Dou Wenjie, Miao Gaohan, Subotnik Joseph E
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA.
Phys Rev Lett. 2017 Jul 28;119(4):046001. doi: 10.1103/PhysRevLett.119.046001. Epub 2017 Jul 25.
We present a universal expression for the electronic friction as felt by a set of classical nuclear degrees of freedom (DOFs) coupled to a manifold of quantum electronic DOFs; no assumptions are made regarding the nature of the electronic Hamiltonian and electron-electron repulsions are allowed. Our derivation is based on a quantum-classical Liouville equation for the coupled electronic-nuclear motion, followed by an adiabatic approximation whereby electronic transitions are assumed to equilibrate faster than nuclear movement. The resulting form of friction is completely general, but does reduce to previously published expressions for the quadratic Hamiltonian (i.e., Hamiltonians without electronic correlation). At equilibrium, the second fluctuation-dissipation theorem is satisfied and the frictional matrix is symmetric. To demonstrate the importance of electron-electron correlation, we study electronic friction within the Anderson-Holstein model, where a proper treatment of electron-electron interactions shows signatures of a Kondo resonance and a mean-field treatment is completely inadequate.
我们给出了一组与量子电子自由度流形耦合的经典核自由度（DOFs）所感受到的电子摩擦的通用表达式；对于电子哈密顿量的性质不做任何假设，并且允许电子 - 电子排斥作用。我们的推导基于耦合电子 - 核运动的量子 - 经典刘维尔方程，随后进行绝热近似，即假设电子跃迁达到平衡的速度比核运动快。由此产生的摩擦形式是完全通用的，但确实可简化为先前发表的关于二次哈密顿量（即无电子关联的哈密顿量）的表达式。在平衡状态下，满足第二个涨落耗散定理，并且摩擦矩阵是对称的。为了证明电子 - 电子关联的重要性，我们在安德森 - 霍尔斯坦模型中研究电子摩擦，其中对电子 - 电子相互作用的恰当处理显示出近藤共振的特征，而平均场处理则完全不适用。
