Pollak Eli
Chemical and Biological Physics Department , Weizmann Institute of Science , 76100 Rehovot , Israel.
J Phys Chem Lett. 2018 Oct 18;9(20):6066-6071. doi: 10.1021/acs.jpclett.8b02712. Epub 2018 Oct 4.
Kramers's original paper on the diffusion model of chemical reactions was based on the consideration that only the barrier region determines the outcome of transmission over a barrier. Subsequently it became understood that Kramers's approach was identical to variational transition state theory (VTST) and as such used only thermodynamic information. Here, using Kramers's philosophy in conjunction with perturbation theory and the realization that the dynamics which is rate-determining usually occurs in the vicinity of the transition state leads to a novel stochastic rate theory in which the momentum change induced by the medium is the stochastic variable. A first successful application of the theory is to the old and challenging problem of motion over a cusped barrier. This has implications for the study of transition path time distributions as well as the theory of tunneling via nonadiabatic coupling.
克莱默斯关于化学反应扩散模型的原始论文基于这样一种考虑，即只有势垒区域决定越过势垒的传输结果。随后人们认识到，克莱默斯的方法与变分过渡态理论（VTST）相同，因此仅使用了热力学信息。在此，将克莱默斯的理念与微扰理论相结合，并认识到决定速率的动力学通常发生在过渡态附近，从而引出了一种新颖的随机速率理论，其中介质引起的动量变化是随机变量。该理论的首次成功应用是针对尖点势垒上运动这一古老且具有挑战性的问题。这对过渡路径时间分布的研究以及通过非绝热耦合的隧穿理论都有影响。
