diff --git a/BSE-PES.tex b/BSE-PES.tex index 6ba01f1..d21bc38 100644 --- a/BSE-PES.tex +++ b/BSE-PES.tex @@ -36,7 +36,6 @@ \newcommand{\QP}{\textsc{quantum package}} \newcommand{\T}[1]{#1^{\intercal}} - % coordinates \newcommand{\br}[1]{\mathbf{r}_{#1}} \newcommand{\dbr}[1]{d\br{#1}} @@ -51,6 +50,11 @@ \newcommand{\Ha}{\text{H}} \newcommand{\co}{\text{x}} +% +\newcommand{\Norb}{N} +\newcommand{\Nocc}{O} +\newcommand{\Nvir}{V} + % operators \newcommand{\hH}{\Hat{H}} @@ -271,7 +275,7 @@ where $\W{}$ is the screened Coulomb operator, and hence the BSE reduces to \XiBSE{}(3,5,4,6) = \delta(3,4) \delta(5,6) \vc{}(3,6) - \delta(3,6) \delta(4,5) \W{}(3,4), \end{equation} where, as commonly done, we have neglected the term $\delta \W{}/\delta \G{}$ in the functional derivative of the self-energy. \cite{Hanke_1980,Strinati_1984,Strinati_1982} -Finally, the static approximation is enforced, \ie, $\W{}(1,2) = \W{}(\{\br{1}, \sigma_1, t_1\},\{\br{2}, \sigma_2, t_2\}) \delta(t_1-t_2)$ which corresponds to restricting $\W{}$ to its static limit, \ie, $\W{}(1,2) = \W{}(\{\br{1},\sigma_1\},\{\br{2},\sigma_2\}; \omega=0)$. +Finally, the static approximation is enforced, \ie, $\W{}(1,2) = \W{}(\{\br{1}, \sigma_1, t_1\},\{\br{2}, \sigma_2, t_2\}) \delta(t_1-t_2)$, which corresponds to restricting $\W{}$ to its static limit, \ie, $\W{}(1,2) = \W{}(\{\br{1},\sigma_1\},\{\br{2},\sigma_2\}; \omega=0)$. %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% \subsection{BSE in a finite basis} @@ -296,10 +300,9 @@ To compute the singlet and triplet BSE excitation energies in a finite basis wit \bY_m \\ \end{pmatrix}, \end{equation} -where $\OmBSE{m}$ is the $m$th excitation energy with eigenvector $\T{(\bX_m \, \bY_m)}$, and we have assumed real-valued orbitals. - -The matrices $\bA$, $\bB$, $\bX$, and $\bY$ are all of size $OV \times OV$ where $O$ and $V$ are the number of occupied and virtual orbitals, respectively. -In the following, the index $m$ labels the $OV$ single excitations, $i$, $j$ are occupied orbitals, $a$ and $b$ are unoccupied orbitals, while $p$, $q$, $r$, and $s$ indicate arbitrary orbitals. +where $\OmBSE{m}$ is the $m$th excitation energy with eigenvector $\T{(\bX_m \, \bY_m)}$, and we have assumed real-valued orbitals $\{\MO{p}(\br{})\}_{1 \le p \le \Norb}$. +The matrices $\bA$, $\bB$, $\bX$, and $\bY$ are all of size $\Nocc \Nvir \times \Nocc \Nvir$ where $\Nocc$ and $\Nvir$ are the number of occupied and virtual orbitals (\ie, $\Norb = \Nocc + \Nvir$), respectively. +In the following, the index $m$ labels the $\Nocc \Nvir$ single excitations, $i$, $j$ are occupied orbitals, $a$ and $b$ are unoccupied orbitals, while $p$, $q$, $r$, and $s$ indicate arbitrary orbitals. In the absence of triplet instabilities, \cite{Dreuw_2005} Eq.~\eqref{eq:LR} is usually transformed into an Hermitian eigenvalue problem of smaller dimension \begin{equation} @@ -324,17 +327,17 @@ where $\eGW{p}$ are the {\GW} quasiparticle energies, \label{eq:W} \W{ia,jb}(\omega) = (1 + \delta_{\sigma \sigma^{\prime}}) (ia|jb) \\ - + \sum_m^{OV} [ia|m] [jb|m] \qty(\frac{1}{\omega - \OmRPA{m} + i \eta} + \frac{1}{\omega + \OmRPA{m} - i \eta}) + + \sum_m^{\Nocc \Nvir} [ia|m] [jb|m] \qty(\frac{1}{\omega - \OmRPA{m} + i \eta} + \frac{1}{\omega + \OmRPA{m} - i \eta}) \end{multline} are the elements of the screened Coulomb operator, \begin{equation} - [pq|m] = \sum_i^O \sum_a^V (pq|ia) (\bX_m+\bY_m)_{ia} + [pq|m] = \sum_i^{\Nocc} \sum_a^{\Nvir} (pq|ia) (\bX_m+\bY_m)_{ia} \end{equation} are the screened two-electron integrals, \begin{equation} (pq|rs) = \iint \frac{\MO{p}(\br{}) \MO{q}(\br{}) \MO{r}(\br{}') \MO{s}(\br{}')}{\abs*{\br{} - \br{}'}} \dbr{} \dbr{}', \end{equation} -are the bare two-electron integrals, $\MO{p}(\br{})$ are the molecular orbitals, $\delta_{pq}$ is the Kronecker delta, and +are the bare two-electron integrals, $\delta_{pq}$ is the Kronecker delta, and \begin{equation} \delta_{\sigma \sigma^{\prime}} = \begin{cases} @@ -349,7 +352,7 @@ In Eq.~\eqref{eq:W}, $\OmRPA{m}$ are the neutral (direct) RPA excitation energie \subsection{Ground- and excited-state BSE energy} \label{sec:BSE_energy} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -The key quantity to define here is the total BSE energy as we are going to compute PES following this definition. +\titou{The key quantity to define here is the total BSE energy as we are going to compute PES following this definition.} Although not unique, we propose to define the BSE total energy of the $m$th state as \begin{equation} \label{eq:EtotBSE} @@ -379,7 +382,7 @@ As a final remark, we point out that Eq.~\eqref{eq:EtotBSE} can be easily genera \section{Computational details} \label{sec:comp_details} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -All the preliminary {\GW} calculations performed to obtain the screened Coulomb operator and the quasiparticle energies have been done using a Hartree-Fock (HF) starting point, which is a very sensible choice in the case of the (small) systems that are considered here. +All the preliminary {\GW} calculations performed to obtain the screened Coulomb operator and the quasiparticle energies have been done using a Hartree-Fock (HF) starting point, which is a very adequate choice in the case of the (small) systems that we consider here. Both perturbative {\GW} (or {\GOWO}) \cite{Hybertsen_1985a, Hybertsen_1986} and partially self-consistent {\evGW} \cite{Hybertsen_1986, Shishkin_2007, Blase_2011, Faber_2011} calculations are performed here. These will be labeled as BSE@{\GOWO} and BSE@{\evGW}, respectively. In the case of {\GOWO}, the quasiparticle energies have been obtained by linearizing the non-linear, frequency-dependent quasiparticle equation.