路径积分的三个应用：（Z）-1，3-戊二烯[1，5] σ迁移氢位移的平衡和动力学同位素效应及速率常数的温度依赖性
Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene
摘要：
最近的实验已经证实了核量子效应的重要性，即使在生理温度下的大生物分子。在这里，我们描述了如何路径积分形式主义可以用来严格描述核量子效应的平衡和分子的动力学性质。具体来说，我们解释了如何路径积分可以用来评估平衡（EIE）和动力学（KIE）同位素效应，以及速率常数的温度依赖性。该方法适用于[1，5] σ迁移的戊二烯氢位移。KIE和速率常数的温度依赖性都证实了隧穿和其他核量子效应以及势能面的非谐性的重要性。此外，以前的结果KIE的改进，通过使用一个高层次的电子结构计算内的谐波近似与路径积分非谐校正使用较低的水平的方法相结合。
英文摘要：
Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibrium and kinetic properties of molecules. Specifically, we explain how path integrals can be employed to evaluate the equilibrium (EIE) and kinetic (KIE) isotope effects, and the temperature dependence of the rate constant. The methodology is applied to the [1,5] sigmatropic hydrogen shift in pentadiene. Both the KIE and the temperature dependence of the rate constant confirm the importance of tunneling and other nuclear quantum effects as well as of the anharmonicity of the potential energy surface. Moreover, previous results on the KIE were improved by using a combination of a high level electronic structure calculation within the harmonic approximation with a path integral anharmonicity correction using a lower level method.
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