Rism Methodology and Its Application to Orientational Correlations and to Excess Electrons in Liquids
Richardson, Diane Mary
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/77311
Description
Title
Rism Methodology and Its Application to Orientational Correlations and to Excess Electrons in Liquids
Author(s)
Richardson, Diane Mary
Issue Date
1985
Department of Study
Chemical Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Physical
Language
eng
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.
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
