reference (6e,9o) active space including valence $\pi$ and three $3p_x$ orbitals.
$^c$Using reference (12e,10o) active space including valence $\pi$, $\nN$ and $3s$ orbitals.
\end{table*}
\end{table}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
\bibliography{CASPT3}