Folding of a donor–acceptor polyrotaxane by using noncovalent bonding interactions

Mechanically interlocked compounds, such as bistable catenanes and bistable rotaxanes, have been used to bring about actuation in nanoelectromechanical systems (NEMS) and molecular electronic devices (MEDs). The elaboration of the structural features of such rotaxanes into macromolecular materials might allow the utilization of molecular motion to impact their bulk properties. We report here the synthesis and characterization of polymers that contain π electron-donating 1,5-dioxynaphthalene (DNP) units encircled by cyclobis(paraquat-p-phenylene) (CBPQT4+), a π electron-accepting tetracationic cyclophane, synthesized by using the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The polyrotaxanes adopt a well defined “folded” secondary structure by virtue of the judicious design of two DNP-containing monomers with different binding affinities for CBPQT4+. This efficient approach to the preparation of polyrotaxanes, taken alongside the initial investigations of their chemical properties, sets the stage for the preparation of a previously undescribed class of macromolecular architectures

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

Atomic scale engines: Cars and wheels

We introduce a new approach to build microscopic engines on the atomic scale that move translationally or rotationally and can perform useful functions such as pulling of a cargo. Characteristic of these engines is the possibility to determine dynamically the directionality of the motion. The approach is based on the transformation of the fed energy to directed motion through a dynamical competition between the intrinsic lengths of the moving object and the supporting carrier.Comment: 4 pages, 3 figures (2 in color), Phys. Rev. Lett. (in print

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

A quantum point contact for neutral atoms

We show that the conductance of neutral atoms through a tightly confining waveguide constriction is quantized in units of lambda_dB^2/pi, where lambda_dB is the de Broglie wavelength of the incident atoms. Such a constriction forms the atom analogue of an electron quantum point contact and is an example of quantum transport of neutral atoms in an aperiodic system. We present a practical constriction geometry that can be realized using a microfabricated magnetic waveguide, and discuss how a pair of such constrictions can be used to study the quantum statistics of weakly interacting gases in small traps.Comment: 5 pages with 3 figures. To appear in Phys. Rev. Let

Quantum Conductance in Semimetallic Bismuth Nanocontacts

Electronic transport properties of bismuth nanocontacts are analyzed by means of a low temperature scanning tunneling microscope. The subquantum steps observed in the conductance versus elongation curves give evidence of atomic rearrangements in the contact. The underlying quantum nature of the conductance reveals itself through peaks in the conductance histograms. The shape of the conductance curves at 77 K is well described by a simple gliding mechanism for the contact evolution during elongation. The strikingly different behaviour at 4 K suggests a charge carrier transition from light to heavy ones as the contact cross section becomes sufficiently small.Comment: 5 pages including 4 figures. Accepted for publication in Phys. Rev. Let

ab initio modeling of open systems: charge transfer, electron conduction, and molecular switching of a C_{60} device

We present an {\it ab initio} analysis of electron conduction through a $C_{60}$ molecular device. Charge transfer from the device electrodes to the molecular region is found to play a crucial role in aligning the lowest unoccupied molecular orbital (LUMO) of the $C_{60}$ to the Fermi level of the electrodes. This alignment induces a substantial device conductance of $\sim 2.2 \times (2e^2/h)$. A gate potential can inhibit charge transfer and introduce a conductance gap near $E_F$, changing the current-voltage characteristics from metallic to semi-conducting, thereby producing a field effect molecular current switch

Point-contact spectroscopy on URu2_2Si2_2

Tunnel and point contact experiments have been made in a URu$_2$Si$_2$ single crystal along the c-axis. The experiments were performed changing temperature and contact size in a low temperature scanning tunneling microscope. A resonance develops at the Fermi level at $T\sim 60$ K. This resonance splits and becomes asymmetric when the 17.5 K phase transition is crossed. These results are consistent with the existence of Kondo like bound states of the U$^{4+}$ ionic configurations and the conduction electrons. Below the transition, these configurations are split by the development of quadrupolar ordering. The peak separation can be interpreted as a direct measurement of the order parameter. Measurements on a policrystalline UAu_2Si_2$ sample are also reported, with a comparative study of the behavior of both materials.Comment: 4 pages (Latex) + 2 postscript figure

Mirror symmetry breaking through an internal degree of freedom leading to directional motion

We analyze here the minimal conditions for directional motion (net flow in phase space) of a molecular motor placed on a mirror-symmetric environment and driven by a center-symmetric and time-periodic force field. The complete characterization of the deterministic limit of the dissipative dynamics of several realizations of this minimal model, reveals a complex structure in the phase diagram in parameter space, with intertwined regions of pinning (closed orbits) and directional motion. This demonstrates that the mirror-symmetry breaking which is needed for directional motion to occur, can operate through an internal degree of freedom coupled to the translational one.Comment: Accepted for publication in Phys. Rev.

Quantum point contact on graphite surface

The conductance through a quantum point contact created by a sharp and hard metal tip on the graphite surface has features which to our knowledge have not been encountered so far in metal contacts or in nanowires. In this paper we first investigate these features which emerge from the strongly directional bonding and electronic structure of graphite, and provide a theoretical understanding for the electronic conduction through quantum point contacts. Our study involves the molecular-dynamics simulations to reveal the variation of interlayer distances and atomic structure at the proximity of the contact that evolves by the tip pressing toward the surface. The effects of the elastic deformation on the electronic structure, state density at the Fermi level, and crystal potential are analyzed by performing self-consistent-field pseudopotential calculations within the local-density approximation. It is found that the metallicity of graphite increases under the uniaxial compressive strain perpendicular to the basal plane. The quantum point contact is modeled by a constriction with a realistic potential. The conductance is calculated by representing the current transporting states in Laue representation, and the variation of conductance with the evolution of contact is explained by taking the characteristic features of graphite into account. It is shown that the sequential puncturing of the layers characterizes the conductance.Comment: LaTeX, 11 pages, 9 figures (included), to be published in Phys. Rev. B, tentatively scheduled for 15 September 1998 (Volume 58, Number 12