Broadband molecular dynamics simulation of fluid inertial effects in confined Brownian motion

Abstract

Hydrodynamic memory governs Brownian motion over a broad range of timescales, from acoustic wave propagation at short times to diffusive relaxation at long times. While confinement-induced corrections to Brownian diffusion are well established, how confinement modifies the full hydrodynamic response remains less explored. In this Letter, we use molecular-dynamics simulations of a neutrally buoyant colloidal particle in an explicit solvent to resolve the velocity autocorrelation function across a broad hydrodynamic spectrum. In the bulk, the simulations recover compressibility, added mass, the hydrodynamic long-time tail, and Stokes-Einstein diffusion without adjustable parameters. Near a rigid wall, the velocity correlations become anisotropic, their algebraic tails are modified, and the diffusion coefficients are reduced. Most importantly, the short-time dynamics reveals a pronounced enhancement of the effective added mass as the wall is approached. As such, the velocity autocorrelation function appears as a central quantity to bridge the zero-frequency mobility and the high-frequency inertial behaviour of a confined Brownian particle.