diff --git a/Revised_Manuscript/eDFT.tex b/Revised_Manuscript/eDFT.tex index cc3a8ca..58deb79 100644 --- a/Revised_Manuscript/eDFT.tex +++ b/Revised_Manuscript/eDFT.tex @@ -1055,21 +1055,7 @@ Figure \ref{fig:EIvsW} reports the behavior of the three KS-eLDA individual ener Unlike in the exact theory, we do not obtain straight horizontal lines when plotting these energies, which is in agreement with -the curvature of the GIC-eLDA ensemble energy discussed previously. Interestingly, the -individual energies do not vary in the same way depending on the state -considered and the value of the weights. -\titou{On one hand,} we see for example that, within the biensemble (\ie, $\ew{2}=0$), the energies of -the ground and \titou{second} excited-state increase with respect to the -first-excited-state weight $\ew{1}$, thus showing that, in this -case, we -``deteriorate'' these states by optimizing the orbitals for the -ensemble, rather than for each state separately. -\titou{The singly excited state is, on the other hand, stabilize in the biensemble, which is reasonable as the weight associated with this state increases. -For the triensemble, as $\ew{2}$ increases, the energy of the ground state increases, while the energy of the first excited state remains stable with a slight increase at large $L$. -The second excited state is obviously stabilized by the increase of its weight in the ensemble. -These are all very sensible observations.} - -The variations in the ensemble weights are essentially linear or quadratic. +the curvature of the GIC-eLDA ensemble energy discussed previously. The variations in the ensemble weights are essentially linear or quadratic. \manurev{This can be rationalized as follows. As readily seen from Eqs.~\eqref{eq:EI-eLDA} and \eqref{eq:ind_HF-like_ener}, the individual HF-like energies do not depend explicitly on the weights, which means @@ -1085,22 +1071,39 @@ weights $\bw$ [see Eqs.~\eqref{eq:ens1RDM}, \eqref{eq:ens_dens_from_ens_1RDM}, and \eqref{eq:decomp_ens_correner_per_part}], the latter contributions will contain both linear and quadratic terms in $\bw$, as evidenced by Eq.~\eqref{eq:Taylor_exp_DDisc_term} [see the second term on the right-hand -side].} -!!! In the biensemble, the weight dependence of the first -excitation energy is \titou{increased?} as the correlation increases, \titou{while the weight dependence of the second excitation energy is reduced}. -On the other hand, switching from a bi- to a triensemble -systematically enhances the weight dependence, due to the lowering of the -ground-state energy, as $\ew{2}$ increases. -The reverse is observed for the second excited state. !!! \titou{THIS PARAGRAPH MIGHT NEED MODIFICATIONS.} -\trashPFL{Finally, we notice that the crossover point of the -first-excited-state energies based on -bi- and triensemble calculations, respectively, disappears in the strong correlation -regime [see the right panel of Fig.~\ref{fig:EIvsW}], thus illustrating -the importance of (individual and ensemble) densities, in -addition to the -weights, in the evaluation of individual energies within -an ensemble. +side].}\\ +Interestingly, the +individual energies do not vary in the same way depending on the state +considered and the value of the weights. +\titou{On one hand,} we see for example that, within the biensemble (\ie, $\ew{2}=0$), the energies of +the ground and \titou{second} excited-state increase with respect to the +first-excited-state weight $\ew{1}$, thus showing that, in this +case, we +``deteriorate'' these states by optimizing the orbitals for the +ensemble, rather than for each state separately. +\titou{The singly excited state is, on the other hand, stabilized in the biensemble, which is reasonable as the weight associated with this state increases. +For the triensemble, as $\ew{2}$ increases, the energy of the ground state increases, while the energy of the first excited state remains stable with a slight increase at large $L$. +The second excited state is obviously stabilized by the increase of its weight in the ensemble. +\manurev{ +These are all very sensible observations.\\ +Let us finally stress that the (well-known) poor performance of the +combined full HF-exchange/LDA correlation scheme in +ground-state DFT [$\bw=(0,0)$] is substantially improved for the +ground state within the equiensemble [$\bw=(1/3,1/3)$]} (see the \SI). +This is a +remarkable and promising result. A similar improvement is observed for +the first excited state, at least in the weak correlation regime, +without deteriorating too much the second excited-state energy. } +%\manu{Finally, we notice that the crossover point of the +%first-excited-state energies based on +%bi- and triensemble calculations, respectively, disappears in the strong correlation +%regime [see the right panel of Fig.~\ref{fig:EIvsW}], thus illustrating +%the importance of (individual and ensemble) densities, in +%addition to the +%weights, in the evaluation of individual energies within +%an ensemble. +%} %%% FIG 3 %%% \begin{figure} \includegraphics[width=\linewidth]{fig5}