We report a universal density-based basis-set incompleteness correction that can be applied to any wave function method.
The present correction, which appropriately vanishes in the complete basis set (CBS) limit, relies on short-range correlation density functionals (with multi-determinant reference) from range-separated density-functional theory (RS-DFT) to estimate the basis-set incompleteness error.
Contrary to conventional RS-DFT schemes which require an \textit{ad hoc} range-separation \textit{parameter}$\mu$, the key ingredient here is a range-separation \textit{function}$\mu(\bf{r})$ that automatically adapts to the spatial non-homogeneity of the basis-set incompleteness error.
As illustrative examples, we show how this density-based correction allows us to obtain CCSD(T) atomization and correlation energies near the CBS limit for the G2 set of molecules with compact Gaussian basis sets.
Contemporary quantum chemistry has developed in two directions --- wave function theory (WFT) \cite{Pop-RMP-99} and density-functional theory (DFT). \cite{Koh-RMP-99}
WFT is attractive as it exists a well-defined path for systematic improvement as well as powerful tools, such as perturbation theory, to guide the development of new WFT \textit{ans\"atze}.
The coupled cluster (CC) family of methods is a typical example of the WFT philosophy and is well regarded as the gold standard of quantum chemistry for weakly correlated systems.
By increasing the excitation degree of the CC expansion, one can systematically converge, for a given basis set, to the exact, full configuration interaction (FCI) limit, although the computational cost associated with such improvement is usually high.
One of the most fundamental drawbacks of conventional WFT methods is the slow convergence of energies and properties with respect to the size of the one-electron basis set.
To palliate this, following Hylleraas' footsteps, \cite{Hyl-ZP-29} Kutzelnigg proposed to introduce explicitly the interelectronic distance $r_{12}=\abs{\br{1}-\br{2}}$ to properly describe the electronic wave function around the coalescence of two electrons. \cite{Kut-TCA-85, KutKlo-JCP-91, NogKut-JCP-94}
The resulting F12 methods yield a prominent improvement of the energy convergence, and achieve chemical accuracy for small organic molecules with relatively small Gaussian basis sets. \cite{Ten-TCA-12, TenNog-WIREs-12, HatKloKohTew-CR-12, KonBisVal-CR-12}
For example, at the CCSD(T) level, one can obtain quintuple-$\zeta$ quality correlation energies with a triple-$\zeta$ basis, \cite{TewKloNeiHat-PCCP-07} although computational overheads are introduced by the large auxiliary basis used to resolve three- and four-electron integrals. \cite{BarLoo-JCP-17}
To reduce further the computational cost and/or ease the transferability of the F12 correction, approximated and/or universal schemes have recently emerged. \cite{TorVal-JCP-09, KonVal-JCP-10, KonVal-JCP-11, BooCleAlaTew-JCP-2012, IrmHumGru-arXiv-2019, IrmGru-arXiv-2019}
Present-day DFT calculations are almost exclusively done within the so-called Kohn-Sham (KS) formalism, which corresponds to an exact dressed one-electron theory. \cite{KohSha-PR-65}
The attractiveness of DFT originates from its very favorable accuracy/cost ratio as it often provides reasonably accurate energies and properties at a relatively low computational cost.
Thanks to this, KS-DFT \cite{HohKoh-PR-64, KohSha-PR-65} has become the workhorse of electronic structure calculations for atoms, molecules and solids. \cite{ParYan-BOOK-89}
Although there is no clear way on how to systematically improve density-functional approximations, \cite{Bec-JCP-14} climbing Perdew's ladder of DFT is potentially the most satisfactory way forward. \cite{PerSch-AIPCP-01, PerRuzTaoStaScuCso-JCP-05}
In the context of the present work, one of the interesting feature of density-based methods is their much faster convergence with respect to the size of the basis set. \cite{FraMusLupTou-JCP-15}
In particular, range-separated DFT (RS-DFT) (see Ref.~\onlinecite{TouColSav-PRA-04} and references therein) rigorously combines these two approaches via a decomposition of the electron-electron (e-e) interaction into a non-divergent long-range part and a (complementary) short-range part treated with WFT and DFT, respectively.
As the WFT method is relieved from describing the short-range part of the correlation hole around the e-e coalescence points, the convergence with respect to the one-electron basis set is greatly improved. \cite{FraMusLupTou-JCP-15}
Therefore, a number of approximate RS-DFT schemes have been developed within single-reference \cite{AngGerSavTou-PRA-05, GolWerSto-PCCP-05, TouGerJanSavAng-PRL-09,JanHenScu-JCP-09, TouZhuSavJanAng-JCP-11, MusReiAngTou-JCP-15} or multi-reference \cite{LeiStoWerSav-CPL-97, FroTouJen-JCP-07, FroCimJen-PRA-10, HedKneKieJenRei-JCP-15, HedTouJen-JCP-18, FerGinTou-JCP-18} WFT approaches.
Very recently, a major step forward has been taken by some of the present authors thanks to the development of a density-based basis-set correction for WFT methods. \cite{GinPraFerAssSavTou-JCP-18}
The present basis-set correction relies on the RS-DFT formalism to capture the missing part of the short-range correlation effects, a consequence of the incompleteness of the one-electron basis set.
Let us assume we have both the energy $\E{\modY}{\Bas}$ and density $\n{\modZ}{\Bas}$ of a $\Ne$-electron system described by two methods $\modY$ and $\modZ$ (potentially identical) in an incomplete basis set $\Bas$.
According to Eq.~(15) of Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, assuming that $\E{\modY}{\Bas}$ and $\n{\modZ}{\Bas}$ are reasonable approximations of the FCI energy and density within $\Bas$, the exact ground state energy $\E{}{}$ may be approximated as
is the basis-dependent complementary density functional, $\hT$ is the kinetic operator and $\hWee{}=\sum_{i<j} r_{ij}^{-1}$ is the interelectronic repulsion operator.
In Eq.~\eqref{eq:E_funcbasis}, $\wf{}{\Bas}$ and $\wf{}{}$ are two general $\Ne$-electron normalized wave functions belonging to the Hilbert space spanned by $\Bas$ and the complete basis set (CBS), respectively.
Provided that the functional $\bE{}{\Bas}[\n{}{}]$ is known exactly, the only sources of error at this stage lie in the potential approximate nature of the methods $\modY$ and $\modZ$, and the lack of self-consistency in the present scheme.
Because 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 two-electron interaction at coalescence.
Therefore, as we shall do later on, it feels natural to approximate $\bE{}{\Bas}[\n{}{}]$ by a short-range density functional which is complementary to a non-divergent long-range interaction.
Contrary to the conventional RS-DFT scheme which requires a range-separation \textit{parameter}$\rsmu{}{}$, here we use a range-separation \textit{function}$\rsmu{}{\Bas}(\br{})$ that automatically adapts to quantify the incompleteness of $\Bas$ in $\mathbb{R}^3$.
The first step of the present basis-set correction consists in obtaining an effective two-electron interaction $\W{}{\Bas}(\br{1},\br{2})$ ``mimicking'' the Coulomb operator in an incomplete basis $\Bas$.
and $\Gam{pq}{rs}=2\mel*{\wf{}{\Bas}}{\aic{r_\downarrow}\aic{s_\uparrow}\ai{p_\uparrow}\ai{q_\downarrow}}{\wf{}{\Bas}}$ are the opposite-spin pair density associated with $\wf{}{\Bas}$ and its corresponding tensor, respectively, $\SO{p}{}$ is a (real-valued) molecular orbital (MO),
Note that the divergence condition of $\W{}{\Bas}(\br{1},\br{2})$ in Eq.~\eqref{eq:def_weebasis} ensures that one-electron systems are free of correction as the present approach must only correct the basis-set incompleteness error originating from the e-e cusp.
As already discussed in Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, $\W{}{\Bas}(\br{1},\br{2})$ is symmetric, \textit{a priori} non translational, nor rotational invariant if $\Bas$ does not have such symmetries.
Because $\W{}{\Bas}(\br{1},\br{2})$ is a non-divergent two-electron interaction, it can be naturally linked to RS-DFT which employs a non-divergent long-range interaction operator.
such that the long-range interaction of RS-DFT, $\w{}{\lr,\mu}(r_{12})=\erf(\mu r_{12})/r_{12}$, coincides with the effective interaction at coalescence, i.e.~$\w{}{\lr,\rsmu{}{\Bas}(\br{})}(0)=\W{}{\Bas}(\br{},\br{})$ at any $\br{}$.
As in Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, we consider here a specific class of short-range correlation functionals known as correlation energy with multi-determinantal reference (ECMD) whose general definition reads \cite{TouGorSav-TCA-05}
The choice of ECMD in the present scheme is motivated by the analogy between the definition of $\bE{}{\Bas}[\n{}{}]$ [Eq.~\eqref{eq:E_funcbasis}] and the ECMD functional [Eq.~\eqref{eq:ec_md_mu}].
where \titou{$\zeta=(\n{\uparrow}{}-\n{\downarrow}{})/\n{}{}$ 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.~\onlinecite{PazMorGorBac-PRB-06}.
The short-range LDA correlation functional 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 $\mu$.
In order to correct such a defect, inspired by the recent functional proposed by some of the authors~\cite{FerGinTou-JCP-18}, we propose here a new Perdew-Burke-Ernzerhof (PBE)-based ECMD functional
\titou{$\be{\text{c,md}}{\sr,\PBE}\qty(\n{}{},s,\zeta,\rsmu{}{})$} interpolates between the usual PBE correlation functional, \cite{PerBurErn-PRL-96}\titou{$\e{\text{c}}{\PBE}(\n{}{},s,\zeta)$}, at $\rsmu{}{}=0$ and the exact large-$\rsmu{}{}$ behavior, \cite{TouColSav-PRA-04, GoriSav-PRA-06, PazMorGorBac-PRB-06} yielding
The difference between the ECMD functional defined in Ref.~\onlinecite{FerGinTou-JCP-18} and the present expression \eqref{eq:epsilon_cmdpbe}-\eqref{eq:beta_cmdpbe} is that we approximate here the on-top pair density by its UEG version, i.e.~\titou{$\n{2}{\Bas}(\br{},\br{})\approx\n{2}{\UEG}(\n{}{}(\br{}),\zeta(\br{}))$, where $\n{2}{\UEG}(\n{}{},\zeta)\approx\n{}{2}(1-\zeta^2) g_0(n)$} with the parametrization of the UEG on-top pair-distribution function $g_0(n)$ given in Eq.~(46) of Ref.~\onlinecite{GorSav-PRA-06}.
This represents a major computational saving without loss of accuracy for weakly correlated systems as we eschew the computation of $\n{2}{\Bas}(\br{},\br{})$.
Depending on the functional choice, the complementary functional $\bE{}{\Bas}[\n{\modZ}{\Bas}]$ is approximated by $\bE{\LDA}{\Bas}[\n{\modZ}{\Bas},\rsmu{}{\Bas}]$ or $\bE{\PBE}{\Bas}[\n{\modZ}{\Bas},\rsmu{}{\Bas}]$ where $\rsmu{}{\Bas}(\br{})$ is given by Eq.~\eqref{eq:mu_of_r}.
As most WFT calculations are performed within the frozen-core (FC) approximation, it is important to define an effective interaction within a subset of MOs.
We then naturally split the basis set as $\Bas=\Cor\bigcup\BasFC$ (where $\Cor$ and $\BasFC$ are the sets of core and active MOs, respectively) and define the FC version of the effective interaction as
Defining $\nFC{\modZ}{\Bas}$ as the FC (i.e.~valence-only) one-electron density obtained with a method $\modZ$ in $\Bas$, the FC contribution of the complementary functional is then approximated by $\bE{\LDA}{\Bas}[\nFC{\modZ}{\Bas},\rsmuFC{}{\Bas}]$ or $\bE{\PBE}{\Bas}[\nFC{\modZ}{\Bas},\rsmuFC{}{\Bas}]$.
\titou{In the general case (i.e.~$\wf{}{\Bas}$ is a multi-determinant expansion), we compute this embarrassingly parallel step in $\order*{\Ng\Nb^4}$ computational cost with a memory requirement of $\order*{\Ng\Nb^2}$, where $\Nb$ is the number of basis functions in $\Bas$.
As shown in Ref.~\onlinecite{GinPraFerAssSavTou-JCP-18}, this choice for $\wf{}{\Bas}$ already provides, for weakly correlated systems, a quantitative representation of the incompleteness of $\Bas$.
In our current implementation, the computational bottleneck is the four-index transformation to get the two-electron integrals in the MO basis which appear in Eqs.~\eqref{eq:n2basis} and \eqref{eq:fbasis}.
Modern integral decomposition techniques (such as density fitting \cite{Whi-JCP-73}) or atomic-orbital-based algorithms could be employed to significantly speed up this step.
To conclude this section, we point out that, thanks to the definitions \eqref{eq:def_weebasis} and \eqref{eq:mu_of_r} as well as the properties \eqref{eq:lim_W} and \eqref{eq:large_mu_ecmd}, independently of the DFT functional, the present basis-set correction
i) can be applied to any WFT method that provides an energy and a density,
Deviation (in \kcal) from CBS atomization energies of \ce{C2} (top left), \ce{O2} (top right), \ce{N2} (bottom left) and \ce{F2} (bottom right) obtained with various methods and basis sets.
Statistical analysis (in \kcal) of the G2 atomization energies depicted in Fig.~\ref{fig:G2_Ec}.
Mean absolute deviation (MAD), root-mean-square deviation (RMSD), and maximum deviation (MAX) with respect to the CCSD(T)/CBS reference atomization energies.
Deviation (in \kcal) from the CCSD(T)/CBS atomization energy obtained with various methods with the cc-pVDZ (top), cc-pVTZ (center) and cc-pVQZ (bottom) basis sets.
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 (X $=$ D, T, Q and 5).
\ce{N2}, \ce{O2} and \ce{F2} are weakly correlated systems and belong to the G2 set \cite{CurRagTruPop-JCP-91} (see below), whereas \ce{C2} already contains a non-negligible amount of strong correlation. \cite{BooCleThoAla-JCP-11}
In a second time, we compute the atomization energies of the entire G2 set \cite{CurRagTruPop-JCP-91} composed by 55 molecules with the cc-pVXZ basis set family.
This molecular set has been intensively 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, HauKlo-JCP-12, PetTouUmr-JCP-12, FelPet-JCP-13, KesSylKohTewMar-JCP-18}) and can be considered as a representative set of small organic and inorganic molecules.
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 $\modZ=\ROHF$ as we use the restricted open-shell HF (ROHF) one-electron density to compute the complementary basis-set correction energy.
CCSD(T) energies are computed with Gaussian09 using standard threshold values, \cite{g09} while RS-DFT and exFCI calculations are performed with {\QP}. \cite{QP2}
Apart from 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.
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}.
In the context of the basis-set correction, the set of active MOs, $\BasFC$, involved in the definition of the effective interaction [see Eq.~\eqref{eq:WFC}] refers to the non-frozen MOs.
To estimate the CBS limit of each method, following Ref.~\onlinecite{HalHelJorKloKocOlsWil-CPL-98}, we perform a two-point X$^{-3}$ extrapolation of the correlation energies using the quadruple- and quintuple-$\zeta$ data that we add up to the HF energies obtained in the largest (i.e.~quintuple-$\zeta$) basis.
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 the cc-pV5Z basis set, and the atomization energies are consistently underestimated.
A small overestimation can occur compared to the CBS value by a few tenths of a {\kcal} (the largest deviation being 0.6 {\kcal} for \ce{N2} at the CCSD(T)+PBE/cc-pV5Z level).
Nevertheless, the deviation observed for the largest basis set is typically within the CBS extrapolation error, which is highly satisfactory knowing the marginal computational cost of the present correction.
In most cases, the basis-set corrected triple-$\zeta$ atomization energies are on par with the uncorrected quintuple-$\zeta$ ones.
Importantly, the sensitivity with respect to the RS-DFT functional is quite large for the double- and triple-$\zeta$ basis sets, where clearly the PBE functional performs better.
As a second set of numerical examples, we compute the error (with respect to the CBS values) of the atomization energies from the G2 test set with $\modY=\CCSDT$, $\modZ=\ROHF$ and the cc-pVXZ basis sets.
Here, all atomization energies have been computed with the same near-CBS HF/cc-pV5Z energies; only the correlation energy contribution varies from one method to the other.
Investigating the convergence of correlation energies (or difference of such quantities) is commonly done to appreciate the performance of basis-set corrections aiming at correcting two-electron effects. \cite{Tenno-CPL-04, TewKloNeiHat-PCCP-07, IrmGru-arXiv-2019}
A statistical analysis of these data is also provided in Table \ref{tab:stats}, where we report the mean absolute deviation (MAD), root-mean-square deviation (RMSD), and maximum deviation (MAX) with respect to the CCSD(T)/CBS atomization energies.
Note that the MAD of our CCSD(T)/CBS atomization energies is only 0.37 {\kcal} compared to the values extracted from Ref.~\onlinecite{HauKlo-JCP-12} which 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 ($E_\text{CCSDT(Q)/cc-pV(D+d)Z}- E_\text{CCSD(T)/cc-pV(D+d)Z})$.
CCSD(T)+LDA/cc-pVQZ and CCSD(T)+PBE/cc-pVQZ return MAD of 0.33 and 0.31 kcal/mol (respectively) while CCSD(T)/cc-pVQZ still yields a fairly large MAD of 2.50 {\kcal}.
Therefore, similar to F12 methods, \cite{TewKloNeiHat-PCCP-07} we can safely claim that the present basis-set correction provides significant basis-set reduction and recovers quintuple-$\zeta$ quality atomization and correlation energies with triple-$\zeta$ basis sets for a much cheaper computational cost.
Encouraged by these promising results, we are currently pursuing various avenues toward basis-set reduction for strongly correlated systems and electronically excited states.
The authors would like to thank the \emph{Centre National de la Recherche Scientifique} (CNRS) and the \emph{Institut des Sciences du Calcul et des Donn\'ees} for funding.
This work was performed using HPC resources from GENCI-TGCC (Grant No.~2018-A0040801738) and CALMIP (Toulouse) under allocation 2019-18005.
