论文标题

Marcus-Levich-Jortner理论的半古典激体式

Semiclassical instanton formulation of Marcus-Levich-Jortner theory

论文作者

Heller, Eric R., Richardson, Jeremy O.

论文摘要

Marcus-Levich-Jortner(MLJ)理论是将核量子效应纳入电子转移速率和解释实验数据的最常用方法之一。它将分子问题分为一个由费米的黄金法则和经典Marcus理论处理的溶剂浴的子系统。作为这一想法的扩展,我们在这里提出了一种“简化”的半经典激体理论,这是一种多尺度方法,用于在谐波浴的情况下以分子细节模拟子系统的量子隧穿。我们证明,Instanton理论通常比累积的扩展或半经典的Franck-Condon总和更准确,后者可能会产生刻板级误差,并且通常不遵守详细的平衡。与基于波函数的MLJ理论相反,Instanton理论基于路径积分,因此不需要Schrödinger方程的解决方案,甚至不需要对子系统内的地面和兴奋状态势的全球知识。因此,它可以有效地应用于复杂的,无谐的多维子系统,而无需进一步近似。除了预测准确的速率外,Instanton理论还通过定位主要的隧道途径,并提供有关反应物和乘积振动状态的信息,从而对反应机理提供了高度的了解,并且提供了与MLJ理论相似的反应和激活能量的信息。

Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into a subsystem treated quantum-mechanically by Fermi's golden rule and a solvent bath treated by classical Marcus theory. As an extension of this idea, we here present a "reduced" semiclassical instanton theory, which is a multiscale method for simulating quantum tunnelling of the subsystem in molecular detail in the presence of a harmonic bath. We demonstrate that instanton theory is typically significantly more accurate than the cumulant expansion or the semiclassical Franck-Condon sum, which can give orders-of-magnitude errors and in general do not obey detailed balance. As opposed to MLJ theory, which is based on wavefunctions, instanton theory is based on path integrals and thus does not require solutions of the Schrödinger equation, nor even global knowledge of the ground- and excited-state potentials within the subsystem. It can thus be efficiently applied to complex, anharmonic multidimensional subsystems without making further approximations. In addition to predicting accurate rates, instanton theory gives a high level of insight into the reaction mechanism by locating the dominant tunnelling pathway as well as providing information on the reactant and product vibrational states involved in the reaction and the activation energy in the bath similarly to what would be found with MLJ theory.

扫码加入交流群

加入微信交流群

微信交流群二维码

扫码加入学术交流群,获取更多资源