No Arabic abstract
Brownian motion with coordinate dependent damping and diffusivity is ubiquitous. Understanding equilibrium of a Brownian particle with coordinate dependent diffusion and damping is a contentious area. In this paper, we present an alternative approach based on already established methods to this problem. We solve for the equilibrium distribution of the over-damped dynamics using Kramers-Moyal expansion. We compare this with the over-damped limit of the generalized Maxwell-Boltzmann distribution. We show that the equipartition of energy helps recover the Stokes-Einstein relation at constant diffusivity and damping of the homogeneous space. However, we also show that, there exists no homogeneous limit of coordinate dependent diffusivity and damping with respect to the applicability of Stokes-Einstein relation when it does not hold locally. In the other scenario where the Stokes-Einstein relation holds locally, one needs to impose a restriction on the local maximum velocity of the Brownian particle to make the modified Maxwell-Boltzmann distribution coincide with the modified Boltzmann distribution in the over-damped limit.
We generalize to higher spatial dimensions the Stokes--Einstein relation (SER) and the leading correction to diffusivity in periodic systems, and validate them using numerical simulations. Using these results, we investigate the evolution of the SER violation with dimension in simple hard sphere glass formers. The analysis suggests that the SER violation disappears around dimension d=8, above which SER is not violated. The critical exponent associated to the violation appears to evolve linearly in 8-d below d=8, as predicted by Biroli and Bouchaud [J. Phys.: Cond. Mat. 19, 205101 (2007)], but the linear coefficient is not consistent with their prediction. The SER violation evolution with d establishes a new benchmark for theory, and a complete description remains an open problem.
The Stokes-Einstein relation (SER) is one of the most robust and widely employed results from the theory of liquids. Yet sizable deviations can be observed for self-solvation, which cannot be explained by the standard hydrodynamic derivation. Here, we revisit the work of Masters and Madden [J. Chem. Phys. 74, 2450-2459 (1981)], who first solved a statistical mechanics model of the SER using the projection operator formalism. By generalizing their analysis to all spatial dimensions and to partially structured solvents, we identify a potential microscopic origin of some of these deviations. We also reproduce the SER-like result from the exact dynamics of infinite-dimensional fluids.
We present Monte Carlo simulation results on the equilibrium relaxation of the two dimensional lattice Coulomb gas with fractional charges, which exhibits a close analogy to the primary relaxation of fragile supercooled liquids. Single particle and collective relaxation dynamics show that the Stokes-Einstein relation is violated at low temperatures, which can be characterized by a fractional power law relation between the self-diffusion coefficient and the characteristic relaxation time. The microscopic spatially heterogeneous structure responsible for the violation is identified.
Protein conformational fluctuations are highly complex and exhibit long-term correlations. Here, molecular dynamics simulations of small proteins demonstrate that these conformational fluctuations directly affect the proteins instantaneous diffusivity $D_I$. We find that the radius of gyration $R_g$ of the proteins exhibits $1/f$ fluctuations, that are synchronous with the fluctuations of $D_I$. Our analysis demonstrates the validity of the local Stokes-Einstein type relation $D_Ipropto1/(R_g + R_0)$, where $R_0sim0.3$ nm is assumed to be a hydration layer around the protein. From the analysis of different protein types with both strong and weak conformational fluctuations the validity of the Stokes-Einstein type relation appears to be a general property.
The effect of a change of noise amplitudes in overdamped diffusive systems is linked to their unperturbed behavior by means of a nonequilibrium fluctuation-response relation. This formula holds also for systems with state-independent nontrivial diffusivity matrices, as we show with an application to an experiment of two trapped and hydrodynamically coupled colloids, one of which is subject to an external random forcing that mimics an effective temperature. The nonequilibrium susceptibility of the energy to a variation of this driving is an example of our formulation, which improves an earlier version, as it does not depend on the time-discretization of the stochastic dynamics. This scheme holds for generic systems with additive noise and can be easily implemented numerically, thanks to matrix operations.