Advances in coherent light sources and development of pump–probe techniques in recent decades have opened the way to study electronic motion in its natural time scale. When an ultrashort laser pulse interacts with a molecular target, a coherent superposition of electronic states is created and the triggered electron dynamics is coupled to the nuclear motion. A natural and computationally efficient choice to simulate this correlated dynamics is a trajectory-based method where the quantum-mechanical electronic evolution is coupled to a classical-like nuclear dynamics. These methods must approximate the initial correlated electron–nuclear state by associating an initial electronic wavefunction to each classical trajectory in the ensemble. Different possibilities exist that reproduce the initial populations of the exact molecular wavefunction when represented in a basis. We show that different choices yield different dynamics and explore the effect of this choice in Ehrenfest, surface hopping, and exact-factorization-based coupled-trajectory schemes in a one-dimensional two-electronic-state model system that can be solved numerically exactly. This work aims to clarify the problems that standard trajectory-based techniques might have when a coherent superposition of electronic states is created to initialize the dynamics, to discuss what properties and observables are affected by different choices of electronic initial conditions and to point out the importance of quantum-momentum-induced electronic transitions in coupled-trajectory schemes.
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7 February 2024
Research Article|
February 02 2024
Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states
Evaristo Villaseco Arribas
;
Evaristo Villaseco Arribas
a)
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Physics, Rutgers University
, Newark, New Jersey 07102, USA
2
Université Paris-Saclay, CNRS, Institut de Chimie Physique UMR8000
, 91405 Orsay, France
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Neepa T. Maitra
;
Neepa T. Maitra
b)
(Conceptualization, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Visualization, Writing – review & editing)
1
Department of Physics, Rutgers University
, Newark, New Jersey 07102, USA
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Federica Agostini
Federica Agostini
c)
(Conceptualization, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – review & editing)
2
Université Paris-Saclay, CNRS, Institut de Chimie Physique UMR8000
, 91405 Orsay, France
c)Author to whom correspondence should be addressed: [email protected]
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c)Author to whom correspondence should be addressed: [email protected]
a)
Electronic mail: [email protected]
b)
Electronic mail: [email protected]
J. Chem. Phys. 160, 054102 (2024)
Article history
Received:
November 10 2023
Accepted:
January 11 2024
Citation
Evaristo Villaseco Arribas, Neepa T. Maitra, Federica Agostini; Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states. J. Chem. Phys. 7 February 2024; 160 (5): 054102. https://doi.org/10.1063/5.0186984
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