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Classical mechanics and the spreading of localized wave packets in condensed phase molecular systems

机译:经典力学与凝聚相分子系统中局部波包的扩散

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The relationship between the diverging of classical trajectories in chaotic many-body systems, the spreading of quantum wave packets, and the validity and use of classical molecular dynamics is explored. This analysis, which is based on the semiclassical description of wave function propagation in terms of a weighted integration over a traveling fixed width coherent state basis, suggests that the exponential divergence of nearby classical trajectories in chaotic many-body systems should result in the rapid delocalization of an initially localized quantum wave packet describing the state of the system. Thus the justification for the use of classical molecular dynamics procedures for these supposedly classical systems cannot be based on the picture of the system wave function remaining localized as its center follows a nearly classical trajectory. The quantum evolution of the system density, on the other hand, requires two propagators, and each of these evolution of the system density, on the other hand, requires two propagators, and each of these propagators is represented as an integration over trajectories in the semiclassical picture. The interference between the contributions from these two integrations over classical trajectories focuses the analysis on the most important points in this trajectory pair space, which are shown to occur when both trajectories in the pair are the same. Given reasonable assumptions for the initial density for a system that is expected to be well described by classical molecular dynamics, and given an appropriate choice for the width of the coherent state basis which is employed in the semiclassical description, it is shown that the semiclassical expressions for time dependent observables and correlation functions reduce the purely classical expressions, despite the fact that an initially localized wave packet would rapidly delocalize for the same system.
机译:探索了混沌多体系统中经典轨迹的发散,量子波包的扩散以及经典分子动力学的有效性和使用之间的关系。该分析基于对波函数传播的半经典描述,即基于在行进的固定宽度相干态上的加权积分,它表明混沌多体系统中附近经典轨迹的指数发散会导致快速离域描述系统状态的初始局部量子波包的示意图。因此,对于这些所谓的经典系统,使用经典分子动力学程序的理由不能基于系统波函数的中心仍然遵循经典轨迹而保留局部的图像。另一方面,系统密度的量子演化需要两个传播子,另一方面,系统密度的这些演化每个都需要两个传播子,并且这些传播子中的每一个都表示为粒子在轨道上的积分。半经典的图片。这两个积分对经典轨迹的贡献之间的干扰将分析重点放在了该轨迹对空间中最重要的点上,这些点显示为在该轨迹对中的两个轨迹相同时会发生。给定合理的假设,以预期可以由经典分子动力学很好地描述的系统的初始密度,并为半经典描述中使用的相干态基础的宽度提供适当的选择,表明半经典表达式随时间变化的观测值和相关函数简化了纯经典的表达式,尽管事实上对于同一系统,最初定位的波包会迅速地离域。

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