论文标题
非绝热的激体速率理论超出了黄金规则极限
Nonadiabatic instanton rate theory beyond the golden-rule limit
论文作者
论文摘要
费米(Fermi)的黄金法则描述了反应速率的领先行为,这是绝热耦合的函数。它的渐近$(\ hbar \ rightArrow 0)$限制是半经典的黄金规则插入率理论,它严格地近似核量子效应,使其自身以有效的数值计算,并对反应机制提供物理上的洞察力。但是,随着绝热耦合的强度的增加,黄金法则本身就不足了,因此必须另外考虑更高的术语。在这项工作中,我们给出了超出黄金法则的下一个术语的第一原理推导,该术语表示为三个组成部分的总和。其中两个导致新的Instanton途径扩展了黄金规则案,除其他因素外,还解释了饲养对全部利率的影响。其余部分来自平衡分区函数,并解释了由于绝热耦合而引起的反应物和产品孔周围势能的变化。新的半经典理论要求超出金色规则intsanton计算之外几乎没有计算努力。它可以严格评估黄金规则近似的准确性,并为将来的一般半经典非绝热率理论设定阶段。
Fermi's golden rule describes the leading-order behaviour of the reaction rate as a function of the diabatic coupling. Its asymptotic $(\hbar \rightarrow 0)$ limit is the semiclassical golden-rule instanton rate theory, which rigorously approximates nuclear quantum effects, lends itself to efficient numerical computation and gives physical insight into reaction mechanisms. However the golden rule by itself becomes insufficient as the strength of the diabatic coupling increases, so higher-order terms must be additionally considered. In this work we give a first-principles derivation of the next-order term beyond the golden rule, represented as a sum of three components. Two of them lead to new instanton pathways that extend the golden-rule case and, among other factors, account for the effects of recrossing on the full rate. The remaining component derives from the equilibrium partition function and accounts for changes in potential energy around the reactant and product wells due to diabatic coupling. The new semiclassical theory demands little computational effort beyond a golden-rule instanton calculation. It makes it possible to rigorously assess the accuracy of the golden-rule approximation and sets the stage for future work on general semiclassical nonadiabatic rate theories.