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ok with response letter and mansucript

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Pierre-Francois Loos 2022-06-10 11:20:28 +02:00
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Response_Letter/Response_Letter.tex
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@ -30,7 +30,7 @@ We look forward to hearing from you.
\noindent \textbf{\large Authors' answer to Reviewer \#1} \noindent \textbf{\large Authors' answer to Reviewer \#1}
{This article presents a survey of spin-flip TD-DFT, spin-flip ADC, multireference (CASSCF and MRPT), and equation-of-motion coupled cluster methods as applied to the automerization and vertical excitation energies of cyclobutadiene (CBD). {This article presents a survey of spin-flip TD-DFT, spin-flip ADC, multireference (CASSCF and MRPT), and equation-of-motion coupled cluster methods as applied to the automerization and vertical excitation energies of cyclobutadiene (CBD).
As the smallest example of anti-aromaticity (and one of the smallest and most interesting exemplars of strong PJT distortion), CBD is an illuminating and challenging test case for these methods. (EOM-)CCSDTQ values, with a “pyramidal” basis set extrapolation scheme are used as the newly-proposed theoretical best estimates, and limited selected full CI (CIPSI) calculations confirm their excellent accuracy. As the smallest example of anti-aromaticity (and one of the smallest and most interesting exemplars of strong PJT distortion), CBD is an illuminating and challenging test case for these methods. (EOM-)CCSDTQ values, with a "pyramidal" basis set extrapolation scheme are used as the newly-proposed theoretical best estimates, and limited selected full CI (CIPSI) calculations confirm their excellent accuracy.
The authors reach some interesting and useful conclusions concerning the tested methods. The authors reach some interesting and useful conclusions concerning the tested methods.
} }
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@ -53,7 +53,7 @@ A justification or rationalization would be helpful.
Also, is it expected that these methods would improve on SF-ADC and/or EOM-CC?} Also, is it expected that these methods would improve on SF-ADC and/or EOM-CC?}
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\alert{The authors thanks the reviewer for this comment. \alert{The authors thanks the reviewer for this comment.
Results for SF-EOM-CCSD, SF-EOM-CCSD(dT) and SF-EOM-CCSD(fT) have been added in the manuscript (and in the supporting information) and are discussed in the text.} Results for SF-EOM-CCSD, SF-EOM-CCSD(dT) and SF-EOM-CCSD(fT) have been added in the manuscript (and in the supporting information) and are now discussed in the text.}
\item \item
{The issue of reference symmetry frame is very important at the D4h geometry. {The issue of reference symmetry frame is very important at the D4h geometry.
@ -79,7 +79,8 @@ 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. 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 $1 ^1 A_{1g}$ excited state has also a strong double-excitation character, while the $1 ^1B_{2g}$ excited state is obtained by one-electron excitation. Then, the $1 ^1 A_{1g}$ 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. 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.
This interesting comment about standard and non-standard orientations has been added to the supporting information alongside the corresponding figure.}
\includegraphics[width=\textwidth]{MOs} \includegraphics[width=\textwidth]{MOs}
@ -97,7 +98,7 @@ Thus, the improvement of our results by including all $\sigma_{CC}$ is rather ex
We believe that the large differences observed between CASPT2 and NEVPT2 for the (4e,4o) active space is a consequence of the small active space. We believe that the large differences observed between CASPT2 and NEVPT2 for the (4e,4o) active space is a consequence of the small active space.
As a matter of fact, when the active space is enlarged, all these issues disappear. As a matter of fact, when the active space is enlarged, all these issues disappear.
Note also that we have minimized the intruder state problem by using an appropriate level shift and that this potential problem is not present at the NEVPT2 level. Note also that we have minimized the intruder state problem by using an appropriate level shift and that this potential problem is not present at the NEVPT2 level.
As suggested by the reviewer, we have now added some results at the MRCI+Q level. As suggested by the reviewer, we have now added some results at the MRCI and MRCI+Q levels in the supporting information of the revised manuscript.
} }
\item \item