Supramolecular Organization of Metal Nanoparticles in Solution and of Phenyleneethynylenes on Surfaces

Most of the procedures reported for the synthesis of metal nanoparticles involve the use of strong reducing agents or elevated temperatures. This limits the possibility of developing metal nanoparticle based sensors for the in situ detection of analytes. One of the objectives of the present investigations is to (i) develop newer methodologies for the synthesis of metal nanoparticles in aqueous medium at ambient conditions and (ii) their use in the detection of metal cations by taking advantage of the unique coordination ability. Ideally, biocompatible molecules which possess both the reducing and stabilizing groups are desirable for such applications. Formation of stable supramolecular assembly, by bringing metal nanoparticles close to each other, results in plasmon coupling and this strategy can be effectively utilized for the development of metal nanoparticle based sensors.Another objective of the present study is to understand the supramolecular organization of molecules on surfaces. Various noncovalent interactions between the molecules and with surface play a decisive role in their organizations. An in-depth understanding of these interactions is essential for device fabrications. Recent photophysical studies have revealed that phenyleneethynylene based molecular systems are ideal for device application. The second objective of the thesis focuses on understanding the (i) organization of phenyleneethynylenes on highly oriented pyrolytic graphite (HOPG) surface with atomic level precision and (ii) weak intermolecular interactions which drive their organization.

Cadmium Selenide Based Core-Shell Quantum Dots for Biosensing and Imaging Applications

The overall focus of the thesis involves the synthesis and characterization of CdSe QDs overcoated with shell materials for various biological and chemical sensing applications. Second chapter deals with the synthesis and characterization of CdSe and CdSe/ZnS core shell QDs. The primary attention of this work is to develop a simple method based on photoinduced charge transfer to optimize the shell thickness. Synthesis of water soluble CdSe QDs, their cytotoxicity analysis and investigation of nonlinear optical properties form the subject of third chapter. Final chapter deals with development of QD based sensor systems for the selective detection of biologically and environmentally important analytes from aqueous media.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Current-density-functional approach to large quantum dots in intense magnetic fields

Within current-density-functional theory, we have studied a quantum dot made of 210 electrons confined in a disk geometry. The ground state of this large dot exhibits some features as a function of the magnetic field (Beta) that can be attributed in a clear way to the formation of compressible and incompressible states of the system. The orbital and spin angular momenta, the total energy, ionization and electron chemical potentials of the ground state, as well as the frequencies of far-infrared edge modes are calculated as a function of Beta, and compared with available experimental and theoretical results.

Structure and far-infrared edge modes of quantum antidots at zero magnetic field

We have investigated edge modes of different multipolarity sustained by quantum antidots at zero magnetic field. The ground state of the antidot is described within a local-density-functional formalism. Two sum rules, which are exact within this formalism, have been derived and used to evaluate the energy of edge collective modes as a function of the surface density and the size of the antidot.

Quantum cavitation in liquid helium

Using a functional-integral approach, we have determined the temperature below which cavitation in liquid helium is driven by thermally assisted quantum tunneling. For both helium isotopes, we have obtained the crossover temperature in the whole range of allowed negative pressures. Our results are compatible with recent experimental results on 4He.

Systematics of properties of the electron gas in deep-etched quantum wires

An efficient method is developed for an iterative solution of the Poisson and Schro¿dinger equations, which allows systematic studies of the properties of the electron gas in linear deep-etched quantum wires. A much simpler two-dimensional (2D) approximation is developed that accurately reproduces the results of the 3D calculations. A 2D Thomas-Fermi approximation is then derived, and shown to give a good account of average properties. Further, we prove that an analytic form due to Shikin et al. is a good approximation to the electron density given by the self-consistent methods.

Spin and density longitudinal response of quantum dots in the time-dependent local-spin-density approximation

The longitudinal dipole response of a quantum dot has been calculated in the far-infrared regime using local-spin-density-functional theory. We have studied the coupling between the collective spin and density modes as a function of the magnetic field. We have found that the spin dipole mode and single-particle excitations have a sizable overlap, and that the magnetoplasmon modes can be excited by the dipole spin operator if the dot is spin polarized. The frequency of the dipole spin edge mode presents an oscillation which is clearly filling factor (v) related. We have found that the spin dipole mode is especially soft for even-n values. Results for selected numbers of electrons and confining potentials are discussed.

Transverse dipole spin modes in quantum dots

We have carried out a systematic analysis of the transverse dipole spin response of a large-size quantum dot within time-dependent current density functional theory. Results for magnetic fields corresponding to integer filling factors are reported, as well as a comparison with the longitudinal dipole spin response. As in the two-dimensional electron gas, the spin response at high-spin magnetization is dominated by a low-energy transverse mode.

Density-functional calculations of magnetoplasmons in quantum rings

We have studied the structure and dipole charge-density response of nanorings as a function of the magnetic field using local-spin-density-functional theory. Two small rings consisting of 12 and 22 electrons confined by a positively charged background are used to represent the cases of narrow and wide rings. The results are qualitatively compared with experimental data existing on microrings and on antidots. A smaller ring containing five electrons is also analyzed to allow for a closer comparison with a recent experiment on a two-electron quantum ring.

Wave-vector dependence of spin and density multipole excitations in quantum dots

We have employed time-dependent local-spin density-functional theory to analyze the multipole spin and charge density excitations in GaAs-AlxGa1-xAs quantum dots. The on-plane transferred momentum degree of freedom has been taken into account, and the wave-vector dependence of the excitations is discussed. In agreement with previous experiments, we have found that the energies of these modes do not depend on the transferred wave vector, although their intensities do. Comparison with a recent resonant Raman scattering experiment [C. Schüller et al., Phys. Rev. Lett. 80, 2673 (1998)] is made. This allows us to identify the angular momentum of several of the observed modes as well as to reproduce their energies

Multiple edges of a quantum Hall system in a strong electric

In this paper we show that if the electrons in a quantum Hall sample are subjected to a constant electric field in the plane of the material, comparable in magnitude to the background magnetic field on the system of electrons, a multiplicity of edge states localized at different regions of space is produced in the sample. The actions governing the dynamics of these edge states are obtained starting from the well-known Schrödinger field theory for a system of nonrelativistic electrons, where on top of the constant background electric and magnetic fields, the electrons are further subject to slowly varying weak electromagnetic fields. In the regions between the edges, dubbed as the "bulk," the fermions can be integrated out entirely and the dynamics expressed in terms of a local effective action involving the slowly varying electromagnetic potentials. It is further shown how the bulk action is gauge noninvariant in a particular way, and how the edge states conspire to restore the U(1) electromagnetic gauge invariance of the system. In the edge action we obtain a heretofore unnoticed gauge-invariant term that depends on the particular edge. We argue that this term may be detected experimentally as different edges respond differently to a monochromatic probe due to this term

Quantum wire with periodic serial structure

Electron wave motion in a quantum wire with periodic structure is treated by direct solution of the Schrödinger equation as a mode-matching problem. Our method is particularly useful for a wire consisting of several distinct units, where the total transfer matrix for wave propagation is just the product of those for its basic units. It is generally applicable to any linearly connected serial device, and it can be implemented on a small computer. The one-dimensional mesoscopic crystal recently considered by Ulloa, Castaño, and Kirczenow [Phys. Rev. B 41, 12 350 (1990)] is discussed with our method, and is shown to be a strictly one-dimensional problem. Electron motion in the multiple-stub T-shaped potential well considered by Sols et al. [J. Appl. Phys. 66, 3892 (1989)] is also treated. A structure combining features of both of these is investigated

Model of single-electron decay from a strongly isolated quantum dot

Recent measurements of electron escape from a nonequilibrium charged quantum dot are interpreted within a two-dimensional (2D) separable model. The confining potential is derived from 3D self-consistent Poisson-Thomas-Fermi calculations. It is found that the sequence of decay lifetimes provides a sensitive test of the confining potential and its dependence on electron occupation