Excited state nuclear forces from the Tamm–Dancoff approximation to time-dependent density functional theory within the plane wave basis set framework

Abstract

An efficient formulation of time-dependent linear response density functional theory for the use within the plane wave basis set framework is presented. The method avoids the transformation of the Kohn–Sham matrix into the canonical basis and references virtual orbitals only through a projection operator. Using a Lagrangian formulation nuclear derivatives of excited state energies within the Tamm–Dancoff approximation are derived. The algorithms were implemented into a pseudo potential/plane wave code and applied to the calculation of adiabatic excitation energies, optimized geometries and vibrational frequencies of three low lying states of formaldehyde. An overall good agreement with other time-dependent density functional calculations, multireference configuration interaction calculations and experimental data was found.