A density-fitting implementation of the density-based basis-set correction method.

This work reports an efficient density-fitting implementation of the density-based basis-set correction (DBBSC) method in the MOLPRO software. This method consists in correcting the energy calculated by a wave-function method with a given basis set by an adapted basis-set correction density functional incorporating the short-range electron correlation effects missing in the basis set, resulting in an accelerated convergence to the complete-basis-set limit. Different basis-set correction density-functional approximations are explored and the complementary-auxiliary-basis-set single-excitation correction is added. The method is tested on a benchmark set of reaction energies at the second-order Møller-Plesset (MP2) level and a comparison with the explicitly correlated MP2-F12 method is provided. The results show that the DBBSC method greatly accelerates the basis convergence of MP2 reaction energies, without reaching the accuracy of the MP2-F12 method but with a lower computational cost.

Basis-set correction based on density-functional theory: Linear-response formalism for excited-state energies.

The basis-set correction method based on density-functional theory consists in correcting the energy calculated by a wave-function method with a given basis set by a density functional. This basis-set correction density functional incorporates the short-range electron correlation effects missing in the basis set. This results in accelerated basis convergences of ground-state energies to the complete-basis-set limit. In this work, we extend the basis-set correction method to a linear-response formalism for calculating excited-state energies. We give the general linear-response equations as well as the more specific equations for configuration-interaction wave functions. As a proof of concept, we apply this approach to the calculations of excited-state energies in a one-dimensional two-electron model system with harmonic potential and a Dirac-delta electron-electron interaction. The results obtained with full-configuration-interaction wave functions expanded in a basis of Hermite functions and a local-density-approximation basis-set correction functional show that the present approach does not help in accelerating the basis convergence of excitation energies. However, we show that it significantly accelerates basis convergences of excited-state total energies.

Effective quantum electrodynamics: One-dimensional model of the relativistic hydrogen-like atom.

We consider a one-dimensional effective quantum electrodynamics (QED) model of the relativistic hydrogen-like atom using delta-potential interactions. We discuss the general exact theory and the Hartree-Fock approximation. The present one-dimensional effective QED model shares the essential physical feature of the three-dimensional theory: the nuclear charge polarizes the vacuum state (creation of electron-positron pairs), which results in a QED Lamb-type shift of the bound-state energy. Yet, this 1D effective QED model eliminates some of the most serious technical difficulties of the three-dimensional theory coming from renormalization. We show how to calculate the vacuum-polarization density at zeroth order in the two-particle interaction and the QED Lamb-type shift of the bound-state energy at first order in the two-particle interaction. The present work may be considered a step toward the development of a quantum-chemistry effective QED theory of atoms and molecules.

Photoionization and core resonances from range-separated time-dependent density-functional theory for open-shell states: Example of the lithium atom.

We consider the calculations of photoionization spectra and core resonances of open-shell systems using range-separated time-dependent density-functional theory. Specifically, we use the time-dependent range-separated hybrid (TDRSH) scheme, combining a long-range Hartree-Fock exchange potential and kernel with a short-range potential and kernel from a local density-functional approximation, and the time-dependent locally range-separated hybrid (TDLRSH) scheme, which uses a local range-separation parameter. To efficiently perform the calculations, we formulate a spin-unrestricted linear-response Sternheimer approach in a non-orthogonal B-spline basis set using appropriate frequency-dependent boundary conditions. We illustrate this approach on the Li atom, which suggests that TDRSH and TDLRSH are adequate simple methods for estimating the single-electron photoionization spectra of open-shell systems.

Systematic lowering of the scaling of Monte Carlo calculations by partitioning and subsampling.

We propose to compute physical properties by Monte Carlo calculations using conditional expectation values. The latter are obtained on top of the usual Monte Carlo sampling by partitioning the physical space in several subspaces or fragments, and subsampling each fragment (i.e., performing side walks) while freezing the environment. No bias is introduced and a zero-variance principle holds in the limit of separability, i.e., when the fragments are independent. In practice, the usual bottleneck of Monte Carlo calculations-the scaling of the statistical fluctuations as a function of the number of particles N-is relieved for extensive observables. We illustrate the method in variational Monte Carlo on the two-dimensional Hubbard model and on metallic hydrogen chains using Jastrow-Slater wave functions. A factor O(N) is gained in numerical efficiency.

Photoionization and core resonances from range-separated density-functional theory: General formalism and example of the beryllium atom.

We explore the merits of linear-response range-separated time-dependent density-functional theory (TDDFT) for the calculation of photoionization spectra. We consider two variants of range-separated TDDFT, namely, the time-dependent range-separated hybrid (TDRSH) scheme, which uses a global range-separation parameter, and the time-dependent locally range-separated hybrid (TDLRSH), which uses a local range-separation parameter, and compare with standard time-dependent local-density approximation (TDLDA) and time-dependent Hartree-Fock (TDHF). We show how to calculate photoionization spectra with these methods using the Sternheimer approach formulated in a non-orthogonal B-spline basis set with appropriate frequency-dependent boundary conditions. We illustrate these methods on the photoionization spectrum of the Be atom, focusing, in particular, on the core resonances. Both the TDRSH and TDLRSH photoionization spectra are found to constitute a large improvement over the TDLDA photoionization spectrum and a more modest improvement over the TDHF photoionization spectrum.

Basis-set correction for coupled-cluster estimation of dipole moments.

The present work proposes an approach to obtain a basis-set correction based on density-functional theory (DFT) for the computation of molecular properties in wave-function theory (WFT). This approach allows one to accelerate the basis-set convergence of any energy derivative of a non-variational WFT method, generalizing previous works on the DFT-based basis-set correction where either only ground-state energies could be computed with non-variational wave functions [Loos et al., J. Phys. Chem. Lett. 10, 2931 (2019)] or properties could be computed as expectation values over variational wave functions [Giner et al., J. Chem. Phys. 155, 044109 (2021)]. This work focuses on the basis-set correction of dipole moments in coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)], which is numerically tested on a set of 14 molecules with dipole moments covering two orders of magnitude. As the basis-set correction relies only on Hartree-Fock densities, its computational cost is marginal with respect to the one of the CCSD(T) calculations. Statistical analysis of the numerical results shows a clear improvement of the basis convergence of the dipole moment with respect to the usual CCSD(T) calculations.

Basis-set correction based on density-functional theory: Rigorous framework for a one-dimensional model.

We re-examine the recently introduced basis-set correction theory based on density-functional theory, which consists of correcting the basis-set incompleteness error of wave-function methods using a density functional. We use a one-dimensional model Hamiltonian with delta-potential interactions, which has the advantage of making easier to perform a more systematic analysis than for three-dimensional Coulombic systems while keeping the essence of the slow basis convergence problem of wave-function methods. We provide some mathematical details about the theory and propose a new variant of basis-set correction, which has the advantage of being suited to the development of an adapted local-density approximation. We show, indeed, how to develop a local-density approximation for the basis-set correction functional, which is automatically adapted to the basis set employed, without resorting to range-separated density-functional theory as in previous studies, but using instead a finite uniform electron gas whose electron-electron interaction is projected on the basis set. The work puts the basis-set correction theory on firmer ground and provides an interesting strategy for the improvement of this approach.

Accurate energies of transition metal atoms, ions, and monoxides using selected configuration interaction and density-based basis-set corrections.

The semistochastic heat-bath configuration interaction method is a selected configuration interaction plus perturbation theory method that has provided near-full configuration interaction (FCI) levels of accuracy for many systems with both single- and multi-reference character. However, obtaining accurate energies in the complete basis-set limit is hindered by the slow convergence of the FCI energy with respect to basis size. Here, we show that the recently developed basis-set correction method based on range-separated density functional theory can be used to significantly speed up basis-set convergence in SHCI calculations. In particular, we study two such schemes that differ in the functional used and apply them to transition metal atoms and monoxides to obtain total, ionization, and dissociation energies well converged to the complete-basis-set limit within chemical accuracy.

Self-consistent density-based basis-set correction: How much do we lower total energies and improve dipole moments?

This work provides a self-consistent extension of the recently proposed density-based basis-set correction method for wave function electronic-structure calculations [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)]. In contrast to the previously used approximation where the basis-set correction density functional was a posteriori added to the energy from a wave-function calculation, here the energy minimization is performed including the basis-set correction. Compared to the non-self-consistent approximation, this allows one to lower the total energy and change the wave function under the effect of the basis-set correction. This work addresses two main questions: (i) What is the change in total energy compared to the non-self-consistent approximation and (ii) can we obtain better properties, namely, dipole moments, with the basis-set corrected wave functions. We implement the present formalism with two different basis-set correction functionals and test it on different molecular systems. The main results of the study are that (i) the total energy lowering obtained by the self-consistent approach is extremely small, which justifies the use of the non-self-consistent approximation, and (ii) the dipole moments obtained from the basis-set corrected wave functions are improved, being already close to their complete basis-set values with triple-zeta basis sets. Thus, the present study further confirms the soundness of the density-based basis-set correction scheme.

Almost exact energies for the Gaussian-2 set with the semistochastic heat-bath configuration interaction method.

The recently developed semistochastic heat-bath configuration interaction (SHCI) method is a systematically improvable selected configuration interaction plus perturbation theory method capable of giving essentially exact energies for larger systems than is possible with other such methods. We compute SHCI atomization energies for 55 molecules that have been used as a test set in prior studies because their atomization energies are known from experiment. Basis sets from cc-pVDZ to cc-pV5Z are used, totaling up to 500 orbitals and a Hilbert space of 1032 Slater determinants for the largest molecules. For each basis, an extrapolated energy well within chemical accuracy (1 kcal/mol or 1.6 mHa/mol) of the exact energy for that basis is computed using only a tiny fraction of the entire Hilbert space. We also use our almost exact energies to benchmark energies from the coupled cluster method with single, double, and perturbative triple excitations. The energies are extrapolated to the complete basis set limit and compared to the experimental atomization energies. The extrapolations are done both without and with a basis-set correction based on density-functional theory. The mean absolute deviations from experiment for these extrapolations are 0.46 kcal/mol and 0.51 kcal/mol, respectively. Orbital optimization methods used to obtain improved convergence of the SHCI energies are also discussed.

Relativistic short-range exchange energy functionals beyond the local-density approximation.

We develop relativistic short-range exchange energy functionals for four-component relativistic range-separated density-functional theory using a Dirac-Coulomb Hamiltonian in the no-pair approximation. We show how to improve the short-range local-density approximation exchange functional for large range-separation parameters by using the on-top exchange pair density as a new variable. We also develop a relativistic short-range generalized-gradient approximation exchange functional that further increases the accuracy for small range-separation parameters. Tests on the helium, beryllium, neon, and argon isoelectronic series up to high nuclear charges show that the latter functional gives exchange energies with a maximal relative percentage error of 3%. The development of this exchange functional represents a step forward for the application of four-component relativistic range-separated density-functional theory to chemical compounds with heavy elements.

A basis-set error correction based on density-functional theory for strongly correlated molecular systems.

We extend to strongly correlated molecular systems the recently introduced basis-set incompleteness correction based on density-functional theory (DFT) [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)]. This basis-set correction relies on a mapping between wave-function calculations in a finite basis set and range-separated DFT (RSDFT) through the definition of an effective non-divergent interaction corresponding to the electron-electron Coulomb interaction projected in the finite basis set. This enables the use of RSDFT-type complementary density functionals to recover the dominant part of the short-range correlation effects missing in this finite basis set. To study both weak and strong correlation regimes, we consider the potential energy curves of the H10, N2, O2, and F2 molecules up to the dissociation limit, and we explore various approximations of complementary functionals fulfilling two key properties: spin-multiplet degeneracy (i.e., independence of the energy with respect to the spin projection Sz) and size consistency. Specifically, we investigate the dependence of the functional on different types of on-top pair densities and spin polarizations. The key result of this study is that the explicit dependence on the on-top pair density allows one to completely remove the dependence on any form of spin polarization without any significant loss of accuracy. Quantitatively, we show that the basis-set correction reaches chemical accuracy on atomization energies with triple-ζ quality basis sets for most of the systems studied here. In addition, the present basis-set incompleteness correction provides smooth potential energy curves along the whole range of internuclear distances.

Density-Based Basis-Set Incompleteness Correction for GW Methods.

Similar to other electron correlation methods, many-body perturbation theory methods based on Green's functions, such as the so-called GW approximation, suffer from the usual slow convergence of energetic properties with respect to the size of the one-electron basis set. This displeasing feature is due to the lack of explicit electron-electron terms modeling the infamous Kato electron-electron cusp and the correlation Coulomb hole around it. Here, we propose a computationally efficient density-based basis-set correction based on short-range correlation density functionals which significantly speeds up the convergence of energetics toward the complete basis set limit. The performance of this density-based correction is illustrated by computing the ionization potentials of the 20 smallest atoms and molecules of the GW100 test set at the perturbative GW (or G0W0) level using increasingly large basis sets. We also compute the ionization potentials of the five canonical nucleobases (adenine, cytosine, thymine, guanine, and uracil) and show that, here again, a significant improvement is obtained.

Self-Consistent Range-Separated Density-Functional Theory with Second-Order Perturbative Correction via the Optimized-Effective-Potential Method.

We extend the range-separated double-hybrid RSH+MP2 method (Ángyán, J. G.; et al. Phys. Rev. A 2005, 72, 012510), combining long-range HF exchange and MP2 correlation with a short-range density functional to a fully self-consistent version using the optimized-effective-potential technique in which the orbitals are obtained from a local potential including the long-range HF and MP2 contributions. We test this approach, that we name RS-OEP2, on a set of small closed-shell atoms and molecules. For the commonly used value of the range-separation parameter µ = 0.5 bohr-1, we find that self-consistency does not seem to bring any improvement for total energies, ionization potentials, and electronic affinities. However, contrary to the non-self-consistent RSH+MP2 method, the present RS-OEP2 method gives a LUMO energy which physically corresponds to a neutral excitation energy and gives local exchange-correlation potentials which are reasonably good approximations to the corresponding Kohn-Sham quantities. At a finer scale, we find that RS-OEP2 gives largely inaccurate correlation potentials and correlated densities, which points to the need of further improvement of this type of range-separated double hybrids.

Chemically accurate excitation energies with small basis sets.

By combining extrapolated selected configuration interaction (sCI) energies obtained with the Configuration Interaction using a Perturbative Selection made Iteratively algorithm with the recently proposed short-range density-functional correction for basis-set incompleteness [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-ζ 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 dimer, and ethylene). The present study clearly evidences that special care has to be taken with very diffuse excited states where the present correction does not catch the radial incompleteness of the one-electron basis set.

Asymptotic behavior of the Hartree-exchange and correlation potentials in ensemble density functional theory.

We report on previously unnoticed features of the exact Hartree-exchange and correlation potentials for atoms and ions treated via ensemble density functional theory, demonstrated on fractional ions of Li, C, and F. We show that these potentials, when treated separately, can reach non-vanishing asymptotic constant values in the outer region of spherical, spin unpolarized atoms. In the next leading order, the potentials resemble Coulomb potentials created by effective charges which have the peculiarity of not behaving as piecewise constants as a function of the electron number. We provide analytical derivations and complement them with numerical results using the inversion of the Kohn-Sham equations for interacting densities obtained by accurate quantum Monte Carlo calculations. The present results expand on the knowledge of crucial exact properties of Kohn-Sham systems, which can guide development of advanced exchange-correlation approximations.

Range-separated double-hybrid density-functional theory with coupled-cluster and random-phase approximations.

We construct range-separated double-hybrid (RSDH) schemes which combine coupled-cluster or random-phase approximations (RPAs) with a density functional based on a two-parameter Coulomb-attenuating-method-like decomposition of the electron-electron interaction. We find that the addition of a fraction of short-range electron-electron interaction in the wave-function part of the calculation is globally beneficial for the RSDH scheme involving a variant of the RPA with exchange terms. Even though the latter scheme is globally as accurate as the corresponding scheme employing only second-order Møller-Plesset perturbation theory for atomization energies, reaction barrier heights, and weak intermolecular interactions of small molecules, it is more accurate for the more complicated case of the benzene dimer in the stacked configuration. The present RSDH scheme employing a RPA thus represents a new member in the family of double hybrids with minimal empiricism which could be useful for general chemical applications.

Linear-response range-separated density-functional theory for atomic photoexcitation and photoionization spectra.

We investigate the performance of the range-separated hybrid (RSH) scheme, which combines long-range Hartree-Fock (HF) and a short-range density-functional approximation (DFA), for calculating the photoexcitation/photoionization spectra of the H and He atoms, using a B-spline basis set in order to correctly describe the continuum part of the spectra. The study of these simple systems allows us to quantify the influence on the spectra of the errors coming from the short-range exchange-correlation DFA and from the missing long-range correlation in the RSH scheme. We study the differences using the long-range HF exchange (nonlocal) potential and the long-range exact exchange (local) potential. Contrary to the former, the latter supports a series of Rydberg states and gives reasonable photoexcitation/photoionization spectra, even without applying linear-response theory. The most accurate spectra are obtained with the linear-response time-dependent RSH (TDRSH) scheme. In particular, for the He atom at the optimal value of the range-separation parameter, TDRSH gives slightly more accurate photoexcitation and photoionization spectra than the standard linear-response time-dependent HF. More generally, this work shows the potential of range-separated density-functional theory for calculating linear and nonlinear optical properties involving continuum states.

A Density-Based Basis-Set Correction for Wave Function Theory.

We report a universal density-based basis-set incompleteness correction that can be applied to any wave function method. This correction, which appropriately vanishes in the complete basis-set (CBS) limit, relies on short-range correlation density functionals (with multideterminant reference) from range-separated density-functional theory (RS-DFT) to estimate the basis-set incompleteness error. Contrary to conventional RS-DFT schemes that require an ad hoc range-separation parameter µ, the key ingredient here is a range-separation function µ(r) that automatically adapts to the spatial nonhomogeneity 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.