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@ -157,13 +157,14 @@
\newcommand{\LCPQ}{Laboratoire de Chimie et Physique Quantiques (UMR 5626), Universit\'e de Toulouse, CNRS, UPS, France} \newcommand{\LCPQ}{Laboratoire de Chimie et Physique Quantiques (UMR 5626), Universit\'e de Toulouse, CNRS, UPS, France}
\newcommand{\LCT}{Laboratoire de Chimie Th\'eorique (UMR 7616), Universit\'e Pierre et Marie Curie, Sorbonne Universit\'e, CNRS, Paris, France} \newcommand{\LCT}{Laboratoire de Chimie Th\'eorique (UMR 7616), Sorbonne Universit\'e, CNRS, Paris, France}
\begin{document} \begin{document}
\title{Chemically-Accurate Excitation Energies With Small Basis Sets} \title{Chemically-Accurate Excitation Energies With Small Basis Sets}
\author{Emmanuel Giner} \author{Emmanuel Giner}
\email[Corresponding author: ]{emmanuel.giner@lct.jussieu.fr}
\affiliation{\LCT} \affiliation{\LCT}
\author{Anthony Scemama} \author{Anthony Scemama}
\affiliation{\LCPQ} \affiliation{\LCPQ}
@ -174,8 +175,8 @@
\affiliation{\LCPQ} \affiliation{\LCPQ}
\begin{abstract} \begin{abstract}
By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range density-functional correction for basis set incompleteness [\href{https://doi.org/10.1063/1.5052714}{Giner et al., \textit{J.~Chem.~Phys.}~\textbf{149}, 194301 (2018)}], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-$\zeta$ basis sets. By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range density-functional correction for basis-set incompleteness [\href{https://doi.org/10.1063/1.5052714}{Giner et al., \textit{J.~Chem.~Phys.}~\textbf{149}, 194301 (2018)}], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-$\zeta$ basis sets.
We illustrate the present approach on various types of excited states (valence, Rydberg and double excitations) in several small organic molecules (methylene, water, ammonia, carbon monoxide, carbon dimer and ethylene). We illustrate the present approach on various types of excited states (valence, Rydberg, and double excitations) in several small organic molecules (methylene, water, ammonia, carbon monoxide, carbon dimer and ethylene).
The present study clearly evidences that special care has to be taken with very diffuse excited states where the present correction might not be enough to catch the radial incompleteness of the one-electron basis set. The present study clearly evidences that special care has to be taken with very diffuse excited states where the present correction might not be enough to catch the radial incompleteness of the one-electron basis set.
\end{abstract} \end{abstract}
@ -186,24 +187,24 @@ The present study clearly evidences that special care has to be taken with very
\section{Introduction} \section{Introduction}
\label{sec:intro} \label{sec:intro}
%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%
One of the most fundamental problems of conventional electronic structure methods is their slow energy convergence with respect to the size of the one-electron basis set. One of the most fundamental problems of conventional wave-function electronic-structure methods is their slow energy convergence with respect to the size of the one-electron basis set.
The overall basis set incompleteness error can be, qualitatively at least, split in two contributions stemming from the radial and angular incompleteness. The overall basis-set incompleteness error can be, qualitatively at least, split in two contributions stemming from the radial and angular incompleteness.
Although for ground-state properties angular incompleteness is by far the main source of error, it is definitely not unusual to have a significant radial incompleteness in the case of excited states (especially for Rydberg states), which can be alleviated by using additional sets of diffuse basis functions (i.e.~augmented basis sets). Although for ground-state properties angular incompleteness is by far the main source of error, it is definitely not unusual to have a significant radial incompleteness in the case of excited states (especially for Rydberg states), which can be alleviated by using additional sets of diffuse basis functions (i.e.~augmented basis sets).
Explicitly-correlated F12 methods \cite{Kut-TCA-85, Kut-TCA-85, KutKlo-JCP-91, NogKut-JCP-94} have been specifically designed to efficiently catch angular incompleteness. \cite{Ten-TCA-12, TenNog-WIREs-12, HatKloKohTew-CR-12, KonBisVal-CR-12, GruHirOhnTen-JCP-17, MaWer-WIREs-18} Explicitly-correlated F12 methods \cite{Kut-TCA-85, Kut-TCA-85, KutKlo-JCP-91, NogKut-JCP-94} have been specifically designed to efficiently catch angular incompleteness. \cite{Ten-TCA-12, TenNog-WIREs-12, HatKloKohTew-CR-12, KonBisVal-CR-12, GruHirOhnTen-JCP-17, MaWer-WIREs-18}
Although they have been extremely successful to speed up convergence of ground-state energies and properties, such as correlation and atomization energies, \cite{TewKloNeiHat-PCCP-07} their performances for excited states \cite{FliHatKlo-JCP-06, NeiHatKlo-JCP-06, HanKoh-JCP-09, Koh-JCP-09, ShiWer-JCP-10, ShiKniWer-JCP-11, ShiWer-JCP-11, ShiWer-MP-13} have been much more conflicting. \cite{FliHatKlo-JCP-06, NeiHatKlo-JCP-06} Although they have been extremely successful to speed up convergence of ground-state energies and properties, such as correlation and atomization energies, \cite{TewKloNeiHat-PCCP-07} their performances for excited states \cite{FliHatKlo-JCP-06, NeiHatKlo-JCP-06, HanKoh-JCP-09, Koh-JCP-09, ShiWer-JCP-10, ShiKniWer-JCP-11, ShiWer-JCP-11, ShiWer-MP-13} have been much more conflicting. \cite{FliHatKlo-JCP-06, NeiHatKlo-JCP-06}
Instead of F12 methods, here we propose to follow a different route and investigate the performance of the recently proposed universal density-based basis set Instead of F12 methods, here we propose to follow a different route and investigate the performance of the recently proposed density-based basis set
incompleteness correction. \cite{GinPraFerAssSavTou-JCP-18} incompleteness correction. \cite{GinPraFerAssSavTou-JCP-18}
Contrary to our recent study on atomization and correlation energies, \cite{LooPraSceTouGin-JPCL-19} the present contribution focuses on vertical and adiabatic excitation energies in molecular systems which is a much tougher test for the reasons mentioned above. Contrary to our recent study on atomization and correlation energies, \cite{LooPraSceTouGin-JPCL-19} the present contribution focuses on vertical and adiabatic excitation energies in molecular systems which is a much tougher test for the reasons mentioned above.
This density-based correction relies on short-range correlation density functionals (with multideterminant reference) from range-separated density-functional theory \cite{TouColSav-PRA-04, AngGerSavTou-PRA-05, GolWerSto-PCCP-05, TouGerJanSavAng-PRL-09,JanHenScu-JCP-09, TouZhuSavJanAng-JCP-11, MusReiAngTou-JCP-15, LeiStoWerSav-CPL-97, FroTouJen-JCP-07, FroCimJen-PRA-10, HedKneKieJenRei-JCP-15, HedTouJen-JCP-18, FerGinTou-JCP-18} (RS-DFT) to capture the missing part of the short-range correlation effects, a consequence of the incompleteness of the one-electron basis set. This density-based correction relies on short-range correlation density functionals (with multideterminant reference) from range-separated density-functional theory \cite{Sav-INC-96, LeiStoWerSav-CPL-97, TouColSav-PRA-04, TouSavFla-IJQC-04, AngGerSavTou-PRA-05, GolWerSto-PCCP-05, PazMorGorBac-PRB-06, FroTouJen-JCP-07, TouGerJanSavAng-PRL-09, JanHenScu-JCP-09, FroCimJen-PRA-10, TouZhuSavJanAng-JCP-11, MusReiAngTou-JCP-15, HedKneKieJenRei-JCP-15, HedTouJen-JCP-18, FerGinTou-JCP-18} (RS-DFT) to capture the missing part of the short-range correlation effects, a consequence of the incompleteness of the one-electron basis set.
Because RS-DFT combines rigorously density-functional theory (DFT) \cite{ParYan-BOOK-89} and wave function theory (WFT) \cite{SzaOst-BOOK-96} via a decomposition of the electron-electron interaction into a non-divergent long-range part and a (complementary) short-range part (treated with WFT and DFT, respectively), the WFT method is relieved from describing the short-range part of the correlation hole around the electron-electron coalescence points. Because RS-DFT combines rigorously density-functional theory (DFT) \cite{ParYan-BOOK-89} and wave function theory (WFT) \cite{SzaOst-BOOK-96} via a decomposition of the electron-electron interaction into a non-divergent long-range part and a (complementary) short-range part (treated with WFT and DFT, respectively), the WFT method is relieved from describing the short-range part of the correlation hole around the electron-electron coalescence points (cusp).
Consequently, the energy convergence with respect to the size of the basis set is significantly improved, \cite{FraMusLupTou-JCP-15} and chemical accuracy can be obtained even with small basis sets. Consequently, the energy convergence with respect to the size of the basis set is significantly improved, \cite{FraMusLupTou-JCP-15} and chemical accuracy can be obtained even with small basis sets.
For example, in Ref.~\onlinecite{LooPraSceTouGin-JPCL-19}, we have shown that one can recover quintuple-$\zeta$ quality atomization and correlation energies with triple-$\zeta$ basis sets for a much lower computational cost than F12 methods. For example, in Ref.~\onlinecite{LooPraSceTouGin-JPCL-19}, we have shown that one can recover quintuple-$\zeta$ quality atomization and correlation energies with triple-$\zeta$ basis sets for a much lower computational cost than F12 methods.
This work is organized as follows. This work is organized as follows.
In Sec.~\ref{sec:theory}, the main working equations of the density-based correction are reported and discussed. In Sec.~\ref{sec:theory}, the main working equations of the density-based correction are reported and discussed.
Computational details are reported in Sec.~\ref{sec:compdetails}. Computational details are given in Sec.~\ref{sec:compdetails}.
In Sec.~\ref{sec:res}, we discuss our results for each system and draw our conclusions in Sec.~\ref{sec:ccl}. In Sec.~\ref{sec:res}, we discuss our results for each system and draw our conclusions in Sec.~\ref{sec:ccl}.
Unless otherwise stated, atomic units are used. Unless otherwise stated, atomic units are used.
@ -212,8 +213,8 @@ Unless otherwise stated, atomic units are used.
\label{sec:theory} \label{sec:theory}
%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%
The present basis set correction assumes that we have, in a given (finite) basis set $\Bas$, the ground-state and the $k$th excited-state energies, $\E{0}{\Bas}$ and $\E{k}{\Bas}$, their one-electron densities, $\n{k}{\Bas}$ and $\n{0}{\Bas}$, as well as their opposite-spin on-top pair densities, $\n{2,0}{\Bas}(\br{})$ and $\n{2,k}{\Bas}(\br{})$, The present basis-set correction assumes that we have, in a given (finite) basis set $\Bas$, the ground-state and the $k$th excited-state energies, $\E{0}{\Bas}$ and $\E{k}{\Bas}$, their one-electron densities, $\n{k}{\Bas}(\br{})$ and $\n{0}{\Bas}(\br{})$, as well as their opposite-spin on-top pair densities, $\n{2,0}{\Bas}(\br{})$ and $\n{2,k}{\Bas}(\br{})$,
Therefore, the complete basis set (CBS) energy of the ground and excited states may be approximated as \cite{GinPraFerAssSavTou-JCP-18} Therefore, the complete-basis-set (CBS) energy of the ground and excited states may be approximated as \cite{GinPraFerAssSavTou-JCP-18}
\begin{align} \begin{align}
\label{eq:ECBS} \label{eq:ECBS}
\E{0}{\CBS} & \approx \E{0}{\Bas} + \bE{}{\Bas}[\n{0}{\Bas}], \E{0}{\CBS} & \approx \E{0}{\Bas} + \bE{}{\Bas}[\n{0}{\Bas}],
@ -233,8 +234,8 @@ is the basis-dependent complementary density functional,
& &
\hWee{} & = \sum_{i<j}^{\Ne} r_{ij}^{-1}, \hWee{} & = \sum_{i<j}^{\Ne} r_{ij}^{-1},
\end{align} \end{align}
are the kinetic and electron-electron repulsion operators, respectively, and $\wf{}{\Bas}$ and $\wf{}{}$ are two general $\Ne$-electron normalized wave functions belonging to the Hilbert space spanned by $\Bas$ and the complete basis set, respectively. are the kinetic and electron-electron repulsion operators, respectively, and $\wf{}{\Bas}$ and $\wf{}{}$ are two general $\Ne$-electron normalized wave functions belonging to the Hilbert spaces spanned by $\Bas$ and in the CBS limit, respectively.
The notation $\wf{}{} \rightsquigarrow \n{}{}$ in Eq.~\eqref{eq:E_funcbasis} states that $\wf{}{}$ yields the one-electron density $\n{}{}$. The notation $\wf{}{} \rightsquigarrow \n{}{}$ in Eq.~\eqref{eq:E_funcbasis} states that $\wf{}{}$ yields the one-electron density $\n{}{}$. \jt{Note that in Eq.~(\ref{eq:ECBS}) we have assumed that the same density functional $\bE{}{\Bas}$ can be used for correcting all excited-state energies, which seems a reasonable approximation since the electron-electron cusp effects are largely universal.}
Hence, the CBS excitation energy associated with the $k$th excited state reads Hence, the CBS excitation energy associated with the $k$th excited state reads
\begin{equation} \begin{equation}
@ -250,7 +251,7 @@ is the excitation energy in $\Bas$ and
\label{eq:DbE} \label{eq:DbE}
\DbE{}{\Bas}[\n{0}{\Bas},\n{k}{\Bas}] = \bE{}{\Bas}[\n{k}{\Bas}] - \bE{}{\Bas}[\n{0}{\Bas}] \DbE{}{\Bas}[\n{0}{\Bas},\n{k}{\Bas}] = \bE{}{\Bas}[\n{k}{\Bas}] - \bE{}{\Bas}[\n{0}{\Bas}]
\end{equation} \end{equation}
its basis set correction. its basis-set correction.
An important property of the present correction is An important property of the present correction is
\begin{equation} \begin{equation}
\label{eq:limitfunc} \label{eq:limitfunc}
@ -273,15 +274,15 @@ The ECMD functional, $\bE{\text{c,md}}{\sr}[\n{}{},\rsmu{}{}]$, is a function of
& &
\lim_{\mu \to 0} \bE{\text{c,md}}{\sr}[\n{}{},\rsmu{}{}] & = \Ec[\n{}{}], \lim_{\mu \to 0} \bE{\text{c,md}}{\sr}[\n{}{},\rsmu{}{}] & = \Ec[\n{}{}],
\end{align} \end{align}
which correspond to the WFT limit ($\mu = \infty$) and the DFT limit ($\mu = 0$). which correspond to the WFT limit ($\mu \to \infty$) and the DFT limit ($\mu = 0$).
In Eq.~\eqref{eq:large_mu_ecmd}, $\Ec[\n{}{}]$ is the usual universal correlation density functional defined in Kohn-Sham DFT. \cite{HohKoh-PR-64, KohSha-PR-65} In Eq.~\eqref{eq:large_mu_ecmd}, $\Ec[\n{}{}]$ is the usual universal correlation density functional defined in Kohn-Sham DFT. \cite{HohKoh-PR-64, KohSha-PR-65}
The key ingredient that allows to exploit ECMD functionals for correcting the basis set incompleteness error is the range-separated function The key ingredient that allows us to exploit ECMD functionals for correcting the basis-set incompleteness error is the range-separated function
\begin{equation} \begin{equation}
\label{eq:def_mu} \label{eq:def_mu}
\rsmu{}{\Bas}(\br{}) = \frac{\sqrt{\pi}}{2} \W{}{\Bas}(\br{},\br{}), \rsmu{}{\Bas}(\br{}) = \frac{\sqrt{\pi}}{2} \W{}{\Bas}(\br{},\br{}),
\end{equation} \end{equation}
which automatically adapts to the spatial non-homogeneity of the basis set incompleteness error. which automatically adapts to the spatial non-homogeneity of the basis-set incompleteness error.
It is defined such that the long-range interaction of RS-DFT, $\w{}{\lr,\mu}(r_{12}) = \erf( \mu r_{12})/r_{12}$, coincides, at coalescence, with an effective two-electron interaction $\W{}{\Bas}(\br{1},\br{2})$ ``mimicking'' the Coulomb operator in an incomplete basis $\Bas$, i.e.~$\w{}{\lr,\rsmu{}{\Bas}(\br{})}(0) = \W{}{\Bas}(\br{},\br{})$ at any $\br{}$. \cite{GinPraFerAssSavTou-JCP-18} It is defined such that the long-range interaction of RS-DFT, $\w{}{\lr,\mu}(r_{12}) = \erf( \mu r_{12})/r_{12}$, coincides, at coalescence, with an effective two-electron interaction $\W{}{\Bas}(\br{1},\br{2})$ ``mimicking'' the Coulomb operator in an incomplete basis $\Bas$, i.e.~$\w{}{\lr,\rsmu{}{\Bas}(\br{})}(0) = \W{}{\Bas}(\br{},\br{})$ at any $\br{}$. \cite{GinPraFerAssSavTou-JCP-18}
The explicit expression of $\W{}{\Bas}(\br{1},\br{2})$ is given by The explicit expression of $\W{}{\Bas}(\br{1},\br{2})$ is given by
\begin{equation} \begin{equation}
@ -325,16 +326,16 @@ The local-density approximation ($\LDA$) of the ECMD complementary functional is
\end{equation} \end{equation}
where $\zeta = (\n{\uparrow}{} - \n{\downarrow}{})/\n{}{}$ is the spin polarization and $\be{\text{c,md}}{\sr,\LDA}(\n{}{},\zeta,\rsmu{}{})$ is the ECMD short-range correlation energy per electron of the uniform electron gas (UEG) \cite{LooGil-WIRES-16} parameterized in Ref.~\citenum{PazMorGorBac-PRB-06}. where $\zeta = (\n{\uparrow}{} - \n{\downarrow}{})/\n{}{}$ is the spin polarization and $\be{\text{c,md}}{\sr,\LDA}(\n{}{},\zeta,\rsmu{}{})$ is the ECMD short-range correlation energy per electron of the uniform electron gas (UEG) \cite{LooGil-WIRES-16} parameterized in Ref.~\citenum{PazMorGorBac-PRB-06}.
The functional $\be{\text{c,md}}{\sr,\LDA}$ from Eq.~\eqref{eq:def_lda_tot} presents two main defects: i) at small $\mu$, it overestimates the correlation energy, and ii) UEG-based quantities are hardly transferable when the system becomes strongly correlated and/or multi-configurational. The functional $\be{\text{c,md}}{\sr,\LDA}$ from Eq.~\eqref{eq:def_lda_tot} presents two main defects: i) at small $\mu$, it overestimates the correlation energy, and ii) UEG-based quantities are hardly transferable when the system becomes strongly correlated and/or multi-configurational\jt{ JTcomment: What is the difference between strongly correlated and multi-configurational? For me, this is the same}.
An attempt to solve these problems was suggested by some of the authors in the context of RS-DFT. \cite{FerGinTou-JCP-18} An attempt to solve these problems was suggested by some of the authors in the context of RS-DFT. \cite{FerGinTou-JCP-18}
They proposed to interpolate between the usual Perdew-Burke-Ernzerhof ($\PBE$) correlation functional \cite{PerBurErn-PRL-96} $\e{\text{c}}{\PBE}(\n{}{},s,\zeta)$ at $\mu = 0$ and the exact large-$\mu$ behavior. \cite{TouColSav-PRA-04, GorSav-PRA-06, PazMorGorBac-PRB-06} They proposed to interpolate between the usual Perdew-Burke-Ernzerhof ($\PBE$) correlation functional \cite{PerBurErn-PRL-96} $\e{\text{c}}{\PBE}(\n{}{},s,\zeta)$ (where $s=\nabla n/n^{4/3}$ is the reduced density gradient) at $\mu = 0$ and the exact large-$\mu$ behavior. \cite{TouColSav-PRA-04, GorSav-PRA-06, PazMorGorBac-PRB-06}
In the context of RS-DFT, the large-$\mu$ behavior corresponds to an extremely short-range interaction. In the context of RS-DFT, the large-$\mu$ behavior corresponds to an extremely short-range interaction in the short-range functional.
In this regime, the ECMD energy In this regime, the ECMD energy
\begin{align} \begin{align}
\label{eq:exact_large_mu} \label{eq:exact_large_mu}
\bE{\text{c,md}}{\sr}[\n{2}{},\rsmu{}{}] \propto \frac{1}{\mu^3} \int \dbr{} \n{2}{}(\br{}) + \order*{\mu^{-4}} \bE{\text{c,md}}{\sr} = \frac{2\sqrt{\pi} (1 - \sqrt{2})}{3\mu^3} \int \dbr{} \n{2}{}(\br{}) + \order*{\mu^{-4}}
\end{align} \end{align}
only depends on the \textit{exact} on-top pair density $\n{2}{}(\br{}) \equiv \n{2}{}(\br{},\br{})$ which is obtained from the \textit{exact} ground state wave function $\Psi$ belonging to the Hilbert space spanned by a complete basis set. only depends on the \textit{exact} on-top pair density $\n{2}{}(\br{}) \equiv \n{2}{}(\br{},\br{})$ which is obtained from the \textit{exact} ground-state wave function $\Psi$ belonging to the many-electron Hilbert space in the CBS limit.
Obviously, an exact quantity such as $\n{2}{}(\br{})$ is out of reach in practical calculations and must be approximated by a function referred here as $\tn{2}{}(\br{})$. Obviously, an exact quantity such as $\n{2}{}(\br{})$ is out of reach in practical calculations and must be approximated by a function referred here as $\tn{2}{}(\br{})$.
For a given $\tn{2}{}(\br{})$, some of the authors proposed the following functional form in order to interpolate between $\e{\text{c}}{\PBE}(\n{}{},s,\zeta)$ at $\mu = 0$ and Eq.~\eqref{eq:exact_large_mu} as $\mu \to \infty$: \cite{FerGinTou-JCP-18} For a given $\tn{2}{}(\br{})$, some of the authors proposed the following functional form in order to interpolate between $\e{\text{c}}{\PBE}(\n{}{},s,\zeta)$ at $\mu = 0$ and Eq.~\eqref{eq:exact_large_mu} as $\mu \to \infty$: \cite{FerGinTou-JCP-18}
@ -367,19 +368,20 @@ In Ref.~\onlinecite{LooPraSceTouGin-JPCL-19}, some of the authors introduced a v
\end{equation} \end{equation}
in which the on-top pair density was approximated by its UEG version, i.e., $\tn{2}{}(\br{}) = \n{2}{\UEG}(\br{})$, with in which the on-top pair density was approximated by its UEG version, i.e., $\tn{2}{}(\br{}) = \n{2}{\UEG}(\br{})$, with
\begin{equation} \begin{equation}
\n{2}{\UEG}(\br{}) = n(\br{})^2 [1-\zeta(\br{})^2] g_0(n(\br{})), \label{eq:n2UEG}
\n{2}{\UEG}(\br{}) \approx n(\br{})^2 [1-\zeta(\br{})^2] g_0(n(\br{})),
\end{equation} \end{equation}
and where $g_0(n)$ is the UEG on-top pair distribution function [see Eq.~(46) of Ref.~\citenum{GorSav-PRA-06}]. and where $g_0(n)$ is the UEG on-top pair distribution function [see Eq.~(46) of Ref.~\citenum{GorSav-PRA-06}]. \jt{Note that in Eq.~\eqref{eq:n2UEG} the dependence on the spin polarization $\zeta$ is only approximate.}
As illustrated in Ref.~\onlinecite{LooPraSceTouGin-JPCL-19}, the $\PBEUEG$ functional has clearly shown, for weakly correlated systems, to improve energetics over the pure UEG-based functional $\bE{\LDA}{\Bas}$ [see Eq.~\eqref{eq:def_lda_tot}] thanks to the leverage brought by the $\PBE$ functional in the small-$\mu$ regime. As illustrated in Ref.~\onlinecite{LooPraSceTouGin-JPCL-19}, the $\PBEUEG$ functional has clearly shown, for weakly correlated systems, to improve energetics over the pure UEG-based functional $\bE{\LDA}{\Bas}$ [see Eq.~\eqref{eq:def_lda_tot}] thanks to the leverage brought by the $\PBE$ functional in the small-$\mu$ regime.
However, the underlying UEG on-top pair density might not be suited for the treatment of excited states and/or strongly correlated systems. However, the underlying UEG on-top pair density might not be suited for the treatment of excited states and/or strongly correlated systems.
Besides, in the context of the present basis set correction, $\n{2}{\Bas}(\br{})$, the on-top pair density in $\Bas$, must be computed anyway to obtain $\rsmu{}{\Bas}(\br{})$ [see Eqs.~\eqref{eq:def_mu} and \eqref{eq:def_weebasis}]. Besides, in the context of the present basis-set correction, $\n{2}{\Bas}(\br{})$, the on-top pair density in $\Bas$, must be computed anyway to obtain $\rsmu{}{\Bas}(\br{})$ [see Eqs.~\eqref{eq:def_mu} and \eqref{eq:def_weebasis}].
Therefore, we define a better approximation of the exact on-top pair density as Therefore, as in Ref.~\onlinecite{FerGinTou-JCP-19}, we define a better approximation of the exact on-top pair density as
\begin{equation} \begin{equation}
\label{eq:ot-extrap} \label{eq:ot-extrap}
\ttn{2}{\Bas}(\br{}) = \n{2}{\Bas}(\br{}) \qty( 1 + \frac{2}{\sqrt{\pi}\rsmu{}{\Bas}(\br{})})^{-1} \ttn{2}{\Bas}(\br{}) = \n{2}{\Bas}(\br{}) \qty( 1 + \frac{2}{\sqrt{\pi}\rsmu{}{\Bas}(\br{})})^{-1}
\end{equation} \end{equation}
which is inspired by the large-$\mu$ extrapolation of the exact on-top pair density proposed by Gori-Giorgi and Savin \cite{GorSav-PRA-06} in the context of RS-DFT. which directly follows from the large-$\mu$ extrapolation of the exact on-top pair density proposed by Gori-Giorgi and Savin \cite{GorSav-PRA-06} in the context of RS-DFT.
Using this new ingredient, we propose here the ``$\PBE$-ontop'' (\PBEot) functional Using this new ingredient, we propose here the ``$\PBE$-ontop'' (\PBEot) functional
\begin{equation} \begin{equation}
\label{eq:def_pbe_tot} \label{eq:def_pbe_tot}
@ -394,21 +396,21 @@ The sole distinction between $\PBEUEG$ and $\PBEot$ is the level of approximatio
\section{Computational details} \section{Computational details}
\label{sec:compdetails} \label{sec:compdetails}
%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%
In the present study, we compute the ground- and excited-state energies, one-electron and on-top densities with a selected configuration interaction (sCI) method known as CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively). \cite{HurMalRan-JCP-73, GinSceCaf-CJC-13, GinSceCaf-JCP-15} In the present study, we compute the ground- and excited-state energies, one-electron densities and on-top pair densities with a selected configuration interaction (sCI) method known as CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively). \cite{HurMalRan-JCP-73, GinSceCaf-CJC-13, GinSceCaf-JCP-15}
The total energy of each state is obtained via an efficient extrapolation procedure of the sCI energies designed to reach near-FCI accuracy. \cite{HolUmrSha-JCP-17, QP2} The total energy of each state is obtained via an efficient extrapolation procedure of the sCI energies designed to reach near-FCI accuracy. \cite{HolUmrSha-JCP-17, QP2}
These energies will be labeled exFCI in the following. These energies will be labeled exFCI in the following.
Using near-FCI excitation energies (within a given basis set) has the indisputable advantage to remove the error inherent to the WFT method. Using near-FCI excitation energies (within a given basis set) has the indisputable advantage to remove the error inherent to the WFT method.
Indeed, in the present case, the only source of error on the excitation energies is due to basis set incompleteness. Indeed, in the present case, the only source of error on the excitation energies is due to basis-set incompleteness.
We refer the interested reader to Refs.~\onlinecite{HolUmrSha-JCP-17, SceGarCafLoo-JCTC-18, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, LooBogSceCafJac-JCTC-19, QP2} for more details. We refer the interested reader to Refs.~\onlinecite{HolUmrSha-JCP-17, SceGarCafLoo-JCTC-18, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, LooBogSceCafJac-JCTC-19, QP2} for more details.
The one-electron and on-top densities are computed from a very large CIPSI expansion containing up to several million determinants. The one-electron densities and on-top pair densities are computed from a very large CIPSI expansion containing up to several millions of Slater determinants.
All the RS-DFT and exFCI calculations have been performed with {\QP}. \cite{QP2} All the RS-DFT and exFCI calculations have been performed with {\QP}. \cite{QP2}
For the numerical quadratures, we employ the SG-2 grid. \cite{DasHer-JCC-17} For the numerical quadratures, we employ the SG-2 grid. \cite{DasHer-JCC-17}
Except for methylene for which FCI/TZVP geometries have been taken from Ref.~\onlinecite{SheLeiVanSch-JCP-98}, the other geometries have been extracted from Refs.~\onlinecite{LooSceBloGarCafJac-JCTC-18, LooBogSceCafJac-JCTC-19} and have been obtained at the CC3/aug-cc-pVTZ level of theory. Except for methylene for which FCI/TZVP geometries have been taken from Ref.~\onlinecite{SheLeiVanSch-JCP-98}, the other molecular geometries have been extracted from Refs.~\onlinecite{LooSceBloGarCafJac-JCTC-18, LooBogSceCafJac-JCTC-19} and have been obtained at the CC3/aug-cc-pVTZ level of theory.
For the sake of completeness, they are also reported in the {\SI}. For the sake of completeness, they are also reported in the {\SI}.
Frozen-core calculations are systematically performed and defined as such: a \ce{He} core is frozen from \ce{Li} to \ce{Ne}, while a \ce{Ne} core is frozen from \ce{Na} to \ce{Ar}. Frozen-core calculations are systematically performed and defined as such: a \ce{He} core is frozen from \ce{Li} to \ce{Ne}, while a \ce{Ne} core is frozen from \ce{Na} to \ce{Ar}.
The frozen-core density-based correction is used consistently with the frozen-core approximation in WFT methods. The frozen-core density-based correction is used consistently with the frozen-core approximation in WFT methods.
We refer the reader to Ref.~\onlinecite{LooPraSceTouGin-JPCL-19} for an explicit derivation of the equations associated with the frozen-core version of the present density-based basis set correction. We refer the reader to Ref.~\onlinecite{LooPraSceTouGin-JPCL-19} for an explicit derivation of the equations associated with the frozen-core version of the present density-based basis-set correction.
Compared to the exFCI calculations performed to compute energies and densities, the basis set correction represents, in any case, a marginal computational cost. Compared to the exFCI calculations performed to compute energies and densities, the basis-set correction represents, in any case, a marginal computational cost.
In the following, we employ the AVXZ shorthand notations for Dunning's aug-cc-pVXZ basis sets. In the following, we employ the AVXZ shorthand notations for Dunning's aug-cc-pVXZ basis sets.
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@ -424,7 +426,7 @@ In the following, we employ the AVXZ shorthand notations for Dunning's aug-cc-pV
Methylene is a paradigmatic system in electronic structure theory. \cite{Sch-Science-86} Methylene is a paradigmatic system in electronic structure theory. \cite{Sch-Science-86}
Due to its relative small size, its ground and excited states have been thoroughly studied with high-level ab initio methods. \cite{Sch-Science-86, BauTay-JCP-86, JenBun-JCP-88, SheVanYamSch-JMS-97, SheLeiVanSch-JCP-98, AbrShe-JCP-04, AbrShe-CPL-05, ZimTouZhaMusUmr-JCP-09, ChiHolAdaOttUmrShaZim-JPCA-18} Due to its relative small size, its ground and excited states have been thoroughly studied with high-level ab initio methods. \cite{Sch-Science-86, BauTay-JCP-86, JenBun-JCP-88, SheVanYamSch-JMS-97, SheLeiVanSch-JCP-98, AbrShe-JCP-04, AbrShe-CPL-05, ZimTouZhaMusUmr-JCP-09, ChiHolAdaOttUmrShaZim-JPCA-18}
As a first test of the present density-based basis set correction, we consider the four lowest-lying states of methylene ($1\,^{3}B_1$, $1\,^{1}A_1$, $1\,^{1}B_1$ and $2\,^{1}A_1$) at their respective equilibrium geometry and compute the corresponding adiabatic transition energies for various basis sets ranging from AVDZ to AVQZ. As a first test of the present density-based basis-set correction, we consider the four lowest-lying states of methylene ($1\,^{3}B_1$, $1\,^{1}A_1$, $1\,^{1}B_1$ and $2\,^{1}A_1$) at their respective equilibrium geometry and compute the corresponding adiabatic transition energies for various basis sets ranging from AVDZ to AVQZ.
We have also computed total energies at the exFCI/AV5Z level and used these alongside the quadruple-$\zeta$ ones to extrapolate the total energies to the CBS limit with the usual extrapolation formula \cite{HelJorOls-BOOK-02} We have also computed total energies at the exFCI/AV5Z level and used these alongside the quadruple-$\zeta$ ones to extrapolate the total energies to the CBS limit with the usual extrapolation formula \cite{HelJorOls-BOOK-02}
\begin{equation} \begin{equation}
\E{}{\text{AVXZ}} = \E{}{\CBS} + \frac{\alpha}{(\tX+1/2)^{3}}. \E{}{\text{AVXZ}} = \E{}{\CBS} + \frac{\alpha}{(\tX+1/2)^{3}}.
@ -434,11 +436,11 @@ These results are illustrated in Fig.~\ref{fig:CH2} and reported in Table \ref{t
Total energies for each state can be found in the {\SI}. Total energies for each state can be found in the {\SI}.
Figure \ref{fig:CH2} clearly shows that, for the double-$\zeta$ basis, the exFCI adiabatic energies are far from being chemically accurate with errors as high as 0.015 eV. Figure \ref{fig:CH2} clearly shows that, for the double-$\zeta$ basis, the exFCI adiabatic energies are far from being chemically accurate with errors as high as 0.015 eV.
From the triple-$\zeta$ basis onward, the exFCI excitation energies are chemically-accurate though, and converge steadily to the CBS limit when one increases the size of the basis set. From the triple-$\zeta$ basis onward, the exFCI excitation energies are chemically-accurate though, and converge steadily to the CBS limit when one increases the size of the basis set.
Concerning the basis set correction, already at the double-$\zeta$ level, the $\PBEot$ correction returns chemically accurate excitation energies. Concerning the basis-set correction, already at the double-$\zeta$ level, the $\PBEot$ correction returns chemically accurate excitation energies.
The performance of the $\PBEUEG$ and $\LDA$ functionals (which does not require the computation of the on-top density of each state) is less impressive. The performance of the $\PBEUEG$ and $\LDA$ functionals (which does not require the computation of the on-top pair density of each state) is less impressive.
Yet, they still yield significant reductions of the basis set incompleteness error, hence representing a good compromise between computational cost and accuracy. Yet, they still yield significant reductions of the basis-set incompleteness error, hence representing a good compromise between computational cost and accuracy.
Note that the results for the $\PBEUEG$ functional are not represented in Fig.~\ref{fig:CH2} as they are very similar to the $\LDA$ ones (similar considerations apply to the other systems studied below). Note that the results for the $\PBEUEG$ functional are not represented in Fig.~\ref{fig:CH2} as they are very similar to the $\LDA$ ones (similar considerations apply to the other systems studied below).
It is also quite evident that, the basis set correction has the tendency of over-correcting the excitation energies via an over-stabilization of the excited states compared to the ground state. It is also quite evident that, the basis-set correction has the tendency of over-correcting the excitation energies via an over-stabilization of the excited states compared to the ground state.
This trend is quite systematic as we shall see below. This trend is quite systematic as we shall see below.
%%% TABLE 1 %%% %%% TABLE 1 %%%
@ -565,9 +567,9 @@ This trend is quite systematic as we shall see below.
For the second test, we consider the water \cite{CaiTozRei-JCP-00, RubSerMer-JCP-08, LiPal-JCP-11, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, SceCafBenJacLoo-RC-19} and ammonia \cite{SchGoe-JCTC-17, BarDelPerMat-JMS-97, LooSceBloGarCafJac-JCTC-18} molecules. For the second test, we consider the water \cite{CaiTozRei-JCP-00, RubSerMer-JCP-08, LiPal-JCP-11, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, SceCafBenJacLoo-RC-19} and ammonia \cite{SchGoe-JCTC-17, BarDelPerMat-JMS-97, LooSceBloGarCafJac-JCTC-18} molecules.
They are both well-studied and possess Rydberg excited states which are highly sensitive to the radial completeness of the one-electron basis set, as evidenced in Ref.~\onlinecite{LooSceBloGarCafJac-JCTC-18}. They are both well-studied and possess Rydberg excited states which are highly sensitive to the radial completeness of the one-electron basis set, as evidenced in Ref.~\onlinecite{LooSceBloGarCafJac-JCTC-18}.
Table \ref{tab:Mol} reports vertical excitation energies for various singlet and triplet excited states of water and ammonia at various levels of theory (see the {\SI} for total energies). Table \ref{tab:Mol} reports vertical excitation energies for various singlet and triplet excited states of water and ammonia at various levels of theory (see the {\SI} for total energies).
The basis set corrected theoretical best estimates (TBEs) have been extracted from Ref.~\onlinecite{LooSceBloGarCafJac-JCTC-18} and have been obtained on the same geometries. The basis-set corrected theoretical best estimates (TBEs) have been extracted from Ref.~\onlinecite{LooSceBloGarCafJac-JCTC-18} and have been obtained on the same geometries.
These results are also depicted in Figs.~\ref{fig:H2O} and \ref{fig:NH3} for \ce{H2O} and \ce{NH3}, respectively. These results are also depicted in Figs.~\ref{fig:H2O} and \ref{fig:NH3} for \ce{H2O} and \ce{NH3}, respectively.
One would have noticed that the basis set effects are particularly strong for the third singlet excited state of water and the third and fourth singlet excited states of ammonia where this effect is even magnified. One would have noticed that the basis-set effects are particularly strong for the third singlet excited state of water and the third and fourth singlet excited states of ammonia where this effect is even magnified.
In these cases, one really needs doubly-augmented basis sets to reach radial completeness. In these cases, one really needs doubly-augmented basis sets to reach radial completeness.
The first observation worth reporting is that all three RS-DFT correlation functionals have very similar behaviors and they significantly reduce the error on the excitation energies for most of the states. The first observation worth reporting is that all three RS-DFT correlation functionals have very similar behaviors and they significantly reduce the error on the excitation energies for most of the states.
However, these results also clearly evidence that special care has to be taken for very diffuse excited states where the present correction might not be enough to catch the radial incompleteness of the one-electron basis set, a feature which is far from being a cusp-related effect. However, these results also clearly evidence that special care has to be taken for very diffuse excited states where the present correction might not be enough to catch the radial incompleteness of the one-electron basis set, a feature which is far from being a cusp-related effect.
@ -748,7 +750,7 @@ They have been recently studied with state-of-the-art methods, and have been sho
The vertical excitation energies associated with these transitions are reported in Table \ref{tab:Mol} and represented in Fig.~\ref{fig:C2}. The vertical excitation energies associated with these transitions are reported in Table \ref{tab:Mol} and represented in Fig.~\ref{fig:C2}.
An interesting point here is that one really needs to consider the $\PBEot$ functional to get chemically-accurate absorption energies with the AVDZ atomic basis set. An interesting point here is that one really needs to consider the $\PBEot$ functional to get chemically-accurate absorption energies with the AVDZ atomic basis set.
We believe that the present result is a direct consequence of the multireference character of the \ce{C2} molecule. We believe that the present result is a direct consequence of the multireference character of the \ce{C2} molecule.
In other words, the UEG on-top density used in the $\LDA$ and $\PBEUEG$ functionals (see Sec.~\ref{sec:func}) is a particularly bad approximation of the true on-top density for the present system. In other words, the UEG on-top pair density used in the $\LDA$ and $\PBEUEG$ functionals (see Sec.~\ref{sec:func}) is a particularly bad approximation of the true on-top pair density for the present system.
%%% FIG 5 %%% %%% FIG 5 %%%
\begin{figure} \begin{figure}
@ -760,16 +762,16 @@ In other words, the UEG on-top density used in the $\LDA$ and $\PBEUEG$ function
\end{figure} \end{figure}
%%% %%% %%% %%% %%% %%%
It is interesting to study the behavior of the key quantities involved in the basis set correction for different states as the basis set incompleteness error is obviously state specific. It is interesting to study the behavior of the key quantities involved in the basis-set correction for different states as the basis-set incompleteness error is obviously state specific.
In Fig.~\ref{fig:C2_mu}, we report $\rsmu{}{\Bas}(z)$, along the nuclear axis ($z$) for the two $^1 \Sigma_g^+$ electronic states of \ce{C2} computed with the AVDZ, AVTZ and AVQZ basis sets. In Fig.~\ref{fig:C2_mu}, we report $\rsmu{}{\Bas}(z)$, along the nuclear axis ($z$) for the two $^1 \Sigma_g^+$ electronic states of \ce{C2} computed with the AVDZ, AVTZ and AVQZ basis sets.
The graphs gathered in Fig.~\ref{fig:C2_mu} illustrate several general features regarding the present basis set correction: The graphs gathered in Fig.~\ref{fig:C2_mu} illustrate several general features regarding the present basis-set correction:
\begin{itemize} \begin{itemize}
\item the maximal values of $\rsmu{}{\Bas}(\br{})$ are systematically close to the nuclei, a signature of the atom-centered basis set; \item the maximal values of $\rsmu{}{\Bas}(\br{})$ are systematically close to the nuclei, a signature of the atom-centered basis set;
\item the overall values of $\rsmu{}{\Bas}(\br{})$ increase with the basis set, which reflects the improvement of the description of the correlation effects when enlarging the basis set; \item the overall values of $\rsmu{}{\Bas}(\br{})$ increase with the basis set, which reflects the improvement of the description of the correlation effects when enlarging the basis set;
\item the absolute value of the energetic correction decreases when the size of the basis set increases; \item the absolute value of the energetic correction decreases when the size of the basis set increases;
\item there is a clear correspondence between the values of the energetic correction and the on-top pair density. \item there is a clear correspondence between the values of the energetic correction and the on-top pair density.
\end{itemize} \end{itemize}
Regarding now the differential effect of the basis set correction in the special case of the two $^1 \Sigma_g^+$ states studied here, we can observe that: Regarding now the differential effect of the basis-set correction in the special case of the two $^1 \Sigma_g^+$ states studied here, we can observe that:
\begin{itemize} \begin{itemize}
\item $\rsmu{}{\Bas}(z)$ has the same overall behavior for the two states, with slightly more fine structure in the case of the ground state. \item $\rsmu{}{\Bas}(z)$ has the same overall behavior for the two states, with slightly more fine structure in the case of the ground state.
Such feature is coherent with the fact that the two states considered are both of $\Sigma_g^+$ symmetry and of valence character. Such feature is coherent with the fact that the two states considered are both of $\Sigma_g^+$ symmetry and of valence character.
@ -799,7 +801,7 @@ Regarding now the differential effect of the basis set correction in the special
As a final example, we consider the ethylene molecule, yet another system which has been particularly scrutinized theoretically using high-level ab initio methods. \cite{SerMarNebLinRoo-JCP-93, WatGwaBar-JCP-96, WibOliTru-JPCA-02, BarPaiLis-JCP-04, Ang-JCC-08, SchSilSauThi-JCP-08, SilSchSauThi-JCP-10, SilSauSchThi-MP-10, Ang-IJQC-10, DadSmaBooAlaFil-JCTC-12, FelPetDav-JCP-14, ChiHolAdaOttUmrShaZim-JPCA-18} As a final example, we consider the ethylene molecule, yet another system which has been particularly scrutinized theoretically using high-level ab initio methods. \cite{SerMarNebLinRoo-JCP-93, WatGwaBar-JCP-96, WibOliTru-JPCA-02, BarPaiLis-JCP-04, Ang-JCC-08, SchSilSauThi-JCP-08, SilSchSauThi-JCP-10, SilSauSchThi-MP-10, Ang-IJQC-10, DadSmaBooAlaFil-JCTC-12, FelPetDav-JCP-14, ChiHolAdaOttUmrShaZim-JPCA-18}
We refer the interested reader to the work of Feller et al.\cite{FelPetDav-JCP-14} for an exhaustive investigation dedicated to the excited states of ethylene using state-of-the-art CI calculations. We refer the interested reader to the work of Feller et al.\cite{FelPetDav-JCP-14} for an exhaustive investigation dedicated to the excited states of ethylene using state-of-the-art CI calculations.
In the present context, ethylene is a particularly interesting system as it contains a mixture of valence and Rydberg excited states. In the present context, ethylene is a particularly interesting system as it contains a mixture of valence and Rydberg excited states.
Our basis set corrected vertical excitation energies are gathered in Table \ref{tab:Mol} and depicted in Fig.~\ref{fig:C2H4}. Our basis-set corrected vertical excitation energies are gathered in Table \ref{tab:Mol} and depicted in Fig.~\ref{fig:C2H4}.
Except for one particular excitation (the lowest singlet-triplet excitation $1\,^{1}A_{1g} \ra 1\,^{3}B_{1u}$), the exFCI+$\PBEot$/AVDZ excitation energies are chemically accurate and the errors drop further when one goes to the triple-$\zeta$ basis. Except for one particular excitation (the lowest singlet-triplet excitation $1\,^{1}A_{1g} \ra 1\,^{3}B_{1u}$), the exFCI+$\PBEot$/AVDZ excitation energies are chemically accurate and the errors drop further when one goes to the triple-$\zeta$ basis.
%(Note that one cannot afford exFCI/AVQZ calculations for ethylene.) %(Note that one cannot afford exFCI/AVQZ calculations for ethylene.)
Consistently with the previous examples, the $\LDA$ and $\PBEUEG$ functionals are slightly less accurate, although they still correct the excitation energies in the right direction. Consistently with the previous examples, the $\LDA$ and $\PBEUEG$ functionals are slightly less accurate, although they still correct the excitation energies in the right direction.
@ -818,11 +820,11 @@ Consistently with the previous examples, the $\LDA$ and $\PBEUEG$ functionals ar
\section{Conclusion} \section{Conclusion}
\label{sec:ccl} \label{sec:ccl}
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We have shown that, by employing the recently proposed density-based basis set correction developed by some of the authors, \cite{GinPraFerAssSavTou-JCP-18} one can obtain, using sCI methods, chemically-accurate excitation energies with typically augmented double-$\zeta$ basis sets. We have shown that, by employing the recently proposed density-based basis-set correction developed by some of the authors, \cite{GinPraFerAssSavTou-JCP-18} one can obtain, using sCI methods, chemically-accurate excitation energies with typically augmented double-$\zeta$ basis sets.
This nicely complements our recent investigation on ground-state properties, \cite{LooPraSceTouGin-JPCL-19} which has evidenced that one recovers quintuple-$\zeta$ quality atomization and correlation energies with triple-$\zeta$ basis sets. This nicely complements our recent investigation on ground-state properties, \cite{LooPraSceTouGin-JPCL-19} which has evidenced that one recovers quintuple-$\zeta$ quality atomization and correlation energies with triple-$\zeta$ basis sets.
The present study clearly shows that, for very diffuse excited states, the present correction relying on short-range correlation functionals from RS-DFT might not be enough to catch the radial incompleteness of the one-electron basis set. The present study clearly shows that, for very diffuse excited states, the present correction relying on short-range correlation functionals from RS-DFT might not be enough to catch the radial incompleteness of the one-electron basis set.
Also, in the case of multireference systems, we have evidenced that the $\PBEot$ functional is more appropriate than the $\LDA$ and $\PBEUEG$ functionals relying on the UEG on-top density. Also, in the case of multireference systems, we have evidenced that the $\PBEot$ functional is more appropriate than the $\LDA$ and $\PBEUEG$ functionals relying on the UEG on-top pair density.
We are currently investigating the performance of the present basis set correction for strongly correlated systems and we hope to report on this in the near future. We are currently investigating the performance of the present basis-set correction for strongly correlated systems and we hope to report on this in the near future.
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\section*{Supporting Information Available} \section*{Supporting Information Available}