Alexandria Digital Research Library

Primitive Model Simulations and Mean-Field Studies of Electric Double Layers

Author:
Giera, Brian
Degree Supervisor:
Todd M. Squires and M. Scott Shell
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2014
Issued Date:
2014
Topics:
Engineering, Chemical
Keywords:
Mean-Field Theory
Dissertation
Theory
Molecular Dynamics
Primitive Model
Electric Double Layer
Genres:
Online resources and Dissertations, Academic
Degree Grantor:
University of California, Santa Barbara. Chemical Engineering
Dissertation:
Ph.D.--University of California, Santa Barbara, 2014
Description:

When a charged surface, such as an electrode, colloid, or protein, is submerged into an electrolyte or ionic liquid, ions within the fluid rearrange into electric double layers (EDLs) that electrostatically screen the interfacial charge. The electrostatic potential and ion distributions within EDLs have long been described by mean-field local-density approximations (LDAs) that assume flat electrodes, uncorrelated ions, and bulk forms for the chemical potential. The objective of this work is to elucidate LDA failure mechanisms and supplement or supplant mean-field treatments of electrochemical systems that fail to capture correlated behavior. We develop an exceedingly general method, which requires no a priori model and identifies whether EDLs in a given electrolyte can obey a LDA, or whether more advanced approaches (e.g. integro-differential equations, atomistic simulations, etc.) are required, irrespective of the source of LDA breakdown. We combine continuum-level theoretical studies with complementary simulations in order to critically assess the accuracy of LDA models of implicit solvent electrolytes with equal and differently sized ions. We also pose a novel LDA model that seeks to address solvation, polarizability, and finite-size interactions present in actual and simulated EDLs with explicit solvent.

Physical Description:
1 online resource (140 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3765cgr
ISBN:
9781321201864
Catalog System Number:
990045115820203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Brian Giera
File Description
Access: Public access
Giera_ucsb_0035D_12145.pdf pdf (Portable Document Format)