Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space

Recent progress on the constraint coordinate-momentum phase space (CPS) formulation of finite-state quantum systems has revealed that the triangle window function approach is an isomorphic representation of the exact population–population correlation function of the two-state system. We use the triangle window (TW) function and the CPS mapping kernel element to formulate a novel useful representation of discrete electronic degrees of freedom (DOFs). When it is employed with nonadiabatic field (NaF) dynamics, a new variant of the NaF approach (i.e., NaF-TW) is proposed. The NaF-TW expression of the population of any adiabatic state is always positive semidefinite. Extensive benchmark tests of model systems in both the condensed phase and gas phase demonstrate that the NaF-TW approach is able to faithfully capture the dynamical interplay between electronic and nuclear DOFs in a broad region, including where the states remain coupled all the time, as well as where the bifurcation characteristic of nuclear motion is important

Recommended citation: He, X.; Cheng, X.; Wu, B.; Liu, J. Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space. J. Phys. Chem. Lett. 2024, 5452–5466. https://doi.org/10.1021/acs.jpclett.4c00793.
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