电子转移体系-浴槽模型的隧穿效应和不对称性
Effects of tunnelling and asymmetry for system-bath models of electron transfer
摘要：
我们应用新推导的非绝热黄金法则瞬子理论描述在溶液中的电子转移的不对称模型。该模型超越了通常的自旋玻色子的描述，并具有不同的值的反应物和产品重组能量的非谐自由能表面。瞬子方法很好地描述了所研究的整个范围内速率常数相对于不对称性的行为。我们推导出一个一般公式的非对称版本的马库斯理论的基础上的经典极限的瞬子，并发现这给了显着的修正标准马库斯理论。给出了一个仅基于平衡模拟来计算该速率的方案。我们还比较了由瞬子方法得到的速率常数与其经典极限，以研究隧道效应和其他量子核效应。这些量子效应可以使速率常数增加几个数量级。
英文摘要：
We apply the newly derived nonadiabatic golden-rule instanton theory to asymmetric models describing electron-transfer in solution. The models go beyond the usual spin-boson description and have anharmonic free-energy surfaces with different values for the reactant and product reorganization energies. The instanton method gives an excellent description of the behaviour of the rate constant with respect to asymmetry for the whole range studied. We derive a general formula for an asymmetric version of Marcus theory based on the classical limit of the instanton and find that this gives significant corrections to the standard Marcus theory. A scheme is given to compute this rate based only on equilibrium simulations. We also compare the rate constants obtained by the instanton method with its classical limit to study the effect of tunnelling and other quantum nuclear effects. These quantum effects can increase the rate constant by orders of magnitude.
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