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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. [ABSTRACT FROM AUTHOR]

Abstract: Previous calculations on model systems for the cooperative binding of two NO2 molecules to carbon nanotubes using density functional theory and second order Moller–Plesset perturbation theory gave results differing by 30kcal/mol. Quantum Monte Carlo calculations are performed to study the role of electronic correlations in these systems and resolve the discrepancy between these previous calculations. Compared to QMC binding energies, MP2 and LDA are shown to overbind, while B3LYP and BPW91 underbind. PW91 gives the best agreement with QMC with a binding energy differing by only 3kcal/mol. Basis set effects are also shown to be important. [Copyright &y& Elsevier]

We present the first application to real molecular systems of the recently proposed linear-response theory for the density-based basis-set correction method [ J. Chem. Phys. , 158 , 234107 (2023)]. We apply this approach to accelerate the basis-set convergence of excitation energies in the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method. We use an approximate linear-response framework that neglects the second-order derivative of the basis-set correction density functional and consists in simply adding to the usual Hamiltonian the one-electron potential generated by the first-order derivative of the functional. This additional basis-set correction potential is evaluated at the Hartree-Fock density, leading to a very computationally cheap basis-set correction. We tested this approach over a set of about 30 excitation energies computed for five small molecular systems and found that the excitation energies from the ground state to Rydberg states are the main source of basis-set error. These excitation energies systematically increase when the size of the basis set is increased, suggesting a biased description in favour of the excited state. Despite the simplicity of the present approach, the results obtained with the basis-set-corrected EOM-CCSD method are encouraging as they yield a mean absolute deviation of 0.02 eV for the aug-cc-pVTZ basis set, while it is 0.04 eV using the standard EOM-CCSD method. This might open the path to an alternative to explicitly correlated approaches to accelerate the basis-set convergence of excitation energies.

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., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

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., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

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., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

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.

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.

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.

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.