Quantum‐classical path integral evaluation of reaction rates with a near‐equilibrium flux formulation
Quantum‐classical path integral evaluation of reaction rates with a near‐equilibrium flux formulation
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DOI：
10.1002/qua.26618
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发表时间：
2021-02
影响因子：
2.2
通讯作者：
Amartya Bose;N. Makri
中科院分区：
文献类型：
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作者：
Amartya Bose;N. Makri
反应通量关联函数的量子经典公式需要热化通量算符的部分Weyl-Wigner变换，但由于相位抵消，其数值计算是不稳定的。在最近的一篇论文中，我们引入了一个非平衡公式，它消除了构造这种分布的需要，并给出了反应速率随反应物总体的时间演化。在这项工作中，我们描述了反应通量的近平衡公式，它解释了量子系统与其环境之间的重要热关联，同时避免了完全Weyl-Wigner变换的数值不稳定性。通过最大限度地减少早期瞬变，近平衡公式导致更早地开始进入高原状态，从而可以根据短时间动态确定反应速率。结合量子经典路径积分方法，近平衡公式为确定凝聚相环境中的反应速率常数提供了一种准确而有效的方法。近平衡公式还可以与各种近似的量子经典传播方法相结合。
Quantum‐classical formulations of reactive flux correlation functions require the partial Weyl–Wigner transform of the thermalized flux operator, whose numerical evaluation is unstable because of phase cancelation. In a recent paper, we introduced a non‐equilibrium formulation which eliminates the need for construction of this distribution and which gives the reaction rate along with the time evolution of the reactant population. In this work, we describe a near‐equilibrium formulation of the reactive flux, which accounts for important thermal correlations between the quantum system and its environment while avoiding the numerical instabilities of the full Weyl–Wigner transform. By minimizing early‐time transients, the near‐equilibrium formulation leads to an earlier onset of the plateau regime, allowing determination of the reaction rate from short‐time dynamics. In combination with the quantum‐classical path integral methodology, the near‐equilibrium formulation offers an accurate and efficient approach for determining reaction rate constants in condensed phase environments. The near‐equilibrium formulation may also be combined with a variety of approximate quantum‐classical propagation methods.