Intersystem Crossings in Late-Row Elements: A Perspective

• Published in: The journal of physical chemistry letters Vol. 13; no. 13; pp. 3039 - 3046
• Main Authors: Valentine, Andrew J. S, Li, Xiaosong
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07.04.2022
• Subjects: Quantum Theory; Transition Elements
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.2c00207

Intersystem crossing (ISC), a vital component of the electronic and nuclear transitions that compose photophysics, has been successfully simulated in light elements and transition metal complexes. Derived from the Z-dependent spin–orbit coupling (SOC), ISC is expected to be of greater importance in heavier elements, but few attempts have been made at the simulation of ISC in lanthanides or actinides. In this work, we explore several of the challenges that will need to be overcome in order to treat ISC in late-row elements, including the loss of spin as a good quantum number, the need to include SOC variationally via two- or four-component electronic structure, and the high density of states present in late-row complexes. Density functional theory (DFT) calculations are used to illustrate several of these effects, while a model Hamiltonian is used to illustrate the importance of momentum rescaling in surface hopping simulations of strongly coupled states.