Short-time Fourier transform analysis of real-time time-dependent Hartree–Fock and time-dependent density functional theory calculations with Gaussian basis functions

Abstract

We propose a novel analysis of real-time (RT) time-dependent Hartree-Fock and time-dependent density functional theory (TDHF/TDDFT) calculations using a short-time Fourier transform (STFT) technique. RT-TDHF/TDDFT calculations of model dimers were carried out and analyzed using the STFT technique, in addition to the usual Fourier transform (FT). STFT analysis revealed that the induced polarization propagated between the molecules through the intermolecular interaction; that is, it directly showed the electron dynamics of the excited system. The dependence of the propagation period on the intermolecular distance of the dimer was investigated. We also proved the possibility of describing, not just the valence, but also the core excitations by FT analysis of the RT-TDHF/TDDFT calculations of a formaldehyde monomer with Gaussian basis functions compared with conventional TDHF/TDDFT results.