In this paper we consider the inclusion of the spin-orbit interaction in surface hopping molecular dynamics simulations to take into account spin forbidden transitions. Two alternative approaches are examined. The spin-diabatic one makes use of eigenstates of the spin-free electronic Hamiltonian and of S2 and is commonly applied when the spin-orbit coupling is weak. We point out some inconsistencies of this approach, especially important when more than two spin multiplets are coupled. The spin-adiabatic approach is based on the eigenstates of the total electronic Hamiltonian including the spin-orbit coupling. Advantages and drawbacks of both strategies are discussed and illustrated with the help of two model systems.
|Autori:||Granucci, Giovanni; Persico, Maurizio; Spighi, G.|
|Titolo:||Surface hopping trajectory simulations with spin-orbit and dynamical couplings|
|Anno del prodotto:||2012|
|Digital Object Identifier (DOI):||10.1063/1.4707737|
|Appare nelle tipologie:||1.1 Articolo in rivista|