论文标题
非平衡反应速率理论：运动方法层次方程内的制定和实施
Nonequilibrium reaction rate theory: Formulation and implementation within the hierarchical equations of motion approach
论文作者
论文摘要
最近，在各种情况下，在非平衡条件下对环境中的化学反应的研究引起了人们的关注，包括分子连接的电流诱导的反应和扫描隧道显微镜实验。在这项工作中，我们概述了在这种非平衡情况下描述化学反应速率的完全量子机械，数值精确的方法。该方法基于通量相关函数形式主义对非平衡条件的扩展，并使用混合的真实和想象的时间分层运动方法的运动方法来计算速率常数。作为一个特定的例子，我们研究了分子连接中电流诱导的分子内质子转移反应，用于不同的施加偏置电压和分子铅耦合强度。
The study of chemical reactions in environments under nonequilibrium conditions has been of interest recently in a variety of contexts, including current-induced reactions in molecular junctions and scanning tunneling microscopy experiments. In this work, we outline a fully quantum mechanical, numerically exact approach to describe chemical reaction rates in such nonequilibrium situations. The approach is based on an extension of the flux correlation function formalism to nonequilibrium conditions and uses a mixed real and imaginary time hierarchical equations of motion approach for the calculation of rate constants. As a specific example, we investigate current-induced intramolecular proton transfer reactions in a molecular junction for different applied bias voltages and molecule-lead coupling strengths.
