Robertson Bryan, Schofield Jeremy, Kapral Raymond
Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
J Chem Phys. 2024 Jan 7;160(1). doi: 10.1063/5.0185361.
We present a derivation from the first principles of the coupled equations of motion of an active self-diffusiophoretic Janus motor and the hydrodynamic densities of its fluid environment that are nonlinearly displaced from equilibrium. The derivation makes use of time-dependent projection operator techniques defined in terms of slowly varying coarse-grained microscopic densities of the fluid species number, total momentum, and energy. The exact equations of motion are simplified using time scale arguments, resulting in Markovian equations for the Janus motor linear and angular velocities with average forces and torques that depend on the fluid densities. For a large colloid, the fluid equations are separated into bulk and interfacial contributions, and the conditions under which the dynamics of the fluid densities can be accurately represented by bulk hydrodynamic equations subject to boundary conditions on the colloid are determined. We show how the results for boundary conditions based on continuum theory can be obtained from the molecular description and provide Green-Kubo expressions for all transport coefficients, including the diffusiophoretic coupling and the slip coefficient.
我们从活性自扩散电泳雅努斯电机运动耦合方程及其偏离平衡态的流体环境的流体动力学密度的第一性原理出发进行推导。该推导利用了根据流体物种数、总动量和能量的缓慢变化的粗粒化微观密度定义的含时投影算符技术。利用时间尺度论证简化了精确的运动方程,得到了雅努斯电机线速度和角速度的马尔可夫方程,其平均力和转矩依赖于流体密度。对于大胶体,流体方程被分离为体相和界面贡献,并确定了在胶体上的边界条件下,流体密度动力学可以由体相流体动力学方程精确表示的条件。我们展示了如何从分子描述中获得基于连续介质理论的边界条件结果,并给出了所有输运系数的格林 - 库博表达式,包括扩散电泳耦合和滑移系数。