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Dipolar Liquids and Their Mixtures: Equilibrium and Nonequilibrium Properties with Field-Theoretic Approaches

Citation

Zhuang, Bilin (2017) Dipolar Liquids and Their Mixtures: Equilibrium and Nonequilibrium Properties with Field-Theoretic Approaches. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9VQ30QR. http://resolver.caltech.edu/CaltechTHESIS:06042017-233656614

Abstract

Liquid is a state of matter that is intermediate between the gas state and the solid state. Though it is an ordinary state of matter, the application of statistical mechanics for understanding its properties is far from complete. Compared to the solid state, the liquid state has molecules that can move around freely, and yet, unlike that in the gas state, the intermolecular correlations are significant in the liquid state. Therefore, the distance dependent correlations in a liquid need to be taken into account to properly describe a liquid. In particular, all molecules are polarizable. The polarizable nature allows the molecules to induce polarization in surrounding molecules, giving rise to van der Waals interactions that have important consequences on the properties of a liquid. In addition to polarizability, many molecules are intrinsically polar. The long-ranged dipole-dipole correlations contribute to the complexity of interactions and lead to a myriad of interesting properties special to a liquid.

In recent years, field-theoretic technique has emerged as a convenient and systematic tool for deriving coarse-grained theories for a wide range of complex-fluid and soft-matter systems while preserving the essential physics. In this thesis, we present the application of field-theoretic approaches to two problems of liquids and their mixtures. The first problem is to describe the dielectric properties of an ordinary liquid or liquid mixture under equilibrium condition, where current field-theoretic methods are inadequate. In this problem, we apply a variational field-theoretic approach to develop a statistical field theory of the liquid, and predict the dielectric constant and the miscibility of liquids using the variational free energies derived. The second problem involves the nonequilibrium solvent composition and orientational polarization surrounding some charged solute in the context of electron transfer reactions. Using a self-consistent-field theory with constrained coarse-grained fields, we derive expressions for the nonequilibrium solvation energy, and apply it to compute the reorganization energy of electron transfer reactions. The theories presented in this thesis lead to simple analytical expressions for the equilibrium and the nonequilibrium free energies, making it possible to theoretically survey a wide range of liquids. In addition, our models involve only a few readily-available molecular parameters and avoid the use of any adjustable parameters, allowing one to make a priori predictions on the properties of liquids and their mixtures.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Field-theoretic methods, charge solvation, nonequilibrium solvation, dielectric properties, liquids, liquid mixtures
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Wang, Zhen-Gang
Thesis Committee:
  • Tirrell, David A. (chair)
  • Wang, Zhen-Gang
  • Miller, Thomas F.
  • Marcus, Rudolph A.
Defense Date:23 May 2016
Funders:
Funding AgencyGrant Number
Agency for Science, Technology and Research, SingaporeUNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Record Number:CaltechTHESIS:06042017-233656614
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:06042017-233656614
DOI:10.7907/Z9VQ30QR
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.4936586DOIArticle adapted for ch. 4
http://dx.doi.org/10.1021/acs.jpcb.6b03295DOIArticle adapted for ch. 5
ORCID:
AuthorORCID
Zhuang, Bilin0000-0003-2934-4264
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10270
Collection:CaltechTHESIS
Deposited By: Bilin Zhuang
Deposited On:05 Jun 2017 23:49
Last Modified:12 Jun 2017 21:05

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