Entropic barriers, activated hopping, and the glass transition in colloidal suspensions

@article{citeulike:1836801, abstract = {A microscopic kinetic description of single-particle transient localization and activated transport in glassy fluids is developed which combines elements of idealized mode-coupling theory, density functional theory, and activated rate theory. Thermal fluctuations are included via a random force which destroys the idealized glass transition and restores ergodicity through activated barrier hopping. The approach is predictive, containing no adjustable parameters or postulated underlying dynamic or thermodynamic divergences. Detailed application to hard-sphere colloidal suspensions reveals good agreement with experiment for the location of the kinetic glass transition volume fraction, the dynamic incoherent scattering relaxation time, apparent localization length, and length scale of maximum nongaussian behavior. Multiple connections are predicted between thermodynamics, short-time dynamics in the nearly localized state, and long-time relaxation by entropic barrier crossing. A critical comparison of the fluid volume fraction dependence of the hopping time with fit formulas which contain ideal divergences has been performed. Application of the derivative Stickel analysis suggests that the fit functions do not provide an accurate description over a wide range of volume fractions. Generalization to treat the kinetic vitrification of more complex colloidal and nanoparticle suspensions, and thermal glass-forming liquids, is possible. \©2003 American Institute of Physics.}, author = {Schweizer, Kenneth S. and Saltzman, Erica J. }, citeulike-article-id = {1836801}, doi = {http://dx.doi.org/10.1063/1.1578632}, journal = {The Journal of Chemical Physics}, keywords = {glass, schweizer, theory}, number = {2}, pages = {1181--1196}, posted-at = {2008-03-01 22:52:21}, priority = {2}, publisher = {AIP}, title = {Entropic barriers, activated hopping, and the glass transition in colloidal suspensions}, url = {http://dx.doi.org/10.1063/1.1578632}, volume = {119}, year = {2003} }

TY - JOUR ID - citeulike:1836801 L3 - citeulike-article-id:1836801 TI - Entropic barriers, activated hopping, and the glass transition in colloidal suspensions JF - The Journal of Chemical Physics VL - 119 IS - 2 SP - 1181 EP - 1196 PB - AIP N2 - A microscopic kinetic description of single-particle transient localization and activated transport in glassy fluids is developed which combines elements of idealized mode-coupling theory, density functional theory, and activated rate theory. Thermal fluctuations are included via a random force which destroys the idealized glass transition and restores ergodicity through activated barrier hopping. The approach is predictive, containing no adjustable parameters or postulated underlying dynamic or thermodynamic divergences. Detailed application to hard-sphere colloidal suspensions reveals good agreement with experiment for the location of the kinetic glass transition volume fraction, the dynamic incoherent scattering relaxation time, apparent localization length, and length scale of maximum nongaussian behavior. Multiple connections are predicted between thermodynamics, short-time dynamics in the nearly localized state, and long-time relaxation by entropic barrier crossing. A critical comparison of the fluid volume fraction dependence of the hopping time with fit formulas which contain ideal divergences has been performed. Application of the derivative Stickel analysis suggests that the fit functions do not provide an accurate description over a wide range of volume fractions. Generalization to treat the kinetic vitrification of more complex colloidal and nanoparticle suspensions, and thermal glass-forming liquids, is possible. ©2003 American Institute of Physics. KW - glass KW - schweizer KW - theory AU - Schweizer, Kenneth AU - Saltzman, Erica PY - 2003/// UR - http://dx.doi.org/10.1063/1.1578632 ER -