Current density analysis of electron transport through molecular wires in open quantum systems.

The current density in molecular wires connected to contacts is investigated within the nonequilibrium Green's function formalism combined with the Landauer approach. Energy-dependent and total current density through a series of molecular junctions are calculated in real space representation. A rich variety of current patterns including pronounced ring currents ("vortices") are found even in the defect-free minimal building blocks of molecular devices. The influences of contact positions, functional groups as well as atomic defects on the transport properties are examined systematically for prototypical ortho-, meta-, and para-substituted benzenes as well as heteroaromatic systems. It is found that substitutional functional groups mainly shift the molecular levels and retain characteristic transport channels, while a significant change of electronic pathways and conductance is induced by hetero-aromaticity. The current distribution is used to calculate the static magnetic field distribution in the carbon-based conductors. © 2017 Wiley Periodicals, Inc.

Compact Nanowire Sensors Probe Microdroplets.

The conjunction of miniature nanosensors and droplet-based microfluidic systems conceptually opens a new route toward sensitive, optics-less analysis of biochemical processes with high throughput, where a single device can be employed for probing of thousands of independent reactors. Here we combine droplet microfluidics with the compact silicon nanowire based field effect transistor (SiNW FET) for in-flow electrical detection of aqueous droplets one by one. We chemically probe the content of numerous (∼10(4)) droplets as independent events and resolve the pH values and ionic strengths of the encapsulated solution, resulting in a change of the source-drain current ISD through the nanowires. Further, we discuss the specificities of emulsion sensing using ion sensitive FETs and study the effect of droplet sizes with respect to the sensor area, as well as its role on the ability to sense the interior of the aqueous reservoir. Finally, we demonstrate the capability of the novel droplets based nanowire platform for bioassay applications and carry out a glucose oxidase (GOx) enzymatic test for glucose detection, providing also the reference readout with an integrated parallel optical detector.

Structural distortions in molecular-based quantum cellular automata: a minimal model based study.

Molecular-based quantum cellular automata (m-QCA), as an extension of quantum-dot QCAs, offer a novel alternative in which binary information can be encoded in the molecular charge configuration of a cell and propagated via nearest-neighbor Coulombic cell-cell interactions. Appropriate functionality of m-QCAs involves a complex relationship between quantum mechanical effects, such as electron transfer processes within the molecular building blocks, and electrostatic interactions between cells. The influence of structural distortions of single m-QCA are addressed in this paper within a minimal model using an diabatic-to-adiabatic transformation. We show that even small changes of the classical square geometry between driver and target cells, such as those induced by distance variations or shape distortions, can make cells respond to interactions in a far less symmetric fashion, modifying and potentially impairing the expected computational behavior of the m-QCA.

Dynamic and electronic transport properties of DNA translocation through graphene nanopores.

Graphene layers have been targeted in the last years as excellent host materials for sensing a remarkable variety of gases and molecules. Such sensing abilities can also benefit other important scientific fields such as medicine and biology. This has automatically led scientists to probe graphene as a potential platform for sequencing DNA strands. In this work, we use robust numerical tools to model the dynamic and electronic properties of molecular sensor devices composed of a graphene nanopore through which DNA molecules are driven by external electric fields. We performed molecular dynamic simulations to determine the relation between the intensity of the electric field and the translocation time spent by the DNA to pass through the pore. Our results reveal that one can have extra control on the DNA passage when four additional graphene layers are deposited on the top of the main graphene platform containing the pore in a 2 × 2 grid arrangement. In addition to the dynamic analysis, we carried electronic transport calculations on realistic pore structures with diameters reaching nanometer scales. The transmission obtained along the graphene sensor at the Fermi level is affected by the presence of the DNA. However, it is rather hard to distinguish the respective nucleobases. This scenario can be significantly altered when the transport is conducted away from the Fermi level of the graphene platform. Under an energy shift, we observed that the graphene pore manifests selectiveness toward DNA nucleobases.

A parabolic model to control quantum interference in T-shaped molecular junctions.

Quantum interference (QI) effects in molecular devices have drawn increasing attention over the past years due to their unique features observed in the conductance spectrum. For the further development of single molecular devices exploiting QI effects, it is of great theoretical and practical interest to develop simple methods controlling the emergence and the positions of QI effects like anti-resonances or Fano line shapes in conductance spectra. In this work, starting from a well-known generic molecular junction with a side group (T-shaped molecule), we propose a simple graphical method to visualize the conditions for the appearance of quantum interference, Fano resonances or anti-resonances, in the conductance spectrum. By introducing a simple graphical representation (parabolic diagram), we can easily visualize the relation between the electronic parameters and the positions of normal resonant peaks and anti-resonant peaks induced by quantum interference in the conductance spectrum. This parabolic model not only can predict the emergence and energetic position of quantum interference from a few electronic parameters but also can enable one to know the coupling between the side group and the main conduction channel from measurements in the case of orthogonal basis. The results obtained within the parabolic model are validated using density-functional based quantum transport calculations in realistic T-shaped molecular junctions.

Molecular Orbital Rule for Quantum Interference in Weakly Coupled Dimers: Low-Energy Giant Conductivity Switching Induced by Orbital Level Crossing.

Destructive quantum interference (QI) in molecular junctions has attracted much attention in recent years. It can tune the conductance of molecular devices dramatically, which implies numerous potential applications in thermoelectric and switching applications. There are several schemes that address and rationalize QI in single molecular devices. Dimers play a particular role in this respect because the QI signal may disappear, depending on the dislocation of monomers. We derive a simple rule that governs the occurrence of QI in weakly coupled dimer stacks of both alternant and nonalternant polyaromatic hydrocarbons (PAHs) and extends the Tada-Yoshizawa scheme. Starting from the Green's function formalism combined with the molecular orbital expansion approach, it is shown that QI-induced antiresonances and their energies can be predicted from the amplitudes of the respective monomer terminal molecular orbitals. The condition is illustrated for a toy model consisting of two hydrogen molecules and applied within density functional calculations to alternant dimers of oligo(phenylene-ethynylene) and nonalternant PAHs. Minimal dimer structure modifications that require only a few millielectronvolts and lead to an energy crossing of the essentially preserved monomer orbitals are shown to result in giant conductance switching ratios.

Switchable Negative Differential Resistance Induced by Quantum Interference Effects in Porphyrin-based Molecular Junctions.

Charge transport signatures of a carbon-based molecular switch consisting of different tautomers of metal-free porphyrin embedded between graphene nanoribbons is studied by combining electronic structure and nonequilibrium transport. Different low-energy and low-bias features are revealed, including negative differential resistance (NDR) and antiresonances, both mediated by subtle quantum interference effects. Moreover, the molecular junctions can display moderate rectifying or nonlinear behavior depending on the position of the hydrogen atoms within the porphyrin core. We rationalize the mechanism leading to NDR and antiresonances by providing a detailed analysis of transmission pathways and frontier molecular orbital distribution.

Generalized multi-terminal decoherent transport: recursive algorithms and applications to SASER and giant magnetoresistance.

Decoherent transport in mesoscopic and nanoscopic systems can be formulated in terms of the D'Amato-Pastawski (DP) model. This generalizes the Landauer-Büttiker picture by considering a distribution of local decoherent processes. However, its generalization for multi-terminal set-ups is lacking. We first review the original two-terminal DP model for decoherent transport. Then, we extend it to a matrix formulation capable of dealing with multi-terminal problems. We also introduce recursive algorithms to evaluate the Green's functions for general banded Hamiltonians as well as local density of states, effective conductances and voltage profiles. We finally illustrate the method by analyzing two problems of current relevance. (1) Assessing the role of decoherence in a model for phonon lasers (SASER). (2) Obtaining the classical limit of giant magnetoresistance from a spin-dependent Hamiltonian. The presented methods should pave the way for computationally demanding calculations of transport through nanodevices, bridging the gap between fully coherent quantum schemes and semiclassical ones.

Unimolecular amplifier: principles of a three-terminal device with power gain.

A single molecule composed of three linked moieties can function as an amplifier of electrical current, when certain conditions are met by the molecular orbitals of the three component parts. This device should exhibit power gain at appropriate voltages. In this work, we will explain a plausible mechanism by which this device should work, and present its operating characteristics. In particular, we find that a fundamental requirement for current amplification is to have the LUMO of the central moiety more strongly coupled to a control electrode than it is to the other orbitals in the molecule, while the HOMO of this moiety should be more strongly coupled to the orbitals in the other moieties than it is to the control electrode.

Oscillation of conductance in molecular junctions of carbon ladder compounds.

The electrical conductances of dithiolates of polyacene (PA(n)DTs) and polyphenanthrene (PPh(n)DTs), which are typical carbon ladder compounds, are calculated by means of the Landauer formulation combined with density functional theory, where n is the number of benzene rings involved. Surface Green function used in the Landauer formulation is calculated with the Slater-Koster parameters. Attention is turned to the wire-length dependence of the conductances of PA(n)DTs and PPh(n)DTs. The damping of conductance of PA(n)DTs is much smaller than that of PPh(n)DTs because of the small HOMO-LUMO gaps of PA(n)DTs. PA(n)DTs are thus good molecular wires for nanosized electronic devices. Conductance oscillation is found for both molecular wires when n is less than 7. The electrical conductance is enhanced in PA(n)DTs with even-numbered benzene rings, whereas it is enhanced in PPh(n)DTs with odd-numbered benzene rings. The observed conductance oscillation of PA(n)DTs and PPh(n)DTs is due to the oscillation of orbital energy and electron population. Other pi-conjugated oligomers (polyacetylene-DT, oligo(thiophene)-DT, oligo(meso-meso-linked zinc(II) porphyrin-butadiynylene)-DT, oligo(p-phenylethynylene)-DT, and oligo(p-phenylene)-DT) are also studied. In contrast to PA(n)DTs and PPh(n)DTs, the five molecular wires show ordinary exponential decays of conductance.