We address the challenge of incorporating non-Markovian electronic friction effects in quantum-mechanical approximations of dynamical observables. A generalized Langevin equation is formulated for ring-polymer molecular dynamics rate calculations, which combines electronic friction with a description of nuclear quantum effects for adsorbates on metal surfaces. An efficient propagation algorithm is introduced that captures both the spatial dependence of friction strength and non-Markovian frictional memory. This framework is applied to a model of hydrogen diffusing on Cu(111) derived from density functional theory calculations, revealing significant alterations in rate constants and tunneling crossover temperatures due to non-Markovian effects. Our findings explain why previous classical molecular dynamics simulations with Markovian friction showed unexpectedly good agreement with experiment, highlighting the critical role of non-Markovian effects in first-principles atomistic simulations. Published by the American Physical Society 2025

中文翻译：

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氢与电子摩擦扩散的量子速率计算中的非马尔可夫效应

我们解决了在动力学可观察物的量子力学近似中加入非马尔可夫电子摩擦效应的挑战。为环聚合物分子动力学速率计算制定了广义 Langevin 方程，该方程将电子摩擦与金属表面吸附物的核量子效应描述相结合。引入了一种高效的传播算法，该算法同时捕获摩擦强度和非马尔可夫摩擦记忆的空间依赖性。该框架应用于从密度泛函理论计算得出的氢在 Cu（111） 上扩散的模型，揭示了由于非马尔可夫效应，速率常数和隧穿交叉温度的显着变化。我们的研究结果解释了为什么以前使用马尔可夫摩擦的经典分子动力学模拟显示出与实验出乎意料的良好一致性，突出了非马尔可夫效应在第一性原理原子模拟中的关键作用。 美国物理学会 2025 年出版