发表机构
Institute of Physics, University of Freiburg; College of Science and Engineering, James Cook University（弗赖堡大学物理研究所; 詹姆斯库恩大学科学与工程学院）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
提出非马尔可夫电子摩擦与朗之万动力学通用框架，通过马尔可夫嵌入和指数分解记忆核，精确模拟非平衡分子振动动力学，优于传统马尔可夫近似。
AI 中文摘要
我们提出了一个通用框架，用于模拟分子与金属表面相互作用的非平衡振动电子动力学，该框架利用非马尔可夫电子摩擦和相应的广义朗之万方程。该方法采用马尔可夫嵌入方案来采样坐标相关的量子色噪声，其底层记忆核通过直接从电子力获得的指数分解系统地表示。通过这种方式，该方法将广泛使用的电子摩擦和朗之万动力学形式扩展到传统马尔可夫近似之外，同时保留了电子反作用的坐标依赖性。我们通过振动耦合分子结的非平衡电荷输运演示了该方法，与数值精确的分层运动方程模拟的比较表明，非马尔可夫公式比其马尔可夫对应物更准确、更稳健。特别是，我们发现非马尔可夫电子力在非平衡振动动力学中起决定性作用，稳定了传统马尔可夫近似失效的区域。
英文摘要
We present a general framework for simulating the nonequilibrium vibronic dynamics of molecules interacting with metal surfaces, which utilizes non-Markovian electronic friction and the corresponding generalized Langevin equation. The method employs a Markovian embedding scheme to sample coordinate-dependent quantum colored noise, with the underlying memory kernels represented systematically by exponential decompositions obtained directly from the electronic forces. In doing so, the approach extends the widely used electronic friction and Langevin dynamics formalism beyond the conventional Markovian approximation while retaining the coordinate dependence of the electronic back-action. We demonstrate the method for nonequilibrium charge transport through a vibrationally coupled molecular junction, where comparisons with numerically exact hierarchical equations of motion simulations show that the non-Markovian formulation is both more accurate and more robust than its Markovian counterpart. In particular, we find that non-Markovian electronic forces play a decisive role in the nonequilibrium vibrational dynamics, stabilizing regimes in which the conventional Markovian approximation fails.
