Abstract
This thesis is concerned with theoretical studies of aqueous solutions and biomolecular systems. Part of the present work is to understand equilibrium solvent and solute properties, while the other part is to study processes that occur in these solutions. Three points were focused: (a) the study of structure and dynamics of 1M aqueous NaCl electrolyte solution at a molecular level, which revealed particular features of these solutions such as the formation of large clusters; (b) the development of a new simulation algorithm for the Reverse Monte Carlo technique aimed to study aqueous solutions and disordered systems. Results for spherical molecules and liquid water are presented; (c) the study of binding small ions to macromolecules (proteins and micelles). The TanfordKirkwood model is critically analysed for models of biomolecules by means of Monte Carlo calculations. Anomalous behaviour found for the binding of ions to macromolecules in the presence of highly charged macroparticles is also reported. And, a titration study is performed to characterize interfacial properties of a prototropic molecule in selfassembled surfactant aggregates.
The core of our discussion is based on electrostatic interactions and statistical mechanics. The studied systems were modeled by effective Hamiltonians within the BornOppenheimer and McMillanMayer model levels. These Hamiltonians were solved by computer simulations (Monte Carlo and Molecular Dynamics), and, in some cases, also by solving the PoissonBoltzmann equation. Dielectric continuum models are largely used, and a discussion of uniform and nonuniform cases for studies with biomolecules and micellar systems is also included.
The core of our discussion is based on electrostatic interactions and statistical mechanics. The studied systems were modeled by effective Hamiltonians within the BornOppenheimer and McMillanMayer model levels. These Hamiltonians were solved by computer simulations (Monte Carlo and Molecular Dynamics), and, in some cases, also by solving the PoissonBoltzmann equation. Dielectric continuum models are largely used, and a discussion of uniform and nonuniform cases for studies with biomolecules and micellar systems is also included.
Original language  English 

Qualification  Doctor 
Awarding Institution 

Supervisors/Advisors 

Award date  2000 Jan 14 
Publisher  
ISBN (Print)  9162839039 
Publication status  Published  1999 
Bibliographical note
Defence detailsDate: 20000114
Time: 10:15
Place: room G, Chemical Center, Sölvegatan 39, Lund, Sweden
External reviewer(s)
Name: Berendsen, Herman J. C.
Title: Prof
Affiliation: [unknown]

Article: A new algorithm for Reverse Monte Carlo simulationsF. L. B. da Silva, B. Svensson, T. Åkesson and B. JönssonThe Journal of Chemical Physics 109, 26242629, 1998
Article: Application of a new Reverse Monte Carlo method to polyatomic molecules. 1. Liquid water caseF. L. B. da Silva, L. Degrève, W. OlivaresRivas and T. ÅkessonSubmitted for publication.
Article: Structure of concentrated aqueous NaCl solution: a Monte Carlo studyL. Degrève and F. L. B. da SilvaThe Journal of Chemical Physics 110, 30703078, 1999.
Article: Large ionic clusters in concentrated aqueous NaCl solutionL. Degrève and F. L. B. da SilvaThe Journal of Chemical Physics 111, 51505156, 1999.
Article: A critical investigation of the TanfordKirkwood scheme by means of Monte Carlo simulationsF. L. B. da Silva, B. Jönsson and R. PenfoldSubmitted for publication.
Article: Titration of fatty acids solubilized in cationic, nonionic and anionic micelles. Theory and experimentF. L. B. da Silva, D. Bogren, O. Söderman and B. JönssonSubmitted for publication.
Article: The binding of charged ligands to macromolecules. Anomalous salt dependenceF. L. B. da Silva, S. Linse and B. JönssonSubmitted for publication.
The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
Subject classification (UKÄ)
 Theoretical Chemistry
Keywords
 highly charged macromolecules
 dielectric discontinuity
 dissociation constant
 TanfordKirkwood model
 protein mutation
 electrostatic interactions
 chemical potential
 titration
 biomolecules
 computer simulations
 radial distribution function
 electrolyte solutions
 continuum model.
 Theoretical chemistry
 quantum chemistry
 Teoretisk kemi
 kvantkemi