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Pierre-Francois Loos 2022-06-09 16:28:16 +02:00
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Manuscript/CBD.bib
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%% This BibTeX bibliography file was created using BibDesk.
%% https://bibdesk.sourceforge.io/
%% Created for Pierre-Francois Loos at 2022-06-08 17:31:37 +0200
%% Created for Pierre-Francois Loos at 2022-06-08 18:49:54 +0200
%% Saved with string encoding Unicode (UTF-8)

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Manuscript/CBD.tex
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@ -203,7 +203,7 @@ For ionic excited states, like the {\sBoneg} state of CBD, it is particularly im
On top of this CASSCF treatment, CASPT2 calculations are performed within the RS2 contraction scheme, while the NEVPT2 energies are computed within both the partially contracted (PC) and strongly contracted (SC) schemes. \cite{Angeli_2001,Angeli_2001a,Angeli_2002}
Note that PC-NEVPT2 is theoretically more accurate than SC-NEVPT2 due to the larger number of external configurations and greater flexibility.
In order to avoid the intruder state problem in CASPT2, a real-valued level shift of \SI{0.3}{\hartree} is set, \cite{Roos_1995b,Roos_1996} with an additional ionization-potential-electron-affinity (IPEA) shift of \SI{0.25}{\hartree} to avoid systematic underestimation of the vertical excitation energies. \cite{Ghigo_2004,Schapiro_2013,Zobel_2017,Sarkar_2022}
\alert{For the sake of comparison, in some cases, we have also performed multi-reference CI calculations including Davidson correction (MRCI+Q). \cite{Knowles_1988,Werner_1988}}
\alert{For the sake of comparison, for the (4e,4o) active space, we have also performed multi-reference CI calculations including Davidson correction (MRCI+Q). \cite{Knowles_1988,Werner_1988}}
All these calculations are carried out with MOLPRO. \cite{Werner_2020}
%and extended multistate (XMS) CASPT2 calculations are also performed in the cas of strong mixing between states with same spin and spatial symmetries.
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
@ -881,7 +881,7 @@ This has been shown to be clearly beneficial for the automerization barrier and
\item At the SF-ADC level, we have found that, as expected, the extended scheme, SF-ADC(2)-x, systematically worsen the results compared to the cheaper standard version, SF-ADC(2)-s.
Moreover, as previously reported, SF-ADC(2)-s and SF-ADC(3) have opposite error patterns which means that SF-ADC(2.5) emerges as an excellent compromise.
\item \alert{EOM-SF-CCSD shows similar performance than cheaper SF-ADC(2)-s formalism, especially for the excitation energies.
\item \alert{EOM-SF-CCSD shows similar performance than the cheaper SF-ADC(2)-s formalism, especially for the excitation energies.
As previously reported, the two variants including non-iterative triples corrections, EOM-SF-CCSD(dT) and EOM-SF-CCSD(fT), improve the results, the (dT) correction performing slightly better for the vertical excitation energies computed at the {\Dtwo} and {\Dfour} equilibrium geometries.}
\item For the {\Dfour} square planar structure, a faithful energetic description of the excited states is harder to reach at the SF-TD-DFT level because of the strong multi-configurational character.

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Manuscript/sup-CBD.tex
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@ -163,7 +163,7 @@ H -2.092429 0.000000 0.000000
\section{Comment about symmetry: standard vs non-standard orientation}
%%%%%%%%%%%%%%%%%%%%%%%%
At the $D_{4h}$ $T_1$ optimized geometry, we have used the conventional standard orientation where two $C_2$ axes run through the carbon atoms.
\alert{At the $D_{4h}$ $T_1$ optimized geometry, we have used the conventional standard orientation where two $C_2$ axes run through the carbon atoms.
In this conventional orientation, the singlet ground state $1 ^1B_{1g}$ remains $1 ^1B_{1g}$ in the $D_{2h}$ point group and the singlet excited state $1 ^1A_{1g}$ becomes $1 ^1A_g$ in the $D_{2h}$ point group.
Upon rotation of the molecular framework by 45 degrees in the $xy$ plane, the two $C_2$ axes then bisect the carbon-carbon bonds.
This induces a different orbital picture.
@ -179,7 +179,7 @@ The $1 ^1B_{1g}$ ground state is obtained as a singly excited state from that re
In the other (non-standard) orientation, the lowest $^1A_g$ state correlates with the $1 ^1B_{1g}$ ground state, which in this orientation has a strong double-excitation character.
Then, the $1 ^1A_{1g}$ excited state has also a strong double-excitation character, while the $1 ^1B_{2g}$ excited state is obtained by one-electron excitation.
Thus, whatever the orientation of the molecule, we will face the same problem for the reference state.
Note that in the case of the SF formalism, these three singlet states should all be described correctly if one takes the $1 ^3A_{2g}$ state as a reference high spin state, whatever the orientation.
Note that in the case of the SF formalism, these three singlet states should all be described correctly if one takes the $1 ^3A_{2g}$ state as a reference high spin state, whatever the orientation.}
\begin{figure}
\includegraphics[width=\textwidth]{MOs}
@ -253,11 +253,11 @@ Literature & $8.53$\fnm[3] & $1.573$\fnm[3] & $3.208$\fnm[3] & $4.247$\fnm[3] &
\fnt[4]{Value obtained from Ref.~\onlinecite{Lefrancois_2015} at the SF-ADC(2)-x/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[5]{Value obtained from Ref.~\onlinecite{Lefrancois_2015} at the SF-ADC(3)/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[6]{Value obtained from Ref.~\onlinecite{Manohar_2008} at the EOM-SF-CCSD/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[7]{Value obtained from Ref.~\onlinecite{Manohar_2008} at the EOM-SF-CCSD(fT)/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[8]{Value obtained from Ref.~\onlinecite{Manohar_2008} at the EOM-SF-CCSD(dT)/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[9]{Value obtained from Ref.~\onlinecite{Gulania_2021} at the EOM-DEA-CCSD/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
\fnt[10]{Value obtained from Ref.~\onlinecite{Ajala_2017} at the DEA-EOM-CC(3p-1h)/cc-pVDZ level with the geometry obtained at the CCSD/cc-pVDZ level.}
\fnt[11]{Value obtained from Ref.~\onlinecite{Ajala_2017} at the DEA-EOM-CC(4p-2h)/cc-pVDZ level with the geometry obtained at the CCSD/cc-pVDZ level.}
\fnt[7]{\alert{Value obtained from Ref.~\onlinecite{Manohar_2008} at the EOM-SF-CCSD(fT)/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}}
\fnt[8]{\alert{Value obtained from Ref.~\onlinecite{Manohar_2008} at the EOM-SF-CCSD(dT)/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}}
\fnt[9]{\alert{Value obtained from Ref.~\onlinecite{Gulania_2021} at the EOM-DEA-CCSD/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}}
\fnt[10]{\alert{Value obtained from Ref.~\onlinecite{Ajala_2017} at the DEA-EOM-CC(3p-1h)/cc-pVDZ level with the geometry obtained at the CCSD/cc-pVDZ level.}}
\fnt[11]{\alert{Value obtained from Ref.~\onlinecite{Ajala_2017} at the DEA-EOM-CC(4p-2h)/cc-pVDZ level with the geometry obtained at the CCSD/cc-pVDZ level.}}
\end{table*}
%\end{squeezetable}