trivial changes

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Julien Toulouse 2019-07-02 09:40:05 +02:00
parent 67aa295e25
commit 7e51936695
2 changed files with 4 additions and 4 deletions

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@ -442,7 +442,7 @@ We have also computed total energies at the exFCI/AV5Z level and used these alon
\end{equation} \end{equation}
These results are illustrated in Fig.~\ref{fig:CH2} and reported in Table \ref{tab:CH2} alongside reference values from the literature obtained with various deterministic and stochastic approaches. \cite{ChiHolAdaOttUmrShaZim-JPCA-18, SheLeiVanSch-JCP-98, JenBun-JCP-88, SheLeiVanSch-JCP-98, ZimTouZhaMusUmr-JCP-09} These results are illustrated in Fig.~\ref{fig:CH2} and reported in Table \ref{tab:CH2} alongside reference values from the literature obtained with various deterministic and stochastic approaches. \cite{ChiHolAdaOttUmrShaZim-JPCA-18, SheLeiVanSch-JCP-98, JenBun-JCP-88, SheLeiVanSch-JCP-98, ZimTouZhaMusUmr-JCP-09}
Total energies for each state can be found in the {\SI}. Total energies for each state can be found in the {\SI}.
The exFCI/CBS values are still off by a few tenths of a {\kcal} compared to the DMC results of Zimmerman et al. \cite{ZimTouZhaMusUmr-JCP-09} which are extremely close from the experimentally-derived adiabatic energies. The exFCI/CBS values are still off by a few tenths of a {\kcal} compared to the DMC results of Zimmerman \textit{et al.} \cite{ZimTouZhaMusUmr-JCP-09} which are extremely close from the experimentally-derived adiabatic energies.
The reason of this discrepancy is probably due to the frozen-core approximation which has been applied in our case and has shown to significantly affect adiabatic energies. \cite{LooGalJac-JPCL-18, LooJac-JCTC-19} The reason of this discrepancy is probably due to the frozen-core approximation which has been applied in our case and has shown to significantly affect adiabatic energies. \cite{LooGalJac-JPCL-18, LooJac-JCTC-19}
However, the exFCI/CBS energies are in perfect agreement with the semistochastic heat-bath CI (SHCI) calculations from Ref.~\onlinecite{ChiHolAdaOttUmrShaZim-JPCA-18}, as expected. However, the exFCI/CBS energies are in perfect agreement with the semistochastic heat-bath CI (SHCI) calculations from Ref.~\onlinecite{ChiHolAdaOttUmrShaZim-JPCA-18}, as expected.
@ -749,7 +749,7 @@ In order to have a miscellaneous test set of excitations, in a third time, we pr
These two valence excitations --- $1\,^{1}\Sigma_g^+ \ra 1\,^{1}\Delta_g$ and $1\,^{1}\Sigma_g^+ \ra 2\,^{1}\Sigma_g^+$ --- are both of $(\pi,\pi) \ra (\si,\si)$ character. These two valence excitations --- $1\,^{1}\Sigma_g^+ \ra 1\,^{1}\Delta_g$ and $1\,^{1}\Sigma_g^+ \ra 2\,^{1}\Sigma_g^+$ --- are both of $(\pi,\pi) \ra (\si,\si)$ character.
They have been recently studied with state-of-the-art methods, and have been shown to be ``pure'' doubly-excited states as they involve an insignificant amount of single excitations. \cite{LooBogSceCafJac-JCTC-19} They have been recently studied with state-of-the-art methods, and have been shown to be ``pure'' doubly-excited states as they involve an insignificant amount of single excitations. \cite{LooBogSceCafJac-JCTC-19}
The vertical excitation energies associated with these transitions are reported in Table \ref{tab:Mol} and represented in Fig.~\ref{fig:C2}. The vertical excitation energies associated with these transitions are reported in Table \ref{tab:Mol} and represented in Fig.~\ref{fig:C2}.
An interesting point here is that one really needs to consider the $\PBEot$ functional to get chemically accurate absorption energies with the AVDZ atomic basis set. An interesting point here is that one really needs to consider the $\PBEot$ functional to get chemically accurate excitation energies with the AVDZ atomic basis set.
We believe that the present result is a direct consequence of the multireference character of the \ce{C2} molecule. We believe that the present result is a direct consequence of the multireference character of the \ce{C2} molecule.
In other words, the UEG on-top pair density used in the $\LDA$ and $\PBEUEG$ functionals (see Sec.~\ref{sec:func}) is a particularly bad approximation of the true on-top pair density for the present system. In other words, the UEG on-top pair density used in the $\LDA$ and $\PBEUEG$ functionals (see Sec.~\ref{sec:func}) is a particularly bad approximation of the true on-top pair density for the present system.
@ -836,7 +836,7 @@ See {\SI} for geometries and additional information (including total energies an
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\begin{acknowledgements} \begin{acknowledgements}
PFL would like to thank Denis Jacquemin for numerous discussions on excited states. PFL would like to thank Denis Jacquemin for numerous discussions on excited states.
This work was performed using HPC resources from GENCI-TGCC (Grant No.~2018-A0040801738), CALMIP (Toulouse) under allocation 2019-18005 and the Ob\'elix cluster from the \textit{Institut Parisien de Chimie Physique et Th\'eorique}. This work was performed using HPC resources from GENCI-TGCC (Grant No.~2018-A0040801738), CALMIP (Toulouse) under allocation 2019-18005 and the Jarvis-Alpha cluster from the \textit{Institut Parisien de Chimie Physique et Th\'eorique}.
\end{acknowledgements} \end{acknowledgements}
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@ -372,7 +372,7 @@ Here, we report the absolute energetic corrections for each state of each molecu
\begin{squeezetable} \begin{squeezetable}
\begin{table*}[h] \begin{table*}[h]
\caption{ \caption{
Basis set energetic corrections (in hartree) on absorption energies for excited states of water, ammonia, carbon dimer and ethylene for various methods and basis sets.} Basis set energetic corrections (in hartree) on vertical excitation energies for excited states of water, ammonia, carbon dimer, and ethylene for various methods and basis sets.}
\begin{ruledtabular}{} \begin{ruledtabular}{}
\begin{tabular}{llddddddddd} \begin{tabular}{llddddddddd}
& & \mc{9}{c}{Deviation with respect to TBE} & & \mc{9}{c}{Deviation with respect to TBE}