Modeling atoms in laser fields using time-dependent density functional theory: Applicability of the frozen-core approximation

We check the validity of the frozen-core approximation (FCA) in time-dependent density functional theory (TDDFT) for an atom interacting with a laser field. For this purpose we investigate an exactly solvable 1D model for Li with the help of TDDFT considering different exchange-correlation (XC) functionals. Observables such as the ionisation rate, the energy absorption rate and the dipole expectation value are obtained with and without FCA. Comparisons among the different TDDFT results on one hand and with the exact numerical solution of the time-dependent Schroedinger equation on the other hand show that the propagation of core electrons in time does significantly affect the observables of the valence electron. Additionally, we find a strong dependency of TDDFT observables on the XC functional used even though the values for the ionisation potentials are equal. We conclude that pseudopotentials (which apply the FCA or even bolder approximations) must yield inaccurate results in TDDFT simulations of strong-field ionization even for an otherwise exact XC functional.