Time-dependent density functional theory for X-ray near-edge spectroscopy

TL;DR

This paper develops a time-dependent density functional theory tailored for calculating X-ray near-edge absorption spectra, enabling efficient numerical solutions and potential extensions to include complex electron interactions.

Contribution

It introduces a novel TDDFT approach with a two-wavefunction framework for X-ray spectroscopy, improving computational feasibility and accuracy.

Findings

Power-law exponents similar to theoretical predictions

Method can be generalized for electron-electron interactions

Equations are solvable with computational effort comparable to standard TDDFT

Abstract

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 Nozieres 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.