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J Chem Phys. 2019 Apr 28;150(16):164126. doi: 10.1063/1.5079426.

Performance of trajectory surface hopping method in the treatment of ultrafast intersystem crossing dynamics.

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Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety and MOE Key Laboratory of Environmental Theoretical Chemistry, SCNU Environmental Research Institute, South China Normal University, Guangzhou 510006, China.
MOE Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China.


We carried out extensive studies to examine the performance of the fewest-switches surface hopping method in the description of the ultrafast intersystem crossing dynamic of various singlet-triplet (S-T) models by comparison with the results of the exact full quantum dynamics. Different implementation details and some derivative approaches were examined. As expected, it is better to perform the trajectory surface hopping calculations in the spin-adiabatic representation or by the local diabatization approach, instead of in the spin-diabatic representation. The surface hopping method provides reasonable results for the short-time dynamics in the S-T model with weak spin-orbital coupling (diabatic coupling), although it does not perform well in the models with strong spin-orbital coupling (diabatic coupling). When the system accesses the S-T potential energy crossing with rather high kinetic energy, the trajectory surface hopping method tends to produce a good description of the nonadiabatic intersystem crossing dynamics. The impact of the decoherence correction on the performance of the trajectory surface hopping is system dependent. It improves the result accuracy in many cases, while its influence may also be minor for other cases.


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