Nonadiabatic Dynamics in a Laser Field: Using Floquet Fewest Switches Surface Hopping To Calculate Electronic Populations for Slow Nuclear Velocities
| Autor: | Abraham Nitzan, Zeyu Zhou, Hsing-Ta Chen, Joseph E. Subotnik |
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| Rok vydání: | 2020 |
| Předmět: |
Floquet theory
Physics 010304 chemical physics Scattering Surface hopping Laser 01 natural sciences Computer Science Applications law.invention Electronic states Molecular dynamics Formalism (philosophy of mathematics) Classical mechanics law 0103 physical sciences Physical and Theoretical Chemistry Adiabatic process |
| Zdroj: | Journal of Chemical Theory and Computation. 16:821-834 |
| ISSN: | 1549-9626 1549-9618 |
| DOI: | 10.1021/acs.jctc.9b00950 |
| Popis: | We investigate two well-known approaches for extending the fewest switches surface hopping (FSSH) algorithm to periodic time-dependent couplings. The first formalism acts as if the instantaneous adiabatic electronic states were standard adiabatic states, which just happen to evolve in time. The second formalism replaces the role of the usual adiabatic states by the time-independent adiabatic Floquet states. For a set of modified Tully model problems, the Floquet FSSH (F-FSSH) formalism gives a better estimate for both transmission and reflection probabilities than the instantaneous adiabatic FSSH (IA-FSSH) formalism, especially for slow nuclear velocities. More importantly, only F-FSSH predicts the correct final scattering momentum. Finally, in order to use Floquet theory accurately, we find that it is crucial to account for the interference between wavepackets on different Floquet states. Our results should be of interest to all those interested in laser-induced molecular dynamics. |
| Databáze: | OpenAIRE |
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