Charge and spin transport in nanoscale junction from first principles

Recently nanoscale junctions consisting of 0-D nanostructures (single molecule) or 1-D nanostructures (semiconducting nanowire) sandwiched between two metal electrodes are successfully fabricated and characterized. What lacks in the recent developments is the understanding of the mechanism behind the observed phenomena at the level of atoms and electrons. For example, the origin of observed switching effect in a semiconducting nanowire due to the influence of an external gate bias is not yet understood at the electronic structure level. On the same context, different experimental groups have reported different signs in tunneling magneto-resistance for the same organic spin valve structure, which has baffled researchers working in this field. In this thesis, we present the answers to some of these subtle questions by investigating the charge and spin transport in different nanoscale junctions. A parameter-free, single particle Green’s function approach in conjunction with a posteriori density functional theory (DFT) involving a hybrid orbital dependent functional is used to calculate the tunneling current in the coherent transport limit. The effect of spin polarization is explicitly incorporated to investigate spin transport in a nanoscale junction. Through the electron transport studies in PbS nanowire junction, a new orbital controlled mechanism behind the switching of the current is proposed. It can explain the switching behavior, not only in PbS nanowire, but in other lead-chalcogenide nanowires as well. Beside this, the electronic structure properties of this nanowire are studied using periodic DFT. The quantum confinement effect was investigated by calculating the bandgap of PbS nanowires with different diameters. Subsequently, we explain an observed semiconducting to metallic phase transition of this nanowire by calculating the bandgap of the nanowire under uniform radial strain. The compressive radial strain on the nanowire was found to be responsible for the metallic to semiconducting phase transition. Apart from studying one dimensional nanostructure, we also present transport properties in zero dimensional single molecular junctions. We proposed a new codoping approach in a single molecular carborane junction, where a cation and an anion are simultaneously doped to find the role of a single atom in the device. The main purpose was to build a molecular junction where a single atom can dictate the flow of electrons in a circuit. Recent observations of both positive and negative sign in tunneling magnetoresistance (TMR) the using same organic spin-valve structure hasmystified researchers. From our spin dependent transport studies in a prototypical organic molecular tunneling device, we found that a 3% change in metal-molecule interfacial distance can alter the sign of TMR. Changing the interfacial distance by 3%, the number of participating eigenstates as well as their orbital characteristic changes for anti-parallel configuration of the magnetization at the two electrodes, leading to the sign reversal of the TMR. Apart from this, the magnetic proximity effect under applied bias is investigated quantitatively, which can be used to understand the observed unexpectedmagnetismin carbon basedmaterials when they are in close proximity with magnetic substrates.

Electronic properties of zig-zag carbon nanotubes : a first-principles study

Carbon nanotube (CNT) is a one dimensional (1-D) nanostructured material, which has been the focal point of research over the past decade for intriguing applications ranging from nanoelectronics to chemical and biological sensors. Using a first-principles gradient corrected density functional approach, we present a comprehensive study of the geometry and energy band gap in zig-zag semi-conducting (n,0) carbon nanotubes (CNT) to resolve some of the conflicting findings. Our calculations confirm that the single wall (n,0) CNTs fall into two distinct classes depending upon n mod 3 equal to 1 (smaller band gaps) or 2 (larger gaps). The effect of longitudinal strain on the band gap further confirms the existence of two distinct classes: for n mod 3 = 1 or 2, changing Eg by ~ ±110 meV for 1% strain in each case. We also present our findings for the origin of metallicity in multiwall CNTs.

Mechanisms contributing to the deep chlorophyll maximum in Lake Superior

The seasonal appearance of a deep chlorophyll maximum (DCM) in Lake Superior is a striking phenomenon that is widely observed; however its mechanisms of formation and maintenance are not well understood. As this phenomenon may be the reflection of an ecological driver, or a driver itself, a lack of understanding its driving forces limits the ability to accurately predict and manage changes in this ecosystem. Key mechanisms generally associated with DCM dynamics (i.e. ecological, physiological and physical phenomena) are examined individually and in concert to establish their role. First the prevailing paradigm, “the DCM is a great place to live”, is analyzed through an integration of the results of laboratory experiments and field measurements. The analysis indicates that growth at this depth is severely restricted and thus not able to explain the full magnitude of this phenomenon. Additional contributing mechanisms like photoadaptation, settling and grazing are reviewed with a one-dimensional mathematical model of chlorophyll and particulate organic carbon. Settling has the strongest impact on the formation and maintenance of the DCM, transporting biomass to the metalimnion and resulting in the accumulation of algae, i.e. a peak in the particulate organic carbon profile. Subsequently, shade adaptation becomes manifest as a chlorophyll maximum deeper in the water column where light conditions particularly favor the process. Shade adaptation mediates the magnitude, shape and vertical position of the chlorophyll peak. Growth at DCM depth shows only a marginal contribution, while grazing has an adverse effect on the extent of the DCM. The observed separation of the carbon biomass and chlorophyll maximum should caution scientists to equate the DCM with a large nutrient pool that is available to higher trophic levels. The ecological significance of the DCM should not be separated from the underlying carbon dynamics. When evaluated in its entirety, the DCM becomes the projected image of a structure that remains elusive to measure but represents the foundation of all higher trophic levels. These results also offer guidance in examine ecosystem perturbations such as climate change. For example, warming would be expected to prolong the period of thermal stratification, extending the late summer period of suboptimal (phosphorus-limited) growth and attendant transport of phytoplankton to the metalimnion. This reduction in epilimnetic algal production would decrease the supply of algae to the metalimnion, possibly reducing the supply of prey to the grazer community. This work demonstrates the value of modeling to challenge and advance our understanding of ecosystem dynamics, steps vital to reliable testing of management alternatives.

First-principles studies of boron nanostructures

Boron is an 'electron deficient' element which has a rather fascinating chemical versatility. In the solid state, the elemental boron has neither a pure covalent nor a pure metallic character. As a result, its vast structural dimensionally and peculiar bonding features hold a unique place among other elements in the periodic table. In order to understand and properly describe these unusual bonding features, a detailed and systematic theoretical study is needed. In this work, I will show that some of the qualitative features of boron nanostructures, including clusters, sheets and nanotubes can easily be extracted from the results of first principles calculations based on density functional theory. Specifically, the size-dependent evolution of topological structures and bonding characteristics of boron clusters, Bn will be discussed. Based on the scenario observed in the boron clusters, the unique properties of boron sheets and boron nanotubes will be described. Moreover, the ballistic electron transport in single-walled carbon nanotubes will be considered. It is expected that the theoretical results obtained in the present thesis will initiate further studies on boron nanostructures, which will be helpful in understanding, designing and realizing boron-based nanoscale devices.

Computational simulations of latent heat thermal energy storage systems - with innovative and first-principles based simulation for the underlying unsteady melting (and solidification) processes

This thesis develops an effective modeling and simulation procedure for a specific thermal energy storage system commonly used and recommended for various applications (such as an auxiliary energy storage system for solar heating based Rankine cycle power plant). This thermal energy storage system transfers heat from a hot fluid (termed as heat transfer fluid - HTF) flowing in a tube to the surrounding phase change material (PCM). Through unsteady melting or freezing process, the PCM absorbs or releases thermal energy in the form of latent heat. Both scientific and engineering information is obtained by the proposed first-principle based modeling and simulation procedure. On the scientific side, the approach accurately tracks the moving melt-front (modeled as a sharp liquid-solid interface) and provides all necessary information about the time-varying heat-flow rates, temperature profiles, stored thermal energy, etc. On the engineering side, the proposed approach is unique in its ability to accurately solve – both individually and collectively – all the conjugate unsteady heat transfer problems for each of the components of the thermal storage system. This yields critical system level information on the various time-varying effectiveness and efficiency parameters for the thermal storage system.

Maximum principle preserving high order schemes for convection-dominated diffusion equations

The maximum principle is an important property of solutions to PDE. Correspondingly, it's of great interest for people to design a high order numerical scheme solving PDE with this property maintained. In this thesis, our particular interest is solving convection-dominated diffusion equation. We first review a nonconventional maximum principle preserving(MPP) high order finite volume(FV) WENO scheme, and then propose a new parametrized MPP high order finite difference(FD) WENO framework, which is generalized from the one solving hyperbolic conservation laws. A formal analysis is presented to show that a third order finite difference scheme with this parametrized MPP flux limiters maintains the third order accuracy without extra CFL constraint when the low order monotone flux is chosen appropriately. Numerical tests in both one and two dimensional cases are performed on the simulation of the incompressible Navier-Stokes equations in vorticity stream-function formulation and several other problems to show the effectiveness of the proposed method.