Atomic-resolution microscopy in water

The scanning tunneling microscope is revolutionizing the study of surfaces. In ultra-high vacuum it is capable not only of imaging individual atoms but also of determining energy states on an atom-by-atom basis. It is now possible to operate this instrument in water. Aqueous optical microscopy is confined to a lateral resolution limit of about 2000 angstroms, and aqueous x-ray microscopy has yielded a lateral resolution of 75 angstroms. With a scanning tunneling microscope, an image of a graphite surface immersed in deionized water was obtained with features less than 3 angstroms apart clearly resolved. Further, an image measured in saline solution demonstrated that the instrument can be operated under conditions useful for many biological samples.     

Images of the DNA double helix in water

The scanning tunneling microscope can image uncoated DNA submerged in water. The grooves of the double helix were clearly resolved in images of the 146-base pair fragment extracted from calf thymus nucleosome. In contrast to images obtained with dry DNA, the helix pitch varied only a small amount (36 +/- 5 angstroms). The path of the helix shows considerable variation. It is quite straight when the molecules are densely packed, but it curves and bends in isolated molecules.     

Evidence for coherent proton tunneling in a hydrogen bond network

We observed coherent proton tunneling in the cyclic network of four hydrogen bonds in calix[4]arene. The tunneling frequency of 35 megahertz was revealed by a peak in the magnetic field dependence of the proton spin-lattice relaxation rate measured with field-cycling nuclear magnetic resonance in the solid state at temperatures below 80 kelvin. The amplitude of the coherent tunneling peak grows with temperature according to a Boltzmann law with energy D/kB = (125 +/- 10) kelvin (where kB is Boltzmann's constant). The tunneling peak can be interpreted in the context of level crossings in the region where the tunneling frequency matches the proton Larmor frequency. The tunneling spectrum reveals fine structure that we attribute to coupling between the hydrogen bonds in the network. The characteristics of the tunneling peak are interpreted in the context of the potential energy surface experienced by the hydrogen atoms in the network.     

Electron tunneling through organic molecules in frozen glasses

Reaction rates extracted from measurements of donor luminescence quenching by randomly dispersed electron acceptors reveal an exponential decay constant of 1.23 per angstrom for electron tunneling through a frozen toluene glass (with a barrier to tunneling of 1.4 electron volts). The decay constant is 1.62 per angstrom (the barrier, 2.6 electron volts) in a frozen 2-methyl-tetrahydrofuran glass. Comparison to decay constants for tunneling across covalently linked xylyl (0.76 per angstrom) and alkyl (1.0 per angstrom) bridges leads to the conclusion that tunneling between solvent molecules separated by approximately 2 angstroms (van der Waals contact) is 20 to 50 times slower than tunneling through a comparable length of a covalently bonded bridge. Our results provide experimental confirmation that covalently bonded pathways can facilitate electron flow through folded polypeptide structures.     

Formation of nanometer-scale grooves in silicon with a scanning tunneling microscope

Grooves a few nanometers wide can be formed on a Si(111) surface with a scanning tunneling microscope when the tip is above a critical voltage. This may provide a promising approach to nanodevice fabrication. The dependence of the critical voltage on tunneling current, tip polarity, and tip material was studied with silver, gold, platinum, and tungsten tips. The results are consistent with field emission of positive and negative silicon ions. The variation of critical voltage with current is explained quantitatively by a simple tunneling equation that includes the effect of the contact potential between tip and sample.     

Macroscopic quantum effects in nanometer-scale magnets

Quantum tunneling, the passage of a microscopic system from one state to another by way of a classically forbidden path, is theoretically possible in the macroscopic world. One can now make direct observations of such macroscopic quantum tunneling in very small magnetic structures. This is possible because of significant advances both in the ability to obtain magnetic systems of almost any desirable size, shape, and composition and in the development of superconducting instrumentation for the detection of extremely weak magnetic signals. As an example, measurements on magnetic horse spleen ferritin proteins with the predictions of quantum tunneling theory are discussed and shown.     

Molecular light emission induced by inelastic electron tunneling

Light emission from molecular layers has been induced by inelastically tunneling electrons in a tunneling junction. The fast quenching of molecular emission on metal surfaces was suppressed by use of the "transparent conductor" indium-tin-oxide for the junction electrodes. The emission measurements have been made in squeezable tunneling junctions as small as 10(-9) square centimeters, coated with 9-10 dichloro-anthracene layers. At a bias of 2.5 to 3.5 volts, yields of 5000 photons per microcoulomb were observed. Evidence for the molecular origin of the emission is given. This method shows good prospects for use in the imaging of chromophores on surfaces with atomic resolution.     

Electron tunneling paths in proteins

One of the crucial issues in biological electron transfer is the determination of the role of spatially intermediate amino acid residues in controlling or directing the electronic tunneling interaction between redox sites. A quantum path integral Monte Carlo method is developed for the analysis of electronic tunneling pathways in a highly structured environment. This path integral method is applied to intramolecular electron transfer in a ruthenium-modified myoglobin that contains a tryptophan in the "line-of-flight." A principal result is the identification of the relevant cylindrical zone swept out by the tunneling electron.     

Quantum low-temperature limit of a chemical reaction rate

The radiation-induced polymerization of formaldehyde has been studied in the solid state. The time of addition of one new link to a polymer chain increases exponentially in accordance with the Arrhenius law at 140 to 80 K, but approaches a constant value (approximately 10(-2) second) at temperatures below 10 K. Thus, a low-temperature limit to a chemical reaction rate has been observed. It is interpreted as a quantum effect caused by tunneling from the zero vibration level of the initial state, and a semiquantitative theory is given. The phenomenon should be taken into account for understanding tunneling of electrons in biological systems when such tunneling is accompanied by conformational changes. It could also be significant in slow, exothermic chemical reactions at low and ultralow temperatures, which may have had a role in chemical and biological evolution (cold prehistory of life?).     

Hole-burning spectroscopy and relaxation dynamics of amorphous solids at low temperatures

The magnitude and temperature dependence of most of the properties of amorphous solids are anomalous at very low temperatures ( less, similar1 Kelvin). Phonon-assisted tunneling of a distribution of glassy bistable configurations, or two-level systems, can account for these anomalies. A unified understanding of the low-temperature properties is required for an understanding of the glassy state. Persistent nonphotochemical hole burning of impurity optical transitions allows a glass state to be produced that is thermally inaccessible to the preburn state, and that allows the probing of tunneling dynamics on time scales that range between picoseconds and days. These data combined with recently obtained distribution functions for the two-level systems offer new insights into the tunneling dynamics.     

Negative differential resistance on the atomic scale: implications for atomic scale devices

Negative differential resistance (NDR) is the essential property that allows fast switching in certain types of electronic devices. With scanning tunneling microscopy (STM) and scanning tunneling spectroscopy, it is shown that the current-voltage characteristics of a diode configuration consisting of an STM tip over specific sites of a boron-exposed silicon(111) surface exhibit NDR. These NDR-active sites are of atomic dimensions ( approximately 1 nanometer). NDR in this case is the result of tunneling through localized, atomic-like states. Thus, desirable device characteristics can be obtained even on the atomic scale.     

Observation of single-electron charging in double-barrier heterostructures

Incremental single-electron charging of size-quantized states has been observed in the well in submicrometer double-barrier resonant tunneling devices. In order to distinguish between the effects of size quantization and the single-electron charging, the heterostructure material was grown asymmetrical so that one barrier is substantially less transparent than the other. In the voltage polarity such that the emitter barrier is more transparent than the collector barrier, electrons accumulate in the well; incremental electron occupation of the well is accompanied by Coulomb blockade, which leads to sharp steps of the tunneling current. In the opposite voltage polarity the emitter barrier is less transparent than the collector barrier and the tunneling current reflects resonant tunneling through size-quantized well states.     

Probing the Local Effects of Magnetic Impurities on Superconductivity

The local effects of isolated magnetic adatoms on the electronic properties of the surface of a superconductor were studied with a low-temperature scanning tunneling microscope. Tunneling spectra obtained near magnetic adsorbates reveal the presence of excitations within the superconductor's energy gap that can be detected over a few atomic diameters around the impurity at the surface. These excitations are locally asymmetric with respect to tunneling of electrons and holes. A model calculation based on the Bogoliubov-de Gennes equations can be used to understand the details of the local tunneling spectra.     

Atomic-scale coupling of photons to single-molecule junctions

Spatial resolution at the atomic scale has been achieved in the coupling of light to single molecules adsorbed on a surface. Electron transfer to a single molecule induced by green to near-infrared light in the junction of a scanning tunneling microscope (STM) exhibited spatially varying probability that is confined within the molecule. The mechanism involves photo-induced resonant tunneling in which a photoexcited electron in the STM tip is transferred to the molecule. The coupling of photons to the tunneling process provides a pathway to explore molecular dynamics with the combined capabilities of lasers and the STM.     

Dynamically controlled protein tunneling paths in photosynthetic reaction centers

Marcus theory has explained how thermal nuclear motions modulate the energy gap between donor and acceptor sites in protein electron transfer reactions. Thermal motions, however, may also modulate electron tunneling between these reactions. Here we identify a new mechanism of nuclear dynamics amplification that plays a central role when interference among the dominant tunneling pathway tubes is destructive. In these cases, tunneling takes place in protein conformations far from equilibrium that minimize destructive interference. As an example, we demonstrate how this dynamical amplification mechanism affects certain reaction rates in the photosynthetic reaction center and therefore may be critical for biological function.     

Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules

The bistability in the position of the two hydrogen atoms in the inner cavity of single free-base naphthalocyanine molecules constitutes a two-level system that was manipulated and probed by low-temperature scanning tunneling microscopy. When adsorbed on an ultrathin insulating film, the molecules can be switched in a controlled fashion between the two states by excitation induced by the inelastic tunneling current. The tautomerization reaction can be probed by resonant tunneling through the molecule and is expressed as considerable changes in the conductivity of the molecule. We also demonstrated a coupling of the switching process so that the charge injection in one molecule induced tautomerization in an adjacent molecule.     

Imaging quasiparticle interference in Bi2Sr2CaCu2O8+delta

Scanning tunneling spectroscopy of the high-Tc superconductor Bi2Sr2CaCu2O8+delta reveals weak, incommensurate, spatial modulations in the tunneling conductance. Images of these energy-dependent modulations are Fourier analyzed to yield the dispersion of their wavevectors. Comparison of the dispersions with photoemission spectroscopy data indicates that quasiparticle interference, due to elastic scattering between characteristic regions of momentum-space, provides a consistent explanation for the conductance modulations, without appeal to another order parameter. These results refocus attention on quasiparticle scattering processes as potential explanations for other incommensurate phenomena in the cuprates. The momentum-resolved tunneling spectroscopy demonstrated here also provides a new technique with which to study quasiparticles in correlated materials.     

动态规划最优控制在非线性系统中的应用

从控股股东掏空行为的视角,采用中国上市公司的贷款数据分析中国的商业银行对企业的监督作用。研究发现,银行对控股股东的掏空行为具有一定的监督作用,在银行贷款数量多、贷款期限长的公司中,控股股东的掏空行为明显减少。对不同所有制的企业,银行的监督作用存在异质性。目前,银行的监督作用主要体现在国有银行中,而国有银行能有效监督的对象仅限于地方政府和私人控制的企业,国有银行对中央企业的监督能力较弱。从事后监督来看,银行会对控股股东的掏空行为做出贷款政策的调整,对于控股股东掏空严重的企业,续新贷款的银行数量、续新贷款比例显著下降,而且贷款利率显著提高。     

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10(10) molecules (a fraction of a monolayer) on a 1-square-millimeter junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.