金属表面非绝热动力学中依赖记忆的电子摩擦
Memory-dependent electronic friction for nonadiabatic dynamics at metal surfaces
AI总结：
该研究提出从第一性原理计算依赖记忆的电子摩擦的理论体系，揭示其对金属表面非绝热动力学能量交换的影响，无需定义单一马尔可夫摩擦系数。
AI中文摘要：
核运动诱导的电子激发是金属表面化学动力学中关键的能量耗散通道，在此非绝热效应可通过带电子摩擦的分子动力学处理，表现为摩擦阻力与涨落力贡献。通常采用马尔可夫近似，忽略记忆效应。本文提出从第一性原理计算张量形式、依赖构型的电子摩擦记忆核的理论形式体系；针对Newns–Anderson哈密顿模型及Kohn–Sham密度泛函理论计算摩擦核，分析其数学性质与构型依赖性。对于超热原子与双原子散射，电子摩擦的频率与构型依赖带来的记忆效应会影响吸附质与金属电子间的能量交换；在NO在Au(111)表面散射的案例中，记忆效应使振动能量损失增加、平动能量损失减少，提升了摩擦的方向各向异性。重要的是，依赖记忆的电子摩擦评估无需从结构化的频率依赖电子响应中定义单一有效马尔可夫摩擦系数。
英文摘要：
Electronic excitation induced by nuclear motion is a key energy dissipation channel in chemical dynamics at metal surfaces. Here, nonadiabatic effects can be treated via molecular dynamics with electronic friction, where they act as frictional drag and fluctuation force contributions. Commonly, the Markov approximation is imposed, so memory effects are ignored. A theoretical formalism is presented to evaluate tensorial and configuration-dependent electronic friction memory kernels from first principles. We evaluate friction kernels for Newns--Anderson Hamiltonian models as well as within Kohn--Sham density functional theory and analyse their mathematical properties and configuration dependence. For hyperthermal atomic and diatomic scattering, memory effects arising from frequency and configuration dependence of electronic friction affect energy exchange between adsorbate and metal electrons. Memory effects lead to an increase of vibrational and a reduction of translational energy loss in the case of nitric oxide scattering on Au(111), leading to an increase of directional anisotropy of friction. Importantly, memory-dependent evaluation of electronic friction removes the need to define a single effective Markovian friction coefficient from the structured frequency-dependent electronic response.
