Ab initio calculation of electron-phonon linewidths and molecular dynamics with electronic friction at metal surfaces with numeric atom-centred orbitals
Ab initio calculation of electron-phonon linewidths and molecular dynamics with electronic friction at metal surfaces with numeric atom-centred orbitals
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DOI：
10.1088/2516-1075/acf3c4
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发表时间：
2023-09-01
影响因子：
2.6
通讯作者：
Maurer, Reinhard J.
中科院分区：
文献类型：
--
作者：
Box, Connor L.;Stark, Wojciech G.;Maurer, Reinhard J.
金属表面的分子运动受到非绝热效应和电子-声子耦合的影响。随后的能量耗散和动力转向效应不能用经典的分子动力学模拟来描述，但可以用分子动力学的电子摩擦法和基于密度泛函理论的线性响应计算来描述。本文在电子结构代码FHI-aims中提出了一种基于全电子数值原子轨道描述的电子-声子响应实现方法。在提供了基本近似和数值考虑的细节之后，我们展示了与以前的实现相比，新代码的可扩展性和性能改进（Maurer等人2016年物理）。Rev. B 94 115432)。我们比较了典型系统的收敛行为和模拟结果，例如H2在Cu（111）上的吸附和CO在Ru（0001）上的吸附与现有平面波实现的对比。我们研究了不同的表达式来计算电子摩擦和振动寿命，因为它们的可靠性和易于收敛。最后，我们通过研究带间和带内激励对大型、以前不可行的周期性表面模型中非周期吸附物运动的振动寿命的贡献来展示新代码的能力。
Molecular motion at metallic surfaces is affected by nonadiabatic effects and electron-phonon coupling. The ensuing energy dissipation and dynamical steering effects are not captured by classical molecular dynamics simulations, but can be described with the molecular dynamics with electronic friction method and linear response calculations based on density functional theory. Herein, we present an implementation of electron-phonon response based on an all-electron numeric atomic orbital description in the electronic structure code FHI-aims. After providing details of the underlying approximations and numerical considerations, we present significant scalability and performance improvements of the new code compared to a previous implementation (Maurer et al 2016 Phys. Rev. B 94 115432). We compare convergence behaviour and results of our simulations for exemplary systems such as H2 adsorption on Cu(111), and CO on Ru(0001) against existing plane wave implementations. We examine different expressions to calculate electronic friction and vibrational lifetimes for their reliability and ease of convergence. Finally, we show the capabilities of the new code by studying the contribution of interband and intraband excitations to the vibrational lifetime of aperiodic adsorbate motion in large, previously unfeasible, periodic surface models.