发表机构
Harvard University（哈佛大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文提出一种基于多轨道安德森-纽恩斯模型的第一性原理非绝热动力学理论，实现DFT到有效哈密顿量的无拟合映射，并应用于Cu表面H和CO，揭示常用近似失效及CO单轨道描述的定性失败。
AI 中文摘要
我们发展了一种用于非绝热表面动力学的第一性原理理论，提供了密度泛函理论（DFT）计算与有效多轨道安德森-纽恩斯（AN）理论之间无需拟合的关联。该理论包含两个主要进展。首先，我们概述了包含轨道重叠的多轨道AN理论，并推导了杂化能、电子动力学和电子摩擦的闭式表达式。其次，我们描述了一种将DFT哈密顿量映射为具有核位置依赖性的有效AN哈密顿量的程序。我们仅从吸附质投影态密度矩阵获得AN哈密顿量的电子部分。然后，我们将裸核势定义为总能量与杂化能之差。该理论应用于Cu表面上的H和CO，发现关于杂化函数的广泛使用的假设（包括宽带极限、半椭圆形式以及能量与核坐标的可分离性）均失效，且对于CO，单轨道描述在定性上崩溃。我们期望这项工作对金属表面上耦合核-电子动力学和化学反应的第一性原理建模具有广泛用途。
英文摘要
We develop a first-principles theory for nonadiabatic surface dynamics, providing a fit-free connection between density functional theory (DFT) calculations and the effective multi-orbital Anderson-Newns (AN) theory. Our theory contains two main advances. First, we outline the multi-orbital AN theory with orbital overlap and derive closed-form expressions for the hybridization energy, electronic dynamics, and electronic friction. Second, we describe a procedure to map the DFT Hamiltonian into the effective AN Hamiltonian with nuclear-position dependence. We obtain the electronic part of the AN Hamiltonian solely from the adsorbate-projected density-of-states matrix. We then define the bare nuclear potential as the difference between the total energy and the hybridization energy. The theory is applied to H and CO on the Cu surface, where widely used assumptions about the hybridization function, including the wide-band limit, semi-elliptical forms, and separability in energy and nuclear coordinate, are found to fail, and the single-orbital description breaks down qualitatively for CO. We expect this work to be broadly useful for first-principles modeling of coupled nuclear-electronic dynamics and chemical reactions at metallic surfaces.
