Thesis (Ph. D.)--University of Chicago, Department of Chemistry, 2002. / Includes bibliographical references. Also available on the Internet.

Thesis (M. Phil.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 64-67). Also available in print.

Thesis (M. Phil.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 64-67). Also available online.

published_or_final_version / Physics / Master / Master of Philosophy

In this work, we develop a many-body theory of electronic transport through single molecule junctions based on nonequilibrium Green’s functions (NEGFs). The central quantity of this theory is the Coulomb self-energy matrix of the junction ∑(C). ∑(C) is evaluated exactly in the sequential-tunneling limit, and the correction due to finite lead-molecule tunneling is evaluated using a conserving approximation based on diagrammatic perturbation theory on the Keldysh contour. In this way, tunneling processes are included to infinite order, meaning that any approximation utilized is a truncation in the physical processes considered rather than in the order of those processes. Our theory reproduces the key features of both the Coulomb blockade and coherent transport regimes simultaneously in a single unified theory. Nonperturbative effects of intramolecular correlations are included, which are necessary to accurately describe the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, essential for a quantitative theory of transport. This work covers four major topics related to transport in single-molecule junctions. First, we use our many-body theory to calculate the nonlinear electrical response of the archetypal Au-1,4-benzenedithiol-Au junction and find irregularly shaped ‘molecular diamonds’ which have been experimentally observed in some larger molecules but which are inaccessible to existing theoretical approaches. Next, we extend our theory to include heat transport and develop an exact expression for the heat current in an interacting nanostructure. Using this result, we discover that quantum coherence can strongly enhance the thermoelectric response of a device, a result with a number of technological applications. We then develop the formalism to include multi-orbital lead-molecule contacts and multi-channel leads, both of which strongly affect the observable transport. Lastly, we include a dynamic screening correction to ∑(C) and investigate the optoelectric response of several molecular junctions.

No description available.

Making spintronic devices is a hot topic for future technical development. In this work the non-equilibrium dynamics of a single spin in a tunnel junction is analyzed and numerically simulated. This is done in order to understand the dynamics of e.g. a magnetic molecule between two metal contacts for future spintronic devices. The work starts with looking at the system in a many-body theory picture in order to derive the interesting properties of the system. An initial solution for the system is analytically calculated as well as for the dynamic case. The dynamic has then been numerically simulated in order to get the time evolution of the system. The results showed that the dynamics of the molecular spin induced a spin dependent charge and spin currents in the system and that the currents could be used to control the molecular spin. It showed qualitatively how different parameters, for example coupling strength, effect the system and what to consider when designing a system similar to this.

This thesis presents the theoretical studies of electronic transport in molecular electronic devices. Such devices have been proposed and investigated as a promising new approach that complements conventional silicon-based electronics. To design and fabricate future nanoelectronic devices, it is essential to understand the conduction mechanism at a molecular or atomic level. Our approach is based on the non-equilibrium Green's function method (NEGF) combined with density functional theory (DFT). We apply the method to study the electronic transport properties of two-probe systems consisting of molecules or atomic wires sandwiched between leads. A few molecular electronic devices are characterized; namely, conducting molecular wires, molecular switches and molecular recognition sensors. The considered applications are interconnection of different nanoelectronic units with cumulene molecular wires; adding switching functionality to the molecular connectors by applying stress to the CNT-cumulene-CNT junction or by introducing phthalocyanine unit; sensing of individual nucleotides, e.g., for DNA sequencing applications. The obtained results provide useful insights into the electron transport properties of molecules. Several interesting and significant features are analyzed and explained in particular such as, level pinning, negative differential resistance, interfering of conducting channels etc.

This thesis begins with a review on the topic of molecular electronics. The purpose of this review is to motivate the need for good theory to understand and predict molecular electronics behaviour. At present the most promising theoretical formalism for dealing with this problem is a combination of density functional theory and nonequilibrium Green's functions (NEGF-DFT). This formalism is especially attractive because it is an ab-initio technique, meaning that it is completely from first principles and does not require any empirical parameters. An implementation of this formalism has been developed by the research group of Hong Guo and is presented and explained here. A few other implementations which are similar but differ in some ways are also discussed briefly to highlight their various advantages and disadvantages. / One of the difficulties of ab-initio calculations is that they can be extremely costly in terms of the computing time and memory that they require. For this reason, in addition to using appropriate approximations, sophisticated numerical analysis tech niques need to be used. One of the bottlenecks in the NEGF-DFT method is solving the Poisson equation on a large real space grid. For studying systems incorporating a gate voltage it is required to be able to solve this problem with nonperiodic boundary conditions. In order to do this a technique called multigrid is used. This thesis examines the multigrid technique and develops an efficient implementation for the purpose of use in the NEGF-DFT formalism. For large systems, where it is necessary to use especially large real space grids, it is desirable to run simulations on parallel computing clusters to handle the memory requirements and make the code run faster. For this reason a parallel implementation of multigrid is developed and tested for performance. The multigrid tool is incorporated into the NEGF-DFT formalism and tested to ensure that it is properly implemented. A few calculations are made on a benzenedithiol system with gold leads to show the effect of an applied gate voltage.

Research into molecular electronics has exploded in recent years due to a proliferation of new and exciting techniques for producing atomic level structures (e-beam lithography, self-assembled monolayers, etc.); coupling these techniques with the ability to accurately manipulate atomic systems (such as with Scanning Tunneling Microscopes (STM), Atomic Force Microscopes (AFM), or Mechanically Controllable Break Junctions (MCBJ)) opens the possibility to create novel quantum coherent devices for both engineering applications, as well as research into fundamental physics. Along these lines, presented here is a series of experiments on superconducting point contacts which were aimed at understanding the dynamics of coupling superconducting effects to the mechanical degrees of freedom of a nanowire. In addition, another series of experiments presented here explore the nature of charge transport at high biases in superconducting point contacts. Specifically, an investigation of point contacts at high voltage biases revealed a suppression of one component of the total current, which is explained through a phenomenological model.