Communication: GAIMS-Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Curchod, Basile F.E.; Rauer, Clemens; Marquetand, Philipp; Gonzalez, Leticia; Martinez, Todd J.

Abstract

Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.

Citation

Curchod, B. F., Rauer, C., Marquetand, P., Gonzalez, L., & Martinez, T. J. (2016). Communication: GAIMS-Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes. The Journal of Chemical Physics, 144(10), Article 101102. https://doi.org/10.1063/1.4943571

• Journal Article Type: Article
• Acceptance Date: Feb 26, 2016
• Online Publication Date: Mar 11, 2016
• Publication Date: Mar 11, 2016
• Deposit Date: Nov 6, 2017
• Publicly Available Date: Dec 8, 2017
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 144
• Issue: 10
• Article Number: 101102
• DOI: https://doi.org/10.1063/1.4943571
• Public URL: https://durham-repository.worktribe.com/output/1340898