Simulation of radiation damage on [M(COD)Cl] ₂ using density functional theory

Theoretical calculations of materials have in recent years shown promise in facilitating the analysis of convoluted experimental data. This is particularly invaluable in complex systems or for materials subject to certain environmental conditions, such as those exposed to X-ray radiation during routine characterisation. Despite the clear benefit in this use case to shed further light on intermolecular damage processes, the use of theory to study radiation damage of samples is still not commonplace, with very few studies in existing literature. In this paper, we demonstrate the potential of density functional theory for modelling the electronic structure of two industrially important organometallic systems of the formula [M(COD)Cl]₂ where M = Ir/Rh and COD = 1,5-cyclooctadiene, which are subject to X-ray irradiation <i>via</i> X-ray diffraction and X-ray photoelectron spectroscopy. Our approach allows calculated spectra to be compared directly to experimental data, in this case, the X-ray photoelectron valence band spectra, enabling the valuable correlation of individual atomic states to the electronic structure.