Analytical Energy Gradients in Range-Separated Hybrid Density Functional Theory with Random Phase Approximation

Abstract

Analytical forces have been derived in the Lagrangian framework for several random phase approximation (RPA) correlated total energy methods based on the range separated hybrid (RSH) approach, which combines a short-range density functional approximation for the short-range exchange-correlation energy with a Hartree-Fock-type long-range exchange and RPA long-range correlation. The RPA correlation energy has been expressed as a ring coupled cluster doubles (rCCD) theory. The resulting analytical gradients have been implemented and tested for geometry optimization of simple molecules and intermolecular charge transfer complexes, where intermolecular interactions are expected to have a non-negligible effect even on geometrical parameters of the monomers.

18 two-column pages + 4 tables and 6 figures

References in corpus (7)

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Cited by in corpus (4)

• Basis convergence of range-separated density-functional theory
• Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights
• Range-separated double-hybrid density-functional theory with coupled-cluster and random-phase approximations
• A route to improving RPA excitation energies through its connection to equation-of-motion coupled cluster theory