Fluids with highly directional attractive forces. III. Multiple attraction sites

Journal Article · Sat Feb 01 04:00:00 EST 1986 · J. Stat. Phys.; (United States)

DOI:https://doi.org/10.1007/BF01127721· OSTI ID:6845533

Wertheim, M S

The authors derive a reformulation of statistical thermodynamics for fluids of molecules which interact by highly directional attraction. The molecular model consists of a repulsive core and several sites of very short-ranged attraction. The authors explore the relationship between graph cancellation in the fugacity expansion and three types of steric incompatibility between repulsive and attractive interactions involving several molecules. The steric effects are used to best advantage in a limited regrouping of bonds. This controls the density parameters which appear when articulation points are eliminated in the graphical representation. Each density parameter is a singlet density for a species consisting of molecules with a specified set of sites bonded. The densities satisfy subsidiary conditions of internal consistency. These conditions are equivalent to a minimization of the Helmholtz free energy A. Graphical expressions for A and for the pressure are derived. Analogs of the s-particle direct correlation functions and of the Ornstein-Zernike equation are found.

• Research Organization: Rutgers Univ., New Brunswick, NJ
• OSTI ID: 6845533
• Journal Information: J. Stat. Phys.; (United States), Journal Name: J. Stat. Phys.; (United States) Vol. 42:3; ISSN JSTPB
• Country of Publication: United States
• Language: English

Related Subjects

640400* -- Fluid Physics
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
BINDING ENERGY
BOLTZMANN STATISTICS
CHEMICAL BONDS
CLASSICAL MECHANICS
CORRELATION FUNCTIONS
DISTANCE
ENERGY
FLUIDS
FREE ENERGY
FUNCTIONS
INTERACTION RANGE
INTERMOLECULAR FORCES
IRREDUCIBLE REPRESENTATIONS
MATHEMATICAL MODELS
MATHEMATICS
MECHANICS
MOLECULAR MODELS
PHYSICAL PROPERTIES
STATISTICAL MECHANICS
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TOPOLOGY