saving work in GW
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%% This BibTeX bibliography file was created using BibDesk.
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%% http://bibdesk.sourceforge.net/
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%% Created for Pierre-Francois Loos at 2020-10-25 13:01:52 +0100
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%% Created for Pierre-Francois Loos at 2020-10-25 21:09:09 +0100
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%% Saved with string encoding Unicode (UTF-8)
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@ -17,7 +17,8 @@
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Pages = {4326},
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Title = {Spin-Flip Methods in Quantum Chemistry},
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Volume = {22},
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Year = {2020}}
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Year = {2020},
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Bdsk-Url-1 = {https://doi.org/10.1039/c9cp06507e}}
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@article{Zhang_2004,
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Author = {Zhang, Fan and Burke, Kieron},
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75
sfBSE.tex
75
sfBSE.tex
@ -40,7 +40,7 @@
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%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
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\alert{Here comes the introduction.}
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Unless otherwise stated, atomic units are used, and we assume real quantities throughout this manuscript.
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In the following, we consider systems with collinear spins and a spin-independent hamiltonian without contributions such as spin?orbit interaction.
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In the following, we consider systems with collinear spins and a spin-independent hamiltonian without contributions such as spin-orbit interaction.
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%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
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\section{Unrestricted $GW$ formalism}
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@ -58,15 +58,15 @@ In a spin-flip excitation, the hole and particle states, $\MO{i_\sig}$ and $\MO{
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%================================
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\subsection{The dynamical screening}
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%================================
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The pillar of Green's function many-body perturbation theory is the (time-ordered) one-body Green's function, which has poles at the charged excitations (i.e., ionization potentials and electron affinities) of the system.
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The spin-$\sig$ component of the one-body Green's function reads
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The pillar of Green's function many-body perturbation theory is the (time-ordered) one-body Green's function, which has poles at the charged excitations (i.e., ionization potentials and electron affinities) of the system. \cite{ReiningBook}
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The spin-$\sig$ component of the one-body Green's function reads \cite{ReiningBook,Bruneval_2016a}
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\begin{equation}
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G^{\sig}(\br_1,\br_2;\omega)
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= \sum_i \frac{\MO{i_\sig}(\br_1) \MO{i_\sig}(\br_2)}{\omega - \e{i_\sig}{} - i\eta}
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+ \sum_a \frac{\MO{a_\sig}(\br_1) \MO{a_\sig}(\br_2)}{\omega - \e{a_\sig}{} + i\eta}
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\end{equation}
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where $\eta$ is a positive infinitesimal.
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Based on it, one can easily compute the non-interacting polarizability (which is a sum over spins)
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Based on the spin-up and spin-down components of $G$, one can easily compute the non-interacting polarizability (which is a sum over spins)
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\begin{equation}
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\chi_0(\br_1,\br_2;\omega) = - \frac{i}{2\pi} \sum_\sig \int G^{\sig}(\br_1,\br_2;\omega+\omega') G^{\sig}(\br_1,\br_2;\omega') d\omega'
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\end{equation}
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@ -74,14 +74,15 @@ and subsequently the dielectric function
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\begin{equation}
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\epsilon(\br_1,\br-2;\omega) = \delta(\br_1 - \br_2) - \int \frac{\chi_0(\br_1,\br_3;\omega) }{\abs{\br_2 - \br_3}} d\br_3
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\end{equation}
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where $\delta(\br_1 - \br_2)$ is the Dirac functions.
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where $\delta(\br_1 - \br_2)$ is the Dirac function.
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Based on this latter ingredient, one can access the dynamically-screened Coulomb potential
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\begin{equation}
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W(\br_1,\br_2;\omega) = \int \frac{\epsilon^{-1}(\br_1,\br_3;\omega) }{\abs{\br_2 - \br_3}} d\br_3
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\end{equation}
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which is spin independent as the bare Coulomb interaction $\abs{\br_1 - \br_2}^{-1}$ does not depend on spin coordinates.
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Therefore, within the $GW$ formalism, the dynamical screening $W(\omega)$ is computed at the RPA level using the spin-conserved neutral excitations.
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In the orbital basis, the spectral representation of $W(\omega)$ reads
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Within the $GW$ formalism, the is computed at the RPA level by considering only the manifold of the spin-conserved neutral excitation.
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In the orbital basis, the spectral representation of $W$ reads
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\begin{multline}
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\label{eq:W}
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W_{p_\sig q_\sig,r_\sigp s_\sigp}(\omega) = \ERI{p_\sig q_\sig}{r_\sigp s_\sigp}
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@ -98,27 +99,27 @@ and the screened two-electron integrals (or spectral weights) are explicitly giv
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\begin{equation}
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\ERI{p_\sig q_\sig}{m} = \sum_{ia\sigp} \ERI{p_\sig q_\sig}{r_\sigp s_\sigp} (\bX{m}{\spc,\RPA}+\bY{m}{\spc,\RPA})_{i_\sigp a_\sigp}
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\end{equation}
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In Eqs.~\eqref{eq:W} and \eqref{eq:sERI}, the RPA spin-conserved neutral excitations $\Om{m}{\spc,\RPA}$ and their corresponding eigenvectors $(\bX{m}{\spc,\RPA}+\bY{m}{\spc,\RPA})$ are obtained by solving the following linear response system
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In Eqs.~\eqref{eq:W} and \eqref{eq:sERI}, the RPA spin-conserved neutral excitations $\Om{m}{\spc,\RPA}$ and their corresponding eigenvectors $(\bX{m}{\spc,\RPA}+\bY{m}{\spc,\RPA})$ are obtained by solving a linear response system of the form
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\begin{equation}
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\label{eq:LR-RPA}
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\begin{pmatrix}
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\bA{}{\spc,\RPA} & \bB{}{\spc,\RPA} \\
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-\bB{}{\spc,\RPA} & -\bA{}{\spc,\RPA} \\
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\bA{}{} & \bB{}{} \\
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-\bB{}{} & -\bA{}{} \\
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\end{pmatrix}
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\cdot
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\begin{pmatrix}
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\bX{m}{\spc,\RPA} \\
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\bY{m}{\spc,\RPA} \\
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\bX{m}{} \\
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\bY{m}{} \\
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\end{pmatrix}
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=
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\Om{m}{\spc,\RPA}
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\Om{m}{}
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\begin{pmatrix}
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\bX{m}{\spc,\RPA} \\
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\bY{m}{\spc,\RPA} \\
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\bX{m}{} \\
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\bY{m}{} \\
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\end{pmatrix}
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\end{equation}
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The spin structure of matrices $\bA{}{}$ and $\bB{}{}$ is general
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where the expressions of the matrix elements of $\bA{}{}$ and $\bB{}{}$ are specific of the method and of the spin manifold.
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The spin structure of these matrices, though, is general
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\begin{align}
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\label{eq:LR-RPA-AB}
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\bA{}{\spc} & = \begin{pmatrix}
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@ -142,7 +143,19 @@ The spin structure of matrices $\bA{}{}$ and $\bB{}{}$ is general
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\bB{}{\dwup,\updw} & \bO \\
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\end{pmatrix}
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\end{align}
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and does not only apply to the RPA but also to RPAx (\ie, RPA with exchange), BSE and TD-DFT.
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In the absence of instabilities, the linear eigenvalue problem \eqref{eq:LR-RPA} has particle-hole symmetry which means that the eigenvalues are obtained by pairs $\pm \Om{m}{}$.
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In such a case, $(\bA{}{}-\bB{}{})^{1/2}$ is positive definite, and Eq.~\eqref{eq:LR-RPA} can be recast as a Hermitian problem of half the dimension
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\begin{equation}
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\label{eq:small-LR}
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(\bA{}{} - \bB{}{})^{1/2} \cdot (\bA{}{} + \bB{}{}) \cdot (\bA{}{} - \bB{}{})^{1/2} \cdot \bZ{}{} = \bOm{2} \cdot \bZ{}{}
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\end{equation}
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where the excitation amplitudes are
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\begin{equation}
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\bX{}{} + \bY{}{} = \bOm{-1/2} \cdot (\bA{}{} - \bB{}{})^{1/2} \cdot \bZ{}{}
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\end{equation}
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Within the Tamm-Dancoff approximation (TDA), the coupling terms between the resonant and anti-resonant parts, $\bA{}{}$ and $-\bA{}{}$, are neglected, which consist in setting $\bB{}{} = \bO$.
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In such a case, Eq.~\eqref{eq:LR-RPA} reduces to $\bA{}{} \cdot \bX{m}{} = \Om{m}{} \bX{m}{}$.
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At the RPA level, the matrix elements of $\bA{}{}$ and $\bB{}{}$ are
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\begin{subequations}
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\begin{align}
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@ -187,7 +200,7 @@ Within the acclaimed $GW$ approximation, \cite{Hedin_1965,Golze_2019} the exchan
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& = \frac{i}{2\pi} \int G^{\sig}(\br_1,\br_2;\omega+\omega') W(\br_1,\br_2;\omega') e^{i \eta \omega'} d\omega'
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\end{split}
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\end{equation}
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is, like the one-body Green's function, spin-diagonal, and its spectral representation read
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is, like the one-body Green's function, spin-diagonal, and its spectral representation reads
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\begin{gather}
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\SigX{p_\sig q_\sig}
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= - \frac{1}{2} \sum_{i\sigp} \ERI{p_\sig i_\sigp}{i_\sigp q_\sig}
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@ -199,7 +212,7 @@ is, like the one-body Green's function, spin-diagonal, and its spectral represen
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& + \sum_{am} \frac{\ERI{p_\sig a_\sig}{m} \ERI{q_\sig a_\sig}{m}}{\omega - \e{a_\sig} - \Om{m}{\spc,\RPA} + i \eta}
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\end{split}
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\end{gather}
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which has been split in exchange (x) and correlation (c) parts for convenience.
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which has been split in its exchange (x) and correlation (c) contributions.
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The Dyson equation linking the Green's function and the self-energy holds separately for each spin component, and the quasiparticle energies $\eGW{p_\sig}$ are obtained by solving the frequency-dependent quasiparticle equation
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\begin{equation}
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\omega = \e{p_\sig}{} - V_{p_\sigma}^{\xc} + \SigX{p\sigma} + \SigC{p\sigma}(\omega)
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@ -209,6 +222,7 @@ with
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V_{p_\sigma}^{\xc} = \int \MO{p_\sig}(\br) v^{\xc}(\br) \MO{p_\sig}(\br) d\br
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\end{equation}
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where $v^{\xc}(\br)$ the Kohn-Sham exchange-correlation.
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\alert{Adding the Dyson equation? Introduce linearization of the quasiparticle equation and different degree of self-consistency.}
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%================================
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\subsection{The Bethe-Salpeter equation formalism}
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@ -242,9 +256,9 @@ Within the $GW$ approximation, the BSE kernel is
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- \delta_{\sig\sigp} W(\br_3,\br_4;\omega) \delta(\br_3 - \br_6) \delta(\br_4 - \br_6)
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\end{multline}
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where, as usual, we have not considered the higher-order terms in $W$ by neglecting the derivative $\partial W/\partial G$. \cite{Hanke_1980, Strinati_1982, Strinati_1984, Strinati_1988}
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Within the static approximation, the spin-conserved and spin-flip optical excitation at the BSE level are obtained by solving a similar linear response problem
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Within the static approximation which consists in neglecting the frequency dependence of the dynamically-screened Coulomb potential, the spin-conserved and spin-flip optical excitation at the BSE level are obtained by solving a similar linear response problem
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\begin{equation}
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\label{eq:LR-RPA}
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\label{eq:LR-BSE}
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\begin{pmatrix}
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\bA{}{\BSE} & \bB{}{\BSE} \\
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-\bB{}{\BSE} & -\bA{}{\BSE} \\
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@ -498,6 +512,23 @@ As explained in Ref.~\onlinecite{Casanova_2020}, there are two sources of spin c
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\section{Computational details}
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\label{sec:compdet}
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%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
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For the systems under investigation here, we consider either an open-shell doublet or triplet reference state.
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We then adopt the unrestricted formalism throughout this work.
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The $GW$ calculations performed to obtain the screened Coulomb operator and the quasiparticle energies are done using a (unrestricted) UHF starting point.
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Perturbative $GW$ (or {\GOWO}) \cite{Hybertsen_1985a,Hybertsen_1986,vanSetten_2013} quasiparticle energies are employed as starting points to compute the BSE neutral excitations.
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These quasiparticle energies are obtained by linearizing the frequency-dependent quasiparticle equation, and the entire set of orbitals is corrected.
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Further details about our implementation of {\GOWO} can be found in Refs.~\onlinecite{Loos_2018b,Veril_2018,Loos_2020,Loos_2020e}.
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%Note that, for the present (small) molecular systems, {\GOWO}@UHF and ev$GW$@UHF yield similar quasiparticle energies and fundamental gap.
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%Moreover, {\GOWO} allows to avoid rather laborious iterations as well as the significant additional computational effort of ev$GW$.
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%In the present study, the zeroth-order Hamiltonian [see Eq.~\eqref{eq:LR-PT}] is always the ``full'' BSE static Hamiltonian, \ie, without TDA.
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The dynamical correction is computed in the TDA throughout.
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As one-electron basis sets, we employ the Dunning families cc-pVXZ and aug-cc-pVXZ (X = D, T, and Q) defined with cartesian Gaussian functions.
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Finally, the infinitesimal $\eta$ is set to $100$ meV for all calculations.
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%It is important to mention that the small molecular systems considered here are particularly challenging for the BSE formalism, \cite{Hirose_2015,Loos_2018b} which is known to work best for larger systems where the amount of screening is more important. \cite{Jacquemin_2017b,Rangel_2017}
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%For comparison purposes, we employ the theoretical best estimates (TBEs) and geometries of Refs.~\onlinecite{Loos_2018a,Loos_2019,Loos_2020b} from which CIS(D), \cite{Head-Gordon_1994,Head-Gordon_1995} ADC(2), \cite{Trofimov_1997,Dreuw_2015} CC2, \cite{Christiansen_1995a} CCSD, \cite{Purvis_1982} and CC3 \cite{Christiansen_1995b} excitation energies are also extracted.
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%Various statistical quantities are reported in the following: the mean signed error (MSE), mean absolute error (MAE), root-mean-square error (RMSE), and the maximum positive [Max($+$)] and maximum negative [Max($-$)] errors.
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All the static and dynamic BSE calculations have been performed with the software \texttt{QuAcK}, \cite{QuAcK} freely available on \texttt{github}.
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%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
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\section{Results}
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