An Ab Initio Correction Vector Restricted Active Space Approach to the L-Edge XAS and 2p3d RIXS Spectra of Transition Metal Complexes
Seunghoon Lee, Huanchen Zhai, Garnet Kin‐Lic Chan
Abstract
High Resolution Image Download MS PowerPoint Slide 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-state 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 [FeCl 4 ] 1–/2– and [Fe(SCH 3 ) 4 ] 1–/2– and interpret the spectra by deconvolving the correction vectors. Our approach represents a step toward simulating the X-ray spectroscopies of larger metal cluster systems that play a pivotal role in biology.