Building an electronic device using individual molecules is one of the ultimate goals in nanotechnology. To achieve this it will be necessary to measure, control and understand electron transport ...through molecules attached to electrodes. Substantial progress has been made over the past decade and we present here an overview of some of the recent advances. Topics covered include molecular wires, two-terminal switches and diodes, three-terminal transistor-like devices and hybrid devices that use various different signals (light, magnetic fields, and chemical and mechanical signals) to control electron transport in molecules. We also discuss further issues, including molecule-electrode contacts, local heating- and current-induced instabilities, stochastic fluctuations and the development of characterization tools.
The methods of spectral geometry are useful for investigating the metric aspects of noncommutative geometry and in these contexts require extensive use of pseudo-differential operators. In a ...foundational paper, Connes showed that, by direct analogy with the theory of pseudo-differential operators on finite-dimensional real vector spaces, one may derive a similar pseudo-differential calculus on noncommutative n-tori, and with the development of this calculus came many results concerning the local differential geometry of noncommutative tori for n=2,4, as shown in the groundbreaking paper in which the Gauss-Bonnet theorem on the noncommutative two-torus is proved and later papers. Certain details of the proofs in the original derivation of the calculus were omitted, such as the evaluation of oscillatory integrals, so we make it the objective of this paper to fill in all the details. After reproving in more detail the formula for the symbol of the adjoint of a pseudo-differential operator and the formula for the symbol of a product of two pseudo-differential operators, we extend these results to finitely generated projective right modules over the noncommutative n-torus. Then we define the corresponding analog of Sobolev spaces and prove equivalents of the Sobolev and Rellich lemmas.
Electron movement within and between moleculesthat is, electron transferis important in many chemical, electrochemical, and biological processes. Recent advances, particularly in scanning ...electrochemical microscopy (SECM), scanning-tunneling microscopy (STM), and atomic force microscopy (AFM), permit the study of electron movement within single molecules. In this Account, we describe electron transport at the single-molecule level. We begin by examining the distinction between electron transport (from semiconductor physics) and electron transfer (a more general term referring to electron movement between donor and acceptor). The relation between these phenomena allows us to apply our understanding of single-molecule electron transport between electrodes to a broad range of other electron transfer processes. Electron transport is most efficient when the electron transmission probability via a molecule reaches 100%; the corresponding conductance is then 2e 2/h (e is the charge of the electron and h is the Planck constant). This ideal conduction has been observed in a single metal atom and a string of metal atoms connected between two electrodes. However, the conductance of a molecule connected to two electrodes is often orders of magnitude less than the ideal and strongly depends on both the intrinsic properties of the molecule and its local environment. Molecular length, means of coupling to the electrodes, the presence of conjugated double bonds, and the inclusion of possible redox centers (for example, ferrocene) within the molecular wire have a pronounced effect on the conductance. This complex behavior is responsible for diverse chemical and biological phenomena and is potentially useful for device applications. Polycyclic aromatic hydrocarbons (PAHs) afford unique insight into electron transport in single molecules. The simplest one, benzene, has a conductance much less than 2e 2/h due to its large LUMO−HOMO gap. At the other end of the spectrum, graphene sheets and carbon nanotubesconsisting of infinite numbers of aromatic ringshave small or even zero energy gaps between the conduction and valence bands. Between these two limits are intermediate molecules with rich properties, such as perylene derivatives made of seven aromatic rings; the properties of these types of molecules have yet to be fully explored. Studying PAHs is important not only in answering fundamental questions about electron transport but also in the ongoing quest for molecular-scale electronic devices. This line of research also helps bridge the gap between electron transfer phenomena in small redox molecules and electron transport properties in nanostructures.
Electrochemical reactions are involved in many natural phenomena, and are responsible for various applications, including energy conversion and storage, material processing and protection, and ...chemical detection and analysis. An electrochemical reaction is accompanied by electron transfer between a chemical species and an electrode. For this reason, it has been studied by measuring current, charge, or related electrical quantities. This approach has led to the development of various electrochemical methods, which have played an essential role in the understanding and applications of electrochemistry. While powerful, most of the traditional methods lack spatial and temporal resolutions desired for studying heterogeneous electrochemical reactions on electrode surfaces and in nanoscale materials. To overcome the limitations, scanning probe microscopes have been invented to map local electrochemical reactions with nanometer resolution. Examples include the scanning electrochemical microscope and scanning electrochemical cell microscope, which directly image local electrochemical reaction current using a scanning electrode or pipet. The use of a scanning probe in these microscopes provides high spatial resolution, but at the expense of temporal resolution and throughput. This Account discusses an alternative approach to study electrochemical reactions. Instead of measuring electron transfer electrically, it detects the accompanying changes in the reactant and product concentrations on the electrode surface optically via surface plasmon resonance (SPR). SPR is highly surface sensitive, and it provides quantitative information on the surface concentrations of reactants and products vs time and electrode potential, from which local reaction kinetics can be analyzed and quantified. The plasmonic approach allows imaging of local electrochemical reactions with high temporal resolution and sensitivity, making it attractive for studying electrochemical reactions in biological systems and nanoscale materials with high throughput. The plasmonic approach has two imaging modes: electrochemical current imaging and interfacial impedance imaging. The former images local electrochemical current associated with electrochemical reactions (faradic current), and the latter maps local interfacial impedance, including nonfaradic contributions (e.g., double layer charging). The plasmonic imaging technique can perform voltammetry (cyclic or square wave) in an analogous manner to the traditional electrochemical methods. It can also be integrated with bright field, dark field, and fluorescence imaging capabilities in one optical setup to provide additional capabilities. To date the plasmonic imaging technique has found various applications, including mapping of heterogeneous surface reactions, analysis of trace substances, detection of catalytic reactions, and measurement of graphene quantum capacitance. The plasmonic and other emerging optical imaging techniques (e.g., dark field and fluorescence microscopy), together with the scanning probe-based electrochemical imaging and single nanoparticle analysis techniques, provide new capabilities for one to study single nanoparticle electrochemistry with unprecedented spatial and temporal resolutions. In this Account, we focus on imaging of electrochemical reactions at single nanoparticles.
The conductance of a single molecule connected to two gold electrodes was determined by repeatedly forming thousands of gold-molecule-gold junctions. Conductance histograms revealed well-defined ...peaks at integer multiples of a fundamental conductance value, which was used to identify the conductance of a single molecule. The resistances near zero bias were$10.5 \pm 0.5$,$51 \pm 5$,$630 \pm 50$, and$1.3 \pm 0.1$megohms for hexanedithiol, octanedithiol, decanedithiol, and 4,4' bipyridine, respectively. The tunneling decay constant (βN) for N-alkanedithiols was$1.0 \pm 0.1$per carbon atom and was weakly dependent on the applied bias. The resistance and βNvalues are consistent with first-principles calculations.
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The quantum Goos-Hänchen effect in graphene is found to be the lateral shift of Dirac fermions on the total reflection at a single p-n interface. In this paper, we investigate the lateral shifts of ...Dirac fermions in transmission through a monolayer graphene barrier. Compared to the smallness of the lateral shifts in total reflection, the lateral shifts can be enhanced by the transmission resonances when the incidence angle is less than the critical angle for total reflection. It is also found that the lateral shifts, as the function of the barrier’s width and incidence angle, can be negative and positive in the cases of Klein tunneling and classical motion. The modulation of the lateral shifts can be realized by changing the electrostatic potential and induced gap, which gives rise to some applications in graphene-based devices.
During the ionization of atoms irradiated by linearly polarized intense laser fields, we find for the first time that the transverse momentum distribution of photoelectrons can be well fitted by a ...squared zeroth-order Bessel function because of the quantum interference effect of glory rescattering. The characteristic of the Bessel function is determined by the common angular momentum of a number of semiclassical paths termed as glory trajectories, which are launched with different nonzero initial transverse momenta distributed on a specific circle in the momentum plane and finally deflected to the same asymptotic momentum, which is along the polarization direction, through post-tunneling rescattering. Glory rescattering theory based on the semiclassical path-integral formalism is developed to address this effect quantitatively. Our theory can resolve the long-standing discrepancies between existing theories and experiments on the fringe location, predict the sudden transition of the fringe structure in holographic patterns, and shed light on the quantum interference aspects of low-energy structures in strong-field atomic ionization.
The behaviour of electrons and holes in a crystal lattice is a fundamental quantum phenomenon, accounting for a rich variety of material properties. Boosted by the remarkable electronic and physical ...properties of two-dimensional materials such as graphene and topological insulators, transition metal dichalcogenides have recently received renewed attention. In this context, the anomalous bulk properties of semimetallic WTe2 have attracted considerable interest. Here we report angle- and spin-resolved photoemission spectroscopy of WTe2 single crystals, through which we disentangle the role of W and Te atoms in the formation of the band structure and identify the interplay of charge, spin and orbital degrees of freedom. Supported by first-principles calculations and high-resolution surface topography, we reveal the existence of a layer-dependent behaviour. The balance of electron and hole states is found only when considering at least three Te-W-Te layers, showing that the behaviour of WTe2 is not strictly two dimensional.
B-cell tumorigenesis results from a host of known and unknown genetic anomalies, including non-random translocations of genes that normally function as determinants of cell proliferation or cell ...survival to regions juxtaposed to active immunoglobulin heavy chain enhancer elements, chromosomal aneuploidy, somatic mutations that further affect oncogenic signaling and loss of heterozygosity of tumor-suppressor genes. However, it is critical to recognize that even in the setting of a genetic disease, the B-cell/plasma cell tumor microenvironment (TME) contributes significantly to malignant transformation and pathogenesis. Over a decade ago, we proposed the concept of cell adhesion-mediated drug resistance to delineate a form of TME-mediated drug resistance that protects hematopoietic tumor cells from the initial effect of diverse therapies. In the interim, it has been increasingly appreciated that TME also contributes to tumor initiation and progression through sustained growth/proliferation, self-renewal capacity, immune evasion, migration and invasion as well as resistance to cell death in a host of B-cell malignancies, including mantle cell lymphoma, diffuse large B-cell lymphoma, Waldenstroms macroglobulinemia, chronic lymphocytic leukemia and multiple myeloma. Within this review, we propose that TME and the tumor co-evolve as a consequence of bidirectional signaling networks. As such, TME represents an important target and should be considered integral to tumor progression and drug response.
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