Local-spin-density functional for multideterminant density functional theory

Range-separated density-functional theory is an alternative approach to Kohn-Sham densityfunctional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components, and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the oneelectron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with the cardinal number X of the Dunning basis sets cc-p(C)VXZ, and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

show abstract

“…Finally, we note that we have found the same convergence behavior with the short-range exchange-correlation LDA density functional of Ref. 83.…”

Section: A Convergence Of the Wave Functionsupporting

confidence: 55%

Basis convergence of range-separated density-functional theory

Franck

Mussard

Luppi

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Similar to the Coulomb case, density functional approximations (DFAs), such as the local density approximation (LDA) and generalized-gradient approximations (GGAs), to the exchangecorrelation (XC) energy functional for a given f (r) are needed in the corresponding KS-DFT [25,26]. Here, the LDA exchange energy functional for the erf interaction is obtained by subtracting the LDA exchange energy functional for the erfc interaction [27] from the LDA exchange energy functional for the Coulomb interaction [28], whereas the LDA correlation energy functional for the erfc interaction is obtained by subtracting the LDA correlation energy functional for the erf interaction [29] from the LDA correlation energy functional for the Coulomb interaction [30]. In addition, as the Perdew-Burke-Ernzerhof (PBE) XC energy functional (i.e., a popular GGA) for the Coulomb interaction [31] and its variant for the erfc interaction [32] are both available, their difference gives the PBE XC energy functional for the erf interaction.…”

Section: Model Systems and Computational Detailsmentioning

confidence: 99%

The van der Waals interactions in rare-gas dimers: the role of interparticle interactions

Chen

Hui

Chai

2016

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We investigate the potential energy curves of rare-gas dimers with various ranges and strengths of interparticle interactions (nuclear-electron, electron-electron, and nuclear-nuclear interactions).Our investigation is based on the highly accurate coupled-cluster theory associated with those interparticle interactions. For comparison, the performance of the corresponding Hartree-Fock theory, second-order Møller-Plesset perturbation theory, and density functional theory is also investigated.Our results reveal that when the interparticle interactions retain the long-range Coulomb tails, the nature of van der Waals interactions in the rare-gas dimers remains similar. By contrast, when the interparticle interactions are sufficiently short-range, the conventional van der Waals interactions in the rare-gas dimers completely disappear, yielding purely repulsive potential energy curves.

show abstract

“…where ǫ sr xc,unif (n) = ǫ xc,unif (n) − ǫ lr xc,unif (n) is the complement short-range exchange-correlation energy per particle obtained from the exchange-correlation energy per particle of the standard uniform electron gas (UEG), ǫ xc,unif (n), [66,67] and the exchange-correlation energy per particle of a UEG with the long-range electronelectron interaction, ǫ lr xc,unif (n), as parametrized from quantum Monte Carlo calculations by Paziani et al [68] (see Ref. 46 for a discussion about the corresponding kernel).…”

Section: Computational Detailsmentioning

confidence: 99%

Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients

Toulouse¹,

Rebolini²,

Gould³

et al. 2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

We assess a variant of linear-response range-separated time-dependent density-functional theory (TDDFT), combining a long-range Hartree-Fock (HF) exchange kernel with a short-range adiabatic exchange-correlation kernel in the local-density approximation (LDA) for calculating isotropic C6 dispersion coefficients of homodimers of a number of closed-shell atoms and small molecules. This range-separated TDDFT tends to give underestimated C6 coefficients of small molecules with a mean absolute percentage error of about 5%, a slight improvement over standard TDDFT in the adiabatic LDA which tends to overestimate them with a mean absolute percentage error of 8%, but close to time-dependent Hartree-Fock which has a mean absolute percentage error of about 6%. These results thus show that introduction of long-range HF exchange in TDDFT has a small but beneficial impact on the values of C6 coefficients. It also confirms that the present variant of rangeseparated TDDFT is a reasonably accurate method even using only a LDA-type density functional and without adding an explicit treatment of long-range correlation.

show abstract

Local-spin-density functional for multideterminant density functional theory

Cited by 120 publications

References 62 publications

Basis convergence of range-separated density-functional theory

Basis convergence of range-separated density-functional theory

The van der Waals interactions in rare-gas dimers: the role of interparticle interactions

Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients

Contact Info

Product

Resources

About