Using a combination of density functional theory and quantum master equations approach, we study the effect of electromagnetic (EM) coupling on the nonequilibrium steady-state behavior of a recently introduced gated molecular junction. This junction was demonstrated in a previous publication to exhibit sharp current switching near a certain critical DC field Ez*, which induces intramolecular charge transfer, and here, we analyze the steady-state population and current when an AC EM field (EMF) is present. The AC EMF at frequency $ømega_0$ produces pronounced population and current features at gate fields Ez = Ez* ± $\hbar ømega_0/ez$ (where $e_z$ is the dipole of the charge-transfer state) and thus allows additional sharp switching capability at lower gate fields. We found that even when EMF is absent, the EM coupling itself changes the overall steady-state population and current distributions because it allows for relaxation via spontaneous emission

A recently introduced molecular junction, for which the gate acts as an on/off switch for intrajunction electron transfer between localized donor and acceptor sites is studied. We demonstrate that a Landauer + density functional (DFT) approach is fundamentally flawed for describing the electronic conductance in this system. By comparing the Landauer + DFT conductance to that predicted by the Redfield quantum master equations, we point out several effects that cannot be explained by the former approach. The molecular junction is unique in the small number of conductance channels and their sharp response to the gate.

We present a molecular junction composed of a donor (polyacetylene strands) and an acceptor (malononitrile) connected together via a benzene ring and coupled weakly to source and drain electrodes on each side, for which a gate electrode induces intramolecular charge transfer, switching reversibly the character of conductance. Using a new brand of density functional theory, for which orbital energies are similar to the quasiparticle energies, we show that the junction displays a single, gate-tunable differential conductance channel in a wide energy range. The gate field must align parallel to the displacement vector between donors and acceptor to affect their potential difference; for strong enough fields, spontaneous intramolecular electron transfer occurs. This event radically affects conductance, reversing the charge of carriers, enabling a spin-polarized current channel. We discuss the physical principles controlling the operation of the junction and find interplay of quantum interference, charging, Coulomb blockade, and electron-hole binding energy effects. We expect that this switching behavior is a generic property for similar donor-acceptor systems of sufficient stability.

Control of conductance in molecular junctions is of key importance in the growing field of molecular electronics. The current in these junctions is often controlled by an electric gate designed to shift conductance peaks into the low bias regime. Magnetic fields, on the other hand, have rarely been used due to the small magnetic flux captured by molecular conductors ( an exception is the Kondo effect in single-molecule transistors). This is in contrast to a related field, electronic transport through mesoscopic devices, where considerable activity with magnetic fields has led to a rich description of transport. The scarcity of experimental activity is due to the belief that significant magnetic response is obtained only when the magnetic flux is of the order of the quantum flux, while attaining such a flux for molecular and nanoscale devices requires unrealistic magnetic fields. Here we review recent theoretical work regarding the essential physical requirements necessary for the construction of nanometer-scale magnetoresistance devices based on an Aharonov-Bohm molecular interferometer. We show that control of the conductance properties using small fractions of a magnetic flux can be achieved by carefully adjusting the lifetime of the conducting electrons through a pre-selected single state that is well separated from other states due to quantum confinement effects. Using a simple analytical model and more elaborate atomistic calculations we demonstrate that magnetic fields which give rise to a magnetic flux comparable to 10(-3) of the quantum flux can be used to switch a class of different molecular and nanometer rings, ranging from quantum corrals, carbon nanotubes and even a molecular ring composed of polyconjugated aromatic materials. The unique characteristics of the magnetic field as a gate is further discussed and demonstrated in two different directions. First, a three-terminal molecular router devices that can function as a parallel logic gate, processing two logic operations simultaneously, is presented. Second, the role of inelastic effects arising from electron-phonon couplings on the magnetoresistance properties is analyzed. We show that a remarkable difference between electric and magnetic gating is also revealed when inelastic effects become significant. The inelastic broadening of response curves to electric gates is replaced by a narrowing of magnetoconductance peaks, thereby enhancing the sensitivity of the device.

Recently, the possibility of transporting electromagnetic energy as local-plasmon-polariton waves along arrays of silver nanoparticles was demonstrated experimentally [S. A. Maier et al., Nat. Mater. 2, 229 (2003)]. It was shown that dipole coupling facilitates phase-coherent excitation waves, which propagate while competing against decoherence effects occurring within each dot. In this article the authors study the ideal coherent shuttling in such a system, leaving decoherence for future investigation. In the weak field limit, the waves obey a Schrödinger equation, to be solved using either time-dependent wave-packet or energy resolved scattering techniques. The authors study some dynamical characteristics of these waves, emphasizing intuition and insight. Scattering from barriers, longitudinal-transverse coupling and acceleration methods are studied in detail. The authors also discuss briefly two-dimensional arrays and a simple decoherence model

Inelastic effects arising from electron-phonon coupling in molecular Aharonov-Bohm (AB) interferometers are studied using the nonequilibrium Green's function method. Results for the magnetoconductance are compared for different values of the electron-phonon coupling strength. At low-bias voltages, the coupling to the phonons does not change the lifetime and leads mainly to scattering phase shifts of the conducting electrons. As a result of these dephasing processes, the magnetoconductance of the molecular AB interferometer becomes more sensitive to the threading magnetic flux as the electron-phonon coupling is increased, opposite to the behavior of an electric gate.

Affecting the current through a molecular or nanoscale junction is usually done by a combination of bias and gate voltages. Magnetic fields are less studied because nanodevices can capture only low values of the magnetic flux. We review recent work done with the aim of finding the conditions for magnetic fields to significantly affect the conductance of such junctions. The basic idea is to create narrow tunneling resonances through a molecular ring-like structure that are highly sensitive to the magnetic field. We describe a computational method that allows us to examine atomistic models of such systems and discuss several specific examples of plausible systems, such as the quantum corral, carbon nanotubes, and polycyclic aromatic hydrocarbon molecules. A unique property of the magnetic field, namely, its ability to split degenerate levels on the ring, is shown to allow prototypes of interesting new nanoscale devices, such as the three-terminal parallel logic gate.

Near-field scanning microscopy and nonlinear spectroscopy on a molecular scale involve weakly interacting subsystems that dynamically exchange electrons and electromagnetic energy. The theoretical description of such processes requires unified approach to the electron-near-field dynamics. By considering electronic structure and dynamics of two distant clusters or atoms we show that adiabatic local spin-density approximation (ALSDA) fails to describe (even qualitatively) essential details of electron dynamics in weakly interacting systems. A recently developed functional addresses these ailments within a time-dependent setting. With this method we study the spectroscopy of a composite system, namely, two weakly coupled metallic clusters. The near-field (dipole-dipole) coupling and electron transfer display an interesting interplay, producing exponential sensitivity of emission yield to the intercomponent distance.

We examine the effects of self-repulsion on the predictions of charge distribution in biased molecular junctions by the local density functional theory methods. This is done using a functional with explicit long-range exchange term effects [R. Baer, D. Neuhauser, Phys. Rev. Lett. 94 (2005) 043002]. We discuss in detail the new density functional, pointing out some of the remaining difficulties in the theory. We find that in weakly coupled junctions (the typical molecular electronics case) local-density functionals fail to describe correctly the charge distribution in the intermediate bias regime. (c) 2006 Elsevier B.V. All rights reserved.

We demonstrate the physical principles for the construction of a nanometer-sized magnetoresistance device based on the Aharonov-Bohm effect [Phys. Rev. 115, 485 (1959)]. The proposed device is made of a short single-walled carbon nanotube (SWCNT) placed on a substrate and coupled to a tip/contacts. We consider conductance due to the motion of electrons along the circumference of the tube (as opposed to the motion parallel to its axis). We find that the circumference conductance is sensitive to magnetic fields threading the SWCNT due to the Aharonov-Bohm effect, and show that by retracting the tip/contacts, so that the coupling to the SWCNT is reduced, very high sensitivity to the threading magnetic field develops. This is due to the formation of a narrow resonance through which the tunneling current flows. Using a bias potential the resonance can be shifted to low magnetic fields, allowing the control of conductance with magnetic fields of the order of 1 T.

The construction of devices based on molecular components depends upon the development of molecular wires with adaptable current-voltage characteristics. Here, we report that quantum interference effects could lead to substantial differences in conductance in molecular wires which include some simple polycyclic aromatic hydrocarbons (PAHs). For molecular wires containing a single benzene. anthracene or tetracene molecule a large peak appears in the electron transmission probability spectrum at an energy just above the lowest unoccupied orbital (LUMO). For a molecular wire containing a single naphthalene molecule, however, this same peak essentially vanishes. Furthermore, the peak can be re-established by altering the attachment points of the molecular leads to the naphthalene molecule. A breakdown of the individual terms contributing the relevant peak confirms that these results are in fact due to quantum interference effects. (C) 2004 Elsevier B.V. All rights reserved.

{We use Huckel theory to examine interference effects on conductance of a wire when a ‘lollypop’ side-chain is bonded to it, acting as a resonance cavity. A clear signature of interference is found at these ballistic conducting systems, stronger in small systems. Gating effects are enhanced by the presence of the loop, where the electronic wavefunctions can experience large changes in phase. Using an ‘interference index’

The small-bias conductance of the C-6 molecule, stretched between two metallic leads, is studied using time-dependent density functional theory within the adiabatic local density approximation. The leads are modeled by jellium slabs, the electronic density and the current density are described on a grid, whereas the core electrons and the highly oscillating valence orbitals are approximated using standard norm-conserving pseudopotentials. The jellium leads are supplemented by a complex absorbing potential that serves to absorb charge reaching the edge of the electrodes and hence mimic irreversible flow into the macroscopic metal. The system is rapidly exposed to a ramp potential directed along the C-6 axis, which gives rise to the onset of charge and current oscillations. As time progresses, a fast redistribution of the molecular charge is observed, which translates into a direct current response. Accompanying the dc signal, alternating current fluctuations of charge and currents within the molecule and the metallic leads are observed. These form the complex impedance of the molecule and are especially strong at the plasmon frequency of the leads and the lowest excitation peak of C-6. We study the molecular conductance in two limits: the strong coupling limit, where the edge atoms of the chain are submerged in the jellium and the weak coupling case, where the carbon atoms and the leads do not overlap spatially. (C) 2004 American Institute of Physics.

We point out and simulate the possible utility of anti-coherence in molecular electronics. In ballistic transfer through a molecule with a large loop that fulfils a certain phase condition on the loop structure, the transfer would be anti-coherent. By applying one or two control voltages to the molecule, that modify the relative phase through the two parts of the loop, the transfer could be controlled, just like in FET or in XOR gates. The simulations use the absorbing-potential based flux-flux formulae with a Huckel-Hamiltonian in a Landauer formulation, and are numerically equivalent to a weighted time-dependent correlation function. (C) 2002 Elsevier Science B.V. All rights reserved.