Adiabatic time-dependent density functional methods for excited state properties

Abstract

This work presents theory, implementation, and validation of excited state properties obtained from time-dependent density functional theory (TDDFT). Based on a fully variational expression for the excited state energy, a compact derivation of first order properties is given. We report an implementation of analytic excited state gradients and charge moments for local, gradient corrected, and hybrid functionals, as well as for the configuration interaction singles (CIS) and time-dependent Hartree–Fock (TDHF) methods. By exploiting analogies to ground state energy and gradient calculations, efficient techniques can be transferred to excited state methods. Benchmark results demonstrate that, for low-lying excited states, geometry optimizations are not substantially more expensive than for the ground state, independent of the molecular size. We assess the quality of calculated adiabatic excitation energies, structures, dipole moments, and vibrational frequencies by comparison with accurate experimental data for a variety of excited states and molecules. Similar trends are observed for adiabatic excitation energies as for vertical ones. TDDFT is more robust than CIS and TDHF, in particular, for geometries differing significantly from the ground state minimum. The TDDFT excited state structures, dipole moments, and vibrational frequencies are of a remarkably high quality, which is comparable to that obtained in ground state density functional calculations. Thus, yielding considerably more accurate results at similar computational cost, TDDFT rivals CIS as a standard method for calculating excited state properties in larger molecules.