title: Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition.
abstract: In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: K
authors.initials: K
authors.lastname: Koperwas
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: A
authors.initials: A
authors.lastname: Grzybowski
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: K
authors.initials: K
authors.lastname: Grzybowska
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: Z
authors.initials: Z
authors.lastname: Wojnarowska
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: M
authors.initials: M
authors.lastname: Paluch