TY - JOUR

T1 - Nonadiabatic Dynamics in a Laser Field

T2 - Using Floquet Fewest Switches Surface Hopping to Calculate Electronic Populations for Slow Nuclear Velocities

AU - Zhou, Zeyu

AU - Chen, Hsing Ta

AU - Nitzan, Abraham

AU - Subotnik, Joseph Eli

N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.

PY - 2020/2/11

Y1 - 2020/2/11

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85078667125&partnerID=8YFLogxK

U2 - 10.1021/acs.jctc.9b00950

DO - 10.1021/acs.jctc.9b00950

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C2 - 31951404

AN - SCOPUS:85078667125

SN - 1549-9618

VL - 16

SP - 821

EP - 834

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 2

ER -