标题： 非绝热 ImF 瞬子速率理论 显示英文标题

标题： Nonadiabatic ImF instanton rate theory

摘要： 半经典瞬子理论能够捕捉化学反应中的核量子效应，如隧穿效应。 它最初是从两个不同的起点推导出来的，即通量相关函数和ImF假设。 在追求非绝热速率理论的过程中，提出了一些方法；几乎所有方法都基于不太严谨的ImF假设。 只有最近，我们在通量相关函数框架中引入了一种严格的非绝热环聚合物瞬子速率理论，该理论成功地从Born-Oppenheimer极限过渡到黄金规则极限。 在这里，我们检查了之前的基于ImF的尝试，并得出结论认为它们未能正确捕捉这两个极限。 特别是，我们将重点说明一系列发展中的最后一种，称为平均场环聚合物瞬子理论，在黄金规则极限下会失效。 我们开发了一种新的非绝热ImF速率理论，以弥补之前尝试的不足，同时从中获得灵感。 我们还考虑了从深隧穿到高温速率理论的过渡。 我们在一系列模型上测试了我们的新非绝热ImF理论，包括不对称和多维系统，并展示了在深隧穿区域的可靠结果，但对于相关的高温速率理论则存在局限性。 显示英文摘要

摘要： Semiclassical instanton theory captures nuclear quantum effects such as tunnelling in chemical reactions. It was originally derived from two different starting points, the flux correlation function and the ImF premise. In pursuit of a nonadiabatic rate theory, a number of methods have been proposed; almost all based on the less rigorous ImF premise. Only recently, we introduced a rigorous nonadiabatic ring-polymer instanton rate theory in the flux-correlation function framework which successfully bridges from the Born-Oppenheimer to the golden-rule limit. Here, we examine the previous ImF-based attempts and conclude that they do not capture the two limits correctly. In particular, we will highlight how the last in a series of developments, called mean-field ring-polymer instanton theory, breaks down in the golden-rule limit. We develop a new nonadiabatic ImF rate theory to remedy the failings of previous attempts while taking inspiration from them. We also consider the crossover from deep tunnelling to a high-temperature rate theory. We test our new nonadiabatic ImF theory on a range of models including asymmetric and multidimensional systems and we show reliable results for the deep-tunnelling regime but limitations for the related high-temperature rate theory.