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

Bastien Mussard (1) , Peter G. Szalay (2) , Janos Angyan (1)

1 CRM2 - Cristallographie, Résonance Magnétique et Modélisations
2 Institute of Chemistry [Budapest]

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.

Mots clés: MOLPRO; Random Phase Approximation; DFT; RPA; Range Separation; Analytical gradient

Domaines: Chimie théorique et/ou physique; Chimie-Physique [physics.chem-ph]

Bastien Mussard, Peter G. Szalay, Janos Angyan. Analytical Energy Gradients in Range-Separated Hybrid Density Functional Theory with Random Phase Approximation. Journal of Chemical Theory and Computation, 2014, 10 (5), pp.10.1021/ct401044h. ⟨10.1021/ct401044h⟩. ⟨hal-01122081v4⟩