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arXiv · 1404.2585

Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions

Wuming Zhu·Julien Toulouse·Andreas Savin·János G. Angyán
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Abstract

Range-separated methods combining a short-range density functional with long-range random phase approximations RPAs with or without exchange response kernel are tested on rare-gas dimers and the S22 benchmark set of weakly interacting complexes of Jurecka et al. [Phys. Chem. Chem. Phys. 8, 1985 (2006 )] . The methods are also compared to full-range RPA approaches. Both range separation and inclusion of the Hartree-Fock exchange kernel largely improve the accuracy of intermolecular interaction energies. The best results are obtained with the method called RSH+RPAx, which yields interaction energies for the S22 set with an estimated mean absolute error of about 0.5-0.6 kcal/mol, corresponding to a mean absolute percentage error of about 7%-9% depending on the reference interaction energies used. In particular, the RSH+RPAx method is found to be overall more accurate than the range-separated method based on long-range second-order Møller-Plesset MP2 perturbation theory RSH+MP2 .

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Wuming Zhu, Julien Toulouse, Andreas Savin, János G. Angyán. 2014-04-09. Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions. https://doi.org/10.1063/1.3431616

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