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1.
The dynamics of dangling bond (DB) diffusion was studied after deuterium desorption from the silicon (100)-2x1 surface. At elevated temperatures, paired DB sites produced after desorption unpaired as deuterium atoms hopped from adjacent dimers. Below 620 kelvin, the unpaired configuration most commonly observed corresponded to two DBs on adjacent silicon dimers. At higher temperatures, unpaired DBs executed one-dimensional walks along the dimer rows, and recombination was observed with the same partner after walks lasting many minutes. The frequency and extent of these excursions increased with temperature. Above 660 kelvin, complete dissociation was observed and was sometimes followed by recombination by means of partner exchange. The implications for low-temperature materials growth are discussed. 相似文献
2.
The ability of scanning tunneling microscopy to probe the pathways of thermally activated high-barrier surface processes is frequently limited by competing low-barrier processes that can confuse measurement of the true initial and final configuration. We introduce an approach to circumvent this difficulty by driving the surface process with nanosecond laser heating. The method is applied to determine the pathway of recombinative desorption in the H/Si(001) system. The observed configuration of dangling bonds after laser heating reveals that the desorbed hydrogen molecules are not formed on single dimers, but rather from neighboring silicon dimers via an interdimer reaction pathway. 相似文献
3.
Quantum reflection allows an atom or molecule to be reflected from a solid before it reaches the region where it would encounter the repulsive potential of the surface. We observed nondestructive scattering of the helium dimer (He(2)), which has a binding energy of 10(-7) electron volt, from a solid reflection grating. We scattered a beam containing the dimer as well as atomic helium and larger clusters, but could differentiate the dimer by its diffraction angle. Helium dimers are quantum reflected tens of nanometers above the surface, where the surface-induced forces are too weak to dissociate the fragile bond. 相似文献
4.
Tomatsu K Nakatsuji K Iimori T Takagi Y Kusuhara H Ishii A Komori F 《Science (New York, N.Y.)》2007,315(5819):1696-1698
When tin (Sn) atoms are deposited on a clean germanium (Ge) (001) surface at room temperature, buckled dimers originating from the Sn atoms are formed at the Ge-dimer position. We identified the dimer as a heterogeneous Sn-Ge dimer by reversing its buckling orientation with a scanning tunneling microscope (STM) at 80 kelvin. An atomic seesaw switch was formed for one-dimensional electronic conduction in the Ge dimer-row direction by using the STM to reversibly flip the buckling orientation of the Sn-Ge dimer and to set up standing-wave states. 相似文献
5.
Crystallographic structure of the octameric histone core of the nucleosome at a resolution of 3.3 A 总被引：13，自引：0，他引：13
R W Burlingame W E Love B C Wang R Hamlin H X Nguyen E N Moudrianakis 《Science (New York, N.Y.)》1985,228(4699):546-553
The structure of the (H2A-H2B-H3-H4)2 histone octamer has been determined by means of x-ray crystallographic techniques at a resolution of 3.3 angstroms. The octamer is a prolate ellipsoid 110 angstroms long and 65 to 70 angstroms in diameter, and its general shape is that of a rugby ball. The size and shape are radically different from those determined in earlier studies. The most striking feature of the histone octamer is its tripartite organization, that is, a central (H3-H4)2 tetramer flanked by two H2A-H2B dimers. The DNA helix, placed around the octamer in a path suggested by the features on the surface of the protein, appears like a spring holding the H2A-H2B dimers at either end of the (H3-H4)2 tetramer. 相似文献
6.
An improved quantum Monte Carlo method has been used to calculate the classical barrier height for the hydrogen exchange reaction H + H(2) --> H(2) + H with accuracies greater than previously attained. The method is exact in that, except for the easily estimated Monte Carlo statistical or sampling error, it requires no mathematical approximations or physical approximations beyond those of the Schr?dinger equation. The minimum in the barrier, occurring for the collinear nuclear configuration with the protons separated by 1.757 bohrs, was found to be 9.61 +/- 0.01 kilocalories per mole above H + H(2). 相似文献
7.
Mo YW 《Science (New York, N.Y.)》1993,261(5123):886-888
The scanning tunneling microscope (STM) was used to control the configuration of antimony clusters on the (001) surface of silicon. In particular, the STM tip induced a reversible rotation between two orthogonal orientations of individual antimony dimers on the surface. This simple rotation can be explained by an atomic-scale torque exerted on the antimony dimers by the STM tip. The reversibility of this process could provide a basis for making atomic-scale memory cells. 相似文献
8.
Manolopoulos DE Stark K Werner HJ Arnold DW Bradforth SE Neumark DM 《Science (New York, N.Y.)》1993,262(5141):1852-1855
The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively. 相似文献
9.
With the use of scanning tunneling microscopy, it is shown that germanium atoms adsorbed on the (100) surface of silicon near room temperature form chainlike structures that are tilted from the substrate dimer bond direction and that consist of two-atom units arranged in adjoining substrate troughs. These units are distinctly different from surface dimers. They may provide the link missing in our understanding of the elementary processes in epitaxial film growth: the step between monomer adsorption and the initial formation of two-dimensional growth islands. 相似文献
10.
Fleming DG Arseneau DJ Sukhorukov O Brewer JH Mielke SL Schatz GC Garrett BC Peterson KA Truhlar DG 《Science (New York, N.Y.)》2011,331(6016):448-450
The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 atomic mass units ((4.1)H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of (4.1)H with (1)H(2) to produce (4.1)H(1)H + (1)H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of (0.11)H (where (0.11)H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10(-4) to 10(-2) range. 相似文献
11.
Garand E Zhou J Manolopoulos DE Alexander MH Neumark DM 《Science (New York, N.Y.)》2008,319(5859):72-75
The degree of electronic and nuclear coupling in the Cl + H2 reaction has become a vexing problem in chemical dynamics. We report slow electron velocity-map imaging (SEVI) spectra of ClH2- and ClD2-. These spectra probe the reactant valley of the neutral reaction potential energy surface, where nonadiabatic transitions responsible for reactivity of the Cl excited spin-orbit state with H2 would occur. The SEVI spectra reveal progressions in low-frequency Cl.H2 bending and stretching modes, and are compared to simulations with and without nonadiabatic couplings between the Cl spin-orbit states. Although nonadiabatic effects are small, their inclusion improves agreement with experiment. This comparison validates the theoretical treatment, especially of the nonadiabatic effects, in this critical region of the Cl + H2 reaction, and suggests strongly that these effects are minor. 相似文献
12.
Asmis KR Pivonka NL Santambrogio G Brümmer M Kaposta C Neumark DM Wöste L 《Science (New York, N.Y.)》2003,299(5611):1375-1377
The protonated water dimer is a prototypical system for the study of proton transfer in aqueous solution. We report infrared photodissociation spectra of cooled H+(H2O)2 [and D+(D2O2] ions, measured between 620 and 1900 wave numbers (cm-1). The experiment directly probes the shared proton region of the potential energy surface and reveals three strong bands below 1600 cm-1 and one at 1740 cm-1 (for H5O2+). From a comparison to multidimensional quantum calculations, the three lower energy bands were assigned to stretching and bending fundamentals involving the O...H+...O moiety, and the highest energy band was assigned to a terminal water bend. These results highlight the importance of intermode coupling in shared proton systems. 相似文献
13.
Limburg J Vrettos JS Liable-Sands LM Rheingold AL Crabtree RH Brudvig GW 《Science (New York, N.Y.)》1999,283(5407):1524-1527
The formation of molecular oxygen from water in photosynthesis is catalyzed by photosystem II at an active site containing four manganese ions that are arranged in di-mu-oxo dimanganese units (where mu is a bridging mode). The complex [H2O(terpy)Mn(O)2Mn(terpy)OH2](NO3)3 (terpy is 2,2':6', 2"-terpyridine), which was synthesized and structurally characterized, contains a di-mu-oxo manganese dimer and catalyzes the conversion of sodium hypochlorite to molecular oxygen. Oxygen-18 isotope labeling showed that water is the source of the oxygen atoms in the molecular oxygen evolved, and so this system is a functional model for photosynthetic water oxidation. 相似文献
14.
Neuhauser D Judson RS Kouri DJ Adelman DE Shafer NE Kliner DA Zare RN 《Science (New York, N.Y.)》1992,257(5069):519-522
A fully quantal wavepacket approach to reactive scattering in which the best available H(3) potential energy surface was used enabled a comparison with experimentally determined rates for the D + H(2)(v = 1, j = 1) --> HD(v' = 0, 1, 2; j') + H reaction at significantly higher total energies (1.4 to 2.25 electron volts) than previously possible. The theoretical results are obtained over a sufficient range of conditions that a detailed simulation of the experiment was possible, thus making this a definitive comparison of experiment and theory. Good to excellent agreement is found for the vibrational branching ratios and for the rotational distributions within each product vibrational level. However, the calculated rotational distributions are slightly hotter than the experimentally measured ones. This small discrepancy is more marked for products for which a larger fraction of the total energy appears in translation. The most likely explanation for this behavior is that refinements are needed in the potential energy surface. 相似文献
15.
Gas-liquid scattering experiments provide direct observations of the fate of hydrogen-bonding molecules striking the surfaces of acidic liquids. Collisions of gaseous formic acid with concentrated sulfuric acid show that impinging monomers (HCOOH and DCOOD) scatter inelastically from the interface or become trapped by surface H2SO4. Most trapped DCOOD molecules undergo proton exchange before desorbing from the acid, indicating that gas-surface accommodation almost always leads to reaction with H2SO4 molecules. This proton transfer is not inhibited by dimerization of the formic acid: The dimers readily undergo intramolecular hydrogen bond cleavage and D-H exchange before desorbing from the acid. 相似文献
16.
A full quantum dynamical study of the reactions of a hydrogen atom with water, on an accurate ab initio potential energy surface, is reported. The theoretical results are compared with available experimental data for the exchange and abstraction reactions in H + D2O and H + H2O. Clear agreement between theory and experiment is revealed for available thermal rate coefficients and the effects of vibrational excitation of the reactants. The excellent agreement between experiment and theory on integral cross sections for the exchange reaction is unprecedented beyond atom-diatom reactions. However, the experimental cross sections for abstraction are larger than the theoretical values by more than a factor of 10. Further experiments are required to resolve this. 相似文献
17.
Kitsopoulos TN Buntine MA Baldwin DP Zare RN Chandler DW 《Science (New York, N.Y.)》1993,260(5114):1605-1610
The differential cross section for the H + D(2) --> HD + D reaction has been measured using a technique called reaction product imaging. In this experiment, a photolytically produced beam of hydrogen (H) atoms crossed a beam of cold deuterium (D(2)) molecules. Product D atoms were ionized at the intersection of the two particle beams and accelerated toward a position-sensitive detector. The ion images appearing on the detector are two-dimensional projections of the three-dimensional velocity distribution of the D atom products. The reaction was studied at nominal center-of-mass collision energies of 0.54 and 1.29 electron volts. At the lower collision energy, the measured differential cross section for D atom production, summed over all final states of the HD(v,J) product, is in good agreement with recent quasi-classical trajectory calculations. At the higher collision energy, the agreement between the theoretical predictions and experimental results is less favorable. 相似文献
18.
Zhang P Smith-Nguyen EV Keshwani MM Deal MS Kornev AP Taylor SS 《Science (New York, N.Y.)》2012,335(6069):712-716
In its physiological state, cyclic adenosine monophosphate (cAMP)-dependent protein kinase (PKA) is a tetramer that contains a regulatory (R) subunit dimer and two catalytic (C) subunits. We describe here the 2.3 angstrom structure of full-length tetrameric RIIβ(2):C(2) holoenzyme. This structure showing a dimer of dimers provides a mechanistic understanding of allosteric activation by cAMP. The heterodimers are anchored together by an interface created by the β4-β5 loop in the RIIβ subunit, which docks onto the carboxyl-terminal tail of the adjacent C subunit, thereby forcing the C subunit into a fully closed conformation in the absence of nucleotide. Diffusion of magnesium adenosine triphosphate (ATP) into these crystals trapped not ATP, but the reaction products, adenosine diphosphate and the phosphorylated RIIβ subunit. This complex has implications for the dissociation-reassociation cycling of PKA. The quaternary structure of the RIIβ tetramer differs appreciably from our model of the RIα tetramer, confirming the small-angle x-ray scattering prediction that the structures of each PKA tetramer are different. 相似文献
19.
Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers. 相似文献
20.
Computer simulations of hydrocarbon and related molecules using empirical force fields have become important tools for studying a number of biological and related processes at the atomic scale. Traditional force fields, however, cannot be used to simulate dynamic chemical reactivity that involves changes in atomic hybridization. Application of a many-body potential function allows such reactivity to occur in a computer simulation. Simulations of the reaction of small hydrocarbon molecules adsorbed on a reconstructed diamond {001}(2x1) surface suggest that these hydrocarbons are highly reactive species and that initial stages of diamond growth proceed through a dimer-opening mechanism. Rates estimated from transition state theory of two interconversions between states where the dimer is open and closed are given. 相似文献