Strengths and limitations of the adiabatic exact-exchange kernel for total energy calculations.

Abstract

We investigate the adiabatic approximation to the exact-exchange kernel for calculating correlation energies within the adiabatic-connection fluctuation-dissipation framework of time-dependent density functional theory. A numerical study is performed on a set of systems having bonds of different character (H2 and N2 molecules, H-chain, H2-dimer, solid-Ar, and the H2O-dimer). We find that the adiabatic kernel can be sufficient in strongly bound covalent systems, yielding similar bond lengths and binding energies. However, for non-covalent systems, the adiabatic kernel introduces significant errors around equilibrium geometry, systematically overestimating the interaction energy. The origin of this behavior is investigated by studying a model dimer composed of one-dimensional, closed-shell atoms, interacting via soft-Coulomb potentials. The kernel is shown to exhibit a strong frequency dependence at small to intermediate atomic separation that affects both the low-energy spectrum and the exchange-correlation hole obtained from the corresponding diagonal of the two-particle density matrix.