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量子轨迹动力学背景下关联函数与波函数投影的计算。

Computation of correlation functions and wave function projections in the context of quantum trajectory dynamics.

作者信息

Garashchuk Sophya

机构信息

Department of Chemistry, University of South Carolina, Columbia, SC 29223, USA.

出版信息

J Chem Phys. 2007 Apr 21;126(15):154104. doi: 10.1063/1.2717931.

Abstract

The de Broglie-Bohm formulation of the Schrodinger equation implies conservation of the wave function probability density associated with each quantum trajectory in closed systems. This conservation property greatly simplifies numerical implementations of the quantum trajectory dynamics and increases its accuracy. The reconstruction of a wave function, however, becomes expensive or inaccurate as it requires fitting or interpolation procedures. In this paper we present a method of computing wave packet correlation functions and wave function projections, which typically contain all the desired information about dynamics, without the full knowledge of the wave function by making quadratic expansions of the wave function phase and amplitude near each trajectory similar to expansions used in semiclassical methods. Computation of the quantities of interest in this procedure is linear with respect to the number of trajectories. The introduced approximations are consistent with approximate quantum potential dynamics method. The projection technique is applied to model chemical systems and to the H+H(2) exchange reaction in three dimensions.

摘要

薛定谔方程的德布罗意 - 玻姆表述意味着在封闭系统中与每个量子轨迹相关的波函数概率密度的守恒。这种守恒性质极大地简化了量子轨迹动力学的数值实现并提高了其准确性。然而,波函数的重构变得昂贵或不准确,因为它需要拟合或插值过程。在本文中,我们提出了一种计算波包相关函数和波函数投影的方法,这些通常包含关于动力学的所有所需信息,而无需完全了解波函数,方法是在每个轨迹附近对波函数的相位和幅度进行二次展开,类似于半经典方法中使用的展开。在此过程中,感兴趣量的计算相对于轨迹数量是线性的。引入的近似与近似量子势动力学方法一致。投影技术被应用于模拟化学系统以及三维的H + H(2)交换反应。

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