TY - JOUR

T1 - Structural and thermodynamic properties of a multicomponent freely jointed hard sphere multi-Yukawa chain fluid

AU - Kalyuzhnyi, Yurij V.

AU - McCabe, Clare

AU - Cummings, Peter T.

AU - Stell, George

N1 - Funding Information:
Y.V.K. was supported by UT-Batelle through research funds provided by Oak Ridge National Laboratory under the Distinguished Scientist program. Oak Ridge National Laboratory is a multiprogram science and technology laboratory managed for the US Department of Energy by UT-Battelle. P.T.C. and C.M.C. were supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy, under Grant FG05-94ER1442 1 to the University of Tennessee. G.S. was supported by the same Division of Chemical Sciences under Grant FG02-88ER13850 at the State University of New York at Stony Brook. The computations were carried out on machines part of the Scalable Intra-campus Research Grid (SInRG) Project at the University of Tennessee supported by the National Science Foundation CISE Research Infrastructure Award EIA-9972889.

PY - 2002

Y1 - 2002

N2 - The product-reactant Ornstein-Zernike approach, represented by the polymer mean-spherical approximation (PMSA), is utilized to describe the structure and thermodynamic properties of the fluid of Yukawa hard sphere chain molecules. An analytical solution of the PMSA for the most general case of the multicomponent freely jointed hard sphere multi-Yukawa chain fluid is presented. As in the case of the regular MSA for the hard sphere Yukawa fluid, the problem is reduced to the solution of a set of nonlinear algebraic equations in the general case, and to a single equation in the case of the factorizable Yukawa potential coefficients. Closed form analytical expressions are presented for the contact values of the monomer-monomer radial distribution function, structure factors, internal energy, Helmholtz free energy, chemical potentials and pressure in terms of the quantities, which follows directly from the PMSA solution. By way of illustration, several different versions of the hard sphere Yukawa chain model are considered, represented by one-Yukawa chains of length m, where m = 2, 4, 8, 16. To validate the accuracy of the present theory, Monte Carlo simulations were carried out and the results are compared systematically with the theoretical results for the structure and thermodynamic properties of the system at hand. In general it is found that the theory performs very well, thus providing an analytical route to the equilibrium properties of a well defined model for chain fluids.

AB - The product-reactant Ornstein-Zernike approach, represented by the polymer mean-spherical approximation (PMSA), is utilized to describe the structure and thermodynamic properties of the fluid of Yukawa hard sphere chain molecules. An analytical solution of the PMSA for the most general case of the multicomponent freely jointed hard sphere multi-Yukawa chain fluid is presented. As in the case of the regular MSA for the hard sphere Yukawa fluid, the problem is reduced to the solution of a set of nonlinear algebraic equations in the general case, and to a single equation in the case of the factorizable Yukawa potential coefficients. Closed form analytical expressions are presented for the contact values of the monomer-monomer radial distribution function, structure factors, internal energy, Helmholtz free energy, chemical potentials and pressure in terms of the quantities, which follows directly from the PMSA solution. By way of illustration, several different versions of the hard sphere Yukawa chain model are considered, represented by one-Yukawa chains of length m, where m = 2, 4, 8, 16. To validate the accuracy of the present theory, Monte Carlo simulations were carried out and the results are compared systematically with the theoretical results for the structure and thermodynamic properties of the system at hand. In general it is found that the theory performs very well, thus providing an analytical route to the equilibrium properties of a well defined model for chain fluids.

UR - http://www.scopus.com/inward/record.url?scp=0037055926&partnerID=8YFLogxK

U2 - 10.1080/00268970210130245

DO - 10.1080/00268970210130245

M3 - Article

AN - SCOPUS:0037055926

SN - 0026-8976

VL - 100

SP - 2499

EP - 2517

JO - Molecular Physics

JF - Molecular Physics

IS - 15

ER -