Numerically exact, time-dependent treatment of vibrationally coupled electron transport in single-molecule junctions

The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) theory within second quantization representation of the Fock space, a novel numerically exact methodology to treat many-body quantum dynamics for systems containing identical particles, is applied to study the effect of vibrational motion on electron transport in a generic model for single-molecule junctions. The results demonstrate the importance of electronic-vibrational coupling for the transport characteristics. For situations where the energy of the bridge state is located close to the Fermi energy, the simulations show the time-dependent formation of a polaron state that results in a pronounced suppression of the current corresponding to the phenomenon of phonon blockade. We show that this phenomenon cannot be explained solely by the polaron shift of the energy but requires methods that incorporate the dynamical effect of the vibrations on the transport. The accurate results obtained with the ML-MCTDH in this parameter regime are compared to results of nonequilibrium Green's function (NEGF) theory.Comment: 39 pages, 11 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

Simulation of charge transport in organic semiconductors: a time-dependent multiscale method based on nonequilibrium Green's functions

In weakly interacting organic semiconductors, static disorder and dynamic disorder often have an important impact on transport properties. Describing charge transport in these systems requires an approach that correctly takes structural and electronic fluctuations into account. Here, we present a multiscale method based on a combination of molecular-dynamics simulations, electronic-structure calculations, and a transport theory that uses time-dependent nonequilibrium Green’s functions. We apply the methodology to investigate charge transport in C60-containing self-assembled monolayers, which are used in organic field-effect transistors

The Physical Basis for Long-lived Electronic Coherence in Photosynthetic Light Harvesting Systems

The physical basis for observed long-lived electronic coherence in photosynthetic light-harvesting systems is identified using an analytically soluble model. Three physical features are found to be responsible for their long coherence lifetimes: i) the small energy gap between excitonic states, ii) the small ratio of the energy gap to the coupling between excitonic states, and iii) the fact that the molecular characteristics place the system in an effective low temperature regime, even at ambient conditions. Using this approach, we obtain decoherence times for a dimer model with FMO parameters of $\approx$ 160 fs at 77 K and $\approx$ 80 fs at 277 K. As such, significant oscillations are found to persist for 600 fs and 300 fs, respectively, in accord with the experiment and with previous computations. Similar good agreement is found for PC645 at room temperature, with oscillations persisting for 400 fs. The analytic expressions obtained provide direct insight into the parameter dependence of the decoherence time scales.Comment: 5 figures; J. Phys. Chem. Lett. (2011

Theory of Vibrationally Inelastic Electron Transport through Molecular Bridges

Vibrationally inelastic electron transport through a molecular bridge that is connected to two leads is investigated. The study is based on a generic model of vibrational excitation in resonant transmission of electrons through a molecular junction. Employing methods from electron-molecule scattering theory, the transmittance through the molecular bridge can be evaluated numerically exactly. The current through the junction is obtained approximately using a Landauer-type formula. Considering different parameter regimes, which include both the case of a molecular bridge that is weakly coupled to the leads, resulting in narrow resonance structures, and the opposite case of a broad resonance caused by strong interaction with the leads, we investigate the characteristic effects of coherent and dissipative vibrational motion on the electron transport. Furthermore, the validity of widely used approximations such as the wide-band approximation and the restriction to elastic transport mechanisms is investigated in some detail.Comment: Submited to PRB, revised version according to comments of referees (minor text changes and new citations

An efficient scheme for numerical simulations of the spin-bath decoherence

We demonstrate that the Chebyshev expansion method is a very efficient numerical tool for studying spin-bath decoherence of quantum systems. We consider two typical problems arising in studying decoherence of quantum systems consisting of few coupled spins: (i) determining the pointer states of the system, and (ii) determining the temporal decay of quantum oscillations. As our results demonstrate, for determining the pointer states, the Chebyshev-based scheme is at least a factor of 8 faster than existing algorithms based on the Suzuki-Trotter decomposition. For the problems of second type, the Chebyshev-based approach has been 3--4 times faster than the Suzuki-Trotter-based schemes. This conclusion holds qualitatively for a wide spectrum of systems, with different spin baths and different Hamiltonians.Comment: 8 pages (RevTeX), 3 EPS figure