# Stimulated X-ray Raman and Absorption Spectroscopy of Iron-Sulfur Dimers

## TL;DR

This paper uses advanced quantum chemical methods to simulate X-ray spectroscopy signals of iron-sulfur complexes, revealing detailed electronic structures and potential for selective state excitation.

## Contribution

It introduces ab initio DMRG calculations of SXRS and absorption spectra for iron-sulfur dimers, providing new insights into their electronic states.

## Key findings

- Simulated spectra reveal dense low-lying excited states.
- Differences in signal intensities suggest selective excitation possibilities.
- Potential to probe electronic dynamics within the d-d manifold.

## Abstract

Iron-sulfur complexes play an important role in biological processes such as metabolic electron transport. A detailed understanding of the mechanism of long range electron transfer requires knowledge of the electronic structure of the complexes, which has traditionally been challenging to obtain, either by theory or by experiment, but the situation has begun to change with advances in quantum chemical methods and intense free electron laser light sources. We compute the signals from stimulated X-ray Raman spectroscopy (SXRS) and absorption spectroscopy of homovalent and mixed-valence [2Fe-2S] complexes, using the {\it ab initio} density matrix renormalization group (DMRG) algorithm. The simulated spectra show clear signatures of the theoretically predicted dense low-lying excited states within the d-d manifold. Furthermore, the difference in signal intensity between the absorption-active and Raman-active states provides a potential mechanism to selectively excite states by a proper tuning of the excitation pump, to access the electronic dynamics within this manifold.