Shu Chun SC Cheng, Chaoyuan C Zhu, Kuo Kan KK Liang, Sheng Hsien SH Lin, Donald G DG Truhlar

Published:

The performance of an analytical expression for algorithmic decoherence time is investigated for non-Born-Oppenheimer molecular dynamics. There are two terms in the function that represents the dependence of the decoherence time on the system parameters; one represents decoherence due to the quantum time-energy uncertainty principle and the other represents a back reaction from the decoherent force on the classical trajectory. We particularly examine the question of whether the first term should dominate. Five one-dimensional two-state model systems that represent limits of multidimensional nonadiabatic dynamics are designed for testing mixed quantum-classical methods and for comparing semiclassical calculations with exact quantum calculations. Simulations are carried out with the semiclassical Ehrenfest method (SE), Tully's fewest switch version (TFS) of the trajectory surface hopping method, and the decay-of-mixing method with natural switching, coherent switching (CSDM), and coherent switching with reinitiation (CSDM-D). The CSDM method is demonstrated to be the most accurate method, and it has several desirable features: (i) It behaves like the representation-independent SE method in the strong nonadiabatic coupling regions; (ii) it behaves physically like the TFS method in noninteractive region; and (iii) the trajectories are continuous with continuous momenta. The CSDM method is also demonstrated to balance coherence well with decoherence, and the results are nearly independent of whether one uses the adiabatic or diabatic representation. The present results provide new insight into the formulation of a physically correct decoherence time to be used with the CSDM method for non-Born-Oppenheimer molecular dynamic simulations.