Vibrational nonequilibrium effects in the conductance of single-molecules with multiple electronic states

Vibrational nonequilibrium effects in charge transport through single-molecule junctions are investigated. Focusing on molecular bridges with multiple electronic states, it is shown that electronic-vibrational coupling triggers a variety of vibronic emission and absorption processes, which influence the conductance properties and mechanical stability of single-molecule junctions profoundly. Employing a master equation and a nonequilibrium Green's function approach, these processes are analyzed in detail for a generic model of a molecular junction and for benzenedibutanethiolate bound to gold electrodes.Comment: 5 pages, 4 figure

Vibrational Instabilities in Resonant Electron Transport through Single-Molecule Junctions

We analyze various limits of vibrationally coupled resonant electron transport in single-molecule junctions. Based on a master equation approach, we discuss analytic and numerical results for junctions under a high bias voltage or weak electronic-vibrational coupling. It is shown that in these limits the vibrational excitation of the molecular bridge increases indefinitely, i.e. the junction exhibits a vibrational instability. Moreover, our analysis provides analytic results for the vibrational distribution function and reveals that these vibrational instabilities are related to electron-hole pair creation processes.Comment: 19 pages, 3 figure

Quantum Interference and Decoherence in Single-Molecule Junctions: How Vibrations Induce Electrical Current

Quantum interference effects and decoherence mechanisms in single-molecule junctions are analyzed employing a nonequilibrium Green's function approach. Electrons tunneling through quasi-degenerate states of a nanoscale molecular junction exhibit interference effects. We show that electronic-vibrational coupling, inherent to any molecular junction, strongly quenches such interference effects. As a result, the electrical current can be significantly larger than without electronic-vibrational coupling. The analysis reveals that the quenching of quantum interference is particularly pronounced if the junction is vibrationally highly excited, e.g. due to current-induced nonequilibrium effects in the resonant transport regime.Comment: 11 pages, 4 figure

Switching the Conductance of a Molecular Junction using a Proton Transfer Reaction

A novel mechanism for switching a molecular junction based on a proton transfer reaction triggered by an external electrostatic field is proposed. As a specific example to demonstrate the feasibility of the mechanism, the tautomers [2,5-(4-hydroxypyridine)] and {2,5-[4(1H)-pyridone]} are considered. Employing a combination of first-principles electronic structure calculations and Landauer transport theory, we show that both tautomers exhibit very different conductance properties and realize the "on" and "off" states of a molecular switch. Moreover, we provide a proof of principle that both forms can be reversibly converted into each other using an external electrostatic field.Comment: 14 pages, 5 figure

The use of the Continuously Regenerating Trap (CRT^TM) and SCRT^TM Systems to meet future emissions legislation

The progressive tightening of particulate matter (PM) legislation presents challenges to the engine development and aftertreatment communities. The Continuously Regenerating Trap (CRTTM) has been developed to enable diesel engines to meet the proposed future legislation. This passive filter system combines an oxidation catalyst with a Diesel Particulate Filter (DPF); the filter traps the PM and the oxidation catalyst generates NO2 which combusts the trapped PM at substantially lower temperatures than is possible using oxygen. This paper outlines the operating principle of the CRTTM, and describes the performance of the system. It has been shown that the very high PM conversions obtained with the CRTTM can enable even Euro 1 engines to meet the PM limits proposed for introduction in Europe in 2005. In addition, the system removes PM across the whole particle size range, including ultrafine particulates. These results will be discussed, as will in-field durability studies which have shown that the system is still capable of converting 90% of PM after very high mileage operation (up to 600,000 km). In addition to requiring very high PM conversion, the proposed future legislation requires substantial reductions in NOx emissions form heavy duty diesel vehicles. To meet these challenges the SCRTTM has been developed. This combines the CRTTM with SCR (Selective Catalytic Reduction) technology, and enables very high simultaneous conversions of CO, HC, PM and NOx to be achieved. The SCRTTM system is described, and its operating characteristics are discussed. It has been shown that the SCRTTM can potentially meet the legislative limits proposed for introduction in Europe in 2008

Resonant vibrations, peak broadening and noise in single molecule contacts: beyond the resonant tunnelling picture

We carry out experiments on single-molecule junctions at low temperatures, using the mechanically controlled break junction technique. Analyzing the results received with more than ten different molecules the nature of the first peak in the differential conductance spectra is elucidated. We observe an electronic transition with a vibronic fine structure, which is most frequently smeared out and forms a broad peak. In the usual parameter range we find strong indications that additionally fluctuations become active even at low temperatures. We conclude that the electrical field feeds instabilities, which are triggered by the onset of current. This is underscored by noise measurements that show strong anomalies at the onset of charge transport