PTEROSOR/sfBSE
10
0
Fork 0
Code Issues Pull Requests Releases Wiki Activity

saving ork in revision

Browse Source
This commit is contained in:
Pierre-Francois Loos 2021-02-25 10:08:39 +01:00
parent 25c0231a50
commit edcc428e04
3 changed files with 14 additions and 2 deletions
Show Stats Download Patch File Download Diff File Expand all files Collapse all files

11
Manuscript/sfBSE-SI.tex
View File

@ -507,6 +507,17 @@ $4.$ & $0 .3189$ & $0 .8867$ & $0 .3328$ & $0 .2172$ & $0 .9453$ & $0 \
\end{figure} \end{figure}
%%% %%% %%% %%% %%% %%%
%%% FIG 3 %%%
\begin{figure}
\includegraphics[width=0.5\linewidth]{H2_BSE_RHF}
\caption{
Excitation energies with respect to the $\text{X}\,{}^1 \Sigma_g^+$ ground state of the $\text{B}\,{}^1\Sigma_u^+$ (red), $\text{E}\,{}^1\Sigma_g^+$ (black), and $\text{F}\,{}^1\Sigma_g^+$ (blue) states of \ce{H2} obtained with the cc-pVQZ basis at the (SF-)BSE level of theory.
The reference EOM-CCSD excitation energies are represented as solid lines, while the results obtained with and without spin-flip are represented as dashed and dotted lines, respectively.
In this case, the spin-conserved calculations have been performed with a restricted reference while the spin-flip calculations have been performed with an unrestricted reference.
\label{fig:H2_RHF}}
\end{figure}
%%% %%% %%%
%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%
\bibliography{sfBSE} \bibliography{sfBSE}
%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%

2
Manuscript/sfBSE.tex
View File

@ -890,7 +890,7 @@ A similar graph comparing (SF-)dBSE and EOM-CCSD excitation energies can be foun
This unfortunate feature is due to the appearance of the symmetry-broken UHF solution and the lack of self-consistent in {\GOWO}. This unfortunate feature is due to the appearance of the symmetry-broken UHF solution and the lack of self-consistent in {\GOWO}.
Indeed, $R = 1.2~\AA$ corresponds to the location of the well-known Coulson-Fischer point. \cite{Coulson_1949} Indeed, $R = 1.2~\AA$ corresponds to the location of the well-known Coulson-Fischer point. \cite{Coulson_1949}
Note that, as mentioned earlier, all the calculations are performed with a UHF reference even the ones based on a closed-shell singlet reference. Note that, as mentioned earlier, all the calculations are performed with a UHF reference even the ones based on a closed-shell singlet reference.
If one relies solely on the restricted HF solution, this kink disappears and one obtains smooth potential energy curves.} If one relies solely on the restricted HF solution, this kink disappears and one obtains smooth potential energy curves (see {\SI}).}
The right side of Fig.~\ref{fig:H2} shows the amount of spin contamination as a function of the bond length for SF-CIS (top), SF-TD-BH\&HLYP (center), and SF-BSE (bottom). The right side of Fig.~\ref{fig:H2} shows the amount of spin contamination as a function of the bond length for SF-CIS (top), SF-TD-BH\&HLYP (center), and SF-BSE (bottom).
Overall, one can see that $\expval{\hS^2}$ behaves similarly for SF-CIS and SF-BSE with a small spin contamination of the $\text{B}\,{}^1\Sigma_u^+$ at short bond length. In contrast, the $\text{B}$ state is much more spin contaminated at the SF-TD-BH\&HLYP level. Overall, one can see that $\expval{\hS^2}$ behaves similarly for SF-CIS and SF-BSE with a small spin contamination of the $\text{B}\,{}^1\Sigma_u^+$ at short bond length. In contrast, the $\text{B}$ state is much more spin contaminated at the SF-TD-BH\&HLYP level.

3
Response_Letter/Response_Letter.tex
View File

@ -66,7 +66,8 @@ I recommend this manuscript for publication after the minor points addressed:}
\alert{The kink in the SF-BSE@$G_0W_0$ and SF-dBSE/$G_0W_0$ curves for \ce{H2} are due to the appearance of the symmetry-broken UHF solution. \alert{The kink in the SF-BSE@$G_0W_0$ and SF-dBSE/$G_0W_0$ curves for \ce{H2} are due to the appearance of the symmetry-broken UHF solution.
Indeed, $R = 1.2~\AA$ corresponds to the location of the well-known Coulson-Fischer point. Indeed, $R = 1.2~\AA$ corresponds to the location of the well-known Coulson-Fischer point.
Note that, as mentioned in our manuscript, all the calculations are performed with a UHF reference (even the ones based on a closed-shell singlet reference). Note that, as mentioned in our manuscript, all the calculations are performed with a UHF reference (even the ones based on a closed-shell singlet reference).
Of course, if one relies solely on the RHF solution, this kink disappears (see figure below). it would be, nonetheless, inconsistent with the rest of the paper. Of course, if one relies solely on the RHF solution, this kink disappears as illustrated by the figure below which has been also included in the Supporting Information.
However, it would be inconsistent with the rest of the paper.
The appearance of this kink is now discussed in the revised version of the manuscript. The appearance of this kink is now discussed in the revised version of the manuscript.
At the ev$GW$ level, this kink would certainly still exist as one does not self-consistently optimised the orbitals in this case. At the ev$GW$ level, this kink would certainly still exist as one does not self-consistently optimised the orbitals in this case.
However, it would likely disappear at the qs$GW$ level but it remains to be confirmed (work is currently being done in this direction). However, it would likely disappear at the qs$GW$ level but it remains to be confirmed (work is currently being done in this direction).