Model energy landscapes

被引:40
作者
Debenedetti, PG [1 ]
Stillinger, FH
Shell, MS
机构
[1] Princeton Univ, Dept Chem Engn, Princeton, NJ 08544 USA
[2] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
关键词
D O I
10.1021/jp030885b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The multidimensional potential-energy "landscape" formalism offers useful insights into the properties of supercooled liquids and glasses. However, its mathematical fundamentals present formidable subtlety and complexity. In the interests of developing a useful approximation for the statistical mechanics of landscapes, we have developed a simple family of models describing the energy-depth distribution of landscape basins. Our analysis begins with the "Gaussian" model that has been advocated in the recent literature, a physically appealing and thermodynamically rather accurate description that straightforwardly predicts a positive-temperature ideal glass transition. Careful enumeration of low-lying basins reveals however that the Gaussian model requires modification in the form of a logarithmic correction. Consequently, we have carried out algebraic and numerical analyses of a logarithmically modified Gaussian model, including depth dependence of the mean intrabasin vibrational free energy. The logarithmic modification has the effect of eliminating the positive-temperature ideal glass transition of the precursor pure-Gaussian model. Nevertheless, it is sufficiently similar to that unmodified model at and above any kinetic glass transition temperature to be able to represent measurable calorimetric data with reasonable accuracy.
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页码:14434 / 14442
页数:9
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