Decoherence and Its Role in Electronically Nonadiabatic Dynamics

Decoherence is the tendency of a time-evolved reduced density matrix for a subsystem to assume a form corresponding to a statistical ensemble of states rather than a coherent combination of pure-state wave functions. When a molecular process involves changes in the electronic state and the coordinat...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2023-01, Vol.19 (2), p.380-395
Main Authors: Shu, Yinan, Truhlar, Donald G.
Format: Article
Language:English
Subjects:
Algorithms
Density
Electron states
Inelastic collisions
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Mathematical analysis
Photochemistry
Subsystems
Wave functions
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Summary:Decoherence is the tendency of a time-evolved reduced density matrix for a subsystem to assume a form corresponding to a statistical ensemble of states rather than a coherent combination of pure-state wave functions. When a molecular process involves changes in the electronic state and the coordinates of the nuclei, as in ultraviolet or visible light photochemistry or electronically inelastic collisions, the reduced density matrix of the electronic subsystem suffers decoherence, due to its interaction with the nuclear subsystem. We present the background necessary to conceptualize this decoherence; in particular, we discuss the density matrix description of pure states and mixed states, and we discuss pointer states and decoherence time. We then discuss how decoherence is treated in the coherent switching with decay of mixing algorithm and the trajectory surface hopping method for semiclassical calculations of electronically nonadiabatic processes.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.2c00988