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Title:Rism Methodology and Its Application to Orientational Correlations and to Excess Electrons in Liquids
Author(s):Richardson, Diane Mary
Department / Program:Chemical Engineering
Discipline:Chemical Engineering
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Physical
Abstract:A theory is presented for the orientational pair correlation factor, g(,2), of a molecular liquid in the interaction site picture. It is based on the so-called proper integral equation theory of molecular fluids and leads to a cluster series expansion for g(,2). A topological reduction which removes the bare Mayer f-bonds in favor of the appropriate pair correlation bonds is performed on this exact series.
The theory is applied to a hard sphere model of CS(,2). The lowest-order terms in a molecular ordering scheme are evaluated exactly by numerical integration. The results agree well with experiment and computer simulation for 192K < T < 298K.
Next a simple model for an electron in a nonpolar solvent is discussed. This problem can be shown to be isomorphic with that of a polymer molecule in solution in the discretized path integral representation. A self-consistent theory for the electron's chemical potential is described in terms of solvent-induced interactions between sites on the isomorphic polymer. Calculation of the equilibrium structural and thermodynamic properties of the electron requires evaluation of non-Gaussian path integrals. These are performed using Feynman's polaron approximation.
For a model hard sphere system characterized by the hard sphere diameter, (sigma), and at a temperature for which the electron's thermal wavelength (lamda)(,e) = 6, a localization transition is found at the reduced density (rho)(sigma)('3) (DBLTURN) .3. The transition is sharper at lower temperatures. Calculations of the electron's correlation length, chemical potential, imaginary time response function, and of the electron-solvent pair correlation function are presented for a variety of temperatures and solvent densities.
Issue Date:1985
Description:88 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985.
Other Identifier(s):(UMI)AAI8521869
Date Available in IDEALS:2015-05-13
Date Deposited:1985

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