Reference interaction site model theory of polymeric liquids: Self-consistent formulation and nonideality effects in dense solutions and melts

Journal Article · Sat Feb 15 00:00:00 EST 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.461965· OSTI ID:7205812

Schweizer, K S ^[1]; Honnell, K G; Curro, J G ^[2]

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1. Departments of Materials Science Engineering and Chemistry, University of Illinois, Urbana, Illinois 61801 (United States)
2. Sandia National Laboratories, Albuquerque, New Mexico 87185 (United States)

The reference interaction site model (RISM) integral-equation approach to polymeric liquids is generalized to allow a self-consistent determination of single-chain and intermolecular pair correlations. Nonlinear medium-induced effects on intrachain statistics are described at the level of self-consistent pair interactions. Tractable schemes to implement the self-consistency aspect are formulated for semiflexible and rotational isomeric state chain models, and applied numerically to concentrated solutions and melts of semiflexible polymers. Theoretical results are in good agreement with off-lattice molecular dynamics simulations, and a rich dependence of the renormalized persistence length on temperature, aspect ratio, density, and degree of polymerization is found. The general formalism for polymer alloys is sketched and the potentially important role of local density and concentration fluctuations as nonuniversal mechanisms for inducing conformational perturbations is emphasized. A detailed analysis is made of the connections between the polymer RISM integral-equation theory and the field theoretic psuedopotential formalism, and remarkable similarities in the predictions of the two distinct approaches for solutions of long thread-like polymers are demonstrated.

• DOE Contract Number: AC04-76DP00789
• OSTI ID: 7205812
• Journal Information: Journal of Chemical Physics; (United States), Vol. 96:4; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
36 MATERIALS SCIENCE
LIQUIDS
NONLINEAR PROBLEMS
POLYMERS
ASPECT RATIO
CHAINS
CONFORMATIONAL CHANGES
CORRELATION FUNCTIONS
COUPLING
DENSITY
INTEGRAL EQUATIONS
INTERMOLECULAR FORCES
POLYMERIZATION
TEMPERATURE DEPENDENCE
CHEMICAL REACTIONS
EQUATIONS
FLUIDS
FUNCTIONS
PHYSICAL PROPERTIES
665000* - Physics of Condensed Matter- (1992-)
360606 - Other Materials- Physical Properties- (1992-)