Statistical mechanical theory of liquid entropy
The multiparticle correlation expansion for the entropy of a classical monatomic liquid is presented. This entropy expresses the physical picture in which there is no free particle motion, but rather, each atom moves within a cage formed by its neighbors. The liquid expansion, including only pair correlations, gives an excellent account of the experimental entropy of most liquid metals, of liquid argon, and the hard sphere liquid. The pair correlation entropy is well approximated by a universal function of temperature. Higher order correlation entropy, due to n-particle irreducible correlations for n{ge}3, is significant in only a few liquid metals, and its occurrence suggests the presence of n-body forces. When the liquid theory is applied to the study of melting, the author discovers the important classification of normal and anomalous melting, according to whether there is not or is a significant change in the electronic structure upon melting, and he discovers the universal disordering entropy for melting of a monatomic crystal. Interesting directions for future research are: extension to include orientational correlations of molecules, theoretical calculation of the entropy of water, application to the entropy of the amorphous state, and correlational entropy of compressed argon. The author clarifies the relation among different entropy expansions in the recent literature.
- Research Organization:
- Los Alamos National Lab., NM (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 10167088
- Report Number(s):
- LA-UR-93-2390; CONF-930680-1; ON: DE93016524; TRN: 93:015520
- Resource Relation:
- Conference: 1. congress of the International Society for Theoretical Chemistry and Physics,Gerona (Spain),28 Jun - 3 Jul 1993; Other Information: PBD: [1993]
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
GENERAL PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
ENTROPY
STATISTICAL MECHANICS
LIQUID METALS
CORRELATIONS
ELECTRONIC STRUCTURE
MELTING
THERMODYNAMIC PROPERTIES
SERIES EXPANSION
THERMODYNAMIC MODEL
TEMPERATURE DEPENDENCE
661300
400200
360104
OTHER ASPECTS OF PHYSICAL SCIENCE
INORGANIC, ORGANIC, AND PHYSICAL CHEMISTRY
PHYSICAL PROPERTIES