On the semiclassical description of quantum coherence in thermal rate constants
On the semiclassical description of quantum coherence in thermal rate constants
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热速率常数中量子相干性的半经典描述
DOI：
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发表时间：
1998
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影响因子：
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通讯作者：
W. Miller
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文献类型：
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作者：
Xiong Sun;Haobin Wang;W. Miller
我们早期的一篇论文[J. Chem. Phys. 108，9726（1998）]使用了近似的（线性化）的半经典初值表示（SC-IVR）来计算单分子异构化模型的反应通量相关函数，即耦合到无限组谐振子的一维双阱势，获得了与该系统的精确量子结果的极好的一致性。在这里，我们进一步分析了这种线性近似（LA），然而，并表明它是不能够描述量子干涉/相干效应的异构化动力学的较长时间的再交叉行为。(The在我们早期工作中看到的再交叉效应是由于经典力学。）为了强调量子效应在交叉动力学，本文考虑了双势阱没有谐波浴，使用LA和全SC-IVR。计算结果表明，由LA给出的通量关联函数与理论计算的精确值符合得很好。
An earlier paper of ours [J. Chem. Phys. 108, 9726 (1998)] used an approximate (linearized) version of the semiclassical initial value representation (SC-IVR) to calculate reactive flux correlation functions for a model of unimolecular isomerization, namely a 1-d double well potential coupled to an infinite set of harmonic oscillators, obtaining excellent agreement with accurate quantum results for this system. Here we analyze this linearized approximation (LA) further, however, and show that it is not capable of describing quantum interference/coherence effects in the longer time recrossing behavior of the isomerization dynamics. (The recrossing effects seen in our earlier work were due to classical mechanics.) To accentuate quantum effects in the recrossing dynamics, the present article considers the double well potential without the harmonic bath, using both the LA and the full SC-IVR. The results of the calculations show that the flux correlation functions given by the LA agrees well with the exact qu...