An ab initio correction vector restricted active space approach to the L-edge XAS and 2p3d RIXS spectra of transition metal clusters

Abstract

We describe an ab initio approach to simulate L-edge X-ray absorption (XAS) and 2p3d resonant inelastic X-ray scattering (RIXS) spectroscopies. We model the strongly correlated electronic structure within a restricted active space and employ a correction vector formulation instead of sum-over-states expressions for the spectra, thus eliminating the need to calculate a large number of intermediate and final electronic states. We present benchmark simulations of the XAS and RIXS spectra of the iron complexes [FeCl4]^{-1/-2} and [Fe(SCH3)4]^{-1/-2} and interpret the spectra by deconvolving the correction vectors. Our approach represents a step towards simulating the X-ray spectroscopies of larger metal cluster systems that play a pivotal role in biology.