Mass-Dependent Solvent Friction of a Hydrophobic Molecule

Abstract

We show by molecular dynamics simulations that the friction constant of a freely diffusing methane molecule in explicit water increases with the methane mass by a factor of up to 1.8 in the infinite mass limit compared to the massless limit. This effect is rationalized by the mass dependence of the friction memory kernel which is extracted from the simulation data by mapping on the generalized Langevin equation. On the basis of the mass-dependent memory kernels, we obtain perfect agreement between simulation results and analytic predictions for both mean-square displacements and force autocorrelation functions. The memory kernels, which account for methane interactions with the solvent, decay significantly slower with increasing methane mass. The mass-dependent friction is correlated with the mean escape time of water molecules from the first hydration shell, which increases monotonically with the methane mass by a factor of 3 over the mass range considered. Our proposed scaling expression allows the direct prediction of diffusion constants for stable methane isotopes, which will help to better understand bacterial methane isotope fractionation. Our scaling analysis suggests that mass-dependent friction will be relevant also for larger solutes in sufficiently viscous solvents.