Charge-transfer excitation energies with a time-dependent density-functional method suitablefor orbital-dependent exchange-correlation kernels

摘要

A time-dependent density-functional (TDDFT) response equation for the effective Kohn-Sham potentialinstead of the electron densities is presented that enables the use of orbital-dependent exchange-correlationkernels. In combination with the frequency-dependent exact-exchange kernel the present approach describeslong-range charge-transfer excitations qualitatively correct in contrast to standard TDDFT methods, as shownby formal analysis and applications to molecular systems. Even charge-transfer excitations obtained with theadiabatic frequency-independent exact-exchange kernel exhibit a long-range dependence with the distance ofthe charge transfer, which, however, is too weak by a factor of 2. This indicates that it is not the frequencydependence of the kernel alone that leads to a correct description of charge-transfer excitations.