The Kauzmann paradox interpreted via the theory of frustration-limited-domains

被引:40
作者
Kivelson, D [1 ]
Tarjus, G
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[2] Univ Paris 06, Phys Theor Liquides Lab, F-75252 Paris 05, France
关键词
D O I
10.1063/1.477166
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 entropy, S-liq(T), Of many supercooled liquids decreases strongly and the structural relaxation time increases dramatically as the temperature T is lowered below the melting point, T-m. Below the glass transition temperature, T-g, the system relaxes too slowly for supercooled liquids to equilibrate in the experimental times; however, if the data above T-g are extrapolated to lower T, one finds that the extrapolated S-liq(T)-->S-xtal(T) as T-->T-K, S-xtal(T) being the entropy of the crystal. This phenomenon is known as the "Kauzmann paradox." If the extrapolation is extended below T-K, it may be that the extrapolated S-liq(T)-->0 as T-->T-Kc>0; we call this apparent violation of the third law, the ''Kauzmann catastrophe." We discuss these phenomena, as well as the general problem of the entropy of supercooled liquids, in terms of the theory of frustration-limited domains. The apparent vanishing of [S-liq(T)- S-xtal(T)] and the apparent violation of the third law that results from extrapolation to rs below T-g are consistent with extension of the scaling result predicted by the theory to inappropriately low Ts. (C) 1998 American institute of Physics. [S0021-9606(98)50437-0].
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页码:5481 / 5486
页数:6
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