Double excitations within time-dependent density functional theory linear response

J Chem Phys. 2004 Apr 1;120(13):5932-7. doi: 10.1063/1.1651060.

Abstract

Within the adiabatic approximation, time-dependent density functional theory yields only single excitations. Near states of double excitation character, the exact exchange-correlation kernel has a strong dependence on frequency. We derive the exact frequency-dependent kernel when a double excitation mixes with a single excitation, well separated from the other excitations, in the limit that the electron--electron interaction is weak. Building on this, we construct a nonempirical approximation for the general case, and illustrate our results on a simple model.