Closed-shell ring coupled cluster doubles theory with range separation applied on weak intermolecular interactions

TL;DR

This paper investigates variants of RPA within range-separated DFT to improve accuracy in modeling weak intermolecular interactions, achieving around 0.4 kcal/mol error on the S22 benchmark set.

Contribution

It introduces and tests new RPA variants in range-separated DFT, demonstrating improved accuracy for weak intermolecular interactions over previous methods.

Findings

Achieved mean absolute errors of about 0.4 kcal/mol on S22 set

Range-separated RPA variants outperform traditional methods

Best variants are those originally proposed by Szabo and Ostlund

Abstract

We explore different variants of the random phase approximation (RPA) to the correlation energy derived from closed-shell ring-diagram approximations to coupled cluster doubles theory. We implement these variants in range-separated density-functional theory, i.e. by combining the long-range random phase approximations with short-range density-functional approximations. We perform tests on the rare-gas dimers He_2, Ne_2, and Ar_2, and on the weakly interacting molecular complexes of the S22 set of Jurecka et al. [Phys. Chem. Chem. Phys. 8, 1985 (2006)]. The two best variants correspond to the ones originally proposed by Szabo and Ostlund [J. Chem. Phys. 67, 4351 (1977)]. With range separation, they reach mean absolute errors on the equilibrium interaction energies of the S22 set of about 0.4 kcal/mol, corresponding to mean absolute percentage errors of about 4 %, with the aug-cc-pVDZ basis set.