Naaman Ron, Waldeck David H
Department of Chemical and Biological Physics, Weizmann Institute of Science, 76100 Rehovot, Israel.
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 United States.
J Phys Chem Lett. 2024 Nov 7;15(44):11002-11006. doi: 10.1021/acs.jpclett.4c02617. Epub 2024 Oct 27.
Electron transfer (eT) processes have garnered the attention of chemists and physicists for more than seven decades, and it is commonly believed that the essential features of the electron transfer mechanism are well understood─despite some open questions relating to the efficiency of long-range eT in some systems and temperature effects that are difficult to reconcile with the existing theories. The chiral induced spin selectivity (CISS) effect, which has been studied experimentally since 1999, demonstrates that eT through chiral systems depends on the electron's spin. Attempts to explain the CISS effect by adding spin-orbit coupling to the existing eT theories fails to reproduce the experimental results quantitatively, and it has become evident that the theory for explaining CISS must consider electron-vibration and/or electron-electron interactions. In this Perspective we identify some features of the CISS effect that imply that we should reconsider and refine the Marcus-Levich-Jortner mechanistic description for eT processes, especially for nonlinear systems and in the case of long-range eT.
七十多年来，电子转移（eT）过程一直备受化学家和物理学家的关注。人们普遍认为，电子转移机制的基本特征已得到充分理解，尽管在某些系统中，与长程电子转移效率相关的一些问题以及难以与现有理论相协调的温度效应仍然存在。自1999年以来一直在进行实验研究的手性诱导自旋选择性（CISS）效应表明，通过手性系统的电子转移取决于电子的自旋。试图通过在现有的电子转移理论中加入自旋 - 轨道耦合来解释CISS效应，但未能定量地重现实验结果。显然，解释CISS效应的理论必须考虑电子 - 振动和/或电子 - 电子相互作用。在这篇综述文章中，我们指出了CISS效应的一些特征，这意味着我们应该重新审视并完善用于电子转移过程的Marcus - Levich - Jortner机制描述，特别是对于非线性系统以及长程电子转移的情况。
