title: Time scale separation leads to position-dependent diffusion along a slow coordinate.
abstract: When there is a separation of time scales, an effective description of the dynamics of the slow variables can be obtained by adiabatic elimination of fast ones. For example, for anisotropic Langevin dynamics in two dimensions, the conventional procedure leads to a Langevin equation for the slow coordinate that involves the potential of the mean force. The friction constant along this coordinate remains unchanged. Here, we show that a more accurate, but still Markovian, description of the slow dynamics can be obtained by using position-dependent friction that is related to the time integral of the autocorrelation function of the difference between the actual force and the mean force by a Kirkwood-like formula. The result is generalized to many dimensions, where the slow or reaction coordinate is an arbitrary function of the Cartesian coordinates. When the fast variables are effectively one-dimensional, the additional friction along the slow coordinate can be expressed in closed form for an arbitrary potential. For a cylindrically symmetric channel of varying cross section with winding centerline, our analytical expression immediately yields the multidimensional version of the Zwanzig-Bradley formula for the position-dependent diffusion coefficient.
authors.affiliation: Mathematical and Statistical Computing Laboratory, Division of Computational Bioscience, Center for Information Technology, National Institutes of Health, Bethesda, Maryland 20892, USA. david.tew@bristol.ac.uk
authors.forename: Alexander
authors.initials: A
authors.lastname: Berezhkovskii
authors.forename: Attila
authors.initials: A
authors.lastname: Szabo
mesh_terms: D004058:Diffusion; D007700:Kinetics; D008956:Models, Chemical; D013997:Time Factors