Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Interaction of Metal Ions with 2'-Deoxyribonucleotides. Crystal and Molecular Structure of a Cobalt(l1) Complex with 2'-Deoxyinosine 5'-Monophosphate

The crystal structure of the cobalt( 11) complex with 2'-deoxyinosine 5'-monophosphate (5'- dlMP), [Co(5'-dlMP) (H,0),]-2H20, has been analysed by X-ray diffraction. The complex crystallizes in the space group P2,2,2, with a = 6.877(3), b = 10.904(2), c = 25.421 (6) A, and Z = 4. The structure was solved by the heavy-atom method and refined to an R value of 0.043 using 1 776 unique reflections. The cobalt ion binds only to the 6-oxopurine base of the nucleotide at the N(7) position, the octahedral co-ordination of the metal being completed by five water oxygens. The phosphate oxygens are involved in hydrogen bonding with the co-ordinated water molecules. The structure is closely similar to that of the corresponding ribonucleotide complex. The nucleotide has the energetically preferred conformation: an anti base, a C(3') -endo sugar pucker, and a gauche-gauche conformation about the C(4')-C( 5') bond. The significance of sugar puckering in the monomeric complexes of general formula [ M (5'-nucleotide) (H20),] is explained in terms of the structural requirements for metal-water-phosphate bridging interactions.

Preparation, Characterization And Properties Of C-60 And C-70 - Spectroscopy, Structure, Anions, Interaction With Electron-Donors And Superconductivity

Preparation and characterization of the fullerenes, C60 and C70, are described in detail, including the design of the generators fabricated locally. The characterization techniques employed are UV-visible, IR, Raman and C-13 NMR spectroscopies, scanning as well as transmission electron microscopy and mass spectrometry. The electron energy level diagram of C60 as well as the one-electron reductions of C60 and C70 leading to various anions are discussed. Electronic absorption spectra of C60- and C60(2-) are reported. Phase transitions from the plastic to the crystalline states of C60 and C70 are examined. Based on a C-13 NMR study in a mixture of nematic liquid crystals, it has been demonstrated that C60 retains its extraordinary symmetry in solution phase as well. Interaction of C60 and C70 with strong electron-donor molecules has been investigated employing cyclic voltammetry. Superconductivity of K(x)C60 has been studied by non-resonant microwave absorption; Na(x)C60 as well as K(c)C70 are shown to be non-superconducting. Doping C60 with iodine does not make it superconducting. Interaction of C60 with SbCl5 and liquid Br2 gives rise to halogenated products.

Solution nuclear magnetic resonance structure of the GATase subunit and structural Basis of the interaction between GATase and ATPPase subunits in a two-subunit-type GMPS from methanocaldococcus jannaschii

The solution structure of the monomeric glutamine amidotransferase (GATase) subunit of the Methanocaldococcus janaschii (Mj) guanosine monophosphate synthetase (GMPS) has been determined using high-resolution nuclear magnetic resonance methods. Gel filtration chromatography and N-15 backbone relaxation studies have shown that the Mj GATase subunit is present in solution as a 21 kDa (188-residue) monomer. The ensemble of 20 lowest-energy structures showed root-mean-square deviations of 0.35 +/- 0.06 angstrom for backbone atoms and 0.8 +/- 0.06 angstrom for all heavy atoms. Furthermore, 99.4% of the backbone dihedral angles are present in the allowed region of the Ramachandran map, indicating the stereochemical quality of the structure. The core of the tertiary structure of the GATase is composed of a seven-stranded mixed beta-sheet that is fenced by five alpha-helices. The Mj GATase is similar in structure to the Pyrococcus horikoshi (Ph) GATase subunit. Nuclear magnetic resonance (NMR) chemical shift perturbations and changes in line width were monitored to identify residues on GATase that were responsible for interaction with magnesium and the ATPPase subunit, respectively. These interaction studies showed that a common surface exists for the metal ion binding as well as for the protein-protein interaction. The dissociation constant for the GATase-Mg2+ interaction has been found to be similar to 1 mM, which implies that interaction is very weak and falls in the fast chemical exchange regime. The GATase-ATPPase interaction, on the other hand, falls in the intermediate chemical exchange regime on the NMR time scale. The implication of this interaction in terms of the regulation of the GATase activity of holo GMPS is discussed.

Synthesis, crystal structure, DNA interaction and cleavage activities of mononuclear and trinuclear copper(II) complexes

Mono- and trinuclear copper(II) complexes with 2-1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL) have been synthesized and structurally characterized. The mononuclear complex Cu(L)(H2O)(ONO2)] (1) crystallizes in monoclinic space group P2(1) /n with a square pyramidal Cu(II) center coordinated by the tridentate Schiff base (L) and a water ligand in the equatorial plane and an oxygen atom from nitrate in the axial position. The trinuclear complex (CuL)(3)(mu(3)-OH)](ClO4)(2)center dot H2O (2) crystallizes in hexagonal space group P6(3); all three copper atoms are five-coordinate with square pyramidal geometries. The interactions of these complexes with calf-thymus DNA have been investigated using absorption spectrophotometry. The mononuclear complex binds more strongly than the trinuclear complex. The DNA cleavage activity of these complexes has been studied on double-stranded pBR 322 plasmid DNA by gel electrophoresis experiments in the absence and in the presence of added oxidant (H2O2). The trinuclear complex cleaves DNA more efficiently than the mononuclear complex in the presence of H2O2.

Analytical Interaction of the Acoustic Wave and Turbulent Flame

A modified resonance model of a weakly turbulent flame in a high-frequency acoustic wave is derived analytically. Under the mechanism of Darrieus-Landau instability, the amplitude of flame wrinkles, which is as functions of the expansion coefficient and the perturbation wave number, increases greatly independent of the 'stationary' turbulence. The high perturbation wave number makes the resonance easier to be triggered but weakened with respect to the extra acoustic wave. In a closed burning chamber with the acoustic wave induced by the flame itself, the high perturbation wave number is to restrain the resonance for a realistic flame.

Combination Of Cfd And Csd Packages For Fluid-Structure Interaction

In this article the UDF script file in the Fluent software was rewritten as the "connecting file" for the Fluent and the ANSYS/ABAQUS in order that the joined file can be used to do aero-elastic computations. In this way the fluid field is computed by solving the Navier-Stokes equations and the structure movement is integrated by the dynamics directly. An analysis of the computed results shows that this coupled method designed for simulating aero-elastic systems is workable and can be used for the other fluid-structure interaction problems.

Numerical Analyses of Transonic Fluid/Structure interaction in Aircraft Engineering

Through the coupling between aerodynamic and structural governing equations, a fully implicit multiblock aeroelastic solver was developed for transonic fluid/stricture interaction. The Navier-Stokes fluid equations are solved based on LU-SGS (lower-upper symmetric Gauss-Seidel) Time-marching subiteration scheme and HLLEW (Harten-Lax-van Leer-Einfeldt-Wada) spacing discretization scheme and the same subiteration formulation is applied directly to the structural equations of motion in generalized coordinates. Transfinite interpolation (TFI) is used for the grid deformation of blocks neighboring the flexible surfaces. The infinite plate spline (IPS) and the principal of virtual work are utilized for the data transformation between fluid and structure. The developed code was fort validated through the comparison of experimental and computational results for the AGARD 445.6 standard aeroelastic wing. In the subsonic and transonic range, the calculated flutter speeds and frequencies agree well with experimental data, however, in the supersonic range, the present calculation overpredicts the experimental flutter points similar to other computations. Then the flutter character of a complete aircraft configuration is analyzed through the calculation of the change of structural stiffness. Finally, the phenomenon of aileron buzz is simulated for the weakened model of a supersonic transport wing/body model at Mach numbers of 0.98 and l.05. The calculated unsteady flow shows, on the upper surface, the shock wave becomes stronger as the aileron deflects downward, and the flow behaves just contrary on the lower surface of the wing. Corresponding to general theoretical analysis, the flow instability referred to as aileron buzz is induced by a stronger shock alternately moving on the upper and lower surfaces of wing. For the rigid structural model, the flow is stable at all calculated Mach numbers as observed in experiment

1. Ultrasonic studies of binary liquid structure in the critical region. Theory and experiment for the 2,6-lutidine/water system. 2. Hartree-Fock calculations of electric polarizabilities of some simple atoms and molecules, and their practicality. 3. Calculation of vibrational transition probabilities in collinear atom-diatom and diatom-diatom collisions with Lennard-Jones interaction

Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H₂, He, Li, Be, LiH, and N₂ by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H₂-H₂ collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

Effect of interaction between periodic delta-doping in both well and barrier layers on modulation of superlattice band structure

The modulation of superlattice band structure via periodic delta-doping in both well and barrier layers have been theoretically investigated, and the importance of interaction between the delta-function potentials in the well layers and those in the barrier layers on SL band structure have been revealed. It is pointed out that the energy dispersion relation Eq. (3) given in [G. Ihm, S.K. Noh, J.I. Lee, J.-S. Hwang, T.W. Kim, Phys. Rev. B 44 (1991) 6266] is an incomplete one, as the interaction between periodic delta-doping in both well and barrier layers had been overlooked. Finally, we have shown numerically that the electron states of a GaAs/Ga0.7Al0.3As superlattice can be altered more efficiently by intelligent tuning the two delta-doping's positions and heights. (c) 2007 Elsevier B.V. All rights reserved.

Interaction between vortices and impurities in a d-wave superconductor /

High temperature superconductors were discovered in 1986, but despite considerable research efforts, both experimental and theoretical, these materials remain poorly understood. Because their electronic structure is both inhomogeneous and highly correlated, a full understanding will require knowledge of quasiparticle properties both in real space and momentum space. In this thesis, we will present a theoretical analysis of the scanning tunneling microscopy (STM) data in BSCCO. We introduce the Bogoliubov-De Gennes Hamiltonian and solve it numerically on a two-dimensional 20 x 20 lattice under a magnetic field perpendicular to the surface. We consider a vortex at the center of our model. We introduce a Zn impurity in our lattice as a microscopic probe of the physical properties of BSCCO. By direct numerical diagonalization of the lattice BogoliubovDe Gennes Hamiltonian for different positions of the impurity, we can calculate the interaction between the vortex and the impurity in a d-wave superconductor.

An Informatics Technical Note on Interaction of DNA - Graphene Chemical Sensor System as Reaction-Diffusion Wave-Based Computing System in Ionised Gaseous environments and their Applications Using Theoretical Studies and Scientific Computation Overview

The physics of plasmas encompasses basic problems from the universe and has assured us of promises in diverse applications to be implemented in a wider range of scientific and engineering domains, linked to most of the evolved and evolving fundamental problems. Substantial part of this domain could be described by R–D mechanisms involving two or more species (reaction–diffusion mechanisms). These could further account for the simultaneous non-linear effects of heating, diffusion and other related losses. We mention here that in laboratory scale experiments, a suitable combination of these processes is of vital importance and very much decisive to investigate and compute the net behaviour of plasmas under consideration. Plasmas are being used in the revolution of information processing, so we considered in this technical note a simple framework to discuss and pave the way for better formalisms and Informatics, dealing with diverse domains of science and technologies. The challenging and fascinating aspects of plasma physics is that it requires a great deal of insight in formulating the relevant design problems, which in turn require ingenuity and flexibility in choosing a particular set of mathematical (and/or experimental) tools to implement them.