Merge branch 'master' of https://git.irsamc.ups-tlse.fr/loos/CBD
This commit is contained in:
commit
5b83268c83
@ -5,6 +5,11 @@
|
|||||||
\usepackage[utf8]{inputenc}
|
\usepackage[utf8]{inputenc}
|
||||||
\usepackage[T1]{fontenc}
|
\usepackage[T1]{fontenc}
|
||||||
\usepackage{txfonts}
|
\usepackage{txfonts}
|
||||||
|
\usepackage{siunitx}
|
||||||
|
\DeclareSIUnit[number-unit-product = {\,}]
|
||||||
|
\cal{cal}
|
||||||
|
\DeclareSIUnit\kcal{\kilo\cal}
|
||||||
|
\newcommand{\kcalmol}{\si{\kcal\per\mole}}
|
||||||
|
|
||||||
\usepackage[
|
\usepackage[
|
||||||
colorlinks=true,
|
colorlinks=true,
|
||||||
@ -39,8 +44,8 @@
|
|||||||
\newcommand{\Dtwo}{$D_{2h}$}
|
\newcommand{\Dtwo}{$D_{2h}$}
|
||||||
\newcommand{\Dfour}{$D_{4h}$}
|
\newcommand{\Dfour}{$D_{4h}$}
|
||||||
|
|
||||||
%\sisetup{range-phrase=--}
|
\sisetup{range-phrase=--}
|
||||||
%\sisetup{range-units=single}
|
\sisetup{range-units=single}
|
||||||
|
|
||||||
%states
|
%states
|
||||||
%D2h states
|
%D2h states
|
||||||
@ -77,6 +82,67 @@
|
|||||||
|
|
||||||
%\maketitle
|
%\maketitle
|
||||||
|
|
||||||
|
\begin{squeezetable}
|
||||||
|
\begin{table*}
|
||||||
|
\caption{Energy differences between the various methods and the reference TBE values.
|
||||||
|
Note that AB stands for the automerization barrier and is reported in \si{\kcalmol}.
|
||||||
|
The numbers reported in parenthesis are the percentage of single excitations involved in the transition ($\%T_1$) calculated at the CC3/aug-cc-pVTZ level.
|
||||||
|
The values between square brackets have been obtained by extrapolation via the procedure described in the corresponding footnote.}
|
||||||
|
\label{tab:TBE}
|
||||||
|
\begin{ruledtabular}
|
||||||
|
\begin{tabular}{lrrrrrrr}
|
||||||
|
%\begin{tabular}{*{1}{*{8}{l}}}
|
||||||
|
& &\mc{3}{c}{{\Dtwo} excitation energies (eV)} & \mc{3}{c}{{\Dfour} excitation energies (eV)} \\
|
||||||
|
\cline{3-5} \cline{6-8}
|
||||||
|
Method & AB & {\tBoneg}(99\%) & {\sBoneg}(95\%)& {\twoAg}(1\%) & {\Atwog} & {\Aoneg} & {\Btwog} \\
|
||||||
|
\hline
|
||||||
|
SF-TD-B3LYP & $10.41$ & $0.241$ & $-0.926$ & $-0.161$ & $-0.164$ & $-1.028$ & $-1.501$ \\
|
||||||
|
SF-TD-PBE0 & $8.95$ & $0.220$ & $-0.829$ & $-0.068$ & $-0.163$ & $-0.903$ & $-1.357$ \\
|
||||||
|
SF-TD-BHHLYP & $3.79$ & $0.078$ & $-0.393$ & $0.343$ & $-0.099$ & $-0.251$ & $-0.603$ \\
|
||||||
|
SF-TD-M06-2X & $1.42$ & $0.000$ & $-0.354$ & $0.208$ & $-0.066$ & $-0.097$ & $-0.432$ \\
|
||||||
|
SF-TD-CAM-B3LYP & $9.90$ & $0.280$ & $-0.807$ & $-0.011$ & $-0.134$ & $-0.920$ & $-1.370$ \\
|
||||||
|
SF-TD-$\omega $B97X-V & $10.01$ & $0.335$ & $-0.774$ & $0.064$ & $-0.118$ & $-0.928$ & $-1.372$ \\
|
||||||
|
SF-TD-LC-$\omega $PBE08 & $10.81$ & $0.435$ & $-0.710$ & $0.199$ & $-0.086$ & $-0.939$ & $-1.376$ \\
|
||||||
|
SF-TD-M11 & $2.29$ & $0.097$ & $-0.474$ & $0.151$ & $-0.063$ & $-0.312$ & $-0.675$ \\[0.1cm]
|
||||||
|
SF-ADC(2)-s & $-0.30$ & $0.069$ & $-0.026$ & $-0.018$ & $0.112$ & $0.112$ & $-0.190$ \\
|
||||||
|
SF-ADC(2)-x & $1.44$ & $0.077$ & $-0.094$ & $-0.446$ & $0.068$ & $-0.409$ & $-0.303$ \\
|
||||||
|
SF-ADC(2.5) & $0.18$ & $0.013$ & $0.006$ & $0.029$ & $0.024$ & $0.094$ & $-0.185$ \\
|
||||||
|
SF-ADC(3) & $0.65$ & $-0.043$ & $0.037$ & $0.075$ & $-0.065$ & $0.075$ & $-0.181$ \\[0.1cm]
|
||||||
|
CCSD & $0.95$ & & & & $-0.059$ & $0.100$ & \\
|
||||||
|
CC3 & $-1.05$ & $-0.060$ & $-0.006$ & $0.628$ & & $0.162$ & $0.686$ \\
|
||||||
|
CCSDT & $-0.25$ & $-0.051$ & $0.014$ & $0.280$ & $0.005$ & $0.131$ & $0.503$ \\
|
||||||
|
CC4 & $-0.11$ & & $0.003$ & $-0.006$ & & $0.011$ & $-0.013$ \\
|
||||||
|
CCSDTQ & $0.00$ & & $0.000$ & $0.000$ & $0.000$ & $0.000$ & $0.000$ \\[0.1cm]
|
||||||
|
CASSCF(4,4) & $-1.55$ & $0.208$ & $1.421$ & $0.292$ & $0.290$ & $0.734$ & $1.390$ \\
|
||||||
|
CASPT2(4,4) & $-1.16$ & $-0.050$ & $-0.202$ & $-0.077$ & $-0.016$ & $0.006$ & $-0.399$ \\
|
||||||
|
%XMS-CASPT2(4,4) & & & & $-0.035$ & & & \\
|
||||||
|
SC-NEVPT2(4,4) & $0.30$ & $-0.083$ & $-0.703$ & $-0.041$ & $-0.120$ & $-0.072$ & $-0.979$ \\
|
||||||
|
PC-NEVPT2(4,4) & $0.31$ & $-0.080$ & $-0.757$ & $-0.066$ & $-0.118$ & $-0.097$ & $-1.031$ \\
|
||||||
|
%MRCI(4,4) & & $0.106$ & $0.553$ & $0.121$ & $0.127$ & $0.324$ & $0.381$ \\[0.1cm]
|
||||||
|
CASSCF(12,12) & $2.66$ & $0.224$ & $0.719$ & $0.068$ & $0.226$ & $0.443$ & $0.600$ \\
|
||||||
|
CASPT2(12,12) & $-0.42$& $0.018$ & $0.058$ & $-0.106$ & $0.039$ & $0.038$ & $-0.108$ \\
|
||||||
|
%XMS-CASPT2(12,12) & & & & $-0.090$ & & & \\
|
||||||
|
SC-NEVPT2(12,12) & $-0.64$ & $0.039$ & $0.063$ & $-0.063$ & $0.021$ & $0.046$ & $-0.142$ \\
|
||||||
|
PC-NEVPT2(12,12) & $-0.65$ & $0.000$ & $-0.062$ & $-0.093$ & $-0.013$ & $-0.024$ & $-0.278$ \\[0.1cm]
|
||||||
|
%CIPSI & & $-0.001\pm 0.030$ & $0.017\pm 0.035$ & $-0.120\pm 0.090$ & $0.025\pm 0.029$ & $0.130\pm 0.050$ & \\
|
||||||
|
\bf{TBE} & $[\bf{8.93}]$\fnm[1] & $[\bf{1.462}]$\fnm[2] & $[\bf{3.125}]$\fnm[3] & $[\bf{4.149}]$\fnm[3] & $[\bf{0.144}]$\fnm[4] & $[\bf{1.500}]$\fnm[3] & $[\bf{2.034}]$\fnm[3] \\[0.1cm]
|
||||||
|
Literature & $8.53$\fnm[5] & $1.573$\fnm[5] & $3.208$\fnm[5] & $4.247$\fnm[5] & $0.266$\fnm[5] & $1.664$\fnm[5] & $1.910$\fnm[5] \\
|
||||||
|
& $10.35$\fnm[6] & $1.576$\fnm[6] & $3.141$\fnm[6] & $3.796$\fnm[6] & $0.217$\fnm[6] & $1.123$\fnm[6] & $1.799$\fnm[6]\\
|
||||||
|
& $9.58$ \fnm[7]& $1.456$\fnm[7] & $3.285$\fnm[7] & $4.334$\fnm[7] & $0.083$\fnm[7] & $1.621$\fnm[7] & $1.930$\fnm[7] \\
|
||||||
|
& $7.48$\fnm[8]& $1.654$\fnm[8] & $3.416$\fnm[8] & $4.360$\fnm[8] & $0.369$\fnm[8] & $1.824$\fnm[8] & $2.143$\fnm[8] \\
|
||||||
|
\end{tabular}
|
||||||
|
|
||||||
|
\end{ruledtabular}
|
||||||
|
\fnt[1]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CC4/aug-cc-pVTZ and CC4/aug-cc-pVDZ.}
|
||||||
|
\fnt[2]{Value obtained using the NEVPT2(12,12) one.}
|
||||||
|
\fnt[3]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CC4/aug-cc-pVTZ and CC4/aug-cc-pVDZ.}
|
||||||
|
\fnt[4]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CCSDT/aug-cc-pVTZ and CCSDT/aug-cc-pVDZ.}
|
||||||
|
\fnt[5]{Value obtained from Ref.~\onlinecite{Lefrancois_2015} at the SF-ADC(2)-s/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
|
||||||
|
\fnt[6]{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[7]{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[8]{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.}
|
||||||
|
\end{table*}
|
||||||
|
\end{squeezetable}
|
||||||
|
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
{\Dtwo} geometry for the autoisomerization barrier obtained at the CASPT2(12,12)/aug-cc-pVTZ
|
{\Dtwo} geometry for the autoisomerization barrier obtained at the CASPT2(12,12)/aug-cc-pVTZ
|
||||||
@ -137,13 +203,13 @@ H -2.092429 0.000000 0.000000
|
|||||||
%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
\begin{squeezetable}
|
\begin{squeezetable}
|
||||||
\begin{table}
|
\begin{table}
|
||||||
\caption{$\left\langle S^2 \right\rangle$ value for the different excited states considered at the aug-cc-pVTZ basis for the {\Dtwo} and {\Dfour} structures.
|
\caption{$\expval*{S^2}$ values for the different excited states computed at the SF-TD-DFT/aug-cc-pVTZ level for the {\Dtwo} and {\Dfour} structures.
|
||||||
}
|
}
|
||||||
% \label{tab:Ssquare}
|
% \label{tab:Ssquare}
|
||||||
\begin{ruledtabular}
|
\begin{ruledtabular}
|
||||||
\begin{tabular}{lrrrrrr}
|
\begin{tabular}{lrrrrrr}
|
||||||
|
|
||||||
&\mc{2}{r}{$\left\langle S^2 \right\rangle$ ({\Dtwo} )} & \mc{3}{r}{{$\left\langle S^2 \right\rangle$ (\Dfour})} \\
|
&\mc{2}{r}{$\expval*{S^2}$ ({\Dtwo} )} & \mc{3}{r}{{$\expval*{S^2}$ (\Dfour})} \\
|
||||||
\cline{2-4} \cline{5-7}
|
\cline{2-4} \cline{5-7}
|
||||||
Method & {\tBoneg} & {\sBoneg} & {\twoAg} & {\Atwog} & {\Aoneg} & {\Btwog} \\
|
Method & {\tBoneg} & {\sBoneg} & {\twoAg} & {\Atwog} & {\Aoneg} & {\Btwog} \\
|
||||||
\hline
|
\hline
|
||||||
@ -178,5 +244,7 @@ SF-TD-M11
|
|||||||
%%% %%% %%% %%%
|
%%% %%% %%% %%%
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
|
|
||||||
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
|
\bibliography{CBD}
|
||||||
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
\end{document}
|
\end{document}
|
||||||
|
|||||||
@ -262,6 +262,9 @@ and so on.
|
|||||||
If neither CC4, nor CCSDT are feasible, then we rely on NEVPT2(12,12).
|
If neither CC4, nor CCSDT are feasible, then we rely on NEVPT2(12,12).
|
||||||
The procedure for each extrapolated value is explicitly mentioned as a footnote.
|
The procedure for each extrapolated value is explicitly mentioned as a footnote.
|
||||||
Note that, due to error bar inherently linked to the CIPSI calculations (see Subsection \ref{sec:SCI}), these are mostly used as an additional safety net to further check the convergence of the CCSDTQ estimates.
|
Note that, due to error bar inherently linked to the CIPSI calculations (see Subsection \ref{sec:SCI}), these are mostly used as an additional safety net to further check the convergence of the CCSDTQ estimates.
|
||||||
|
|
||||||
|
A table gathering these TBEs as well as literature data for the automerization barrier and the vertical excitation energies can be found in the {\SupInf}.
|
||||||
|
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
|
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
@ -314,13 +317,13 @@ Table \ref{tab:geometries} reports the key geometrical parameters obtained at th
|
|||||||
%%% %%% %%% %%%
|
%%% %%% %%% %%%
|
||||||
|
|
||||||
%================================================
|
%================================================
|
||||||
\subsection{automerization barrier}
|
\subsection{Automerization barrier}
|
||||||
\label{sec:auto}
|
\label{sec:auto}
|
||||||
|
|
||||||
%%% TABLE I %%%
|
%%% TABLE I %%%
|
||||||
\begin{squeezetable}
|
\begin{squeezetable}
|
||||||
\begin{table}
|
\begin{table}
|
||||||
\caption{automerization barrier (in \kcalmol) of CBD computed with various computational methods and basis sets.
|
\caption{Automerization barrier (in \kcalmol) of CBD computed with various computational methods and basis sets.
|
||||||
The values in square parenthesis have been obtained by extrapolation via the procedure described in the corresponding footnote.}
|
The values in square parenthesis have been obtained by extrapolation via the procedure described in the corresponding footnote.}
|
||||||
\label{tab:auto_standard}
|
\label{tab:auto_standard}
|
||||||
\begin{ruledtabular}
|
\begin{ruledtabular}
|
||||||
@ -372,7 +375,7 @@ CCSDTQ & $7.51$ & $[ 7.89]$\fnm[4]& $[ 8.93]$\fnm[5]& $[ 9.11]$\fnm[6]\\
|
|||||||
%%% FIGURE II %%%
|
%%% FIGURE II %%%
|
||||||
\begin{figure*}
|
\begin{figure*}
|
||||||
\includegraphics[width=\linewidth]{AB_AVTZ}
|
\includegraphics[width=\linewidth]{AB_AVTZ}
|
||||||
\caption{automerization barrier (in \si{\kcalmol}) of CBD at various levels of theory using the aug-cc-pVTZ basis.}
|
\caption{Automerization barrier (in \si{\kcalmol}) of CBD at various levels of theory using the aug-cc-pVTZ basis.}
|
||||||
\label{fig:AB}
|
\label{fig:AB}
|
||||||
\end{figure*}
|
\end{figure*}
|
||||||
%%% %%% %%% %%%
|
%%% %%% %%% %%%
|
||||||
@ -616,36 +619,43 @@ This further motivates the ``pyramidal'' extrapolation scheme that we have emplo
|
|||||||
Again, the extended version, SF-ADC(2)-x, does not seem to be relevant in the present context with much larger errors than the other schemes.
|
Again, the extended version, SF-ADC(2)-x, does not seem to be relevant in the present context with much larger errors than the other schemes.
|
||||||
Also, as reported previously, \cite{Loos_2020d} SF-ADC(2)-s and SF-ADC(3) have mirror error patterns which makes SF-ADC(2.5) particularly accurate with a maximum error of \SI{0.029}{\eV} for the doubly-excited state {\twoAg}.
|
Also, as reported previously, \cite{Loos_2020d} SF-ADC(2)-s and SF-ADC(3) have mirror error patterns which makes SF-ADC(2.5) particularly accurate with a maximum error of \SI{0.029}{\eV} for the doubly-excited state {\twoAg}.
|
||||||
|
|
||||||
|
Let us now move to the discussion of the results concerning standard wave function methods that are reported in Table \ref{tab:D2h}.
|
||||||
|
Regarding the multi-configurational calculations, the most striking result is the poor description of the {\sBoneg} ionic state, especially with the (4e,4o) active space where CASSCF predicts this state higher in energy than the {\twoAg} state.
|
||||||
|
Of course, the PT2 correction is able to correct the root-flipping problem but cannot provide quantitative excitation energies due to the poor zeroth-order treatment.
|
||||||
|
Another ripple effect of the unreliability of the reference wave function is the large difference between CASPT2 and NEVPT2 that differ by half an \si{\eV}.
|
||||||
|
This feature is characteristic of the inadequacy of the active space.
|
||||||
|
For the two other states, {\tBoneg} and {\twoAg}, the errors at the CASPT2(4,4) and NEVPT2(4,4) levels are much smaller and typically below \SI{0.1}{\eV}.
|
||||||
|
Using a larger active resolves most of these issues: CASSCF predicts the correct state ordering (though the ionic state is still badly described in term of energetics), CASPT2 and NEVPT2 excitation energies are much closer, and their accuracy is often improved (especially for the triplet state) although it is difficult to reach chemical accuracy (\ie, an error below \SI{0.043}{\eV}) on a systematic basis.
|
||||||
|
|
||||||
\alert{Due to the lack of dynamic correlation, CASSCF poorly describes the {\sBoneg} ionic state.
|
Finally, for the CC models, the two states with a large $\%T_1$ value, {\tBoneg} and {\sBoneg}, are already extremely accurate at the CC3 level, and systematically improved by CCSDT and CC4.
|
||||||
Although the automerization barrier is not bad with the (4e,4o) active space, the {\sBoneg} is poorly describe mainly due to the poor CASSCF treatement that the second-order correction cannot fix.}
|
For the doubly-excited state, {\twoAg}, the convergence of the CC expansion is much slower but it is worth pointing out that the inclusion of approximate quadruples via CC4 is particularly effective in the present case.
|
||||||
|
The CCSDTQ excitation energies (which are used to define the TBEs) are systematically within the error bar of the CIPSI calculations.
|
||||||
|
|
||||||
Let us now move to discussion of the results of standard wave function methods that are reported in Table \ref{tab:D2h}.
|
%For the multi-configurational methods, the smallest active space considered is four electrons in four orbitals, for CASSCF(4,4) we have small energy variations throughout bases for the {\tBoneg} and the {\twoAg} states but a larger variation for the {\sBoneg} state with around \SI{0.1}{\eV}.
|
||||||
Then we review the vertical energies obtained with multi-reference methods.
|
%We can observe that we have the inversion of the states compared to all methods discussed so far between the {\twoAg} and {\sBoneg} states with {\sBoneg} higher than {\twoAg} due to the lack of dynamical correlation in the CASSCF methods.
|
||||||
For the multi-configurational methods, the smallest active space considered is four electrons in four orbitals, for CASSCF(4,4) we have small energy variations throughout bases for the {\tBoneg} and the {\twoAg} states but a larger variation for the {\sBoneg} state with around \SI{0.1}{\eV}.
|
%The {\sBoneg} state values in CASSCF(4,4) is much higher than for any of the other methods discussed so far.
|
||||||
We can observe that we have the inversion of the states compared to all methods discussed so far between the {\twoAg} and {\sBoneg} states with {\sBoneg} higher than {\twoAg} due to the lack of dynamical correlation in the CASSCF methods.
|
%With CASPT2(4,4) we retrieve the right ordering between the states and we see large energy differences with the CASSCF values.
|
||||||
The {\sBoneg} state values in CASSCF(4,4) is much higher than for any of the other methods discussed so far.
|
%Indeed, we have approximatively \SIrange{0.22}{0.25}{\eV} of energy difference for the triplet state for all bases and \SIrange{0.32}{0.36}{\eV} for the {\twoAg} state, the largest energy difference is for the {\sBoneg} state with \SIrange{1.5}{1.6}{\eV}.
|
||||||
With CASPT2(4,4) we retrieve the right ordering between the states and we see large energy differences with the CASSCF values.
|
%For the XMS-CASPT2(4,4) only the {\twoAg} state is described with values similar than for the CAPST2(4,4) method.
|
||||||
Indeed, we have approximatively \SIrange{0.22}{0.25}{\eV} of energy difference for the triplet state for all bases and \SIrange{0.32}{0.36}{\eV} for the {\twoAg} state, the largest energy difference is for the {\sBoneg} state with \SIrange{1.5}{1.6}{\eV}.
|
%For the NEVPT2(4,4) methods (SC-NEVPT2 and PC-NEVPT2) the vertical energies are similar for the {\sBoneg} and the {\twoAg} states with approximatively \SIrange{0.002}{0.003}{\eV} and \SIrange{0.02}{0.03}{\eV} of energy difference for all bases, respectively.
|
||||||
For the XMS-CASPT2(4,4) only the {\twoAg} state is described with values similar than for the CAPST2(4,4) method.
|
%The energy difference for the {\sBoneg} state is slightly larger with \SI{0.05}{\eV} for all bases.
|
||||||
For the NEVPT2(4,4) methods (SC-NEVPT2 and PC-NEVPT2) the vertical energies are similar for the {\sBoneg} and the {\twoAg} states with approximatively \SIrange{0.002}{0.003}{\eV} and \SIrange{0.02}{0.03}{\eV} of energy difference for all bases, respectively.
|
%Note that for this state the vertical energy varies of \SI{0.23}{eV} from the 6-31+G(d) basis to the aug-cc-pVDZ one.
|
||||||
The energy difference for the {\sBoneg} state is slightly larger with \SI{0.05}{\eV} for all bases.
|
%Then we use a larger active space with twelve electrons in twelve orbitals, the CASSF(12,12) values are close to the CASSCF(4,4) value for the triplet state with 0.01-0.02 eV of energy differences.
|
||||||
Note that for this state the vertical energy varies of \SI{0.23}{eV} from the 6-31+G(d) basis to the aug-cc-pVDZ one.
|
%For the {\twoAg} state we have an energy difference of about \SI{0.2}{eV} between the CASSCF(4,4) and the CASSCF(12,12) values.
|
||||||
Then we use a larger active space with twelve electrons in twelve orbitals, the CASSF(12,12) values are close to the CASSCF(4,4) value for the triplet state with 0.01-0.02 eV of energy differences.
|
%We can notice that increasing the size of the active space gives the right ordering for the states and we have an energy difference of around \SI{0.7}{\eV} for the {\sBoneg} state between CASSCF(4,4) and the CASSCF(12,12) values.
|
||||||
For the {\twoAg} state we have an energy difference of about \SI{0.2}{eV} between the CASSCF(4,4) and the CASSCF(12,12) values.
|
%The CASPT2(12,12) method decreases the energy of all states compared to the CASSCF(12,12) method, again the decrease is not the same for all states.
|
||||||
We can notice that increasing the size of the active space gives the right ordering for the states and we have an energy difference of around \SI{0.7}{\eV} for the {\sBoneg} state between CASSCF(4,4) and the CASSCF(12,12) values.
|
%We have a diminution from CASSCF to CASPT2 of about \SIrange{0.17}{0.2}{\eV} for the {\tBoneg} and the {\twoAg} states and for the different bases.
|
||||||
The CASPT2(12,12) method decreases the energy of all states compared to the CASSCF(12,12) method, again the decrease is not the same for all states.
|
%Again, the energy difference for the {\twoAg} state is larger with \SIrange{0.5}{0.7}{\eV} depending on the basis.
|
||||||
We have a diminution from CASSCF to CASPT2 of about \SIrange{0.17}{0.2}{\eV} for the {\tBoneg} and the {\twoAg} states and for the different bases.
|
%In a similar way than with XMS-CASPT2(4,4), XMS-CASPT(12,12) only describes the {\twoAg} state and the vertical energies for this state are close to the CASPT(12,12) values.
|
||||||
Again, the energy difference for the {\twoAg} state is larger with \SIrange{0.5}{0.7}{\eV} depending on the basis.
|
%For the NEVPT2(12,12) schemes we see that for the triplet and the {\twoAg} states the energies are similar with an energy difference between the SC-NEVPT2(12,12) and the PC-NEVPT2(12,12) values of about \SIrange{0.03}{0.04}{\eV} and \SIrange{0.02}{0.03}{\eV} respectively.
|
||||||
In a similar way than with XMS-CASPT2(4,4), XMS-CASPT(12,12) only describes the {\twoAg} state and the vertical energies for this state are close to the CASPT(12,12) values.
|
|
||||||
For the NEVPT2(12,12) schemes we see that for the triplet and the {\twoAg} states the energies are similar with an energy difference between the SC-NEVPT2(12,12) and the PC-NEVPT2(12,12) values of about \SIrange{0.03}{0.04}{\eV} and \SIrange{0.02}{0.03}{\eV} respectively.
|
|
||||||
|
|
||||||
First we discuss the CC values, we have computed the vertical energies at the CCSDT and CCSDTQ level as well as their approximation the CC3 and CC4 methods, respectively.
|
|
||||||
We can notice that for the {\tBoneg} and the {\sBoneg} states the CCSDT and the CC3 values are close with an energy difference of \SIrange{0.01}{0.02}{\eV} for all bases.
|
%First we discuss the CC values, we have computed the vertical energies at the CCSDT and CCSDTQ level as well as their approximation the CC3 and CC4 methods, respectively.
|
||||||
The energy difference is larger for the {\twoAg} state with around \SIrange{0.35}{0.38}{\eV}.
|
%We can notice that for the {\tBoneg} and the {\sBoneg} states the CCSDT and the CC3 values are close with an energy difference of \SIrange{0.01}{0.02}{\eV} for all bases.
|
||||||
The same observation can be done for CCSDTQ and CC4 with similar vertical energies for all bases.
|
%The energy difference is larger for the {\twoAg} state with around \SIrange{0.35}{0.38}{\eV}.
|
||||||
Note that the {\tBoneg} state can not be described with these methods.
|
%The same observation can be done for CCSDTQ and CC4 with similar vertical energies for all bases.
|
||||||
For the CC methods taking into account the quadruple excitations is necessary to have a good description of the doubly excited state {\twoAg}.
|
%Note that the {\tBoneg} state can not be described with these methods.
|
||||||
|
%For the CC methods taking into account the quadruple excitations is necessary to have a good description of the doubly excited state {\twoAg}.
|
||||||
|
|
||||||
%Figure \ref{fig:D2h} shows the vertical energies of the studied excited states described in Tables \ref{tab:sf_tddft_D2h} and \ref{tab:D2h}.
|
%Figure \ref{fig:D2h} shows the vertical energies of the studied excited states described in Tables \ref{tab:sf_tddft_D2h} and \ref{tab:D2h}.
|
||||||
%We see that the SF-TD-DFT vertical energies are rather close to the TBE one for the doubly excited state {\twoAg}.
|
%We see that the SF-TD-DFT vertical energies are rather close to the TBE one for the doubly excited state {\twoAg}.
|
||||||
@ -876,134 +886,74 @@ Note that CASPT2 improve a lot the description of all the states compared to CAS
|
|||||||
The various TD-DFT functionals are not able to describe correctly the two singlet excited states.
|
The various TD-DFT functionals are not able to describe correctly the two singlet excited states.
|
||||||
|
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
\subsubsection{Theoretical best estimates}
|
%\subsubsection{Theoretical best estimates}
|
||||||
\label{sec:TBE}
|
%\label{sec:TBE}
|
||||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
|
|
||||||
\begin{squeezetable}
|
|
||||||
\begin{table*}
|
|
||||||
\caption{Energy differences between the various methods and the reference TBE values.
|
|
||||||
Note that AB stands for the automerization barrier and is reported in \si{\kcalmol}.
|
|
||||||
The numbers reported in parenthesis are the percentage of single excitations involved in the transition ($\%T_1$) calculated at the CC3/aug-cc-pVTZ level.
|
|
||||||
The values between square brackets have been obtained by extrapolation via the procedure described in the corresponding footnote.}
|
|
||||||
\label{tab:TBE}
|
|
||||||
\begin{ruledtabular}
|
|
||||||
\begin{tabular}{lrrrrrrr}
|
|
||||||
%\begin{tabular}{*{1}{*{8}{l}}}
|
|
||||||
& &\mc{3}{c}{{\Dtwo} excitation energies (eV)} & \mc{3}{c}{{\Dfour} excitation energies (eV)} \\
|
|
||||||
\cline{3-5} \cline{6-8}
|
|
||||||
Method & AB & {\tBoneg}(99\%) & {\sBoneg}(95\%)& {\twoAg}(1\%) & {\Atwog} & {\Aoneg} & {\Btwog} \\
|
|
||||||
\hline
|
|
||||||
SF-TD-B3LYP & $10.41$ & $0.241$ & $-0.926$ & $-0.161$ & $-0.164$ & $-1.028$ & $-1.501$ \\
|
|
||||||
SF-TD-PBE0 & $8.95$ & $0.220$ & $-0.829$ & $-0.068$ & $-0.163$ & $-0.903$ & $-1.357$ \\
|
|
||||||
SF-TD-BHHLYP & $3.79$ & $0.078$ & $-0.393$ & $0.343$ & $-0.099$ & $-0.251$ & $-0.603$ \\
|
|
||||||
SF-TD-M06-2X & $1.42$ & $0.000$ & $-0.354$ & $0.208$ & $-0.066$ & $-0.097$ & $-0.432$ \\
|
|
||||||
SF-TD-CAM-B3LYP & $9.90$ & $0.280$ & $-0.807$ & $-0.011$ & $-0.134$ & $-0.920$ & $-1.370$ \\
|
|
||||||
SF-TD-$\omega $B97X-V & $10.01$ & $0.335$ & $-0.774$ & $0.064$ & $-0.118$ & $-0.928$ & $-1.372$ \\
|
|
||||||
SF-TD-LC-$\omega $PBE08 & $10.81$ & $0.435$ & $-0.710$ & $0.199$ & $-0.086$ & $-0.939$ & $-1.376$ \\
|
|
||||||
SF-TD-M11 & $2.29$ & $0.097$ & $-0.474$ & $0.151$ & $-0.063$ & $-0.312$ & $-0.675$ \\[0.1cm]
|
|
||||||
SF-ADC(2)-s & $-0.30$ & $0.069$ & $-0.026$ & $-0.018$ & $0.112$ & $0.112$ & $-0.190$ \\
|
|
||||||
SF-ADC(2)-x & $1.44$ & $0.077$ & $-0.094$ & $-0.446$ & $0.068$ & $-0.409$ & $-0.303$ \\
|
|
||||||
SF-ADC(2.5) & $0.18$ & $0.013$ & $0.006$ & $0.029$ & $0.024$ & $0.094$ & $-0.185$ \\
|
|
||||||
SF-ADC(3) & $0.65$ & $-0.043$ & $0.037$ & $0.075$ & $-0.065$ & $0.075$ & $-0.181$ \\[0.1cm]
|
|
||||||
CCSD & $0.95$ & & & & $-0.059$ & $0.100$ & \\
|
|
||||||
CC3 & $-1.05$ & $-0.060$ & $-0.006$ & $0.628$ & & $0.162$ & $0.686$ \\
|
|
||||||
CCSDT & $-0.25$ & $-0.051$ & $0.014$ & $0.280$ & $0.005$ & $0.131$ & $0.503$ \\
|
|
||||||
CC4 & $-0.11$ & & $0.003$ & $-0.006$ & & $0.011$ & $-0.013$ \\
|
|
||||||
CCSDTQ & $0.00$ & & $0.000$ & $0.000$ & $0.000$ & $0.000$ & $0.000$ \\[0.1cm]
|
|
||||||
CASSCF(4,4) & $-1.55$ & $0.208$ & $1.421$ & $0.292$ & $0.290$ & $0.734$ & $1.390$ \\
|
|
||||||
CASPT2(4,4) & $-1.16$ & $-0.050$ & $-0.202$ & $-0.077$ & $-0.016$ & $0.006$ & $-0.399$ \\
|
|
||||||
%XMS-CASPT2(4,4) & & & & $-0.035$ & & & \\
|
|
||||||
SC-NEVPT2(4,4) & $0.30$ & $-0.083$ & $-0.703$ & $-0.041$ & $-0.120$ & $-0.072$ & $-0.979$ \\
|
|
||||||
PC-NEVPT2(4,4) & $0.31$ & $-0.080$ & $-0.757$ & $-0.066$ & $-0.118$ & $-0.097$ & $-1.031$ \\
|
|
||||||
%MRCI(4,4) & & $0.106$ & $0.553$ & $0.121$ & $0.127$ & $0.324$ & $0.381$ \\[0.1cm]
|
|
||||||
CASSCF(12,12) & $2.66$ & $0.224$ & $0.719$ & $0.068$ & $0.226$ & $0.443$ & $0.600$ \\
|
|
||||||
CASPT2(12,12) & $-0.42$& $0.018$ & $0.058$ & $-0.106$ & $0.039$ & $0.038$ & $-0.108$ \\
|
|
||||||
%XMS-CASPT2(12,12) & & & & $-0.090$ & & & \\
|
|
||||||
SC-NEVPT2(12,12) & $-0.64$ & $0.039$ & $0.063$ & $-0.063$ & $0.021$ & $0.046$ & $-0.142$ \\
|
|
||||||
PC-NEVPT2(12,12) & $-0.65$ & $0.000$ & $-0.062$ & $-0.093$ & $-0.013$ & $-0.024$ & $-0.278$ \\[0.1cm]
|
|
||||||
%CIPSI & & $-0.001\pm 0.030$ & $0.017\pm 0.035$ & $-0.120\pm 0.090$ & $0.025\pm 0.029$ & $0.130\pm 0.050$ & \\
|
|
||||||
\bf{TBE} & $[\bf{8.93}]$\fnm[1] & $[\bf{1.462}]$\fnm[2] & $[\bf{3.125}]$\fnm[3] & $[\bf{4.149}]$\fnm[3] & $[\bf{0.144}]$\fnm[4] & $[\bf{1.500}]$\fnm[3] & $[\bf{2.034}]$\fnm[3] \\[0.1cm]
|
|
||||||
Literature & $8.53$\fnm[5] & $1.573$\fnm[5] & $3.208$\fnm[5] & $4.247$\fnm[5] & $0.266$\fnm[5] & $1.664$\fnm[5] & $1.910$\fnm[5] \\
|
|
||||||
& $10.35$\fnm[6] & $1.576$\fnm[6] & $3.141$\fnm[6] & $3.796$\fnm[6] & $0.217$\fnm[6] & $1.123$\fnm[6] & $1.799$\fnm[6]\\
|
|
||||||
& $9.58$ \fnm[7]& $1.456$\fnm[7] & $3.285$\fnm[7] & $4.334$\fnm[7] & $0.083$\fnm[7] & $1.621$\fnm[7] & $1.930$\fnm[7] \\
|
|
||||||
& $7.48$\fnm[8]& $1.654$\fnm[8] & $3.416$\fnm[8] & $4.360$\fnm[8] & $0.369$\fnm[8] & $1.824$\fnm[8] & $2.143$\fnm[8] \\
|
|
||||||
\end{tabular}
|
|
||||||
|
|
||||||
\end{ruledtabular}
|
|
||||||
\fnt[1]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CC4/aug-cc-pVTZ and CC4/aug-cc-pVDZ.}
|
|
||||||
\fnt[2]{Value obtained using the NEVPT2(12,12) one.}
|
|
||||||
\fnt[3]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CC4/aug-cc-pVTZ and CC4/aug-cc-pVDZ.}
|
|
||||||
\fnt[4]{Value obtained using CCSDTQ/aug-cc-pVDZ corrected by the difference between CCSDT/aug-cc-pVTZ and CCSDT/aug-cc-pVDZ.}
|
|
||||||
\fnt[5]{Value obtained from Ref.~\onlinecite{Lefrancois_2015} at the SF-ADC(2)-s/cc-pVTZ level with the geometry obtained at the CCSD(T)/cc-pVTZ level.}
|
|
||||||
\fnt[6]{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[7]{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[8]{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.}
|
|
||||||
\end{table*}
|
|
||||||
\end{squeezetable}
|
|
||||||
|
|
||||||
|
|
||||||
%================================================
|
%================================================
|
||||||
|
|
||||||
Table \ref{tab:TBE} shows the energy differences, for the automerization barrier (AB) and the different states considered, between the various methods treated and the Theoretical Best Estimate (TBE) at the aug-cc-pVTZ level for the AB and the states.
|
%Table \ref{tab:TBE} shows the energy differences, for the automerization barrier (AB) and the different states considered, between the various methods treated and the Theoretical Best Estimate (TBE) at the aug-cc-pVTZ level for the AB and the states.
|
||||||
The percentage $\%T_1$ shown in parentheses for the excited states of the {\Dtwo} geometry is a metric that gives the percentage of single excitation calculated at the CC3/aug-cc-pVTZ level and it allows us to characterize the transition.
|
%The percentage $\%T_1$ shown in parentheses for the excited states of the {\Dtwo} geometry is a metric that gives the percentage of single excitation calculated at the CC3/aug-cc-pVTZ level and it allows us to characterize the transition.
|
||||||
First, we look at the AB energy difference.
|
%First, we look at the AB energy difference.
|
||||||
SF-TD-DFT shows large variations of the energy with errors of \SIrange{1.42}{10.81}{\kcalmol} compared to the TBE value.
|
%SF-TD-DFT shows large variations of the energy with errors of \SIrange{1.42}{10.81}{\kcalmol} compared to the TBE value.
|
||||||
SF-ADC schemes provide smaller errors with \SIrange{0.30}{1.44}{\kcalmol} where we have that the SF-ADC(2)-x gives a worse error than the SF-ADC(2)-s method.
|
%SF-ADC schemes provide smaller errors with \SIrange{0.30}{1.44}{\kcalmol} where we have that the SF-ADC(2)-x gives a worse error than the SF-ADC(2)-s method.
|
||||||
CC methods also give small energy differences with \SIrange{0.11}{1.05}{\kcalmol} and where the CC4 provides an energy very close to the TBE one.
|
%CC methods also give small energy differences with \SIrange{0.11}{1.05}{\kcalmol} and where the CC4 provides an energy very close to the TBE one.
|
||||||
|
%
|
||||||
Then we look at the vertical energy errors for the {\Dtwo} structure.
|
%Then we look at the vertical energy errors for the {\Dtwo} structure.
|
||||||
First we consider the {\tBoneg} state and we look at the SF-TD-DFT results.
|
%First we consider the {\tBoneg} state and we look at the SF-TD-DFT results.
|
||||||
We see that increasing the amount of exact exchange in the functional give closer results to the TBE, indeed we have \SI{0.24}{\eV} and \SI{0.22}{\eV} of errors for the B3LYP and the PBE0 functionals, respectively whereas we have an error of \SI{0.08}{\eV} for the BH\&HLYP functional.
|
%We see that increasing the amount of exact exchange in the functional give closer results to the TBE, indeed we have \SI{0.24}{\eV} and \SI{0.22}{\eV} of errors for the B3LYP and the PBE0 functionals, respectively whereas we have an error of \SI{0.08}{\eV} for the BH\&HLYP functional.
|
||||||
For the other functionals we have errors of \SIrange{0.10}{0.43}{\eV}, note that for this state the M06-2X functional gives the same result than the TBE.
|
%For the other functionals we have errors of \SIrange{0.10}{0.43}{\eV}, note that for this state the M06-2X functional gives the same result than the TBE.
|
||||||
We can also notice that all the functionals considered overestimate the vertical energies.
|
%We can also notice that all the functionals considered overestimate the vertical energies.
|
||||||
The ADC schemes give closer energies with errors of \SIrange{0.04}{0.08}{\eV}, note that ADC(2)-x does not improve the result compared to ADC(2)-s and that ADC(3) understimate the vertical energy whereas ADC(2)-s and ADC(2)-x overestimate the vertical energy.
|
%The ADC schemes give closer energies with errors of \SIrange{0.04}{0.08}{\eV}, note that ADC(2)-x does not improve the result compared to ADC(2)-s and that ADC(3) understimate the vertical energy whereas ADC(2)-s and ADC(2)-x overestimate the vertical energy.
|
||||||
The CC3 and CCSDT results provide energy errors of \SIrange{0.05}{0.06}{\eV} respectively.
|
%The CC3 and CCSDT results provide energy errors of \SIrange{0.05}{0.06}{\eV} respectively.
|
||||||
Then we go through the multi-reference methods with the two different active spaces, four electrons in four orbitals and twelve electrons in twelve orbitals.
|
%Then we go through the multi-reference methods with the two different active spaces, four electrons in four orbitals and twelve electrons in twelve orbitals.
|
||||||
For the smaller active space we have errors of \SIrange{0.05}{0.21}{\eV}, the largest error comes from CASSCF(4,4) which is improved by CASPT2(4,4) that gives the smaller error.
|
%For the smaller active space we have errors of \SIrange{0.05}{0.21}{\eV}, the largest error comes from CASSCF(4,4) which is improved by CASPT2(4,4) that gives the smaller error.
|
||||||
Then for the largest active space multi-reference methods provide energy errors of \SIrange{0.02}{0.22}{\eV} with again the largest error coming from CASSCF(12,12) which is again improved by CASPT2(12,12) gives the smaller error.
|
%Then for the largest active space multi-reference methods provide energy errors of \SIrange{0.02}{0.22}{\eV} with again the largest error coming from CASSCF(12,12) which is again improved by CASPT2(12,12) gives the smaller error.
|
||||||
|
%
|
||||||
For the {\sBoneg} state of the {\Dtwo} structure we see that all the xc-functional underestimate the vertical excitation energy with energy differences of about \SIrange{0.35}{0.93}{\eV}.
|
%For the {\sBoneg} state of the {\Dtwo} structure we see that all the xc-functional underestimate the vertical excitation energy with energy differences of about \SIrange{0.35}{0.93}{\eV}.
|
||||||
The ADC values are much closer to the TBE with energy differences around \SIrange{0.03}{0.09}{\eV}.
|
%The ADC values are much closer to the TBE with energy differences around \SIrange{0.03}{0.09}{\eV}.
|
||||||
Obviously, the CC vertical energies are close to the TBE one with around or less than \SI{0.01}{\eV} of energy difference.
|
%Obviously, the CC vertical energies are close to the TBE one with around or less than \SI{0.01}{\eV} of energy difference.
|
||||||
For the CASSCF(4,4) vertical energy we have a large difference of around \SI{1.42}{\eV} compared to the TBE value due to the lack of dynamical correlation in the CASSCF method.
|
%For the CASSCF(4,4) vertical energy we have a large difference of around \SI{1.42}{\eV} compared to the TBE value due to the lack of dynamical correlation in the CASSCF method.
|
||||||
As previously seen the CAPT2(4,4) method correct this and we obtain a value of \SI{0.20}{\eV}.
|
%As previously seen the CAPT2(4,4) method correct this and we obtain a value of \SI{0.20}{\eV}.
|
||||||
The others multi-reference methods in this active space give energy differences of around \SIrange{0.55}{0.76}{\eV} compared the the TBE reference.
|
%The others multi-reference methods in this active space give energy differences of around \SIrange{0.55}{0.76}{\eV} compared the the TBE reference.
|
||||||
For the largest active space with twelve electrons in twelve orbitals we have an improvement of the vertical energies with \SI{0.72}{eV} of energy difference for the CASSCF(12,12) method and around 0.06 eV for the others multi-configurational methods.
|
%For the largest active space with twelve electrons in twelve orbitals we have an improvement of the vertical energies with \SI{0.72}{eV} of energy difference for the CASSCF(12,12) method and around 0.06 eV for the others multi-configurational methods.
|
||||||
|
%
|
||||||
Then, for the {\twoAg} state we obtain closer results of the SF-TD-DFT methods to the TBE than in the case of the {\sBoneg} state.
|
%Then, for the {\twoAg} state we obtain closer results of the SF-TD-DFT methods to the TBE than in the case of the {\sBoneg} state.
|
||||||
Indeed, we have an energy difference of about \SIrange{0.01}{0.34}{\eV} for the {\twoAg} state whereas we have \SIrange{0.35}{0.93}{\eV} for the {\sBoneg} state.
|
%Indeed, we have an energy difference of about \SIrange{0.01}{0.34}{\eV} for the {\twoAg} state whereas we have \SIrange{0.35}{0.93}{\eV} for the {\sBoneg} state.
|
||||||
The ADC schemes give the same error to the TBE value than for the other singlet state with \SI{0.02}{\eV} for the ADC(2) scheme and \SI{0.07}{\eV} for the ADC(3) one.
|
%The ADC schemes give the same error to the TBE value than for the other singlet state with \SI{0.02}{\eV} for the ADC(2) scheme and \SI{0.07}{\eV} for the ADC(3) one.
|
||||||
The ADC(2)-x scheme provides a larger error with \SI{0.45}{\eV} of energy difference.
|
%The ADC(2)-x scheme provides a larger error with \SI{0.45}{\eV} of energy difference.
|
||||||
Here, the CC methods manifest more variations with \SI{0.63}{\eV} for the CC3 value and \SI{0.28}{\eV} for the CCSDT compared to the TBE values.
|
%Here, the CC methods manifest more variations with \SI{0.63}{\eV} for the CC3 value and \SI{0.28}{\eV} for the CCSDT compared to the TBE values.
|
||||||
The CC4 method provides a small error with less than 0.01 eV of energy difference.
|
%The CC4 method provides a small error with less than 0.01 eV of energy difference.
|
||||||
The multi-configurational methods globally give smaller error than for the other singlet state with, for the two active spaces, \SIrange{0.03}{0.12}{\eV} compared to the TBE value.
|
%The multi-configurational methods globally give smaller error than for the other singlet state with, for the two active spaces, \SIrange{0.03}{0.12}{\eV} compared to the TBE value.
|
||||||
We can notice that CC3 and CCSDT provide larger energy errors for the {\twoAg} state than for the {\sBoneg} state, this is due to the strong multi-configurational character of the {\twoAg} state whereas the {\sBoneg} state has a very weak multi-configurational character.
|
%We can notice that CC3 and CCSDT provide larger energy errors for the {\twoAg} state than for the {\sBoneg} state, this is due to the strong multi-configurational character of the {\twoAg} state whereas the {\sBoneg} state has a very weak multi-configurational character.
|
||||||
It is interesting to see that SF-TD-DFT and SF-ADC methods give better results compared to the TBE than CC3 and even CCSDT meaning that spin-flip methods are able to describe double excited states.
|
%It is interesting to see that SF-TD-DFT and SF-ADC methods give better results compared to the TBE than CC3 and even CCSDT meaning that spin-flip methods are able to describe double excited states.
|
||||||
Note that multi-reference methods obviously give better results too for the {\twoAg} state.
|
%Note that multi-reference methods obviously give better results too for the {\twoAg} state.
|
||||||
|
%
|
||||||
Finally we look at the vertical energy errors for the \Dfour structure.
|
%Finally we look at the vertical energy errors for the \Dfour structure.
|
||||||
First, we consider the {\Atwog} state, the SF-TD-DFT methods give errors of about \SIrange{0.07}{1.6}{\eV} where the largest energy differences are provided by the hybrid functionals.
|
%First, we consider the {\Atwog} state, the SF-TD-DFT methods give errors of about \SIrange{0.07}{1.6}{\eV} where the largest energy differences are provided by the hybrid functionals.
|
||||||
The ADC schemes give similar error with around \SIrange{0.06}{1.1}{\eV} of energy difference.
|
%The ADC schemes give similar error with around \SIrange{0.06}{1.1}{\eV} of energy difference.
|
||||||
For the CC methods we have an energy error of \SI{0.06}{\eV} for CCSD and less than \SI{0.01}{\eV} for CCSDT.
|
%For the CC methods we have an energy error of \SI{0.06}{\eV} for CCSD and less than \SI{0.01}{\eV} for CCSDT.
|
||||||
Then for the multi-reference methods with the four by four active space we have for CASSCF(4,4) \SI{0.29}{\eV} of error and \SI{0.02}{\eV} for CASPT2(4,4), again CASPT2 demonstrates its improvement compared to CASSCF.
|
%Then for the multi-reference methods with the four by four active space we have for CASSCF(4,4) \SI{0.29}{\eV} of error and \SI{0.02}{\eV} for CASPT2(4,4), again CASPT2 demonstrates its improvement compared to CASSCF.
|
||||||
The other methods provide energy differences of about \SIrange{0.12}{0.13}{\eV}.
|
%The other methods provide energy differences of about \SIrange{0.12}{0.13}{\eV}.
|
||||||
A larger active space shows again an improvement with \SI{0.23}{\eV} of error for CASSCF(12,12) and around \SIrange{0.01}{0.04}{\eV} for the other multi-reference methods.
|
%A larger active space shows again an improvement with \SI{0.23}{\eV} of error for CASSCF(12,12) and around \SIrange{0.01}{0.04}{\eV} for the other multi-reference methods.
|
||||||
CIPSI provides similar error with \SI{0.02}{\eV}.
|
%CIPSI provides similar error with \SI{0.02}{\eV}.
|
||||||
Then, we look at the {\Aoneg} state where the SF-TD-DFT shows large variations of error depending on the functionals, the energy error is about \SIrange{0.10}{1.03}{\eV}.
|
%Then, we look at the {\Aoneg} state where the SF-TD-DFT shows large variations of error depending on the functionals, the energy error is about \SIrange{0.10}{1.03}{\eV}.
|
||||||
The ADC schemes give better errors with around \SIrange{0.07}{0.41}{\eV} and where again the ADC(2)-x does not improve the ADC(2)-s energy but also gives worse results.
|
%The ADC schemes give better errors with around \SIrange{0.07}{0.41}{\eV} and where again the ADC(2)-x does not improve the ADC(2)-s energy but also gives worse results.
|
||||||
For the CC methods we have energy errors of about \SIrange{0.10}{0.16}{\eV} and CC4 provides really close energy to the TBE one with \SI{0.01}{\eV} of error.
|
%For the CC methods we have energy errors of about \SIrange{0.10}{0.16}{\eV} and CC4 provides really close energy to the TBE one with \SI{0.01}{\eV} of error.
|
||||||
For the multi-reference methods we globally have an improvement of the energies from the four by four to the twelve by twelve active space with errors of \SIrange{0.01}{0.73}{\eV} and \SIrange{0.02}{0.44}{\eV} respectively with the largest errors coming from the CASSCF method.
|
%For the multi-reference methods we globally have an improvement of the energies from the four by four to the twelve by twelve active space with errors of \SIrange{0.01}{0.73}{\eV} and \SIrange{0.02}{0.44}{\eV} respectively with the largest errors coming from the CASSCF method.
|
||||||
Lastly, we look at the {\Btwog} state where we have globally larger errors.
|
%Lastly, we look at the {\Btwog} state where we have globally larger errors.
|
||||||
The SF-TD-DFT exhibits errors of \SIrange{0.43}{1.50}{\eV} whereas ADC schemes give errors of \SIrange{0.18}{0.30}{\eV}.
|
%The SF-TD-DFT exhibits errors of \SIrange{0.43}{1.50}{\eV} whereas ADC schemes give errors of \SIrange{0.18}{0.30}{\eV}.
|
||||||
CC3 and CCSDT provide energy differences of \SIrange{0.50}{0.69}{\eV} and the CC4 shows again close energy to the CCSDTQ TBE energy with \SI{0.01}{\eV} of error.
|
%CC3 and CCSDT provide energy differences of \SIrange{0.50}{0.69}{\eV} and the CC4 shows again close energy to the CCSDTQ TBE energy with \SI{0.01}{\eV} of error.
|
||||||
The multi-reference methods give energy differences of \SIrange{0.38}{1.39}{\eV} and \SIrange{0.11}{0.60}{\eV} for the four by four and twelve by twelve active spaces respectively.
|
%The multi-reference methods give energy differences of \SIrange{0.38}{1.39}{\eV} and \SIrange{0.11}{0.60}{\eV} for the four by four and twelve by twelve active spaces respectively.
|
||||||
We can notice that we have larger variations for the vertical energies of the square CBD than for the rectangular one.
|
%We can notice that we have larger variations for the vertical energies of the square CBD than for the rectangular one.
|
||||||
This can be explained by the fact that because of the degeneracy in the {\Dfour} structure it leads to strong multi-configurational character states where single reference methods are unreliable.
|
%This can be explained by the fact that because of the degeneracy in the {\Dfour} structure it leads to strong multi-configurational character states where single reference methods are unreliable.
|
||||||
We can also see that for the CC methods we have a better description of the {\Aoneg} state than the {\Btwog} state, this can be related, as previously said in Subsubsection \ref{sec:D4h}, to the fact that {\Btwog} corresponds to a double excitation from the reference state.
|
%We can also see that for the CC methods we have a better description of the {\Aoneg} state than the {\Btwog} state, this can be related, as previously said in Subsubsection \ref{sec:D4h}, to the fact that {\Btwog} corresponds to a double excitation from the reference state.
|
||||||
To obtain an improved description of the {\Btwog} state we have to include quadruples.
|
%To obtain an improved description of the {\Btwog} state we have to include quadruples.
|
||||||
At the end of Table \ref{tab:TBE} we show some literature results obtain from Ref.~\onlinecite{Lefrancois_2015,Manohar_2008} where the cc-pVTZ basis is used.
|
%At the end of Table \ref{tab:TBE} we show some literature results obtain from Ref.~\onlinecite{Lefrancois_2015,Manohar_2008} where the cc-pVTZ basis is used.
|
||||||
The SF-ADC(2)-s, SF-ADC(2)-x and SF-ADC(3)results are presented and are consistent with our results with the exact same schemes but with the aug-cc-pVTZ basis.
|
%The SF-ADC(2)-s, SF-ADC(2)-x and SF-ADC(3)results are presented and are consistent with our results with the exact same schemes but with the aug-cc-pVTZ basis.
|
||||||
|
|
||||||
|
|
||||||
%Here again we can make the same comment for the $2\,{}^1A_{1g}$ and $1\,{}^1B_{2g}$ states of the square CBD than the $1\,{}^1B_{1g}$ and $2\,{}^1A_{g}$ states of the rectangular CBD. The first state ($2\,{}^1A_{1g}$) has a strong multi-configurational character
|
%Here again we can make the same comment for the $2\,{}^1A_{1g}$ and $1\,{}^1B_{2g}$ states of the square CBD than the $1\,{}^1B_{1g}$ and $2\,{}^1A_{g}$ states of the rectangular CBD. The first state ($2\,{}^1A_{1g}$) has a strong multi-configurational character
|
||||||
@ -1137,5 +1087,7 @@ This work was performed using HPC ressources from CALMIP (Toulouse) under alloca
|
|||||||
Included in the {\SupInf} are the raw data, additional calculations and geometries, and the cartesian coordinates of the various optimized geometries.
|
Included in the {\SupInf} are the raw data, additional calculations and geometries, and the cartesian coordinates of the various optimized geometries.
|
||||||
%================================================
|
%================================================
|
||||||
|
|
||||||
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
\bibliography{CBD}
|
\bibliography{CBD}
|
||||||
|
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||||
\end{document}
|
\end{document}
|
||||||
|
|||||||
Loading…
Reference in New Issue
Block a user