Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited-state spectra. In this article, theCTM4XASsoftware package is extended to simulateM2,3- andL2,3-edge spectra for the excited states of first-row transition metals and also interpret CTM eigenfunctions in terms of Russell–Saunders term symbols. These new programs are used to reinterpret the recently reported excited-stateM2,3-edge difference spectra of photogenerated ferrocenium cations and to propose alternative assignments for the electronic state of these cations responsible for the spectroscopic features. These new programs were also used to model theL2,3-edge spectra of FeIIcompounds during nuclear relaxation following photoinduced spin crossover and to propose spectroscopic signatures for their vibrationally hot states.
Resonant X-Ray Absorption of Neon Clusters: The Influence of Cluster Size on the Character of Core Excited States
