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Pierre-Francois Loos 2020-05-28 15:13:39 +02:00
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Manuscript/BSE_JPCL.tex
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@ -446,6 +446,7 @@ $(ia|jb)$ bare Coulomb term defined as
\phi_i(\br) \phi_a(\br) v(\br-\br')
\phi_j(\br') \phi_b(\br'),
\end{equation}
Neglecting the anti-resonant term $C$ in Eq.~\eqref{eq:BSE-eigen}, which is usually much smaller than its resonant counterpart $R$, leads to the well-known Tamm-Dancoff approximation.
As compared to TD-DFT,
\begin{itemize}
\item the $GW$ quasiparticle energies $\lbrace \varepsilon_{i/a}^{\GW} \rbrace$ replace the KS eigenvalues
@ -572,11 +573,13 @@ These ongoing developments pave the way to applying the $GW$@BSE formalism to sy
\subsection{The triplet instability challenge}
%==========================================
The analysis of the singlet-triplet splitting is central to numerous applications such as singlet fission, thermally activated delayed fluorescence (TADF) or
stability analysis of restricted closed-shell solutions at the HF \cite{Seeger_1977} and TD-DFT \cite{Bauernschmitt_1996} levels.
contaminating as well TD-DFT calculations with popular range-separated hybrids that generally contains a large fraction of exact exchange in the long-range. \cite{Sears_2011}
While TD-DFT with range-separated hybrids can benefit from tuning the range-separation parameter as a mean to act on the triplet instability, \cite{Sears_2011} BSE calculations do not offer this pragmatic way-out since the screened Coulomb potential that builds the kernel does not offer any parameter to tune.
stability analysis of restricted closed-shell solutions at the HF \cite{Seeger_1977} and TD-DFT \cite{Bauernschmitt_1996} levels. \titou{[REFS]}
\titou{contaminating as well TD-DFT calculations with popular range-separated hybrids that generally contains a large fraction of exact exchange in the long-range. \cite{Sears_2011}}
While TD-DFT with range-separated hybrids can benefit from tuning the range-separation parameter(s) as a mean to act on the triplet instability, \cite{Sears_2011} BSE calculations do not offer this pragmatic way-out since the screened Coulomb potential that builds the kernel does not offer any parameter to tune.
Benchmark calculations \cite{Jacquemin_2017b,Rangel_2017} clearly concluded that triplets are notably located at too low an energy within BSE and that the use of the TDA was able to partly reduce this error. However, the error remains rather unsatisfactory for reliable applications. An alternative cure was offered by hybridizing TD-DFT and BSE, namely adding to the BSE kernel the correlation part of the underlying DFT functional used to build the susceptibility and resulting screened Coulomb potential $W$. \cite{Holzer_2018b}\\
Benchmark calculations \cite{Jacquemin_2017b,Rangel_2017} clearly concluded that triplets are notably too low in energy within BSE and that the use of the Tamm-Dancoff approximation was able to partly reduce this error. However, the error remains rather unsatisfactory for reliable applications.
An alternative cure was offered by hybridizing TD-DFT and BSE, that is, by adding to the BSE kernel the correlation part of the underlying DFT functional used to build the susceptibility and resulting screened Coulomb potential $W$. \cite{Holzer_2018b}
\\
%==========================================
\subsection{The challenge of analytical nuclear gradients}
@ -611,7 +614,7 @@ A promising route, which closely follows RPA-type formalisms, \cite{Furche_2008,
Thanks to comparisons with both similar and state-of-art computational approaches, we have recently showed that the ACFDT@BSE@$GW$ approach yields extremely accurate PES around equilibrium, and can even compete with high-order coupled cluster methods in terms of absolute ground-state energies and equilibrium distances. \cite{Loos_2020}
Their accuracy near the dissociation limit remains an open question. \cite{Caruso_2013,Olsen_2014,Colonna_2014,Hellgren_2015,Holzer_2018}
Indeed, in the largest available benchmark study \cite{Holzer_2018} encompassing the total energies of the atoms \ce{H}--\ce{Ne}, the atomization energies of the 26 small molecules forming the HEAT test set, and the bond lengths and harmonic vibrational frequencies of $3d$ transition-metal monoxides, the BSE correlation energy, as evaluated within the ACFDT framework, \cite{Furche_2005} was mostly discarded from the set of tested techniques due to instabilities (negative frequency modes in the BSE polarization propagator) and replaced by an approximate (RPAsX) approach where the screened-Coulomb potential matrix elements was removed from the resonant electron-hole contribution. \cite{Maggio_2016,Holzer_2018}
Moreover, we also observe \cite{Loos_2020} that, in some cases, unphysical irregularities on the ground-state PES due to the appearance of discontinuities as a function of the bond length for some of the $GW$ quasiparticle energies.
Moreover, we also observe in Ref.~\citenum{Loos_2020} that, in some cases, unphysical irregularities on the ground-state PES due to the appearance of discontinuities as a function of the bond length for some of the $GW$ quasiparticle energies.
Such an unphysical behavior stems from defining the quasiparticle energy as the solution of the quasiparticle equation with the largest spectral weight in cases where several solutions can be found.
This shortcoming has been thoroughly described in several previous studies.\cite{vanSetten_2015,Maggio_2017,Loos_2018,Veril_2018,Duchemin_2020}
\\
@ -651,7 +654,7 @@ However, dynamical corrections permit, in any case, to recover, for transitions
From a more practical point of view, dynamical effects have been found to affect the positions and widths of core-exciton resonances in semiconductors, \cite{Strinati_1982,Strinati_1984} rare gas solids, and transition metals. \cite{Ankudinov_2003}
Thanks to first-order perturbation theory, Rohlfing and coworkers have developed an efficient way of taking into account the dynamical effects via a plasmon-pole approximation combined with the Tamm-Dancoff approximation. \cite{Rohlfing_2000,Ma_2009a,Ma_2009b,Baumeier_2012b}
With such as scheme, they have been able to compute the excited states of biological chromophores, showing that taking into account the electron-hole dynamical screening is important for an accurate description of the lowest $n \ra \pi^*$ excitations. \cite{Ma_2009a,Ma_2009b,Baumeier_2012b}
With such a scheme, they have been able to compute the excited states of biological chromophores, showing that taking into account the electron-hole dynamical screening is important for an accurate description of the lowest $n \ra \pi^*$ excitations. \cite{Ma_2009a,Ma_2009b,Baumeier_2012b}
Studying PYP, retinal and GFP chromophore models, Ma \textit{et al.}~found that \textit{``the influence of dynamical screening on the excitation energies is about $0.1$ eV for the lowest $\pi \ra \pi^*$ transitions, but for the lowest $n \ra \pi^*$ transitions the influence is larger, up to $0.25$ eV.''} \cite{Ma_2009b}
Zhang \textit{et al.}~have studied the frequency-dependent second-order Bethe-Salpeter kernel and they have observed an appreciable improvement over configuration interaction with singles (CIS), time-dependent Hartree-Fock (TDHF), and adiabatic TD-DFT results. \cite{Zhang_2013}
Rebolini and Toulouse have performed a similar investigation in a range-separated context, and they have reported a modest improvement over its static counterpart. \cite{Rebolini_2016,Rebolini_PhD}