Merge branch 'master' of https://github.com/pfloos/srDFT_G2
This commit is contained in:
commit
78661ea899
@ -12233,3 +12233,15 @@
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Year = {1998},
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Bdsk-Url-1 = {http://www.sciencedirect.com/science/article/pii/S0009261498001110},
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Bdsk-Url-2 = {https://doi.org/10.1016/S0009-2614(98)00111-0}}
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@article{DasHer-JCC-17,
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author = {Dasgupta, Saswata and Herbert, John M.},
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title = {Standard grids for high-precision integration of modern density functionals: SG-2 and SG-3},
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journal = {Journal of Computational Chemistry},
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volume = {38},
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number = {12},
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pages = {869-882},
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doi = {10.1002/jcc.24761},
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eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/jcc.24761},
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year = {2017}
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}
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@ -207,7 +207,7 @@ Importantly, in the limit of a complete basis set $\Bas$ (which we refer to as $
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\end{equation}
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where $\E{\modX}{\infty}$ is the energy associated with the method $\modX$ in the complete basis set.
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In the case $\modX = \FCI$, we have as strict equality as $E_{\FCI}^\infty = E$.
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Provided that the functional $\bE{}{\Bas}[\n{}{}]$ is known exactly, the only source of error at this stage lies in the potential approximate nature of the methods $\modX$ and $\modY$ for the FCI energy and density within $\Bas$.
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Provided that the functional $\bE{}{\Bas}[\n{}{}]$ is known exactly, the only source of error at this stage lies in the potential approximate nature of the methods $\modX$ and $\modY$ for the FCI energy and density within $\Bas$, respectively.
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%Here we propose to generalize such approach to a general WFT model, referred here as $\model$, projected in a basis set $\Bas$ which must provides a density $\denmodel$ and an energy $\emodel$.
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%As any wave function model is necessary an approximation to the FCI model, one can write
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@ -300,12 +300,16 @@ Provided that the functional $\bE{}{\Bas}[\n{}{}]$ is known exactly, the only so
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%\end{equation}
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Rigorously speaking, the functional $\bE{}{\Bas}[\n{}{}]$ is obviously \textit{not} universal as it depends on $\Bas$.
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Nevertheless, as $\bE{}{\Bas}[\n{}{}]$ aims at fixing the incompleteness of $\Bas$, its main role is to correct for the lack of electronic cups in $\wf{}{\Bas}$ (i.e.~a discontinuous derivative) at the electron-electron (e-e) coalescence points, which is universal.
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Nevertheless, as $\bE{}{\Bas}[\n{}{}]$ aims at fixing the incompleteness of $\Bas$, its main role is to correct
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for the lack of electronic cups in $\wf{}{\Bas}$ (i.e.~a discontinuous derivative) at the electron-electron (e-e)
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coalescence points.
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Therefore, the physical role of $\bE{}{\Bas}[\n{}{}]$ is to account for a universal condition of exact wave functions.
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As the e-e cusp originates from the divergence of the Coulomb operator at $r_{12} = 0$, a cuspless wave function could equivalently originate from a Hamiltonian with a non-divergent Coulomb interaction at $r_{12} = 0$.
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Therefore, as we shall do later on, it feels natural to approximate $\bE{}{\Bas}[\n{}{}]$ with short-range density functionals which deal with a smooth non divergent two-electron interaction.
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Contrary to the conventional RS-DFT scheme which requires a range-separated \textit{parameter} $\rsmu{}{}$, here we use a range-separated \textit{function} $\rsmu{}{}(\br{})$ which quantifies the incompleteness of a basis set $\Bas$ for each point in ${\rm I\!R}^3$.
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Contrary to the conventional RS-DFT scheme which requires a range-separated \textit{parameter} $\rsmu{}{}$, here we use a range-separated \textit{function} $\rsmu{}{}(\br{})$ which automatically adapts to quantify the incompleteness of a basis set $\Bas$ for each point in ${\rm I\!R}^3$.
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The first step of the basis set correction consists in obtaining an effective interaction $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ which i) is finite at the e-e coalescence point as long as an incomplete basis set is used, and ii) tends to the genuine, unbounded $r_{12}^{-1}$ Coulomb interaction in the limit of a complete basis set.
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The first step of the basis set correction consists in obtaining an effective two-electron interaction $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ which represents the effect of the projection in an incomplete basis set $\Bas$ of the Coulomb operator.
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We use a definition for which $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ i) is finite at the e-e coalescence point as long as an incomplete basis set is used, and ii) tends to the genuine, unbounded $r_{12}^{-1}$ Coulomb interaction in the limit of a complete basis set.
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In a second step, we shall link $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ to $\rsmu{}{}(\br{})$.
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In the final step, we employ short-range density functionals\cite{TouGorSav-TCA-05} with $\rsmu{}{}(\br{})$ as the range separation.
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%Following Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, we approximate $\bE{}{\Bas}[\n{}{}]$ following a two-step procedure which guarantees the correct behaviour in the limit $\Bas \to \infty$ [see Eq.~\eqref{eq:limitfunc}].
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@ -325,20 +329,20 @@ In the final step, we employ short-range density functionals\cite{TouGorSav-TCA-
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%=================================================================
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%\subsection{Effective Coulomb operator}
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%=================================================================
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We define the effective operator $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ as (see equation (27) of Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18})
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We define the effective operator $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ as
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\begin{equation}
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\label{eq:def_weebasis}
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\W{\wf{}{\Bas}}{}(\br{1},\br{2}) = \left\{
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\begin{array}{ll}
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\f{\wf{}{\Bas}}{}(\br{1},\br{2})/\n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) & \mbox{if } \n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) \ne 0\\
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\,\,\,\,+\infty & \mbox{if not.}
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\f{\wf{}{\Bas}}{}(\br{1},\br{2})/\n{2}{\wf{}{\Bas}}(\br{1},\br{2}) & \mbox{if } \n{2}{\wf{}{\Bas}}(\br{1},\br{2}) \ne 0\\
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\,\,\,\,+\infty & \mbox{otherwise.}
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\end{array}
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\right.
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\end{equation}
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where $\n{\wf{}{\Bas}}{(2)}(\br{1},\br{2})$ is the opposite-spin two-body density associated with $\wf{}{\Bas}$
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where $\n{2}{\wf{}{\Bas}}(\br{1},\br{2})$ is the opposite-spin two-body density associated with $\wf{}{\Bas}$
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\begin{equation}
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\label{eq:n2basis}
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\n{\wf{}{\Bas}}{(2)}(\br{1},\br{2})
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\n{2}{\wf{}{\Bas}}(\br{1},\br{2})
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= \sum_{pqrs \in \Bas} \SO{p}{1} \SO{q}{2} \Gam{pq}{rs}[\wf{}{\Bas}] \SO{r}{1} \SO{s}{2},
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\end{equation}
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$\Gam{pq}{rs}[\wf{}{\Bas}] = \mel*{\wf{}{\Bas}}{ \aic{r}\aic{s}\ai{p}\ai{q} }{\wf{}{\Bas}}$ is the opposite-spin two-body density tensor of $\wf{}{\Bas}$, $\SO{i}{}$ are spinorbitals, $\f{\wf{}{\Bas}}{}(\br{1},\br{2})$ is defined as
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@ -349,31 +353,32 @@ $\Gam{pq}{rs}[\wf{}{\Bas}] = \mel*{\wf{}{\Bas}}{ \aic{r}\aic{s}\ai{p}\ai{q} }{\w
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= \sum_{pqrstu \in \Bas} \SO{p}{1} \SO{q}{2} \V{pq}{rs} \Gam{rs}{tu}[\wf{}{\Bas}] \SO{t}{1} \SO{u}{2},
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\end{multline}
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and $\V{pq}{rs}$ are the usual Coulomb two-electron integrals.
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The definition of equation \eqref{eq:def_weebasis} is the same of equation (27) of Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, but here we add the extra condition that $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ diverges when the two-body density vanishes, which ensures that one-electron systems do not have any basis set correction.
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With such a definition, $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ verifies (see Appendix A of Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18})
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\begin{equation}
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\label{eq:int_eq_wee}
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\mel*{\wf{}{\Bas}}{\hWee{}}{\wf{}{\Bas}} = \iint \W{\wf{}{\Bas}}{}(\br{1},\br{2}) \n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) \dbr{1} \dbr{2},
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\mel*{\wf{}{\Bas}}{\hWee{}}{\wf{}{\Bas}} = \iint \W{\wf{}{\Bas}}{}(\br{1},\br{2}) \n{2}{\wf{}{\Bas}}(\br{1},\br{2}) \dbr{1} \dbr{2},
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\end{equation}
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where the $\hWee{}$ contains only the opposite-spins component of the two-electron interaction, and \eqref{eq:int_eq_wee} can be rewritten as
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where here $\hWee{}$ contains only the opposite-spins component of the two-electron interaction, and \eqref{eq:int_eq_wee} can be rewritten as
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\begin{equation}
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\iint r_{12}^{-1} \n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) \dbr{1} \dbr{2} = \iint \W{\wf{}{\Bas}}{}(\br{1},\br{2}) \n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) \dbr{1} \dbr{2},
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\iint r_{12}^{-1} \n{2}{\wf{}{\Bas}}(\br{1},\br{2}) \dbr{1} \dbr{2} = \iint \W{\wf{}{\Bas}}{}(\br{1},\br{2}) \n{2}{\wf{}{\Bas}}(\br{1},\br{2}) \dbr{1} \dbr{2},
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\end{equation}
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which intuitively motivates $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ as a potential candidate for an effective interaction.
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As already discussed in Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ is symmetric, \textit{a priori} non translational nor rotational invariant if $\Bas$ does not have such symmetries.
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An important quantity to define is $\W{\wf{}{\Bas}}{}(\br{})$ which is the value of the effective interaction at $\br{}$ for opposite spins at coalescence
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An important quantity to define in the present context is $\W{\wf{}{\Bas}}{}(\br{})$ which is the value of the effective interaction at $\br{}$ for opposite spins at coalescence
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\begin{equation}
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\label{eq:wcoal}
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\W{\wf{}{\Bas}}{}(\br{}) = \W{\wf{}{\Bas}}{}(\br{},{\br{}})
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\end{equation}
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and which is necessarily \textit{finite} at for an \textit{incomplete} basis set.
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and which is necessarily \textit{finite} at for an \textit{incomplete} basis set as long as the on-top two-body density is non vanishing.
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Of course, there exists \textit{a priori} an infinite set of functions in ${\rm I\!R}^6$ satisfying \eqref{eq:int_eq_wee}, but thanks to its very definition one can show (see Appendix B of Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}) that
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\begin{equation}
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\label{eq:lim_W}
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\lim_{\Bas \to \infty}\W{\wf{}{\Bas}}{}(\br{1},\br{2}) = r_{12}^{-1}\
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\end{equation}
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for all points $(\br{1},\br{2})$ such that $\n{\wf{}{\Bas}}{(2)}(\br{1},\br{2}) \ne 0$ and for any choice of $\wf{}{\Bas}$, which therefore guarantees a physically satisfying limit.
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An important point here is that, with the present definition of $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$, one can see the effect of the incompleteness of $\Bas$ on the Coulomb operator itself as a removal of the divergence of the two-electron interaction near the electron coalescence.
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for all points $(\br{1},\br{2})$ such that $\n{2}{\wf{}{\Bas}}(\br{1},\br{2}) \ne 0$ and for any choice of $\wf{}{\Bas}$, which therefore guarantees a physically satisfying limit.
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An important point here is that, with the present definition of $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$, one can quantify the effect of the incompleteness of $\Bas$ on the Coulomb operator itself as a removal of the divergence of the two-electron interaction near the electron coalescence.
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As it has been shown in Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18} (see for instance Fig 1,2 and 3 therein), choosing a HF wave function as $\wf{}{\Bas}$ to define the effective interaction $\W{\wf{}{\Bas}}{}(\br{1},\br{2})$ already provides a quantitative representation of the incompleteness of the basis set $\Bas$ for weakly correlated systems.
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%=================================================================
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@ -472,7 +477,7 @@ The ECMD functionals admit, for any density $\n{}{}(\br{})$, the two following l
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\end{subequations}
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where $\Ec[\n{}{}(\br{})]$ is the usual universal correlation functional defined in KS-DFT.
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The choice of the ECMD as the functionals to be used in this scheme is motivated by the analogy between the definition of $\bE{}{\Bas}[\n{}{}]$ [see equation \eqref{eq:E_funcbasis}] and that of the ECMD functionals [see equation \eqref{eq:ec_md_mu}].
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Indeed, provided that $\w{}{\lr,\rsmu{\wf{}{\Bas}}{}}(\br{1},\br{2}) \approx \W{\wf{}{\Bas}}{}(\br{1},\br{2})$, then the wave function $\wf{}{\rsmu{\wf{}{\Bas}}{}(\br{})}[\n{}{}(\br{})]$ coincides with $\wf{}{\Bas}$.
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Indeed, provided that $\w{}{\lr,\rsmu{\wf{}{\Bas}}{}}(\br{1},\br{2}) \approx \W{\wf{}{\Bas}}{}(\br{1},\br{2})$, then the wave function $\wf{}{\rsmu{\wf{}{\Bas}}{}(\br{})}$ coincides with $\wf{}{\Bas}$.
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%The ECMD functionals differ from the standard RS-DFT correlation functional by the fact that the reference is not the KS Slater determinant but a multi-determinantal wave function.
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%This makes them particularly well adapted to the present context where one aims at correcting a general WFT method.
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@ -484,25 +489,25 @@ Following Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, we approximate $\bE{}{\Ba
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\label{eq:def_lda_tot}
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\bE{\LDA}{\sr}[\n{}{}(\br{}),\rsmu{}{}(\br{})] = \int \be{\LDA}{\sr}\big(\n{}{}(\br{}),\rsmu{}{}(\br{})\big) \n{}{}(\br{}) \dbr{},
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\end{equation}
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where $\be{\LDA}{\sr}(\n{}{},\rsmu{}{})$ is the multi-determinant short-range correlation energy per particle of the uniform electron gas (UEG) \cite{LooGil-WIRES-16} for which a parametrization can be found in Ref.~\onlinecite{PazMorGorBac-PRB-06}.
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where $\be{\LDA}{\sr}(\n{}{},\rsmu{}{})$ is the short-range ECMD per particle of the uniform electron gas (UEG) \cite{LooGil-WIRES-16} for which a parametrization can be found in Ref.~\onlinecite{PazMorGorBac-PRB-06}.
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%In practice, for open-shell systems, we use the spin-resolved version of this functional (i.e., depending on both spin densities) but for simplicity we will continue to use only the notation of the spin-unpolarized case.
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%--------------------------------------------
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%\subsubsection{New PBE functional}
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%--------------------------------------------
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The short-range LDA correlation functional defined in Eq.~\eqref{eq:def_lda_tot} relies on the transferability of the physics of the UEG which is certainly valid for large $\mu$ but is known to over correlate for small $\mu$.
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In order to correct such a defect, we propose here a new ECMD functional inspired by the recent functional proposed by some of the present authors \cite{FerGinTou-JCP-18} which interpolates between the usual PBE correlation functional $\e{\PBE}{}(\n{}{},\nabla \n{}{})$ for small $\rsmu{}{}$ and the exact large-$\rsmu{}{}$ behavior, \cite{TouColSav-PRA-04, GoriSav-PRA-06, PazMorGorBac-PRB-06} yielding
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In order to correct such a defect, we propose here a new ECMD functional inspired by the recent functional proposed by some of the present authors \cite{FerGinTou-JCP-18} which interpolates between the usual PBE correlation functional $\e{\PBE}{}(\n{}{},\nabla \n{}{})$ for $\rsmu{}{}=0$ and the exact large-$\rsmu{}{}$ behavior, \cite{TouColSav-PRA-04, GoriSav-PRA-06, PazMorGorBac-PRB-06} yielding
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\begin{subequations}
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\begin{gather}
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\label{eq:epsilon_cmdpbe}
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\be{\PBE}{\sr}(\n{}{},\nabla \n{}{},\rsmu{}{}) = \frac{\e{\PBE}{}(\n{}{},\nabla \n{}{})}{1 + \beta(n,\nabla n, \rsmu{}{})\rsmu{}{3} },
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\\
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\label{eq:beta_cmdpbe}
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\beta(n,\nabla n,\rsmu{}{}) = \frac{3}{2\sqrt{\pi} (1 - \sqrt{2} )} \frac{\e{\PBE}{}(\n{}{},\nabla \n{}{})}{\n{\UEG}{(2)}(\n{}{})}.
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\beta(n,\nabla n,\rsmu{}{}) = \frac{3}{2\sqrt{\pi} (1 - \sqrt{2} )} \frac{\e{\PBE}{}(\n{}{},\nabla \n{}{})}{\n{2}{\UEG}(\n{}{})}.
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\end{gather}
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\end{subequations}
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The difference between the ECMD PBE functional defined in Ref.~\onlinecite{FerGinTou-JCP-18} and the present expression \eqref{eq:epsilon_cmdpbe} is that we approximate here the \textit{exact} ground-state on-top pair density of the system $\n{}{(2)}$ by its UEG version, i.e.~$\n{}{(2)} \approx \n{\UEG}{(2)} = \n{}{2} g_0(\n{}{})$, where $g_0(\n{}{})$ is the UEG correlation factor whose parametrization can be found in Eq.~(46) of Ref.~\onlinecite{GorSav-PRA-06}.
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This represents a major computational saving without loss of performance as we eschew the computation of $\n{}{(2)}$.
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The difference between the ECMD PBE functional defined in Ref.~\onlinecite{FerGinTou-JCP-18} and the present expression \eqref{eq:epsilon_cmdpbe} is that we approximate here the \textit{exact} ground-state on-top pair density of the system $\n{2}{}(\br{})$ by its UEG version, i.e.~$\n{2}{}(\br{}) \approx \n{2}{\UEG}(\br{}) = \left(\n{}{}(\br{})\right)^2 g_0(\n{}{}(\br{}) )$, where $g_0(\n{}{})$ is the UEG correlation factor whose parametrization can be found in Eq.~(46) of Ref.~\onlinecite{GorSav-PRA-06}.
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This represents a major computational saving without loss of performance as we eschew the computation of $\n{2}{}$.
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Therefore, the PBE complementary functional reads
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\begin{equation}
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\label{eq:def_pbe_tot}
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@ -536,8 +541,8 @@ We therefore define the valence-only effective interaction
|
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% \label{eq:Wval}
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\W{\wf{}{\Bas}}{\Val}(\br{1},\br{2}) = \left\{
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\begin{array}{ll}
|
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\f{\wf{}{\Bas}}{\Val}(\br{1},\br{2})/\n{\wf{}{\Bas},\Val}{(2)}(\br{1},\br{2}) & \mbox{if } \n{\wf{}{\Bas},\Val}{(2)}(\br{1},\br{2})\ne 0\\
|
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\,\,\,\,+\infty & \mbox{if not.}
|
||||
\f{\wf{}{\Bas}}{\Val}(\br{1},\br{2})/\n{2}{\wf{}{\Bas},\Val}(\br{1},\br{2}) & \mbox{if } \n{2}{\wf{}{\Bas},\Val}(\br{1},\br{2})\ne 0\\
|
||||
\,\,\,\,+\infty & \mbox{otherwise. }
|
||||
\end{array}
|
||||
\right.
|
||||
\end{equation}
|
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@ -548,14 +553,14 @@ with
|
||||
\f{\wf{}{\Bas}}{\Val}(\br{1},\br{2})
|
||||
= \sum_{pq \in \Bas} \sum_{rstu \in \Val} \SO{p}{1} \SO{q}{2} \V{pq}{rs} \Gam{rs}{tu}[{\wf{}{\Bas}}] \SO{t}{1} \SO{u}{2},
|
||||
\\
|
||||
\n{\wf{}{\Bas},\Val}{(2)}(\br{1},\br{2})
|
||||
\n{2}{\wf{}{\Bas},\Val}(\br{1},\br{2})
|
||||
= \sum_{pqrs \in \Val} \SO{p}{1} \SO{q}{2} \Gam{pq}{rs}[\wf{}{\Bas}] \SO{r}{1} \SO{s}{2},
|
||||
\end{gather}
|
||||
\end{subequations}
|
||||
and the corresponding valence range separation function $\rsmu{\wf{}{\Bas}}{\Val}(\br{})$
|
||||
\begin{equation}
|
||||
\label{eq:muval}
|
||||
\rsmu{\wf{}{\Bas}}{\Val}(\br{}) = \frac{\sqrt{\pi}}{2} \W{\wf{}{\Bas}}{\Val}(\br{},\Bar{\br{}}).
|
||||
\rsmu{\wf{}{\Bas}}{\Val}(\br{}) = \frac{\sqrt{\pi}}{2} \W{\wf{}{\Bas}}{\Val}(\br{},\br{}).
|
||||
\end{equation}
|
||||
%\begin{equation}
|
||||
% \twodmrdiagpsival = \sum_{klmn \in \Val} \SO{m}{1} \SO{n}{2} \gammamnkl[\wf{}{\Bas}] \SO{k}{1} \SO{l}{2} .
|
||||
@ -586,7 +591,11 @@ It is worth noting that, within the present definition, $\W{\wf{}{\Bas}}{\Val}(\
|
||||
%\end{equation}
|
||||
Defining $\n{\wf{}{\Bas}}{\Val}$ as the valence one-electron density, the valence part of the complementary functional $\bE{}{\Val}[\n{\wf{}{\Bas}}{\Val}]$ is then evaluated as $\bE{\LDA}{\sr}[\n{\wf{}{\Bas}}{\Val}(\br{}),\rsmu{\wf{}{\Bas}}{\Val}(\br{})]$ or $\bE{\PBE}{\sr}[\n{\wf{}{\Bas}}{\Val}(\br{}),\rsmu{\wf{}{\Bas}}{\Val}(\br{})]$.
|
||||
|
||||
Regarding now the main computational source of the present approach, it consists in the computation of $\W{\wf{}{\Bas}}{}(\br{})$ [See Eqs.~\eqref{eq:wcoal}] at each quadrature grid point. All through this paper, we use two-body density matrix of a single Slater determinant (typically HF) for $\Gam{rs}{tu}[\wf{}{\Bas}]$ and therefore the computational bottleneck reduces to the evaluation at each quadrature grid point of
|
||||
Regarding now the main computational source of the present approach, it consists in the evaluation
|
||||
of $\W{\wf{}{\Bas}}{}(\br{})$ [See Eqs.~\eqref{eq:wcoal}] at each quadrature grid point.
|
||||
All through this paper, we use two-body density matrix of a single Slater determinant (typically HF)
|
||||
for $\Gam{rs}{tu}[\wf{}{\Bas}]$ and therefore the computational bottleneck reduces to the evaluation
|
||||
at each quadrature grid point of
|
||||
\begin{equation}
|
||||
\label{eq:fcoal}
|
||||
f_{\text{HF}}^{\Bas}(\br{}) = \sum_{p,q\in\Bas} \sum_{i\in \nocca} \sum_{j\in \noccb} \V{pq}{ij} \SO{p}{} \SO{q}{} \SO{i}{} \SO{j}{}
|
||||
@ -595,8 +604,9 @@ which scales as $\Nb^2\times N_{elec}^2 \times \Ng$ and is embarassingly paralle
|
||||
When the four-index transformation become prohibitive, by performing successive matrix multiplications, one could rewrite the equations directly in the AO basis where it scales formally as $\order{\Ng \Nb^4}$ but where one can take advantage of the sparsity atomic-orbital-based algorithms to significantly spped up the calculations.
|
||||
|
||||
|
||||
To conclude this theory session, it is important to notice that in the limit of a complete basis set, because of the behaviour of the effective interaction [see \eqref{eq:lim_W}], the range separation function $\rsmu{\wf{}{\Bas}}{}(\br{})$ tends to infinity. Therefore, in the limit of a complete basis set, according to equation \eqref{eq:large_mu_ecmd}, the complementary functional tends to zero \textit{whatever the approximated functional} used for the DFT part.
|
||||
Thefore in the limit of a complete basis set one recovers the correct limit of the WFT model whatever approximations are made in the DFT part, just like in equation \eqref{eq:limitfunc}.
|
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To conclude this theory session, it is important to notice that the basis set correction proposed here has the folowing properties whatever the approximations made in the DFT part: i) it can be applied to any wave function models that provide an energy and density, ii) it vanishes for one-electron systems,
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iii) it vanishes in the limit of a complete basis set and thus garentees the correct CBS limit of the WFT model.
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%, because of the behaviour of the effective interaction [see \eqref{eq:lim_W}], the range separation function $\rsmu{\wf{}{\Bas}}{}(\br{})$ tends to infinity. Therefore, in the limit of a complete basis set, according to equation \eqref{eq:large_mu_ecmd}, the complementary functional tends to zero \textit{whatever the approximated functional} used for the DFT part.
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%%%%%%%%%%%%%%%%%%%%%%%%
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\section{Results}
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@ -693,28 +703,27 @@ Thefore in the limit of a complete basis set one recovers the correct limit of t
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We begin our investigation of the performance of the basis set correction by computing the atomization energies of \ce{C2}, \ce{N2}, \ce{O2} and \ce{F2} obtained with Dunning's cc-pVXZ basis sets (X $=$ D, T, Q and 5).
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In the case of \ce{C2} and \ce{N2}, we also perform calculations with the cc-pCVXZ family.
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\ce{N2}, \ce{O2} and \ce{F2} are weakly correlated systems and belong to the G2 set, whereas \ce{C2} already contains a non-negligible amount of strong correlation. \cite{BooCleThoAla-JCP-11}
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In a second time, we compute the entire atomization energies of the G2 set \cite{CurRagTruPop-JCP-91} composed by 55 molecules with the cc-pVXZ family.
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In a second time, we compute the entire atomization energies of the G2 set \cite{CurRagTruPop-JCP-91} composed by 55 molecules with the cc-pVXZ family, except for Li, Be and Na for which we use the cc-pCVXZ basis sets.
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This molecular set has been exhausively studied in the last 20 years (see, for example, Refs.~\onlinecite{FelPetDix-JCP-08,Gro-JCP-09,FelPet-JCP-09,NemTowNee-JCP-10,FelPetHil-JCP-11,PetTouUmr-JCP-12,FelPet-JCP-13,KesSylKohTewMar-JCP-18}).
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%The reference values for the atomization energies are extracted from Ref.~\onlinecite{HauKlo-JCP-12} and corresponds to frozen-core non-relativistic atomization energies obtained at the CCSD(T)(F12)/cc-pVQZ-F12 level of theory corrected for higher-excitation contributions ($E_\text{CCSDT(Q)/cc-pV(D+d)Z} - E_\text{CCSD(T)/cc-pV(D+d)Z})$.
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As a method $\modX$ we employ either CCSD(T) or exFCI.
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Here, exFCI stands for extrapolated FCI energies computed with the CIPSI algorithm. \cite{HurMalRan-JCP-73, GinSceCaf-CJC-13, GinSceCaf-JCP-15}
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||||
We refer the interested reader to Refs.~\onlinecite{HolUmrSha-JCP-17, SceGarCafLoo-JCTC-18, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, LooBogSceCafJAc-JCTC-19} for more details.
|
||||
In the case of the CCSD(T) calculations, we have $\modY = \HF$ as we use the Restricted Open Shel Hartree-Fock (ROHF) one-electron density to compute the complementary energy, and for the CIPSI calculations we use the density of a converged variational wave function.
|
||||
For the definition of the interaction, we use a single Slater determinant in the ROHF basis.
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||||
For the definition of the interaction, we use a single Slater determinant built in the ROHF basis for the CCSD(T) calculations, and built with the natural orbitals of the converged variational wave function for the exFCI calculations.
|
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The CCSD(T) calculations have been performed with Gaussian09 with standard threshold values. \cite{g09}
|
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RS-DFT and exFCI calculations are performed with {\QP}. \cite{QP2}
|
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\titou{For the quadrature grid, we employ ... radial and angular points.}
|
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For the quadrature grid, we employ the radial and angular points of the SG2 grid\cite{DasHer-JCC-17}.
|
||||
Except for the carbon dimer where we have taken the experimental equilibrium bond length (\InAA{1.2425}), all geometries have been extracted from Ref.~\onlinecite{HauJanScu-JCP-09} and have been obtained at the B3LYP/6-31G(2df,p) level of theory.
|
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Frozen core calculations are defined as such: an \ce{He} core is frozen from \ce{B} to \ce{Mg}, while a \ce{Ne} core is frozen from \ce{Al} to \ce{Xe}.
|
||||
In the context of the basis set correction, the set of valence spinorbitals $\Val$ involved in the definition of the effective interaction [see Eq.~\eqref{eq:Wval}] refers to the non-frozen spinorbitals.
|
||||
In the context of the basis set correction, the set of valence spinorbitals $\Val$ involved in the definition of the effective interaction refers to the non-frozen spinorbitals.
|
||||
The ``valence'' correction was used consistently when the FC approximation was applied.
|
||||
In order to estimate the complete basis set (CBS) limit for each model, we employed the two-point extrapolation proposed in Ref.~\onlinecite{HalHelJorKloKocOlsWil-CPL-98} for the correlation energies.
|
||||
We refer to these atomization energies as $\CBS$.
|
||||
|
||||
%\subsection{Convergence of the atomization energies with the WFT models }
|
||||
As the exFCI calculations were converged with a precision of about 0.1 {\kcal}, we can consider these atomization energies as near-FCI values.
|
||||
They will be our references for a given system in a given basis.
|
||||
The results for four diatomics mentioned above are reported in Table \ref{tab:diatomics}.
|
||||
They will be our references for \ce{C2}, \ce{N2}, \ce{O2} and \ce{F2} in a given basis, and the results for these diatomics are reported in Table \ref{tab:diatomics}.
|
||||
As one can see, the convergence of the exFCI atomization energies is, as expected, slow with respect to the basis set: chemical accuracy (error below 1 {\kcal}) is barely reached for \ce{C2}, \ce{O2} and \ce{F2} even with cc-pV5Z.
|
||||
Also, the atomization energies are consistently underestimated, reflecting that, in a given basis, the atom is always better described than the molecule due to the larger number of interacting electron pairs in the molecular system.
|
||||
A similar trend holds for CCSD(T).
|
||||
@ -728,6 +737,7 @@ Nevertheless, the deviation observed for the largest basis set is typically with
|
||||
%Also, the values obtained with the largest basis sets tends to converge toward a value close to the estimated CBS values.
|
||||
Importantly, the sensitivity with respect to the SR-DFT functional is quite large for the double- and triple-$\zeta$ basis sets, where clearly the PBE functional performs better.
|
||||
However, from the quadruple-$\zeta$ basis, the LDA and PBE functionals agree within a few tenths of a {\kcal}.
|
||||
Such weak sensitivity to the approximated functionals in the DFT part when reaching large basis sets shows the robustness of the approach.
|
||||
|
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%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
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\section*{Supporting information}
|
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|
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