diff --git a/Manuscript/FarDFT.tex b/Manuscript/FarDFT.tex index d6474a0..a9e4bde 100644 --- a/Manuscript/FarDFT.tex +++ b/Manuscript/FarDFT.tex @@ -238,12 +238,14 @@ Unless otherwise stated, atomic units are used throughout. \section{Theory} \label{sec:theo} -Let us consider a GOK ensemble of $\nEns$ electronic states with individual energies $\E{}{(0)} \le \ldots \le \E{}{(\nEns-1)}$, and (normalised) monotonically decreasing weights $\bw = (\ew{1},\ldots,\ew{M-1})$, \ie, $\ew{0}=1-\sum_{I=1}^{\nEns-1} \ew{I}$, and $\ew{0} \ge \ldots \ge \ew{\nEns-1}$. +Let us consider a GOK ensemble of $\nEns$ electronic states with +individual energies $\E{}{(0)} \le \ldots \le \E{}{(\nEns-1)}$, and +(normalised) monotonically decreasing weights $\bw \equiv (\ew{1},\ldots,\ew{M-1})$, \ie, $\ew{0}=1-\sum_{I=1}^{\nEns-1} \ew{I}$, and $\ew{0} \ge \ldots \ge \ew{\nEns-1}$. The corresponding ensemble energy \begin{equation} \E{}{\bw} = \sum_{I=0}^{\nEns-1} \ew{I} \E{}{(I)} \end{equation} -can be obtained from the variational principle +can be obtained from the GOK variational principle as follows\cite{Gross_1988a} \begin{eqnarray}\label{eq:ens_energy} \E{}{\bw} = \min_{\hGam{\bw}} \Tr[\hGam{\bw} \hH], @@ -259,20 +261,21 @@ where $\lbrace \overline{\Psi}^{(I)} \rbrace_{0 \le I \le \nEns-1}$ is a set of The lower bound of Eq.~\eqref{eq:ens_energy} is reached when the set of wave functions correspond to the exact eigenstates of $\hH$, \ie, $\lbrace \overline{\Psi}^{(I)} \rbrace_{0 \le I \le \nEns-1} = \lbrace \Psi^{(I)} \rbrace_{0 \le I \le \nEns-1}$. Multiplet degeneracies can be easily handled by assigning the same weight to the degenerate states. \cite{Gross_1988b} -One of the key feature of the GOK ensemble is that individual excitation -energies can be extracted from the ensemble energy via differentiation with respect to individual weights: +One of the key feature of the GOK ensemble is that \trashEF{individual} excitation +energies can be extracted from the ensemble energy via differentiation +with respect to the individual \manu{excited-state} weights \manu{$\ew{I}$ ($I>0$)}: \begin{equation}\label{eq:diff_Ew} \pdv{\E{}{\bw}}{\ew{I}} = \E{}{(I)} - \E{}{(0)} = \Ex{}{(I)}. \end{equation} -Turning to GOK-DFT, the extension of the Hohenberg--Kohn theorem to ensembles allows to rewrite the exact variational expression for the ensemble energy as\cite{Gross_1988a} +Turning to GOK-DFT, the extension of the Hohenberg--Kohn theorem to ensembles allows to rewrite the exact variational expression for the ensemble energy as\cite{Gross_1988b} \begin{equation} \label{eq:Ew-GOK} \E{}{\bw} = \min_{\n{}{}} \qty{ \F{}{\bw}[\n{}{}] + \int \vne(\br{}) \n{}{}(\br{}) d\br{} }, \end{equation} where $\vne(\br{})$ is the external potential and $\F{}{\bw}[\n{}{}]$ is the universal ensemble functional (the weight-dependent analog of the Hohenberg--Kohn universal functional for ensembles). -In the KS formulation, this functional can be decomposed as +In the KS formulation, this functional is decomposed as \begin{equation}\label{eq:FGOK_decomp} \F{}{\bw}[\n{}{}] = \Tr{ \hgamdens{\bw} \hT }+ \E{\Ha}{}[\n{}{}]+\E{\xc}{\bw}[\n{}{}],