Generalization of the Linearized Approximation to the Semiclassical Initial Value Representation for Reactive Flux Correlation Functions
Generalization of the Linearized Approximation to the Semiclassical Initial Value Representation for Reactive Flux Correlation Functions
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无功通量相关函数的半经典初值表示的线性化近似的推广
DOI：
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发表时间：
1999
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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：
W. Miller
半经典（SC）初值表示（IVR）为经典分子动力学模拟中包含量子效应提供了一种通用而实用的方法。对SC-IVR的线性化近似（LA）进一步简化了描述，将其简化为众所周知的经典维格纳模型（即，一个经典的轨道计算与维格纳分布的初始条件）; LA是能够很好地描述量子效应的短时间（t {approx{underscore}lt} {Dirac{underscore}h}{beta}），但不是这样的较长的时间。它在这里示出了如何完整的SC-IVR方法，这是能够描述量子效应很长一段时间，可以铸造在一个非常类似的形式在结构上的LA，与特定的应用程序相关的化学反应速率的通量相关函数。因此，该公式可以进行完整的SC-IVR计算，同时仍然保留其线性化近似的许多简化方面。
The semiclassical (SC) initial value representation (IVR) provides a general and practical approach for including quantum effects in classical molecular dynamics simulations. The linearized approximation (LA) to the SC-IVR simplifies the description much further, reducing it to the well-known classical Wigner model (i.e., a classical trajectory calculation with a Wigner distribution of initial conditions); the LA is able to describe quantum effects well for short times (t {approx{underscore}lt} {Dirac{underscore}h}{beta}) but not so for longer times. It is shown here how the full SC-IVR approach, which is able to describe quantum effects for long times, can be cast in a form very similar in structure to the LA, with specific application to flux correlation functions relevant to chemical reaction rates. This formulation may thus make it possible to carry out full SC-IVR calculations while still retaining much of the simplifying aspects of its linearized approximation.