title: Necessity of capillary modes in a minimal model of nanoscale hydrophobic solvation.
abstract: Modern theories of the hydrophobic effect highlight its dependence on length scale, emphasizing the importance of interfaces in the vicinity of sizable hydrophobes. We recently showed that a faithful treatment of such nanoscale interfaces requires careful attention to the statistics of capillary waves, with significant quantitative implications for the calculation of solvation thermodynamics. Here, we show that a coarse-grained lattice model like that of Chandler [Chandler D (2005)Nature437(7059):640-647], when informed by this understanding, can capture a broad range of hydrophobic behaviors with striking accuracy. Specifically, we calculate probability distributions for microscopic density fluctuations that agree very well with results of atomistic simulations, even many SDs from the mean and even for probe volumes in highly heterogeneous environments. This accuracy is achieved without adjustment of free parameters, because the model is fully specified by well-known properties of liquid water. As examples of its utility, we compute the free-energy profile for a solute crossing the air-water interface, as well as the thermodynamic cost of evacuating the space between extended nanoscale surfaces. These calculations suggest that a highly reduced model for aqueous solvation can enable efficient multiscale modeling of spatial organization driven by hydrophobic and interfacial forces.
authors.affiliation: Department of Chemistry, The University of Chicago, Chicago, IL 60637; svaikunt@uchicago.edu.
authors.forename: Suriyanarayanan
authors.initials: S
authors.lastname: Vaikuntanathan
authors.affiliation: Biophysics Graduate Group, University of California, Berkeley, CA 94720;
authors.forename: Grant
authors.initials: G
authors.lastname: Rotskoff
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720.
authors.forename: Alexander
authors.initials: A
authors.lastname: Hudson
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720.
authors.forename: Phillip L
authors.initials: PL
authors.lastname: Geissler
mesh_terms: D057927:Hydrophobic and Hydrophilic Interactions; D008956:Models, Chemical; D013816:Thermodynamics
keywords: coarse-grained model; hydrophobic effect; lattice models; self-assembly