From 95ada257710968efe598c26356ba59fb632b7857 Mon Sep 17 00:00:00 2001 From: Pierre-Francois Loos Date: Wed, 20 May 2020 17:24:51 +0200 Subject: [PATCH] basis effects and TDA --- BSEdyn.tex | 25 ++++++++++++++++--------- 1 file changed, 16 insertions(+), 9 deletions(-) diff --git a/BSEdyn.tex b/BSEdyn.tex index c3c3e7b..b912bcd 100644 --- a/BSEdyn.tex +++ b/BSEdyn.tex @@ -641,7 +641,7 @@ All the BSE calculations have been performed with our locally developed $GW$ sof %%% TABLE I %%% \begin{table*} \caption{ - Excitation energies (in eV) of \ce{N2} at the BSE@{\GOWO}@HF level for various basis sets. + Singlet and triplet excitation energies (in eV) of \ce{N2} at the BSE@{\GOWO}@HF level for various basis sets. \label{tab:N2} } \begin{ruledtabular} @@ -650,9 +650,9 @@ All the BSE calculations have been performed with our locally developed $GW$ sof & \mc{3}{c}{aug-cc-pVTZ ($\Eg^{\GW} = 19.20$ eV)} & \mc{3}{c}{aug-cc-pVQZ ($\Eg^{\GW} = $ eV)} \\ \cline{2-4} \cline{5-7} \cline{8-10} - State & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn,\TDA}$} & \tabc{$\Delta\Om{m}{\dyn}$} - & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn,\TDA}$} & \tabc{$\Delta\Om{m}{\dyn}$} - & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn,\TDA}$} & \tabc{$\Delta\Om{m}{\dyn}$} \\ + State & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn}$(TDA)} & \tabc{$\Delta\Om{m}{\dyn}$} + & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn}$(TDA)} & \tabc{$\Delta\Om{m}{\dyn}$} + & \tabc{$\Om{m}{\stat}$} & \tabc{$\Delta\Om{m}{\dyn}$(TDA)} & \tabc{$\Delta\Om{m}{\dyn}$} \\ \hline $^1\Pi_g(n \ra \pis)$ & 10.18 & -0.41 & -0.43 & 10.42 & -0.42 & -0.40 & & & \\ $^1\Sigma_u^-(\pi \ra \pis)$ & 9.95 & -0.44 & -0.44 & 10.11 & -0.45 & -0.45 & & & \\ @@ -661,6 +661,7 @@ All the BSE calculations have been performed with our locally developed $GW$ sof $^1\Pi_u$(R) & 14.07 & -0.05 & -0.05 & 13.98 & -0.04 & -0.04 & & & \\ $^1\Sigma_u^+$(R) & 13.80 & -0.08 & -0.08 & 13.98 & -0.07 & -0.08 & & & \\ $^1\Pi_u$(R) & 14.22 & -0.04 & -0.03 & 14.24 & -0.03 & -0.03 & & & \\ + \\ $^3\Sigma_u^+(\pi \ra \pis)$ & 9.21 & -1.01 & -0.71 & 9.50 & -1.04 & -0.73 & & & \\ $^3\Pi_g(n \ra \pis)$ & 9.58 & -0.57 & -0.34 & 9.85 & -0.58 & -0.33 & & & \\ $^3\Delta_u(\pi \ra \pis)$ & 9.97 & -0.92 & -0.58 & 10.19 & -0.95 & -0.36 & & & \\ @@ -675,7 +676,7 @@ All the BSE calculations have been performed with our locally developed $GW$ sof \caption{ Singlet excitation energies (in eV) for various molecules obtained with the aug-cc-pVTZ basis set at various levels of theory. The dynamical correction is computed in the TDA. - \label{tab:BigTab} + \label{tab:BigTabSi} } \begin{ruledtabular} \begin{tabular}{llrrrrrrrrrrrrrrr} @@ -686,9 +687,11 @@ All the BSE calculations have been performed with our locally developed $GW$ sof & CIS(D) & ADC(2) & CCSD & CC2 & CC3 \\ \hline \ce{HCl} & $^1\Pi$(CT) & 13.43 & 8.30 & 8.19 & -0.11 & 1.009 & & & & & & 6.07 & 7.97 & 7.91 & 7.96 & 7.84 \\ + \\ \ce{H2O} & $^1B_1(n \ra 3s)$ & 13.58 & 8.09 & 8.00 & -0.09 & 1.007 & & & & & & 7.62 & 7.18 & 7.60 & 7.23 & 7.65 \\ & $^1A_2(n \ra 3p)$ & & 9.79 & 9.72 & -0.07 & 1.005 & & & & & & 9.41 & 8.84 & 9.36 & 8.89 & 9.43 \\ & $^1A_1(n \ra 3s)$ & & 10.42 & 10.35 & -0.07 & 1.006 & & & & & & 9.99 & 9.52 & 9.96 & 9.58 & 10.00 \\ + \\ \ce{N2} & $^1\Pi_g(n \ra \pis)$ & 19.20 & 10.42 & 9.99 & -0.42 & 1.031 & & & & & & 9.66 & 9.48 & 9.41 & 9.44 & 9.34 \\ & $^1\Sigma_u^-(\pi \ra \pis)$ & & 10.11 & 9.66 & -0.45 & 1.029 & & & & & & 10.31 & 10.26 & 10.00 & 10.32 & 9.88 \\ & $^1\Delta_u(\pi \ra \pis)$ & & 10.75 & 10.33 & -0.42 & 1.030 & & & & & & 10.85 & 10.79 & 10.44 & 10.86 & 10.29 \\ @@ -696,18 +699,18 @@ All the BSE calculations have been performed with our locally developed $GW$ sof & $^1\Pi_u$(R) & & 13.98 & 13.94 & -0.04 & 1.004 & & & & & & 13.64 & 13.32 & 13.43 & 13.15 & 13.22 \\ & $^1\Sigma_u^+$(R) & & 13.98 & 13.91 & -0.07 & 1.008 & & & & & & 13.75 & 13.07 & 13.26 & 12.89 & 13.12 \\ & $^1\Pi_u$(R) & & 14.24 & 14.21 & -0.03 & 1.002 & & & & & & 14.52 & 14.00 & 13.67 & 13.96 & 13.49 \\ + \\ \ce{CO} & $^1\Pi(n \ra \pis)$ & 16.46 & 9.54 & 9.19 & -0.34 & 1.029 & & & & & & 8.78 & 8.69 & 8.59 & 8.64 & 8.49 \\ & $^1\Sigma^-(\pi \ra \pis)$ & & 10.25 & 9.90 & -0.35 & 1.023 & & & & & & 10.13 & 10.03 & 9.99 & 10.30 & 9.99 \\ & $^1\Delta(\pi \ra \pis)$ & & 10.71 & 10.39 & -0.32 & 1.023 & & & & & & 10.41 & 10.30 & 10.12 & 10.60 & 10.12 \\ & $^1\Sigma^+$(R) & & 11.88 & 11.85 & -0.03 & 1.005 & & & & & & 11.48 & 11.32 & 11.22 & 11.11 & 10.94 \\ & $^1\Sigma^+$(R) & & 12.39 & 12.37 & -0.02 & 1.003 & & & & & & 11.71 & 11.83 & 11.75 & 11.63 & 11.49 \\ & $^1\Pi$(R) & & 12.37 & 12.32 & -0.05 & 1.004 & & & & & & 12.06 & 12.03 & 11.96 & 11.83 & 11.69 \\ + \\ \ce{C2H4} & $^1B_{3u}(\pi \ra 3s)$ & & & & & & & & & & & 7.35 & 7.34 & 7.42 & 7.29 & 7.35 \\ & $^1B_{1u}(\pi \ra \pis)$ & & & & & & & & & & & 7.95 & 7.91 & 8.02 & 7.92 & 7.91 \\ & $^1B_{1g}(\pi \ra 3p)$ & & & & & & & & & & & 8.01 & 7.99 & 8.08 & 7.95 & 8.03 \\ - & $^3B_{1u}(\pi \ra \pis)$ & & & & & & & & & & & 4.62 & 4.59 & 4.46 & 4.59 & 4.53 \\ - & $^3B_{3u}(\pi \ra 3s)$ & & & & & & & & & & & 7.26 & 7.23 & 7.29 & 7.19 & 7.24 \\ - & $^3B_{1g}(\pi \ra 3p)$ & & & & & & & & & & & 7.97 & 7.95 & 8.03 & 7.91 & 7.98 \\ + \\ \ce{CH2O} & $^1A_2(n \ra \pis)$ & 12.00 & 5.03 & 4.68 & -0.35 & 1.027 & & & & & & 4.04 & 3.92 & 4.01 & 4.07 & 3.97 \\ & $^1B_2(n \ra 3s)$ & & 7.87 & 7.85 & -0.02 & 1.001 & & & & & & 6.64 & 6.50 & 7.23 & 6.56 & 7.18 \\ & $^1B_2(n \ra 3p)$ & & 8.76 & 8.72 & -0.04 & 1.003 & & & & & & 7.56 & 7.53 & 8.12 & 7.57 & 8.07 \\ @@ -724,7 +727,7 @@ All the BSE calculations have been performed with our locally developed $GW$ sof \caption{ Triplet excitation energies (in eV) for various molecules obtained with the aug-cc-pVTZ basis set at various levels of theory. The dynamical correction is computed in the TDA. - \label{tab:BigTab} + \label{tab:BigTabTr} } \begin{ruledtabular} \begin{tabular}{llrrrrrrrrrrrrrrr} @@ -737,18 +740,22 @@ All the BSE calculations have been performed with our locally developed $GW$ sof \ce{H2O} & $^3B_1(n \ra 3s)$ & 13.58 & 8.14 & 7.98 & -0.15 & 1.014 & & & & & & 7.25 & 6.86 & 7.20 & 6.91 & 7.28 \\ & $^3A_2(n \ra 3p)$ & & 9.97 & 9.89 & -0.07 & 1.008 & & & & & & 9.24 & 8.72 & 9.20 & 8.77 & 9.26 \\ & $^3A_1(n \ra 3s)$ & & 10.28 & 10.13 & -0.15 & 1.012 & & & & & & 9.54 & 9.15 & 9.49 & 9.20 & 9.56 \\ + \\ \ce{N2} & $^3\Sigma_u^+(\pi \ra \pis)$ & 19.20 & 9.50 & 8.46 & -1.04 & 1.060 & & & & & & 8.20 & 8.15 & 7.66 & 8.19 & 7.68 \\ & $^3\Pi_g(n \ra \pis)$ & & 9.85 & 9.27 & -0.58 & 1.050 & & & & & & 8.33 & 8.20 & 8.09 & 8.19 & 8.04 \\ & $^3\Delta_u(\pi \ra \pis)$ & & 10.19 & 9.24 & -0.95 & 1.060 & & & & & & 9.30 & 9.25 & 8.91 & 9.30 & 8.87 \\ & $^3\Sigma_u^-(\pi \ra \pis)$ & & 10.89 & 10.06 & -0.82 & 1.058 & & & & & & 10.29 & 10.23 & 9.83 & 10.29 & 9.68 \\ + \\ \ce{CO} & $^3\Pi(n \ra \pis)$ & 16.46 & 8.10 & 7.33 & -0.77 & 1.055 & & & & & & 6.51 & 6.45 & 6.36 & 6.42 & 6.30 \\ & $^3\Sigma^+(\pi \ra \pis)$ & & 9.61 & 9.04 & -0.57 & 1.037 & & & & & & 8.63 & 8.54 & 8.34 & 8.72 & 8.45 \\ & $^3\Delta(\pi \ra \pis)$ & & 10.20 & 9.69 & -0.50 & 1.036 & & & & & & 9.44 & 9.33 & 9.23 & 9.56 & 9.30 \\ & $^3\Sigma_u^-(\pi \ra \pis)$ & & 10.79 & 10.38 & -0.42 & 1.034 & & & & & & 10.10 & 10.01 & 9.81 & 10.27 & 9.82 \\ & $^3\Sigma_u^+$(R) & & 11.48 & 11.38 & -0.10 & 1.010 & & & & & & 10.98 & 10.83 & 10.71 & 10.60 & 10.45 \\ + \\ \ce{C2H4} & $^3B_{1u}(\pi \ra \pis)$ & & & & & & & & & & & 4.62 & 4.59 & 4.46 & 4.59 & 4.53 \\ & $^3B_{3u}(\pi \ra 3s)$ & & & & & & & & & & & 7.26 & 7.23 & 7.29 & 7.19 & 7.24 \\ & $^3B_{1g}(\pi \ra 3p)$ & & & & & & & & & & & 7.97 & 7.95 & 8.03 & 7.91 & 7.98 \\ + \\ \ce{CH2O} & $^3A_2(n \ra \pis)$ & 12.00 & 5.53 & 5.05 & -0.47 & 1.049 & & & & & & 3.58 & 3.46 & 3.56 & 3.59 & 3.57 \\ & $^3A_1(\pi \ra \pis)$ & & 8.15 & 7.32 & -0.83 & 1.067 & & & & & & 6.27 & 6.20 & 5.97 & 6.30 & 6.05 \\ & $^3B_2(n \ra 3s)$ & & 7.51 & 7.54 & 0.03 & 0.994 & & & & & & 6.66 & 6.39 & 7.08 & 6.44 & 7.03 \\