Merge branch 'master' of git.irsamc.ups-tlse.fr:loos/srDFT_SC

Manuscript/srDFT_SC.tex

@@ -276,7 +276,7 @@
 
 \begin{document}	
 
-\title{A density-based basis-set correction for strongly correlated molecular systems}
+\title{A basis-set error correction based on density-functional theory for strongly correlated molecular systems}
 
 \author{Emmanuel Giner}
 \email{emmanuel.giner@lct.jussieu.fr}
@@ -314,9 +314,10 @@ Beside the difficulties of accurately describing the molecular electronic struct
 
 An alternative way to improve the convergence towards the complete-basis-set (CBS) limit is to treat the short-range correlation effects within DFT and to use WFT methods to deal only with the long-range and/or strong correlation effects. A rigorous approach achieving this mixing of DFT and WFT is range-separated DFT (RSDFT) (see Ref.~\onlinecite{TouColSav-PRA-04} and references therein) which relies on a decomposition of the electron-electron Coulomb interaction in terms of the interelectronic distance thanks to a range-separation parameter $\mu$. The advantage of this approach is at least two-fold: i) the DFT part deals primarily with the short-range part of the Coulomb interaction, and consequently the usual semilocal density-functional approximations are more accurate than for standard KS DFT; ii) the WFT part deals only with a smooth non-divergent interaction, and consequently the wave function has no electron-electron cusp \cite{GorSav-PRA-06} and the basis-set convergence is much faster. \cite{FraMusLupTou-JCP-15} A number of approximate RSDFT schemes have been developed involving single-reference \cite{AngGerSavTou-PRA-05, GolWerSto-PCCP-05, TouGerJanSavAng-PRL-09,JanHenScu-JCP-09, TouZhuSavJanAng-JCP-11, MusReiAngTou-JCP-15,KalTou-JCP-18,KalMusTou-JCP-19} and multi-reference \cite{LeiStoWerSav-CPL-97, FroTouJen-JCP-07, FroCimJen-PRA-10, HedKneKieJenRei-JCP-15, HedTouJen-JCP-18, FerGinTou-JCP-18} WFT methods. Nevertheless, there are still some open issues in RSDFT, such as remaining fractional-charge and fractional-spin errors in the short-range density functionals \cite{MusTou-MP-17} or the dependence of the quality of the results on the value of the range-separation parameter $\mu$. 
 
+
 Building on the development of RSDFT, a possible solution to the basis-set convergence problem has been recently proposed by some of the present authors~\cite{GinPraFerAssSavTou-JCP-18} in which RSDFT functionals are used to recover only the correlation effects outside a given basis set. The key point here is to realize that a wave function developed in an incomplete basis set is cuspless and could also originate from a Hamiltonian with a non-divergent long-range electron-electron interaction. Therefore, a mapping with RSDFT can be performed through the introduction of an effective non-divergent interaction representing the usual electron-electron Coulomb interaction projected in an incomplete basis set. First applications to weakly correlated molecular systems have been successfully carried out, \cite{LooPraSceTouGin-JCPL-19} together with extensions of this approach to the calculations of excitation energies \cite{GinSceTouLoo-JCP-19} and ionization potentials. \cite{LooPraSceGinTou-JCTC-20} The goal of the present work is to further develop this approach for the description of strongly correlated systems. 
 
-The paper is organized as follows. In Sec.~\ref{sec:theory}, we recall the mathematical framework of the basis-set correction and we present its extension for strongly correlated systems. In particular, our focus is primarily set on imposing two key formal properties: spin-multiplet degeneracy and size consistency.
+The paper is organized as follows. In Sec.~\ref{sec:theory}, we recall the mathematical framework of the basis-set correction and we present its extension for strongly correlated systems. In particular, our focus is primarily set on imposing two key formal properties which are highly desirable in the context of strong correlation: spin-multiplet degeneracy and size consistency. To reach these goals, we introduce i) new functionals using different flavours of spin-polarization and on-top pair density, ii) an effective interaction based on multi-configurational wave functions. This generalizes the mathematical framework used in the previous work on weakly correlated systems\cite{LooPraSceTouGin-JCPL-19} where a single-reference based effective interaction was used together with the usual density and spin-polarization. 
 Then, in Sec.~\ref{sec:results}, we apply the method to the calculation of the potential energy curves of the \ce{H10}, \ce{N2}, \ce{O2}, and \ce{F2} molecules up to the dissociation limit. Finally, we conclude in Sec.~\ref{sec:conclusion}. 
 
 %%%%%%%%%%%%%%%%%%%%%%%%
@@ -702,7 +703,8 @@ For diatomics with the aug-cc-pVDZ and aug-cc-pVTZ basis sets,~\cite{KenDunHar-J
 For the three diatomics, we performed an additional exFCI calculation with the aug-cc-pVQZ basis set at the equilibrium geometry to obtain reliable estimates of the FCI/CBS dissociation energy.
 In the case of the \ce{H10} chain, the approximation to the FCI energies together with the estimated exact potential energy curves are obtained from the data of Ref.~\onlinecite{h10_prx} where the authors performed MRCI+Q calculations with a minimal valence active space as reference (see below for the description of the active space). 
 
-Regarding the complementary functional, we first perform full-valence CASSCF calculations with the GAMESS-US software~\cite{gamess} to obtain the wave function $\psibasis$. Then, all density-related quantities involved in the functional [density $n(\br{})$, effective spin polarization $\tilde{\zeta}(\br{})$, reduced density gradient $s(\br{})$, and on-top pair density $n_2(\br{})$] together with the local range-separation function $\mu(\br{})$ are calculated with this full-valence CASSCF wave function. The CASSCF calculations are performed with the following active spaces: (10e,10o) for \ce{H10}, (10e,8o) for \ce{N2}, (12e,8o) for \ce{O2}, and (14e,8o) for \ce{F2}. We note that, instead of using CASSCF wave functions for $\psibasis$, one could of course use the same selected-CI wave functions used for calculating the energy but the calculations of $n_2(\br{})$ and $\mu(\br{})$ would then be more costly. Another strategy would be to use for $\psibasis$ size-consistent truncated versions of the selected-CI wave functions but we did not explore this possibility in this work.
+Regarding the complementary functional, we first perform full-valence CASSCF calculations with the GAMESS-US software~\cite{gamess} to obtain the wave function $\psibasis$. Then, all density-related quantities involved in the functional [density $n(\br{})$, effective spin polarization $\tilde{\zeta}(\br{})$, reduced density gradient $s(\br{})$, and on-top pair density $n_2(\br{})$] together with the local range-separation function $\mu(\br{})$ are calculated with this full-valence CASSCF wave function. The CASSCF calculations are performed with the following active spaces: (10e,10o) for \ce{H10}, (10e,8o) for \ce{N2}, (12e,8o) for \ce{O2}, and (14e,8o) for \ce{F2}. We note that, instead of using CASSCF wave functions for $\psibasis$, one could of course use the same selected-CI wave functions used for calculating the energy but the calculations of $n_2(\br{})$ and $\mu(\br{})$ would then be more costly. 
+%Another strategy would be to use for $\psibasis$ size-consistent truncated versions of the selected-CI wave functions but we did not explore this possibility in this work.
 
 Also, as the frozen-core approximation is used in all our selected-CI calculations, we use the corresponding valence-only complementary functionals (see Subsec.~\ref{sec:FC}). Therefore, all density-related quantities exclude any contribution from the 1s core orbitals, and the range-separation function follows the definition given in Eq.~\eqref{eq:def_mur_val}. 
 

new/O2_avtz/plots/DFT_avtzE_relat.eps

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new/O2_avtz/plots/DFT_avtzE_relat_zoom.eps

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