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1.
Properties of copper condensed on selected areas of a thermally cleaned tungsten surface have been studied by probe hole field emission microscopy. Interpretation of the φhkl?\?gq relationship observed on (211), (111) and (310) for adsorption at T > 300 K is based on hardsphere models of the plane surfaces upon which the first monolayer of copper raises φithkl, the second reduces it to a minimum value, and the third achieves \?gfsat on each plane. At T > 300 K the relatively low binding energy of copper on (110) prevents is population below ~2\?gq as previously observed for lead, and the plateaux in the φ110?\?gq curves are thought to result from the difficulty of nucleating the first and second monolayers of copper on (110). Comparison of our observations with those made by LEED/Auger techniques emphasise significant differences between the substrates used, in that, on field emitters (110) is step-free and surrounded by a sink/ source of adatoms, while the LEED specimen is stepped but has no comparable local sink/ source. The initial changes in φ are ascribed to formation of an adsorbate-substrate dipole whose sign and magnitude is controlled by electron equilibration between the substrate metal and a broadened and partly-filled resonance level lying approximately 5.2 eV below the vacuum level. Measurement of the total energy distribution of electrons field emitted from (110) and (132) supports this picture which contrasts with that of Polanski and Sidorski who consider the dipole sign and strength to be controlled principally by adsite geometry. Low activation energies characterise surface transport which is controlled by one-plane processes, and in some cases transport across the probed area is controlled by processes of relatively high activation energy which take place outside the examined plane.  相似文献   

2.
On atomically rough areas of a thermally cleaned rhenium field emitter, adsorbed gold behaves like it does on tungsten. The average work function \?gf increases at low average gold coverage \?gq due to formation of gold-rhenium dipoles, and at high coverage a structural transformation in the gold layer leads to a \?gq-independent work function. Broadly similar behaviour is found for gold on the low-index planes of tungsten, but on low-index rhenium planes gold behaves rather differently. When thermally cleaned at > 2200 K and annealed below 800 K, the work function, φ(clean), of (101&#x0304;1&#x0304;) takes one of two values 5.25 ± 0.04 eV, and 5.36 ± 0.04 eV, which are tentatively attributed to the two possible structures of this plane. Similar behaviour is expected and observed for (101&#x0304;0),but the values taken by φ(clean) are not well defined. Both forms of (101&#x0304;1&#x0304;) are thought to undergo reconstruction above 800 K forming a single structure with φ(clean) = 5.55 ± 0.03 eV. (112&#x0304;0) and (112&#x0304;2&#x0304;) each have only one possible structure, and in keeping with this, φ(clean) has a single well-defined value for each plane. The flatness of (101&#x0304;1&#x0304;) and (101&#x0304;0) leads to field reduction at their centres which produces an increase in their measured work functions by up to 10%. The initial increase in φ produced by gold condensed at 78 K and spread at low equilibration temperatures Ts on (112&#x0304;2&#x0304;), (101&#x0304;1&#x0304;) and (112&#x0304;0) is attributed to gold-rhenium dipoles, which, on the latter two planes approximate to the Topping model, giving dipoles characterised by μ0(1011) = 0.1 × 10?30 C-m with α = 10 Å3 and μ0(112&#x0304;0) = 0.32 × 10?30 C-m with α = 22 Å3, where μ0 is the zero-coverage dipole moment and α its polarizability. Failure of the Topping model on (112&#x0304;2&#x0304;) is attributed to its atomically rough structure. No dipole effect is seen on (101&#x0304;0). Energy spectroscopy of electrons field emitted at (202&#x0304;1&#x0304;) and (101&#x0304;1&#x0304;) demonstrates the non-free character of electrons in rhenium, while the small effect of adsorbed gold strengthens the belief that gold is bound through a greatly broadened 6s level centred 5.6 eV below the Fermi level and the dipolar nature of the bond supports this model. At higher values of Ts and \?gq gold appears to form states which are well-characterised by a coverage-independent work function. (101&#x0304;0), (101&#x0304;1&#x0304;) and (112&#x0304;0) each form two such states, one in the range 2 < \?gq < 4 (state 1), and the second at \?gq > 4 (state 2). The atomic radii of gold and rhenium are thought to be sufficiently similar to allow the possibility that state 1 is a replication of the Re plane structure by gold. The high work function and thermal stability of state 2, taken together with the observed temperature dependence of the transformation of state 1 to state 2, encourages the belief that state 2 results from atomic rearrangement of state 1 into a close-packed Au(111) structure. State 2 also forms on (112&#x0304;2&#x0304;) and the absence of state 1 on this plane suggests some surface alloying at coverages below 4 \?gq.  相似文献   

3.
An increase in the work function of a copper layer approximately three monolayers deep on tungsten (100) can be thermally induced at temperatures above 540 K. Helium ion microscopy reveals a consequent but small increase in structural perfection of the tungsten substrate surface, which is akin to the rearrangement of gold, but the change in work function of the copper layer appears not to depend upon the rearrangement. Detailed investigation of changes in work function at (100) using a probe-hole field emission microscope shows that copper in the first monolayer increases φ100 by 0.42 eV at monolayer coverage, probably by formation of an array of dipoles of moment μ0 = (1.6 ± 0.5) × 10?30 C m with polarizability α = 3.80 ± 1.8 Å3. A large apparent increase in φ100 of 1.6 eV takes place when a thicker copper layer is spread so that it surrounds and approaches (100), and this is ascribed to a reduction in the field enhancement factor β produced by the surrounding copper. Comparison of the present findings with those of Bauer et al. reveals substantial agreement on the behaviour of the first monolayer and two major differences in the behaviour of thicker layers: (i) an increase in φ100 from 4.25 to 7.1 eV which we observe above 540 K, and (ii) absence of any evidence for breakup of third and higher layers to form crystallites. It is tentatively suggested that (i) results from band-structure changes accompanying structural reorganisation within the adsorbed layer, which take place under experimental conditions not used by Bauer et al., and that (ii) is due to the absence of steps in the probed area of (100) which can act as nucleating centres for crystallite formation on a macroscopic (100) surface.  相似文献   

4.
Alkali atoms were scattered with hyperthermal energies from a clean and an oxygen covered (θ ≈ 0.5 ML) W(110) surface. The trapping probability of K and Na atoms on oxygen covered W(110) has been measured as a function of incoming energy (0–30 eV) and incident angle. A considerable enhancement of trapping on the oxygen covered surface compared to a clean surface was observed. At energies above 25 eV there are still K and Na atoms being trapped by the oxygen covered surface. From the temperature dependence of the mean residence time τ of the initially trapped atoms the pre-exponential factor τ0 and the desorption energy Q were derived using the relation: τ = τ0exp(QkTs). On clean W(110) we obtained for Li: τ0 = (8 ± 84) × 10?14sec, Q = (2.78 ± 0.09) eV; for Na: τ0 = (9 ± 3) × 10?14 sec, Q = (2.55 ± 0.04) eV; and for K: τ0 = (4 ± 1) × 10?13 sec, Q = (2.05 ± 0.02) eV. Oxygen covered W(110) gave for Na: τ0 = (7 ±3) × 10?15 sec, Q = (2.88 ± 0.05) eV; and for K: τ0 = (1.3 ± 0.90.6) × 10?14sec, Q = (2.48 ±0.05) eV. The adsorption on clean W(110) has the features of a supermobile two-dimentional gas; on the oxygen covered W(110) adsorbed atoms have the partition function of a one-dimen-sional gas. The binding of the adatoms to the surface has a highly ionic character in the systems of the present experiment. An estimate is given for the screening length of the non-perfect conductor W(110):ks?1≈ 0.5 Å.  相似文献   

5.
The decomposition of HCOOD was studied on Ni(100). Low temperature adsorption of HCOOD resulted in the desorption of D2O, CO2, CO, and H2. The D2O was evolved below room temperature. CO2 and H2 were evolved in coincident peaks at a temperature above that at which h2 desorbed following H2 adsorption and well above that for CO2 desorption from CO2 adsorption; CO desorbed primarily in a desorption limited step. The decomposition of formic acid on the clean surface was found to yield equal amounts of H2, CO, and CO2 within experimental error. The kinetics and mechanism of the decomposition of formic acid on Ni (110) and Ni(100) single crystal surfaces were compared. The reaction proceeded by the dehydration of formic acid to formic anhydride on both surfaces. The anhydride intermediate condensed into islands due to attractive dipole-dipole interactions. Within the islands the rate of the decomposition reaction to form CO2 was given by:
Rate = 6 × 1015 exp{?[25,500 + ω(ccsat)]/RT} × c
, where c is the local surface concentration, csat is the saturation coverage for the particular crystal plane, and ω is the interaction potential. The interaction potential was determined to be 2.7 kcal/mole on Ni(110) and 1.4 kcal/mole on Ni(100); the difference observed was due to structural differences of the surfaces relating to the alignment of the dipole moments within the islands. These attractive interactions resulted in an autocatalytic reaction on Ni(110), whereas the interaction was not strong enough on Ni(100) to sustain the autocatalytic behavior. Formic acid decomposition oxidized the Ni(100) surface resulting in the formation of a stable surface oxide. The buildup of the oxide resulted in a change in the selectivity reducing the amount of CO formed. This trend indicated that on the oxide surface the decomposition proceeded via a formate intermediate as on Ni(110) O.  相似文献   

6.
The decomposition of D2CO, CH3OD and HCOOH on Pt(110) and of D2CO on Pt(S)-[9(111) × (100)] was studied by molecular beam relaxation spectroscopy. D2CO and CH3OD evolved CO and H2 via a desorption limited sequence of elementary steps. The rate constant for CO desorption from Pt(110) was 6 × 1014exp(? 35.5 kcalgmol · RT) s?1, and from Pt(S)-[9(111) × (100)] it was 1 × 1015 exp(?36.2 kcalgmol·RT) s?1. On Pt(110) the rate constant for hydrogen formation was 100 ± 1exp(?24 kcalgmol·RT) m?2atom · s. On Pt(S)-[9(111) × (100)] two pathways for H2 formation existed with rate constants of 8.7 × 10?2exp( ?24.9 kcalgmol· RT) cm2atom· s and 3.2 × 10?3 exp(?19.5 kcalgmol·RT) cm2atom· s. These pre-exponential factors are in order of magnitude agreement with values typical of hydrogen recombination on other metals. When a small amount of sulfur ( ~ 0.1 ML) was adsorbed on the stepped Pt surface, only one pathway for H2 formation existed due to blockage of stepped sites. A similar result was obtained when a beam of CO was impinged on the surface. Formic acid decomposed via a branched process to form primarily CO2 and H2.  相似文献   

7.
We propose three models which lead to a p.v. nucleon-nucleon interaction mediated by charged and neutral vector mesons. Besides the ad hoc hypothesis of octet dominance, we consider two quark models (the Bose quark and colour Fermi quark model), which give a dynamical explanation of the ΔI = 12 rule in strangeness changing hyperon decays. They lead to p.v. potentials with different isospin dependence. We also derive the weak NN?ρ° coupling from a SU(2) × U(1) gauge theory with neutral currents. The circular polarization Pγ of the γ-quanta in the capture of thermal neutrons on protons is calculated for these different models. The Reid hard-core (HC) and soft-core (SC) potentials have been chosen to take into account the strong interaction. Then the naively factorized Cabbibo current-current interaction with charged rho exchange only gives PγHC = ?2.7 × 10?8 and PγSC = ?2.1 × 10?8. The strong octet dominance and Bose quark model lead to a vanishing circular polarization |Pγ| ≈ (1–4) × 10?9. The colour Fermi quark model enhances the circular polarization and gives Pγ ≈ ?5 × 10?8.  相似文献   

8.
Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D for this direction has roughly the same value for all investigated surfaces: D=7.8×10?2 cm2s?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.  相似文献   

9.
In this work, three different preparation conditions were used for testing the performance of p-conducting copper phthalocyanine (CuPc) organic field-effect transistors (OFETs). The charge carrier mobility (μ sat=(1.5±0.6)×10?3 cm2/V?s) of the CuPc OFETs with the CuPc film deposited while keeping the substrate at room temperature could be improved when the gate dielectric was modified by a self-assembled monolayer of n-octadecyltrichlorosilane (μ sat=(3.8±0.4)×10?3 cm2/V?s) or when elevated temperatures were applied to the substrate (T S,av=127 °C) during the deposition of the organic film (μ sat=(6.5±0.8)×10?3 cm2/V?s). For the latter case, the dependence of the mobility and threshold voltage with increasing thickness of the organic film was tested—above 13 nm film thickness, no further significant increase of the hole mobility or change in the threshold voltage could be observed. The environmental stability of the OFETs was checked by performing ex situ measurements immediately as the sample was exposed to atmosphere and after 40 days of exposure. The effect of the different preparation conditions on the morphology of the organic films prepared in this work is also discussed in this context.  相似文献   

10.
Adsorption of monolayer amounts of bismuth on the 100 surface plane of tungsten has been studied by probe hole field emission microscopy and electron spectroscopy. Sub-monolayer bismuth forms a relatively strongly bound layer of bismuth-tungsten dipoles with dipole moment μ = (0.18 ± 0.02) × 10?30C m and polarizability α = (6.3 ± 1.3) × 10?40J V?2m2. Changes in work function and their dependence on temperature closely parallel those produced by adsorbed lead which was shown by LEED to form c(2 × 2), p(2 × 2) and (1 × 1) structures. Bismuth is thought to behave in a similar way, but, unlike lead, forms a second monolayer which replicates the first. Electron spectroscopy shows that sub-monolayer bismuth removes the surface state (Swanson) peak and at monolayer coverage a new peak emerges and shifts with increasing coverage. Using Gadzuk's theory, this peak is tentatively attributed to the 2P level in bismuth adatoms which form a p(2 × 2) structure in the first and second monolayers. Its shift with coverage is ascribed to an increase in the local surface field. There remains the difficulty of reconciling the proposed occupation of the 2P level with the observed small positive charge on the bismuth adatom.  相似文献   

11.
The ν4 infrared and Raman bands of CH3Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH335Cl, including A0 = 5.20530 ± 0.00010 cm?1 and DK = (8.85 ± 0.13) × 10?5cm?1. For CH337Cl an incomplete set of constants was obtained from the infrared band, and A0 = 5.2182 ± 0.0010 cm?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is r(CH) = 1.0854 ± 0.0005 A?, r(CCl) = 1.7760 ± 0.0003 A?, and <(HCH) = 110°.35 ± 0°.05.  相似文献   

12.
The microwave spectra of 2-fluorophenol and its deuterated species have been observed and analyzed in the frequency ranges 12.5–18.0 GHz (KU band) and 21.5–26.0 GHz (K band) in the ground vibrational state at room temperature. For the normal species, the radio frequency-microwave double resonance spectrum has been recorded in the frequency range 30.0–38.0 GHz. Three rotational and five quartic centrifugal distortion constants for the normal species, A? = 3337.86 ± 0.02, B? = 2231.92 ± 0.01, C? = 1337.52 ± 0.01, dJ = (3.5 ± 2.9) × 10?4, dJK = (?4.9 ± 1.5) × 10?3, dK = (?3.2 ± 1.0) × 10?3, dWJ = (?2.0 ± 1.0) × 10?7, dWK = (2.6 ± 0.8) × 10?6 (in MHz), and three rotational constants for the deuterated species, A? = 3324.70 ± 0.03, B? = 2177.95 ± 0.03, C? = 1315.96 ± 0.03 (in MHz), have been obtained. Consideration of the rs coordinate of the hydroxyl hydrogen atom leads to the assignment of the spectra to the cis conformer of the molecule. An r0 structure for the cis conformer has been proposed. The nonbonded OH ? F distance is lower by about 0.3 Å than the sum of the van der Waals radii.  相似文献   

13.
The isovector part of the parity violating two-pion-exchange NN potential is constructed from the field theoretic amplitude. The parity violating NN coupling is described by the phenomenological Lagrangian gWψ(τ × φ)3ψ, with gW = 3.2 × 10?8. The effect of p-wave ππ correlations is taken into account.  相似文献   

14.
The diffusion constants for C and O adsorbates on Pt(111) surfaces have been calculated with Monte-Carlo/Molecular Dynamics techniques. The diffusion constants are determined to be DC(T)=(3.4 × 10?3e?13156T)cm2s?1 for carbon and DO(T) = (1.5×10?3 e?9089T) cm2 s?1 for oxygen. Using a recently developed diffusion model for surface recombination kinetics an approximate upper bound to the recombination rate constant of C and O on Pt(111) to produce CO(g) is found to be (9.4×10?3 e?9089T) cm2 s?1.  相似文献   

15.
S.B. Lee  M. Weiss  G. Ertl 《Surface science》1981,108(2):357-367
Adsorption of K on Fe(110), (100) and (111) surfaces was studied by means of LEED, AES, thermal desorption and work function measurements. The monolayer capacity is about 5.5 × 1014 K-atoms/cm2 in all three cases. With Fe(111) an ordered 3 × 3 overlayer was found at fairly low coverages. The work function decreases to a minimum and the initial dipole moments were determined to μ0 = 7.0 Debye for Fe(110), μ0 = 4.4 Debye for K/Fe(100) and μ0 = 3.9 Debye for K/Fe(111). The heat of adsorption decreases from its initial value (Fe(110): 57; Fe(100): 54; Fe(111): 52 kcal/mole) continuously with increasing coverage which parallels the continuous decrease of the dipole moment of the adsorbate complex.  相似文献   

16.
The adsorption of Xe on a Ni(100) surface has been studied in UHV between 30 and 100 K using LEED, thermal desorption spectroscopy (TDS), work function (Δφ) measurements, and UV photoemission (UPS). At and below 80 K, Xe adsorbs readily with high initial sticking probability and via precursor state adsorption kinetics to form a partially ordered phase. This phase has a binding energy of ~5.2 kcal/mole as determined by isosteric heat measurements. The heat of adsorption is fairly constant up to medium coverages and then drops continuously as the coverage increases, indicating repulsive mutual interactions. The thermal desorption is first order with a preexponential factor of about 1012 s?1, indicative of completely mobile adsorption. Adsorbed Xe lowers the work function of the Ni surface by 376 mV at monolayer coverage. (This coverage is determined from LEED to be 5.65 × 1014 Xe molecules/cm-2.) For not too high coverages, θ, Δφ(θ) can be described by the Topping model, with the initial dipole moment μ0 = 0.29 D and the polarizability α being 3.5 × 10?24 cm3. In photoemission, the Xe 5p32 and 5p12 orbitals show up as intense peaks at 5.56 and 6.83 eV below Ef which do not shift their position as the coverage varies. Multilayer adsorption (i.e. the filling of the second and third layers) can be seen by TDS. The binding energies of these α states can be estimated to range between 4.5 and 3.5 kcal/mole. The results are compared and contrasted with previous findings of Xe adsorption on other transition metal surfaces and are discussed with respect to the nature of the inert-gas-metal adsorptive bond.  相似文献   

17.
Laser atom-molecule reaction interaction through polarizability and dipole moment contribution leads to potential energy surface barrier reshaping and bound states along the reaction path. The polarizability is maximum in the transition state. We will show here by using gauge representation (electric field gauge) for wave length λ = 20.6 μm, intensity I = 1 × 1012 W/cm2, I = 5 × 1012 W/cm2, I = 1 × 1013 W/cm2, I = 3 × 1013 W/cm2, that we can create laser induced potential energy surface barrier reshaping in the transition state region (–1–0.5 a. u.). We illustrate such effects for the LiH + CH3 ? Li + CH4 reaction with a barrier using ab-initio methods for calculating the reaction path, polarizability and dipole moment contribution of the atom-molecule reaction.  相似文献   

18.
A method to grow single crystals of ammonium vanadate (IV, V) (NH4)2V3O8 has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are a = 8.891 ± 0.004 A? and c = 5.582 + 0.002 A?. The V5+ atom lies at the center of a triangular pyramide (VO4 tetrahedron) while the V4+ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO5 whose symmetry point group is almost C4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g = 1.9263 et gτ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T2 = 0.4 × 10?7s and for spin-lattice relaxation T1 = 1.6 × 10?7s. The magnetic structure is characterized by an exchange narrowing ωe = 3 × 1010rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P2c4bm as the interaction between V4+ ions from consecutive planes parallel to (001).  相似文献   

19.
Previous values of the pressure dependence of the magnetocrystalline anisotropy constant K1 of iron and nickel were revised. These values of K1?1 (dK1dp) depend on the magnetic field for iron, and do not for nickel. The value in iron extrapolated to infinitely strong magnetic field is ?7.8×10?6 bar?1 at room temperature and ?7.3×10?6 bar?1 at 77K, and in nickel at 15 KOe is ?7.5×10?6 bar?1 at room temperature and ?2.8×10?6 bar?1 at 77K.  相似文献   

20.
The hadronic part aH of the muon g-factor anomaly a ≡ (g ? 2)2 is evaluated from latest data on σ(e+e? → hadrons). For a p-wave ππ scattering length of a1 = 0.04±0.005 we calculate aH = (66±10) × 10?9, compared to a(experiment) ? a(QED) = (60±29) × 10?9. Half of the uncertainty on aH is associated with the energy interval 0.92 < s < 2 GeV.  相似文献   

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