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Confined counterions surrounding a Macroion : a field theoretic approach

Thesis (PhD)--Stellenbosch University, 2011.

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Main Author: Boonzaaier, Leandro
Other Authors: Muller-Nedebock, Kristian K.
Format: Thesis
Language:en_ZA
Published: Stellenbosch : Stellenbosch University 2011
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access_status_str Open Access
author Boonzaaier, Leandro
author2 Muller-Nedebock, Kristian K.
author_browse Boonzaaier, Leandro
Muller-Nedebock, Kristian K.
author_facet Muller-Nedebock, Kristian K.
Boonzaaier, Leandro
author_sort Boonzaaier, Leandro
collection Thesis
dc_rights_str_mv Stellenbosch University
description Thesis (PhD)--Stellenbosch University, 2011.
format Thesis
id oai:scholar.sun.ac.za:10019.1/17853
institution Stellenbosch University (South Africa)
language en_ZA
last_indexed 2026-06-10T12:41:29.531Z
license_str Other — see source repository
provenance_str_mv Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository
publishDate 2011
publishDateRange 2011
publishDateSort 2011
publisher Stellenbosch : Stellenbosch University
publisherStr Stellenbosch : Stellenbosch University
record_format dspace
source_str SUNScholar — Stellenbosch University Repository
spelling oai:scholar.sun.ac.za:10019.1/17853 Confined counterions surrounding a Macroion : a field theoretic approach Boonzaaier, Leandro Muller-Nedebock, Kristian K. Scholtz, Frederik G. Stellenbosch University. Faculty of Science. Dept. of Physics. Macroions Electrolytes Field theory Dissertations -- Physics Theses -- Physics Macro-ions Counterions Charged classical systems Thesis (PhD)--Stellenbosch University, 2011. ENGLISH ABSTRACT: Several experiments [1, 2, 3, 4] have shown that e ective attractive interactions exist between con ned like-charged macromolecules. Theoretical approaches have not reached consensus as to precisely what the mechanism for the attraction is, but it is agreed that comprehending the role of the counterion arrangement around macromolecules is crucial for understanding the e ective macromolecule interactions. It is generally assumed that attraction only occurs in the limit of strong electrostatic coupling and is driven by correlation e ects that are neglible in a mean- eld approach, which is valid in the weak-coupling limit. However, in some experimental situations attraction occurs even in the limit of weak-coupling. We consider a eld-theoretic approach that includes uctuations to study the Coulomb interactions of con ned counterions with a single exible charged spherical macromolecule that can expand or collapse uniformly by changing its radius. We show how the linearised eld-theory (valid in the weak-coupling limit) is mapped onto the square-well potential of Quantum Mechanics. The con nement leads to bound states being present in the spectrum at all times. Bound states are non-perturbative and we investigate the role they play in the physics of the system. Some of the e ects are rather counter-intuitive. Firstly, upon expanding the macromolecule in a xed con nement volume, the uctuation part of the free energy favours a decrease in the free energy. Secondly, upon increasing the temperature to high but nite values, the uctuation contribution does not dominate the free energy as would be expected. The mathematical origins of these e ects are dicussed in detail and as part of the analysis we introduce a novel regularisation scheme for computing the functional determinant arising in the model considered where the cut-o is speci ed unambiguously in terms of physical parameters. AFRIKAANSE OPSOMMING: Verskeie eksperimente [1, 2, 3, 4] toon dat makro-ione met gelyksoortige ladings, in `n eindige volume, `n e ektiewe aantrekkende krag ondervind. Alhoewel daar nog geen konsensus oor die presiese meganisme vir die aantrekking bereik is nie, is dit duidelik dat die rol van \counter-ion" rangskikking rondom die makro-ione belangrik is om die e ektiewe wisselwerkings te verstaan. Dit word algemeen aanvaar dat die aantrekkende krag slegs in die limiet van sterk elektrostatiese koppeling plaasvind en dat dit `n gevolg van \counter-ion" korrelasies is wat weglaatbaar is in `n gemiddelde veld benadering, wat geldig is in die limiet van swak elektrostatiese koppeling. Daar bestaan egter eksperimentele situasies waar die aantrekking in die limiet van swak elektrostatiese koppeling waargeneem word. Ons bestudeer die Coulomb wisselwerking tussen \counter-ions" en `n enkele rekbare sferiese makro-ioon vanuit `n veld-teoretiese beskouing wat uktuasies in ag neem. Die sferiese makro-ioon kan vergroot of verklein deur sy radius uniform te verander. Ons toon aan dat die gelineariseerde veldeteorie (geldig in die limiet van swak elektrostatiese koppeling) op die eindige-diepte put Kwantummeganiese model afgebeeld kan word. Die eindige volume van die sisteem het tot gevolg dat daar altyd gebonde toestande in die spektrum voorkom. Gebonde toestande is `n suiwer nie-steuringsteoretiese e ek en ons ondersoek die rol wat dit speel in die sika van die sisteem. Die teenwoordigheid van die gebonde toestande in die spektrum het `n paar teen-intuitiewe e ekte tot gevolg. Eerstens word die vrye energie verlaag soos die makro-ioon in `n eindige volume vergroot. Tweedens oorheers die uktuasie bydrae nie die vrye energie met toenemende temperatuur soos verwag sou word nie. Ons bespreek die wiskundige oorsprong van hierdie e ekte. As deel van die analise ontwikkel ons `n nuwe regulariseringstegniek vir die berekening van funksionaalintegrale waar die regulariseringsparameter ondubbelsinnig in terme van siese hoeveelhede uitgedruk kan word. Doctoral 2011-11-22T10:36:38Z 2011-12-05T13:05:01Z 2011-11-22T10:36:38Z 2011-12-05T13:05:01Z 2011-12 Thesis http://hdl.handle.net/10019.1/17853 en_ZA Stellenbosch University 57 p. application/pdf Stellenbosch : Stellenbosch University
spellingShingle Macroions
Electrolytes
Field theory
Dissertations -- Physics
Theses -- Physics
Macro-ions
Counterions
Charged classical systems
Boonzaaier, Leandro
Confined counterions surrounding a Macroion : a field theoretic approach
title Confined counterions surrounding a Macroion : a field theoretic approach
title_full Confined counterions surrounding a Macroion : a field theoretic approach
title_fullStr Confined counterions surrounding a Macroion : a field theoretic approach
title_full_unstemmed Confined counterions surrounding a Macroion : a field theoretic approach
title_short Confined counterions surrounding a Macroion : a field theoretic approach
title_sort confined counterions surrounding a macroion a field theoretic approach
topic Macroions
Electrolytes
Field theory
Dissertations -- Physics
Theses -- Physics
Macro-ions
Counterions
Charged classical systems
url http://hdl.handle.net/10019.1/17853
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