diff --git a/Manuscript/FCI2-MC.tex b/Manuscript/FCI2-MC.tex index de5603c..af65abd 100644 --- a/Manuscript/FCI2-MC.tex +++ b/Manuscript/FCI2-MC.tex @@ -173,10 +173,10 @@ Benzene &$^1B_{2u} (\Val; \pi \ra \pis)$ &5.32$^a$,5.32$^b$ \\ \end{tabularx} \begin{flushleft} \begin{footnotesize} -$^a$Using reference (6e,6o) active space including valence $\pis$ orbitals. -$^b$Using reference (6e,9o) active space including valence $\pis$ and three $3p_z$ orbitals. -$^c$Using reference (6e,7o) active space including valence $\pis$ and 3s orbitals. -$^d$Using reference (6e,8o) active space including valence $\pis$, $3p_x$ and $3p_y$ orbitals. +$^a$Using reference (6e,6o) active space including valence $\pi$ orbitals. +$^b$Using reference (6e,9o) active space including valence $\pi$ and three $3p_z$ orbitals. +$^c$Using reference (6e,7o) active space including valence $\pi$ and 3s orbitals. +$^d$Using reference (6e,8o) active space including valence $\pi$, $3p_x$ and $3p_y$ orbitals. \end{footnotesize} \end{flushleft} \end{table} @@ -216,18 +216,18 @@ $^e$Using reference (10e,12o) active space including valence $\pi$, $\si_\text{C \caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanoacetylene.} \begin{tabularx}{\textwidth}{XXX} \hline -Molecule & State & NEVPT2 \\ +Molecule & State & NEVPT2$^a$ \\ \hline -Cyanoacetylene &$^1\Sigma^- (\Val; \pi \ra \pis)$ & \\ - &$^1\Delta (\Val; \pi \ra \pis)$ & \\ - &$^3\Sigma^+ (\Val; \pi \ra \pis)$ & \\ - &$^3\Delta (\Val; \pi \ra \pis)$ & \\ - &$^1A'' [\mathrm{F}] (\Val; \pi \ra \pis)$ & \\ +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 \\ + &$^1A'' [\mathrm{F}] (\Val; \pi \ra \pis)$ & 3.50 \\ \hline \end{tabularx} \begin{flushleft} \begin{footnotesize} - +$^a$All calculations using a full valence $\pi$ active space of (8e,8o). \end{footnotesize} \end{flushleft} \end{table} @@ -258,17 +258,17 @@ $^b$ Using reference (6e,6o) active space including valence $\pi$ orbitals. \caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyanogen.} \begin{tabularx}{\textwidth}{XXX} \hline -Molecule & State & NEVPT2 \\ +Molecule & State & NEVPT2$^a$ \\ \hline -Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & \\ - & $^1\Delta_u (\Val; \pi \ra \pis)$ & \\ - & $^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & \\ - & $^1\Sigma_u^- [\mathrm{F}] (\Val; \pi \ra \pis)$ & \\ +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 \\ \hline \end{tabularx} \begin{flushleft} \begin{footnotesize} - +$^a$All calculations using a full valence $\pi$ active space of (8e,8o). \end{footnotesize} \end{flushleft} \end{table} @@ -280,14 +280,14 @@ Cyanogen & $^1\Sigma_u^- (\Val; \pi \ra \pis)$ & \\ \hline Molecule & State & NEVPT2 \\ \hline -Cyclopentadiene &$^1B_2 (\Val; \pi \ra \pis)$ &4.96$^a$,4.92$^b$,5.65$^c$ \\ +Cyclopentadiene &$^1B_2 (\Val; \pi \ra \pis)$ &4.96$^a$,4.92$^b$,5.65$^c$ \\ &$^1A_2 (\Ryd; \pi \ra 3s)$ &5.92$^d$ \\ &$^1B_1 (\Ryd; \pi \ra 3p)$ &6.42$^e$ \\ &$^1A_2 (\Ryd; \pi \ra 3p)$ &6.59$^d$ \\ - &$^1B_2 (\Ryd; \pi \ra 3p)$ &6.58$^c$ \\ - &$^1A_1 (\Val; \pi \ra \pis)$ &6.75$^{a,f}$ \\ + &$^1B_2 (\Ryd; \pi \ra 3p)$ &6.58$^b$,6.60$^c$ \\ + &$^1A_1 (\Val; \pi \ra \pis)$ &6.75$^{a,f}$ \\ &$^3B_2 (\Val; \pi \ra \pis)$ &3.41$^a$ \\ - &$^3A_1 (\Val; \pi \ra \pis)$ &5.36$^a$ \\ + &$^3A_1 (\Val; \pi \ra \pis)$ &5.30$^a$ \\ &$^3A_2 (\Ryd; \pi \ra 3s)$ &5.73$^g$ \\ &$^3B_1 (\Ryd; \pi \ra 3p)$ &6.40$^e$ \\ \hline @@ -311,26 +311,24 @@ $^g$Using reference (4e,5o) active space including valence $\pi$ and 3s orbitals \caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of cyclopropenone.} \begin{tabularx}{\textwidth}{XXX} \hline -Molecule & State & NEVPT2 \\ +Molecule & State & NEVPT2$^a$ \\ \hline -Cyclopropenone &$^1B_1 (\Val; n \ra \pis)$ & 4.04$^a$,4.20$^b$,4.21$^c$ \\ - &$^1A_2 (\Val; n \ra \pis)$ & 5.85$^a$,5.86$^b$,5.94$^c$ \\ - &$^1B_2 (\Ryd; n \ra 3s)$ & 6.51$^a$,6.64$^b$,6.75$^c$ \\ - &$^1B_2 (\Val; \pi \ra \pis$) & 6.82$^a$,6.93$^b$,7.06$^c$ \\ - &$^1B_2 (\Ryd; n \ra 3p)$ & 7.07$^a$,7.25$^b$,7.38$^c$ \\ - &$^1A_1 (\Ryd; n \ra 3p)$ & 7.28$^a$,7.08$^b$,7.28$^c$ \\ - &$^1A_1 (\Val; \pi \ra \pis)$ & 8.19$^a$,8.19$^c$ \\ - &$^3B_1 (\Val; n \ra \pis)$ & 3.51$^a$,3.68$^b$,3.67$^c$ \\ - &$^3B_2 (\Val; \pi \ra \pis)$ & 5.10$^a$,5.09$^b$,5.29$^c$ \\ - &$^3A_2 (\Val; n \ra \pis)$ & 5.60$^a$,5.60$^b$,5.69$^c$ \\ - &$^3A_1 (\Val; \pi \ra \pis)$ & 7.16$^a$,7.21$^b$,7.16$^c$ \\ +Cyclopropenone &$^1B_1 (\Val; n \ra \pis)$ & 4.04 \\ + &$^1A_2 (\Val; n \ra \pis)$ & 5.85 \\ + &$^1B_2 (\Ryd; n \ra 3s)$ & 6.51 \\ + &$^1B_2 (\Val; \pi \ra \pis$) & 6.82 \\ + &$^1B_2 (\Ryd; n \ra 3p)$ & 7.07 \\ + &$^1A_1 (\Ryd; n \ra 3p)$ & 7.28 \\ + &$^1A_1 (\Val; \pi \ra \pis)$ & 8.19 \\ + &$^3B_1 (\Val; n \ra \pis)$ & 3.51 \\ + &$^3B_2 (\Val; \pi \ra \pis)$ & 5.10 \\ + &$^3A_2 (\Val; n \ra \pis)$ & 5.60 \\ + &$^3A_1 (\Val; \pi \ra \pis)$ & 7.16 \\ \hline \end{tabularx} \begin{flushleft} \begin{footnotesize} -$^a$Using reference (6e,7o) active space averaging with the ground state for each irreducible representation. -$^b$Using reference (6e,7o) active space averaging between three states of the same irreducible representation. -$^c$Using reference (6e,7o) active space averaging between four states of the same irreducible representation. +$^a$All calculation using reference (6e,7o) active space averaging with the ground state for each irreducible representation. \end{footnotesize} \end{flushleft} \end{table} @@ -369,17 +367,17 @@ $^c$Using reference (4e,4o) active space. \caption{NEVPT2/aug-cc-pVTZ vertical transition energies (in eV) of diacetylene.} \begin{tabularx}{\textwidth}{XXX} \hline -Molecule & State & NEVPT2 \\ +Molecule & State & NEVPT2$^a$ \\ \hline -Diacetylene &$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & \\ - &$^1\Delta_u (\Val; \pi \ra \pis)$ & \\ - &$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & \\ - &$^3\Delta_u (\Val; \pi \ra \pis)$ & \\ +Diacetylene &$^1\Sigma_u^- (\Val; \pi \ra \pis)$ & 5.33 \\ + &$^1\Delta_u (\Val; \pi \ra \pis)$ & 5.61 \\ + &$^3\Sigma_u^+ (\Val; \pi \ra \pis)$ & 4.08 \\ + &$^3\Delta_u (\Val; \pi \ra \pis)$ & 4.78 \\ \hline \end{tabularx} \begin{flushleft} \begin{footnotesize} - +$^a$All calculations using a full valence $\pi$ active space of (8e,8o). \end{footnotesize} \end{flushleft} \end{table} @@ -436,10 +434,10 @@ Glyoxal &$^1A_u (\Val; n \ra \pis)$ & 2.90$^a$ \\ \end{tabularx} \begin{flushleft} \begin{footnotesize} -$^a$Using reference (14e,12o) active space including valence $\pi$, two nO, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$ and $\si^*_\text{CO}$ orbitals. -$^b$Using reference (14e,13o) active space including valence $\pi$, two nO, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_z$ orbitals. +$^a$Using reference (14e,12o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$ and $\si^*_\text{CO}$ orbitals. +$^b$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_z$ orbitals. $^c$Non-negligible doubly-excited and Rydberg character. -$^d$Using reference (14e,13o) active space including valence $\pi$, two nO, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_x$ orbitals. +$^d$Using reference (14e,13o) active space including valence $\pi$, two $n_\text{O}$, $\si_\text{CC}$, $\si_\text{CO}$, $\si^*_\text{CC}$, $\si^*_\text{CO}$ and $3p_x$ orbitals. \end{footnotesize} \end{flushleft} \end{table} @@ -505,7 +503,7 @@ Molecule & State & NEVPT2 \\ Methylenecyclopropene& $^1B_2 (\Val; \pi \ra \pis)$ &4.37$^a$ \\ &$^1B_1 (\Ryd; \pi \ra 3s)$ &5.51$^b$,5.49$^c$ \\ &$^1A_2 (\Ryd; \pi \ra 3p)$ &6.00$^c$ \\ - &$^1A_1(\Val; \pi \ra \pis)$ &7.55$^d$,7.95$^e$ \\ + &$^1A_1(\Val; \pi \ra \pis)$ &6.33$^d$,6.36$^e$ \\ &$^3B_2 (\Val; \pi \ra \pis)$ &3.66$^a$ \\ &$^3A_1 (\Val; \pi \ra \pis)$ &4.87$^d$ \\ \hline @@ -517,8 +515,6 @@ $^b$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. -$^f$The $\pi^*$ orbital has some diffuse character, even in the case of natural orbitals. -$^g$Heavily mixed states. \end{footnotesize} \end{flushleft} \end{table} @@ -592,14 +588,14 @@ Molecule & State & NEVPT2 \\ \hline Pyridazine &$^1B_1 (\Val; n \ra \pis)$ & 3.80$^a$ \\ &$^1A_2 (\Val; n \ra \pis)$ & 4.40$^a$ \\ - &$^1A_1 (\Val; \pi \ra \pis)$ & 5.58b \\ + &$^1A_1 (\Val; \pi \ra \pis)$ & 5.58$^b$ \\ &$^1A_2 (\Val; n \ra \pis)$ & 5.88$^a$ \\ - &$^1B_2 (\Ryd; n \ra 3s)$ & 6.21c \\ + &$^1B_2 (\Ryd; n \ra 3s)$ & 6.21$^c$ \\ &$^1B_1 (\Val; n \ra \pis)$ & 6.64$^a$ \\ - &$^1B_2 (\Val; \pi \ra \pis)$ & 7.82b,7.19d,7.10e \\ + &$^1B_2 (\Val; \pi \ra \pis)$ & 7.82$^b$,7.19$^d$,7.10$^e$ \\ &$^3B_1 (\Val; n \ra \pis)$ & 3.13$^a$ \\ &$^3A_2 (\Val; n \ra \pis)$ & 4.14$^a$ \\ - &$^3B_2 (\Val; \pi \ra \pis)$ & 4.65b,4.55d,4.49e \\ + &$^3B_2 (\Val; \pi \ra \pis)$ & 4.65$^b$,4.55$^d$,4.49$^e$ \\ &$^3A_1 (\Val; \pi \ra \pis)$ & 4.94$^a$ \\ \hline \end{tabularx} @@ -608,7 +604,7 @@ Pyridazine &$^1B_1 (\Val; n \ra \pis)$ & 3.80$^a$ \\ $^a$Using reference (10e,8o) active space including valence $\pi$ and $n_\text{N}$ orbitals. $^b$Using reference (6e,6o) active space including valence $\pi$ orbitals. $^c$Using reference (10e,9o) active space including valence $\pi$, $n_\text{N}$ and 3s orbitals. -$^d$Using reference (6e,9o) active space including valence $\pi$, $n_\text{N}$ and three $3p_X$ orbitals. +$^d$Using reference (6e,9o) active space including valence $\pi$, $n_\text{N}$ and three $3p_x$ orbitals. $^e$Using reference (6e,12o) active space including valence $\pi$, $n_\text{N}$ and six $3p_x$ orbitals. \end{footnotesize} \end{flushleft} @@ -622,21 +618,21 @@ $^e$Using reference (6e,12o) active space including valence $\pi$, $n_\text{N}$ \hline Molecule & State & NEVPT2 \\ \hline -Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 5.17$^a$,5.15b \\ - &$^1B_2 (\Val; \pi \ra \pis)$ & 5.44c,5.31d \\ - &$^1A_2 (\Val; n \ra \pis)$ & 5.32$^a$,5.29e \\ - &$^1A_1 (\Val; \pi \ra \pis)$ & 6.69c \\ - &$^1A_1 (\Ryd; n \ra 3s)$ & 6.99e \\ - &$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.96f,6.86e\\ - &$^1B_2 (\Val; \pi \ra \pis)$ & 8.61$^a$,7.83d \\ - &$^1B_1 (\Ryd; \pi \ra 3p)$ & 7.57g,7.45b \\ - &$^1A_1 (\Val; \pi \ra \pis)$ & 6.97c \\ - &$^3A_1 (\Val; \pi \ra \pis)$ & 4.60c \\ +Pyridine &$^1B_1 (\Val; n \ra \pis)$ & 5.17$^a$,5.15$^b$ \\ + &$^1B_2 (\Val; \pi \ra \pis)$ & 5.44$^c$,5.31$^d$ \\ + &$^1A_2 (\Val; n \ra \pis)$ & 5.32$^a$,5.29$^e$ \\ + &$^1A_1 (\Val; \pi \ra \pis)$ & 6.69$^c$ \\ + &$^1A_1 (\Ryd; n \ra 3s)$ & 6.99$^e$ \\ + &$^1A_2 (\Ryd; \pi \ra 3s)$ & 6.96$^f$,6.86$^e$\\ + &$^1B_2 (\Val; \pi \ra \pis)$ & 8.61$^a$,7.83$^d$ \\ + &$^1B_1 (\Ryd; \pi \ra 3p)$ & 7.57$^g$,7.45$^b$ \\ + &$^1A_1 (\Val; \pi \ra \pis)$ & 6.97$^c$ \\ + &$^3A_1 (\Val; \pi \ra \pis)$ & 4.60$^c$ \\ &$^3B_1 (\Val; n \ra \pis)$ & 4.58$^a$ \\ - &$^3B_2 (\Val; \pi \ra \pis)$ & 4.90c,4.88d \\ - &$^3A_1 (\Val; \pi \ra \pis)$ & 5.19c \\ + &$^3B_2 (\Val; \pi \ra \pis)$ & 4.90$^c$,4.88$^d$ \\ + &$^3A_1 (\Val; \pi \ra \pis)$ & 5.19$^c$ \\ &$^3A_2 (\Val; n \ra \pis)$ & 5.33$^a$ \\ - &$^3B_2 (\Val; \pi \ra \pis)$ & 7.00c,6.29d \\ + &$^3B_2 (\Val; \pi \ra \pis)$ & 7.00$^c$,6.29$^d$ \\ \hline \end{tabularx} \begin{flushleft} diff --git a/Manuscript/FCI2.tex b/Manuscript/FCI2.tex index 1a9d463..7fe411d 100644 --- a/Manuscript/FCI2.tex +++ b/Manuscript/FCI2.tex @@ -120,6 +120,13 @@ \begin{document} + +\begin{tocentry} +\begin{center} +\includegraphics[scale=.27]{TOC.pdf} +\end{center} +\end{tocentry} + \begin{abstract} Following our previous work focussing on compounds containing up to 3 non-hydrogen atoms [\emph{J. Chem. Theory Comput.} {\bfseries 14} (2018) 4360--4379], we present here highly-accurate vertical transition energies obtained for 27 molecules encompassing 4, 5, and 6 non-hydrogen atoms: acetone, acrolein, benzene, butadiene, cyanoacetylene, cyanoformaldehyde, cyanogen, cyclopentadiene, cyclopropenone, cyclopropenethione, @@ -1532,13 +1539,5 @@ This work has been supported through the EUR grant NanoX ANR-17-EURE-0009 in the \end{acknowledgement} \bibliography{biblio-new} -\clearpage - -\begin{tocentry} -\begin{center} -\includegraphics[scale=.27]{TOC.pdf} -\end{center} -\end{tocentry} - \end{document}