Quantum Dynamics of Photoactive Transition Metal Complexes. A Case Study of Model Reduction

Abstract

Transition metal complexes for photochemical applications often feature a high density of electron-vibrational states characterized by nonadiabatic and spin-orbit couplings. Overall, the dynamics after photoexcitation is shaped by rapid transitions between states of different character and multiplicity. Even though transient absorption experiments enable characterization in terms of kinetic rates, the complexity of the systems usually prevents a more detailed analysis. Quantum dynamics simulations using quantum chemically determined model Hamiltonians may provide such details. In particular, one is tempted to pursue a model reduction, such as to identify couplings or vibrational modes most relevant for the dynamics. Here, we address how such an endeavor is challenged by the particular nature of transition metal complexes. For that purpose, we performed quantum dynamics simulations for a recently studied iron(II) homoleptic complex.