Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
J Chem Phys. 2018 Nov 7;149(17):174115. doi: 10.1063/1.5049710.
The relationship between electronic interactions and electronic decoherence is a fundamental problem in chemistry. Here we show that varying the electron-electron interactions does not affect the electronic decoherence in the pure-dephasing limit. In this limit, the effect of varying the electronic interactions is to rigidly shift in energy the diabatic potential energy surfaces without changing their shape, thus keeping the nuclear dynamics in these surfaces that leads to the electronic decoherence intact. This analysis offers a simple and intuitive understanding of previous theoretical and computational efforts to characterize the influence of electronic interactions on the decoherence and opens opportunities to study exact electronic decoherence with approximate electronic structure theories.
电子相互作用与电子退相干之间的关系是化学中的一个基本问题。在这里，我们表明在纯退相干极限下，改变电子相互作用并不影响电子退相干。在这个极限下，改变电子相互作用的效果是刚性地移动绝热势能表面的能量，而不改变其形状，从而保持导致电子退相干的核动力学在这些表面上的完整性。这种分析为以前用理论和计算方法来描述电子相互作用对退相干的影响提供了一个简单直观的理解，并为用近似电子结构理论研究精确电子退相干提供了机会。
