Gaussian field theory for the Brownian motion of a solvated particle

TL;DR

This paper introduces a Gaussian field theory approach to derive Brownian motion of a solvated particle, providing explicit formulas for diffusion coefficients based on solvent velocity fluctuations and boundary conditions.

Contribution

It presents a novel derivation of Brownian motion using Gaussian action functionals, focusing on solvent velocity fluctuations and boundary conditions instead of fluctuating forces.

Findings

Derived explicit expressions for solvent mean flow and velocity correlations.

Reproduced Brownian motion probability distribution from solvent fluctuations.

Calculated translational and rotational diffusion coefficients for spherical particles.

Abstract

An alternative derivation of Brownian motion is presented. Instead of supplementing the linearized Navier-Stokes equation with a fluctuating force, we directly assume a Gaussian action functional for solvent velocity fluctuations. Solvating a particle amounts to expelling the solvent and prescribing a boundary condition to the solvent on the interface that is shared with the solute. We study the dynamical effects of this boundary condition on the solvent and derive explicit expressions for the solvent mean flow and velocity correlations. Moreover, we show that the probability to observe solvent velocity fluctuations that are compatible with the boundary condition reproduces random Brownian motion of the solvated particle. We explicitly calculate the translational and rotational diffusion coefficients of a spherical particle using the presented formalism.