Assessment of range-separated time-dependent density-functional theory for calculating <i>C</i>6 dispersion coefficients

Toulouse, Julien; Rebolini, Elisa; Gould, Tim; Dobson, John F.; Seal, Prasenjit; Ángyán, János G.

doi:10.1063/1.4804981

Cited by 23 publications

(22 citation statements)

References 101 publications

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“…In range-separated time-dependent DFT, the excitation energies of the long-range interacting Hamiltonian act as starting approximations to the excitation energies of the physical system and are corrected using a short-range density-functional kernel, in the same manner as the KS excitation energies act as starting approximations in linearresponse TDDFT. Several such range-separated linear-response schemes have been developed, in which the short-range part is described by an approximate adiabatic semi-local density-functional kernel and the long-range linear-response part is treated at the Hartree-Fock [32][33][34][35], multiconfiguration self-consistent field (MCSCF) [34,35], second-order polarization-propagator approximation (SOPPA) [35], or density-matrix functional theory (DMFT) [36] level.…”

Section: Introductionmentioning

confidence: 99%

“…Several such range-separated linear-response schemes have been developed, in which the short-range part is described by an approximate adiabatic semi-local density-functional kernel and the long-range linear-response part is treated at the Hartree-Fock [32][33][34][35], multiconfiguration self-consistent field (MCSCF) [34,35], second-order polarization-propagator approximation (SOPPA) [35], or density-matrix functional theory (DMFT) [36] level.…”

Section: Introductionmentioning

confidence: 99%

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Calculating excitation energies by extrapolation along adiabatic connections

et al. 2015

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In this paper, an alternative method to range-separated linear-response time-dependent densityfunctional theory and perturbation theory is proposed to improve the estimation of the energies of a physical system from the energies of a partially interacting system. Starting from the analysis of the Taylor expansion of the energies of the partially interacting system around the physical system, we use an extrapolation scheme to improve the estimation of the energies of the physical system at an intermediate point of the range-separated or linear adiabatic connection where either the electron-electron interaction is scaled or only the long-range part of the Coulomb interaction is included. The extrapolation scheme is first applied to the range-separated energies of the helium and beryllium atoms and of the hydrogen molecule at its equilibrium and stretched geometries. It improves significantly the convergence rate of the energies toward their exact limit with respect to the range-separation parameter. The range-separated extrapolation scheme is compared with a similar approach for the linear adiabatic connection, highlighting the relative strengths and weaknesses of each approach.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Calculating excitation energies by extrapolation along adiabatic connections

et al. 2015

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“…Such calculations are necessarily important benchmarks for theoretical methods applied to photoabsorption [14], photodetachment [15], blackbody radiation shifts [16][17][18] and AC Stark shifts [19], magic wavelengths [20], and parity non conservation amplitudes [21], as well as being helpful in the ongoing development of density functional theory (DFT) methods for dispersion forces (cf. [22][23][24][25][26]). In addition, for metals experimental data at a wide spectrum of photon energies are relatively scarce though X-ray data, and sometimes optical data [27,28], are available.…”

Section: Arxiv:150801986v2 [Physicsatom-ph] 27 Aug 2015mentioning

confidence: 99%

Empirically constructed dynamic electric dipole polarizability function of magnesium and its applications

Babb

2015

Phys. Rev. A

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The dynamic electric dipole polarizability function for the magnesium atom is formed by assembling the atomic electric dipole oscillator strength distribution from combinations of theoretical and experimental data for resonance oscillator strengths and for photoionization cross sections of valence and inner shell electrons. Consistency with the oscillator strength (Thomas-Reiche-Kuhn) sum rule requires the adopted principal resonance line oscillator strength to be several percent lower than the values given in two critical tabulations, though the value adopted is consistent with a number of theoretical determinations. The static polarizability is evaluated. Comparing the resulting dynamic polarizability as a function of photon energy with more elaborate calculations reveals the contributions of inner shell electron excitations. The present results are applied to calculate the long-range interactions between two and three magnesium atoms and the interaction between a magnesium atom and a perfectly conducting metallic plate. Extensive comparisons of prior results for the principal resonance line oscillator strength, for the static polarizability, and for the van der Waals coefficient are given in an Appendix.

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“…The results and their statistical analysis are collected in Table 1 for a set of small molecules taken from the database compiled by Tkatchenko and Scheffler [16], as used in [58].…”

Section: H F Hmentioning

confidence: 99%

Local random phase approximation with projected oscillator orbitals

Mussard

Ángyán

2015

Péter R. Surján

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An approximation to the many-body London dispersion energy in molecular systems is expressed as a functional of the occupied orbitals only. The method is based on the local-RPA theory. The occupied orbitals are localized molecular orbitals and the virtual space is described by projected oscillator orbitals, i.e. functions obtained by multiplying occupied localized orbitals with solid spherical harmonic polynomials having their origin at the orbital centroids. Since we are interested in the long-range part of the correlation energy, responsible for dispersion forces, the electron repulsion is approximated by its multipolar expansion. This procedure leads to a fully non-empirical longrange correlation energy expression. Molecular dispersion coefficients calculated from determinant wave functions obtained by a range-separated hybrid method reproduce experimental values with less than 15% error.

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

Cited by 23 publications

References 101 publications

Calculating excitation energies by extrapolation along adiabatic connections

Calculating excitation energies by extrapolation along adiabatic connections

Empirically constructed dynamic electric dipole polarizability function of magnesium and its applications

Local random phase approximation with projected oscillator orbitals

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