The trials and triumphs of modelling X-ray absorption spectra of transition metal phthalocyanines

Abstract

This study explores the electronic structure of Co, Fe and Mn phthalocyanines (TMPcs) as well as their perfluorinated counterparts through a series of electronic structure calculations utilizing multireference methods and by simulating their metal L-edge and ligand (nitrogen and fluorine) K-edge X-ray absorption spectra (XAS) in an angle-resolved manner. Simulations targeting different ground-state symmetries, where relevant, have been conducted to observe changes in the N K-edge lineshape. The applicability of the quasi-degenerate formulation of n-electron valence state perturbation theory (QD-NEVPT2) for L-edge X-ray absorption spectroscopy (XAS) is evaluated, alongside the use of a restricted active space (RAS) formalism to describe the final-state multiplets generated by L-shell X-ray processes. Our findings provide valuable insights into the electronic properties of TMPcs, in particular with respect to the effect of fluorination, and demonstrate the broad applicability of various formulations of NEVPT2 in spectral simulations. Moreover, this study highlights the utility of manual truncation of the configuration spaces in order to allow for large active orbital spaces in aforementioned calculations.