We present a local time-correlation function method for real-time calculations of core level x-ray spectra (RTXS). The approach is implemented in a local orbital basis using a Crank-Nicolson timeevolution algorithm applied to an extension of the SIESTA code, together with projector augmented wave (PAW) atomic transition matrix elements. Our RTXS is formally equivalent to ∆SCF Fermi's golden rule calculations with a screened core-hole and an effective independent particle approximation. Illustrative calculations are presented for several molecular and condensed matter systems and found to be in good agreement with experiment. The method can also be advantageous compared to conventional frequency-space methods.

We derive a time-dependent density functional theory appropriate for calculating the near-edge X-ray absorption spectrum in molecules and condensed matter. The basic assumption is to increase the space of many-body wave functions from one Slater determinant to two. The equations of motion derived from Dirac's variational principle provide an exact solution for the linear response when the interaction Hamiltonian has only a core-electron field. The equations can be solved numerically nearly as easily as the ordinary real-time time-dependent Kohn-Sham equations. We carry out the solution under conditions that permit comparison with the expected power-law behavior. Our extracted power-law exponents are similar to those derived by Nozières and DeDominicis, but are not in quantitative agreement. We argue that our calculational method can be readily generalized to density functionals that take into account the more general electron-electron interactions that are needed for treating dynamic effects such as plasmon excitations.