论文标题

离散的离子随机连续体过度阻尼溶剂算法,用于对电解质进行建模

A Discrete Ion Stochastic Continuum Overdamped Solvent Algorithm for Modeling Electrolytes

论文作者

Ladiges, Daniel R., Carney, Sean P., Nonaka, Andrew, Klymko, Katherine, Moore, Guy C., Garcia, Alejandro L., Natesh, Sachin R., Donev, Aleksandar, Bell, John B.

论文摘要

在本文中,我们开发了一种用于强力电解质的中尺度模拟的方法。该方法是波动浸入边界(FIB)方法的扩展,该方法将溶质视为与Eulerian流体动力学和静电场相互作用的离散拉格朗日颗粒。在这两种情况下,佩斯金浸没的边界(IB)方法均用于颗粒磁场耦合。流体动力相互作用被认为是过度阻尼的,使用波动的Stokes方程进行了热噪声,包括“干燥扩散”的布朗尼运动,以说明溶剂的粗粒模型无法解决的尺度。远程静电相互作用是通过求解泊松方程来计算的,其中包括使用新型的经典粒子粒子粒子网(P3M)技术的新型浸入式结合变体的校正。还包括基于几周的Chandler-Andersen(WCA)潜力的短距离排斥力。通过与Deby-h {ü} Ckel理论进行比较,可以验证新方法的离子对相关函数,而Debye-H {ü} CKEL-HONSAGER理论用于电导率,包括对强电场的WEIN效应。在每种情况下,都会观察到良好的一致性,前提是通过流体网格解决典型离子离子分离处的流体动力相互作用。

In this paper we develop a methodology for the mesoscale simulation of strong electrolytes. The methodology is an extension of the Fluctuating Immersed Boundary (FIB) approach that treats a solute as discrete Lagrangian particles that interact with Eulerian hydrodynamic and electrostatic fields. In both cases the Immersed Boundary (IB) method of Peskin is used for particle-field coupling. Hydrodynamic interactions are taken to be overdamped, with thermal noise incorporated using the fluctuating Stokes equation, including a "dry diffusion" Brownian motion to account for scales not resolved by the coarse-grained model of the solvent. Long range electrostatic interactions are computed by solving the Poisson equation, with short range corrections included using a novel immersed-boundary variant of the classical Particle-Particle Particle-Mesh (P3M) technique. Also included is a short range repulsive force based on the Weeks-Chandler-Andersen (WCA) potential. The new methodology is validated by comparison to Debye-H{ü}ckel theory for ion-ion pair correlation functions, and Debye-H{ü}ckel-Onsager theory for conductivity, including the Wein effect for strong electric fields. In each case good agreement is observed, provided that hydrodynamic interactions at the typical ion-ion separation are resolved by the fluid grid.

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