Theoretical Principles of Single-Molecule Electronics: A Chemical and Mesoscopic View

Physics – Condensed Matter – Mesoscale and Nanoscale Physics

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To appear in International Journal of Quantum Chemistry, Special Issue in memory of J.A. Pople. 13 pages, 9 figures

Scientific paper

Exploring the use of individual molecules as active components in electronic devices has been at the forefront of nanoelectronics research in recent years. Compared to semiconductor microelectronics, modeling transport in single-molecule devices is much more difficult due to the necessity of including the effects of the device electronic structure and the interface to the external contacts at the microscopic level. Theoretical formulation of the problem therefore requires integrating the knowledge base in surface science, electronic structure theory, quantum transport and device modeling into a single unified framework starting from the first-principles. In this paper, we introduce the theoretical framework for modeling single-molecule electronics and present a simple conceptual picture for interpreting the results of numerical computation. We model the device using a self-consistent matrix Green's function method that combines Non-Equilibrium Green's function theory of quantum transport with atomic-scale description of the device electronic structure. We view the single-molecule device as "heterostructures" composed of chemically well-defined atomic groups, and analyze the device characteristics in terms of the charge and potential response of these atomic groups to perturbation induced by the metal-molecule coupling and the applied bias voltage. We demonstrate the power of this approach using as examples devices formed by attaching benzene-based molecules of different size and internal structure to the gold electrodes through sulfur end atoms.

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