Max-Planck Institut für Mikrostrukturphysik, Weinberg 2, D-06120 Halle, Germany.
Department of Chemistry, School of Natural Science, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798, Korea.
Phys Rev Lett. 2015 Aug 14;115(7):073001. doi: 10.1103/PhysRevLett.115.073001. Epub 2015 Aug 10.
We present a novel quantum-classical approach to nonadiabatic dynamics, deduced from the coupled electronic and nuclear equations in the framework of the exact factorization of the electron-nuclear wave function. The method is based on the quasiclassical interpretation of the nuclear wave function, whose phase is related to the classical momentum and whose density is represented in terms of classical trajectories. In this approximation, electronic decoherence is naturally induced as an effect of the coupling to the nuclei and correctly reproduces the expected quantum behavior. Moreover, the splitting of the nuclear wave packet is captured as a consequence of the correct approximation of the time-dependent potential of the theory. This new approach offers a clear improvement over Ehrenfest-like dynamics. The theoretical derivation presented in this Letter is supported by numerical results that are compared to quantum mechanical calculations.
我们提出了一种新的量子经典方法来研究非绝热动力学，该方法源自电子和核方程在电子-核波函数精确分解框架下的耦合。该方法基于对核波函数的准经典解释，核波函数的相位与经典动量有关，密度则用经典轨迹来表示。在这种近似下，电子退相干是由于与原子核的耦合而自然产生的，并正确地再现了预期的量子行为。此外，核波包的分裂是由于理论中时变势的正确近似而产生的。与 Ehrenfest 类动力学相比，这种新方法有了明显的改进。本文提出的理论推导得到了数值结果的支持，并与量子力学计算进行了比较。
