The relationship between fragility, configurational entropy and the potential energy landscape of glass forming liquids

Abstract

Glass is a microscopically disordered, solid form of matter that results when a fluid is cooled or compressed in such a fashion that it does not crystallise. Almost all types of materials are capable of glass formation -- polymers, metal alloys, and molten salts, to name a few. Given such diversity, organising principles which systematise data concerning glass formation are invaluable. One such principle is the classification of glass formers according to their fragility\cite{fragility}. Fragility measures the rapidity with which a liquid's properties such as viscosity change as the glassy state is approached. Although the relationship between features of the energy landscape of a glass former, its configurational entropy and fragility have been analysed previously (e. g.,\cite{speedyfr}), an understanding of the origins of fragility in these features is far from being well established. Results for a model liquid, whose fragility depends on its bulk density, are presented in this letter. Analysis of the relationship between fragility and quantitative measures of the energy landscape (the complicated dependence of energy on configuration) reveal that the fragility depends on changes in the vibrational properties of individual energy basins, in addition to the total number of such basins present, and their spread in energy. A thermodynamic expression for fragility is derived, which is in quantitative agreement with {\it kinetic} fragilities obtained from the liquid's diffusivity.