通过在瞬子速率理论中引入第一性原理电子摩擦的耗散瞬子速率I：理论
Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
摘要：
涉及金属表面上的吸附物和块体金属中的杂质的反应在广泛的技术应用中普遍存在。这种反应的理论建模对理论提出了巨大的挑战，因为核量子效应（NQE）可以发挥突出的作用，并且原子运动与金属中电子的耦合引起改变原子动力学的重要非绝热效应（NAE）。在这项工作中，我们得到了一个理论框架，捕获NQE和NAES，由于其高效率，可以应用到第一性原理计算的反应速率在高维现实系统。更详细地说，我们开发了一种方法，我们硬币环聚合物瞬子与显式摩擦（RPI-EF），从环聚合物瞬子形式主义适用于系统浴模型。我们推导出一般方程，将空间和频率依赖的摩擦张量，然后结合这种方法与\textit{ab initio}电子摩擦形式主义的热反应速率的计算。我们表明，RPI-EF和电子摩擦张量的形式在这项工作中提出的连接不需要任何进一步的近似，它预计是有效的，只要两个基本理论的近似仍然有效。
英文摘要：
Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modelling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to first-principles calculations of reaction rates in high-dimensional realistic systems. In more detail, we develop a method that we coin ring polymer instanton with explicit friction (RPI-EF), starting from the ring-polymer instanton formalism applied to a system-bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor, and then combine this method with the \textit{ab initio} electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between RPI-EF and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.
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