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

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 .

References in corpus (4)

• The Ground State Correlation Energy of the Random Phase Approximation from a Ring Coupled Cluster Doubles Approach
• Adiabatic-connection fluctuation-dissipation density-functional theory based on range separation
• Long-range-corrected hybrids including RPA correlation
• Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory

Cited by in corpus (9)

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• Range-separated density-functional theory with random phase approximation: detailed formalism and illustrative applications
• Basis convergence of range-separated density-functional theory
• Accuracy of basis-set extrapolation schemes for DFT-RPA correlation energies in molecular calculations
• Excitation energies along a range-separated adiabatic connection