Dynamical second-order Bethe-Salpeter equation kernel: a method for electronic excitation beyond the adiabatic approximation

J Chem Phys. 2013 Oct 21;139(15):154109. doi: 10.1063/1.4824907.

Abstract

We present a dynamical second-order kernel for the Bethe-Salpeter equation to calculate electronic excitation energies. The derivation takes explicitly the functional derivative of the exact second-order self energy with respect to the one-particle Green's function. It includes naturally a frequency dependence, going beyond the adiabatic approximation. Perturbative calculations under the Tamm-Dancoff approximation, using the configuration interaction singles (CIS) eigenvectors, reveal an appreciable improvement over CIS, time-dependent Hartree-Fock, and adiabatic time-dependent density functional theory results. The perturbative results also compare well with equation-of-motion coupled-cluster and experimental results.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Electrons
  • Quantum Theory*
  • Time Factors