Current-Driven Conformational Changes, Charging and Negative Differential Resistance in Molecular Wires

We introduce a theoretical approach based on scattering theory and total energy methods that treats transport non-linearities, conformational changes and charging effects in molecular wires in a unified way. We apply this approach to molecular wires consisting of chain molecules with different electronic and structural properties bonded to metal contacts. We show that non-linear transport in all of these systems can be understood in terms of a single physical mechanism and predict that negative differential resistance at high bias should be a generic property of such molecular wires.Comment: 9 pages, 4 figure

Antiresonances in Molecular Wires

We present analytic and numerical studies based on Landauer theory of conductance antiresonances of molecular wires. Our analytic treatment is a solution of the Lippmann-Schwinger equation for the wire that includes the effects of the non-orthogonality of the atomic orbitals on different atoms exactly. The problem of non-orthogonality is treated by solving the transport problem in a new Hilbert space which is spanned by an orthogonal basis. An expression is derived for the energies at which antiresonances should occur for a molecular wire connected to a pair of single-channel 1D leads. From this expression we identify two distinct mechanisms that give rise to antiresonances under different circumstances. The exact treatment of non-orthogonality in the theory is found to be necessary to obtain reliable results. Our numerical simulations extend this work to multichannel leads and to molecular wires connected to 3D metallic nanocontacts. They demonstrate that our analytic results also provide a good description of these more complicated systems provided that certain well-defined conditions are met. These calculations suggest that antiresonances should be experimentally observable in the differential conductance of molecular wires of certain types.Comment: 22 pages, 5 figure

Electrical Conductance of Molecular Wires

Molecular wires (MW) are the fundamental building blocks for molecular electronic devices. They consist of a molecular unit connected to two continuum reservoirs of electrons (usually metallic leads). We rely on Landauer theory as the basis for studying the conductance properties of MW systems. This relates the lead to lead current to the transmission probability for an electron to scatter through the molecule. Two different methods have been developed for the study of this scattering. One is based on a solution of the Lippmann-Schwinger equation and the other solves for the {\bf t} matrix using Schroedinger's equation. We use our methodology to study two problems of current interest. The first MW system consists of 1,4 benzene-dithiolate (BDT) bonded to two gold nanocontacts. Our calculations show that the conductance is sensitive to the chemical bonding between the molecule and the leads. The second system we study highlights the interesting phenomenon of antiresonances in MW. We derive an analytic formula predicting at what energies antiresonances should occur in the transmission spectra of MW. A numerical calculation for a MW consisting of filter molecules attached to an active molecule shows the existence of an antiresonance at the energy predicted by our formula.Comment: 14 pages, 5 figure

Electron Standing Wave Formation in Atomic Wires

Using the Landauer formulation of transport theory and tight binding models of the electronic structure, we study electron transport through atomic wires that form 1D constrictions between pairs of metallic nano-contacts. Our results are interpreted in terms of electron standing waves formed in the atomic wires due to interference of electron waves reflected at the ends of the atomic constrictions. We explore the influence of the chemistry of the atomic wire-metal contact interfaces on these standing waves and the associated transport resonances by considering two types of atomic wires: gold wires attached to gold contacts and carbon wires attached to gold contacts. We find that the conductance of the gold wires is roughly $1 G_0 = 2 e^2/h$ for the wire lengths studied, in agreement with experiments. By contrast, for the carbon wires the conductance is found to oscillate strongly as the number of atoms in the wire varies, the odd numbered chains being more conductive than the even numbered ones, in agreement with previous theoretical work that was based on a different model of the carbon wire and metal contacts.Comment: 14 pages, includes 6 figure

Charging induced asymmetry in molecular conductors

We investigate the origin of asymmetry in various measured current-voltage (I-V) characteristics of molecules with no inherent spatial asymmetry, with particular focus on a recent break junction measurement. We argue that such asymmetry arises due to unequal coupling with the contacts and a consequent difference in charging effects, which can only be captured in a self-consistent model for molecular conduction. The direction of the asymmetry depends on the sign of the majority carriers in the molecule. For conduction through highest occupied molecular orbitals (i.e. HOMO or p-type conduction), the current is smaller for positive voltage on the stronger contact, while for conduction through lowest unoccupied molecular orbitals (i.e. LUMO or n-type conduction), the sense of the asymmetry is reversed. Within an extended Huckel description of the molecular chemistry and the contact microstructure (with two adjustable parameters, the position of the Fermi energy and the sulphur-gold bond length), an appropriate description of Poisson's equation, and a self-consistently coupled non-equilibrium Green's function (NEGF) description of transport, we achieve good agreement between theoretical and experimental I-V characteristics, both in shape as well as overall magnitude.Comment: length of the paper has been extended (4 pages to 6 pages), two new figures have been added (3 figures to 5 figures), has been accepted for PR

Quantum Conductance in Silver Nanowires: correlation between atomic structure and transport properties

We have analyzed the atomic arrangements and quantum conductance of silver nanowires generated by mechanical elongation. The surface properties of Ag induce unexpected structural properties, as for example, predominance of high aspect ratio rod-like wires. The structural behavior was used to understand the Ag quantum conductance data and the proposed correlation was confirmed by means of theoretical calculations. These results emphasize that the conductance of metal point contacts is determined by the preferred atomic structures and, that atomistic descriptions are essential to interpret the quantum transport behavior of metal nanostructures.Comment: 4 pages, 4 figure

Real space finite difference method for conductance calculations

We present a general method for calculating coherent electronic transport in quantum wires and tunnel junctions. It is based upon a real space high order finite difference representation of the single particle Hamiltonian and wave functions. Landauer's formula is used to express the conductance as a scattering problem. Dividing space into a scattering region and left and right ideal electrode regions, this problem is solved by wave function matching (WFM) in the boundary zones connecting these regions. The method is tested on a model tunnel junction and applied to sodium atomic wires. In particular, we show that using a high order finite difference approximation of the kinetic energy operator leads to a high accuracy at moderate computational costs.Comment: 13 pages, 10 figure

Control of quantum interference in molecular junctions: Understanding the origin of Fano and anti- resonances

We investigate within a coarse-grained model the conditions leading to the appearance of Fano resonances or anti-resonances in the conductance spectrum of a generic molecular junction with a side group (T-junction). By introducing a simple graphical representation (parabolic diagram), we can easily visualize the relation between the different electronic parameters determining the regimes where Fano resonances or anti-resonances in the low-energy conductance spectrum can be expected. The results obtained within the coarse-grained model are validated using density-functional based quantum transport calculations in realistic T-shaped molecular junctions.Comment: 5 pages, 5 figure

State Orthogonalization by Building a Hilbert Space: A New Approach to Electronic Quantum Transport in Molecular Wires

Quantum descriptions of many complex systems are formulated most naturally in bases of states that are not mutually orthogonal. We introduce a general and powerful yet simple approach that facilitates solving such models exactly by embedding the non-orthogonal states in a new Hilbert space in which they are by definition mutually orthogonal. This novel approach is applied to electronic transport in molecular quantum wires and is used to predict conductance antiresonances of a new type that arise solely out of the non-orthogonality of the local orbitals on different sites of the wire.Comment: 4 pages 1 figur

The role of structural evolution on the quantum conductance behavior of gold nanowires during stretching

Gold nanowires generated by mechanical stretching have been shown to adopt only three kinds of configurations where their atomic arrangements adjust such that either the [100], [111] or [110] zone axes lie parallel to the elongation direction. We have analyzed the relationship between structural rearrangements and electronic transport behavior during the elongation of Au nanowires for each of the three possibilities. We have used two independent experiments to tackle this problem, high resolution transmission high resolution electron microscopy to observe the atomic structure and a mechanically controlled break junction to measure the transport properties. We have estimated the conductance of nanowires using a theoretical method based on the extended H\"uckel theory that takes into account the atom species and their positions. Aided by these calculations, we have consistently connected both sets of experimental results and modeled the evolution process of gold nanowires whose conductance lies within the first and third conductance quanta. We have also presented evidence that carbon acts as a contaminant, lowering the conductance of one-atom-thick wires.Comment: 10 page