论文标题

确认核隧道在水铁液体特有电子转移中的作用

Confirming the role of nuclear tunnelling in aqueous ferrous-ferric electron transfer

论文作者

Lawrence, Joseph E., Manolopoulos, David E.

论文摘要

我们重新审视了众所周知的亚铁特性电子转移反应,以解决最近的建议,即核隧道可能会导致与电子传递的Marcus图片固有的线性响应假设显着偏差。理查森(Richardson)和同事对这一反应的最新研究发现,他们的新路径综合法,GR-QTST和Wolynes的马鞍点近似(Wolynes Theory)之间存在很大差异(Wolynes Theory)。他们认为这种差异可以归因于多个隧道途径的存在,这使沃利尼斯理论显着高估了速率。这被用来争辩说,当隧道很重要时,MARCUS理论的线性响应假设可能会破坏液体系统。如果是的,这将暗示研究问题的常用方法,即问题被映射到自旋 - 玻色子模型上是无效的。但是,我们最近表明,GR-QTST中的大小不一致可能导致对自由度多种程度的系统速率的预测较差。我们还提出了一种改进的方法,即路径综合线性黄金规则(LGR)近似,它可以解决此问题。在这里,我们证明了亚铁质电子转移的GR-QTST结果确实是其大小一致性误差所主导的。此外,通过比较LGR和Wolynes理论结果,我们确认了该系统中核隧道的既定图片。最后,通过将我们的路径综合结果与通过映射到自旋 - 玻璃模型获得的结果进行比较,我们重新评估了非谐效应的重要性以及这种常用的映射方法的准确性。

We revisit the well-known aqueous ferrous-ferric electron transfer reaction in order to address recent suggestions that nuclear tunnelling can lead to significant deviation from the linear response assumption inherent in the Marcus picture of electron transfer. A recent study of this reaction by Richardson and coworkers has found a large difference between their new path-integral method, GR-QTST, and the saddle point approximation of Wolynes (Wolynes theory). They suggested that this difference could be attributed to the existence of multiple tunnelling pathways, leading Wolynes theory to significantly overestimate the rate. This was used to argue that the linear response assumptions of Marcus theory may break down for liquid systems when tunnelling is important. If true, this would imply that the commonly used method for studying such systems, where the problem is mapped onto a spin-boson model, is invalid. However, we have recently shown that size inconsistency in GR-QTST can lead to poor predictions of the rate in systems with many degrees of freedom. We have also suggested an improved method, the path-integral linear golden-rule (LGR) approximation, which fixes this problem. Here we demonstrate that the GR-QTST results for ferrous-ferric electron transfer are indeed dominated by its size consistency error. Furthermore, by comparing the LGR and Wolynes theory results, we confirm the established picture of nuclear tunnelling in this system. Finally, by comparing our path-integral results to those obtained by mapping onto the spin-boson model, we reassess the importance of anharmonic effects and the accuracy of this commonly used mapping approach.

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