Xie Rixin, Shi Zhecun, Wang Linjun
Zhejiang Key Laboratory of Excited-State Energy Conversion and Energy Storage, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Chem Phys. 2025 Apr 28;162(16). doi: 10.1063/5.0264049.
The framework of exact factorization (XF) has inspired a series of trajectory-based nonadiabatic dynamics methods by introducing different approximations. Recently, the coupled-trajectory surface hopping (CTSH) method has been proposed to combine the key advantages of the coupled-trajectory mixed quantum-classical method based on XF and the fewest switches surface hopping. We here present a novel variant of CTSH, namely, sign-consistent CTSH (SC-CTSH), which considers proper trajectory clustering to reconstruct the nuclear density distribution and the consistency between wave function and active states to introduce decoherence. Using the exact quantum solutions as references, the high performance of SC-CTSH is benchmarked in the widely studied scattering models and compared with other related XF-based methods. Due to the incorporation of new trajectory clustering and sign consistency algorithms, SC-CTSH obtains more accurate quantum momentum and decoherence during the nonadiabatic dynamics, which makes the combination of XF and surface hopping more consistent and reliable. This study further highlights the significance of internal consistency between wave function and active states, which is important in the further development of mixed quantum-classical dynamics methods.
精确因子分解（XF）框架通过引入不同近似方法，激发了一系列基于轨迹的非绝热动力学方法。最近，耦合轨迹表面跳跃（CTSH）方法被提出来，以结合基于XF的耦合轨迹混合量子-经典方法和最少开关表面跳跃的关键优势。我们在此提出CTSH的一种新颖变体，即符号一致CTSH（SC-CTSH），它考虑适当的轨迹聚类以重构核密度分布，并考虑波函数与活性态之间的一致性以引入退相干。以精确量子解为参考，SC-CTSH的高性能在广泛研究的散射模型中得到了基准测试，并与其他相关的基于XF的方法进行了比较。由于纳入了新的轨迹聚类和符号一致性算法，SC-CTSH在非绝热动力学过程中获得了更精确的量子动量和退相干，这使得XF与表面跳跃的结合更加一致和可靠。这项研究进一步突出了波函数与活性态之间内部一致性的重要性，这在混合量子-经典动力学方法的进一步发展中具有重要意义。
