Forward-backward initial value representation for semiclassical time correlation functions
Forward-backward initial value representation for semiclassical time correlation functions
复制标题
半经典时间相关函数的前向-后向初始值表示
DOI：
10.1063/1.478571
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发表时间：
1999
影响因子：
4.4
通讯作者：
W. Miller
中科院分区：
文献类型：
--
作者：
Xiong Sun;W. Miller
时间演化算子 e−iĤt/ℏ 的半经典 (SC) 初始值表示 (IVR) 涉及经典轨迹初始条件上的相空间积分。本文展示了如何将典型量子力学时间相关函数中的两个时间演化算子的 IVR 组合成一个这样的相空间积分；即，从 0 到 t 以及从 t 到 0 的时间演化被组合成一个整体 SC-IVR 传播。这不仅降低了相空间平均值的维数，而且净轨迹的前向-后向（FB）性质具有部分自抵消，从而减少了被积函数的振荡行为。介绍了该 FB-IVR 在无功磁通相关函数中的几种应用，以说明其可能性。
The semiclassical (SC) initial value representation (IVR) for the time evolution operator e−iĤt/ℏ involves a phase space integral over the initial conditions of classical trajectories. It is shown in this paper how an IVR for the two time evolution operators in a typical quantum mechanical time correlation function, CAB(t)≡tr[ÂeiĤt/ℏBe−iĤt/ℏ], can be combined into one such phase space integral; i.e., time evolution from 0 to t and from t to 0 is combined into one overall SC-IVR propagation. This not only reduces the dimensionality of the phase space average, but the forward–backward (FB) nature of the net trajectory has a partial self-cancellation that reduces the oscillatory behavior of the integrand. Several applications of this FB-IVR to reactive flux correlation functions are presented to illustrate its possibilities.