Added more discussion on the results about LIM (or MOM).
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@ -901,13 +901,16 @@ Eqs.~\eqref{eq:MOM1} and \eqref{eq:MOM2}.
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The results gathered in Table \ref{tab:BigTab_H2} show that the GOK-DFT excitation energies obtained with the CC-SeVWN5 functional at zero weights are the most accurate with an improvement of $0.25$ eV as compared to CC-SVWN5, which is due to the ensemble derivative contribution of the eVWN5 functional.
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The CC-SeVWN5 excitation energies at equi-weights (\ie, $\ew{} = 1/3$) are less satisfactory, but still remain in good agreement with FCI.
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Interestingly, the CC-S functional
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leads to a substantial improvement of the LIM
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excitation energy, getting close to the reference value
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(with an error of up to 0.24 eV) when no correlation
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functional is used. When correlation functionals are
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added (\ie VWN5 or eVWN5), LIM tends to overestimate
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the excitation energy by about 1 eV but still performs
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better than when no correction of the curvature is considered.
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It is also important to mention that the CC-S functional does not alter the MOM excitation energy as the correction vanishes in this limit (\textit{vide supra}).
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Finally, although we had to design a system-specific, weight-dependent exchange functional to reach such accuracy, we have not used any high-level reference data (such as FCI) to tune our functional, the only requirement being the linearity of the ensemble energy (obtained with LDA exchange) between the ghost-interaction-free pure-state limits.
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\manuf{There is a quite detailed discussion about LIM but nothing about
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its performance. One should say something. LIM is a ``poor man (or
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woman)'' approach when weight-dependent functionals are not available. I
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would at least compare regular LDA LIM with results obtained (by
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differentiations) with the more advanced CC-S+eVWN5 approach.}
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%%% TABLE III %%%
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\begin{table}
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@ -1003,6 +1006,9 @@ For $\RHH = 3.7$ bohr, it is much harder to get an accurate estimate of the exci
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%work. I guess the latter option is what you did. We need to explain more
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%what we do!!!}
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As expected from the linearity of the ensemble energy, the CC-S functional coupled or not with a correlation functional yield extremely stable excitation energies as a function of the weight, with only a few tenths of eV difference between the zero- and equi-weights limits.
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As a direct consequence of this linearity, LIM and MOM
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do not provide any noticeable improvement on the excitation
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energy.
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Nonetheless, the excitation energy is still off by $3$ eV.
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The fundamental theoretical reason of such a poor agreement is not clear.
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The fact that HF exchange yields better excitation energies hints at the effect of self-interaction error.
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@ -1074,7 +1080,13 @@ The CC-S exchange functional attenuates significantly this dependence, and when
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As in the case of \ce{H2}, the excitation energies obtained at
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zero-weight are more accurate than at equi-weight, while the opposite
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conclusion was made in Ref.~\onlinecite{Loos_2020}.
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This motivates further the importance of developing weight-dependent functionals that yields linear ensemble energies in order to get rid of the weight-dependency of the excitation energy.
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This motivates further the importance of developing weight-dependent functionals that yields linear ensemble energies in order to get rid of the weight-dependency of the excitation energy. Here again, the LIM excitation energy
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when the CC-S functional is used is very accurate with
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only 22 millihartree error compared to the reference value,
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while adding the correlation contribution to the functional
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tends to overestimate the excitation energy.
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Hence, in the light of the results obtained in this paper, it seems that the weight-dependent curvature correction to the exchange functional makes the biggest impact in providing
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accurate excitation energies.
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As a final comment, let us stress again that the present protocol does not rely on high-level calculations as the sole requirement for constructing the CC-S functional is the linearity of the ensemble energy with respect to the weight of the double excitation.
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%%% TABLE V %%%
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