论文标题
电解质溶液中的传输现象：非平衡热力学和统计力学
Transport phenomena in electrolyte solutions: Non-equilibrium thermodynamics and statistical mechanics
论文作者
论文摘要
多组分电解质溶液中的运输现象通过连续性力学，电磁作和非平衡热力学的整合来提出。得出了不可逆转的热力学的管理方程，包括平衡定律，麦克斯韦方程，内部熵产生以及与热力学力和磁通有关的线性定律。根据通量 - 液压时间相关性，获得了连接电化势梯度和扩散通量的运输系数的绿色kubo关系。提出了派生的运输系数与Stefan-Maxwell的关系与无限稀释框架之间的关系，并描述了传输矩阵与实验可测量数量之间的连接。为了体现在分子模拟中衍生的绿色关系的应用，使用经典的分子动力学计算锂和氯离子离子的转运系数矩阵，并与实验测量相比。
The theory of transport phenomena in multicomponent electrolyte solutions is presented here through the integration of continuum mechanics, electromagnetism, and non-equilibrium thermodynamics. The governing equations of irreversible thermodynamics, including balance laws, Maxwell's equations, internal entropy production, and linear laws relating the thermodynamic forces and fluxes, are derived. Green-Kubo relations for the transport coefficients connecting electrochemical potential gradients and diffusive fluxes are obtained in terms of the flux-flux time correlations. The relationship between the derived transport coefficients and those of the Stefan-Maxwell and infinitely dilute frameworks are presented, and the connection between the transport matrix and experimentally measurable quantities is described. To exemplify application of the derived Green-Kubo relations in molecular simulations, the matrix of transport coefficients for lithium and chloride ions in dimethyl sulfoxide is computed using classical molecular dynamics and compared with experimental measurements.
