Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients - Sorbonne Université Access content directly
Journal Articles The Journal of Chemical Physics Year : 2013

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

Abstract

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 range-separated TDDFT is a reasonably accurate method even using only a LDA-type density functional and without adding an explicit treatment of long-range correlation.
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Dates and versions

hal-00819369 , version 1 (30-04-2013)
hal-00819369 , version 2 (21-05-2013)

Identifiers

Cite

Julien Toulouse, Elisa Rebolini, Tim Gould, John F. Dobson, Prasenjit Seal, et al.. Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients. The Journal of Chemical Physics, 2013, 138, pp.194106. ⟨10.1063/1.4804981⟩. ⟨hal-00819369v2⟩
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