A measurement of surface diffusion across steps on a curved surface (Pd on W)

The surface diffusion of palladium on the curved part of a tungsten crystal is studied by field electron microscopy. The variation of the local coverage distribution is measured by a probe-hole device on the stepped surface region around (001). The measured data allow a determination of the mass transport surface diffusion coefficient D of Pd on W across atomic steps as a function of temperature, coverage and step density. D has been found (1) to be constant for a given step density and for coverages lower than about 5 × 10¹⁴ Pd adatoms/cm², (2) to increase for higher coverages, and (3) to increase with increasing step density for a given coverage. The activation energy of the process is nearly constant (about 24 kcal/mol) for all coverages up to about 6 × 10¹⁴ adatoms/cm², while the pre-exponential factor of D increases with increasing step density. Interpretation of the results gives some information on the diffusion mechanism.     

Quasi-elastic neutron scattering of benzene in Na-mordenite

The rotational and translational dynamics of benzene adsorbed in Na-mordenite have been studied by incoherent quasi-elastic neutron scattering. The measurements were performed at two benzene coverages at 300, 400 and 450 K. The observed quasi-elastic broadenings are described by a uniaxial rotational model about the six-fold axis of benzene. The mean time between successive jumps, at 300 K, is τ=1.45 × 10^?12 s at low coverage and 2.05×10^?12 s at high coverage. The correlation times follow an Arrhenius law with E_A=4.51 kJ mol^?1, at both coverages. The translational diffusion coefficient has been measured at 300 K and was found to be 0.67 × 10^?6 cm²s^?1.     

Chemisorption of H2 on W(100): Absolute sticking probability,coverage, and electron stimulated desorption

Measurements of both the absolute sticking probability near normal incidence and the coverage of H₂ adsorbed on W(100) at ~ 300K have been made using a precision gas dosing system; a known fraction of the molecules entering the vacuum chamber struck the sample crystal before reaching a mass spectrometer detector. The initial sticking probability S₀ for H₂/W(100) is 0.51 ± 0.03; the hydrogen coverage extrapolated to S = 0 is 2.0 × 10¹⁵ atoms cm^?2. The initial sticking probability S₀ for D₂/W(100) is 0.57 ± 0.03; the isotope effect for sticking probability is smaller than previously reported. Electron stimulated desorption (ESD) studies reveal that the low coverage β₂ hydrogen state on W(100) yields H⁺ ions upon bombardment by 100 eV electrons; the ion desorption cross section is ~ 1.8 × 10^?23 cm². The H⁺ ion cross section at saturation hydrogen coverage when the β₁ state is fully populated is ? 10^?25 cm². An isotope effect in electron stimulated desorption of H⁺ and D⁺ has been found. The H⁺ ion yield is ? 100 × greater than the D⁺ ion yield, in agreement with theory.     

Adsorption of nitrogen on platinum

The adsorption and desorption of nitrogen on a platinum filament have been studied by thermal desorption techniques. Nitrogen adsorption becomes significant only after any carbon contamination is removed from the surface by heating the platinum filament in oxygen, and after the CO content in the background gas is reduced substantially. At room temperature nitrogen populates an atomic tightly bound β-state, E^≠ = 19 kcal mole^?1. The saturation coverage of the (3-state is 4.5 × 10¹⁴ atoms cm^?2. Formation of the (β-state is a zero order process in the pressure range studied. At 90 K two additional α₁- and α₂-desorption peaks are observed. The activation energy for desorption for the α₂-state is 7.4 kcal mole^?1 at low coverage decreasing to 3 kcal mole^?1 at saturation of this state, 6 × 10 molecules cm^?2. The maximum total coverage in the α-states was 1.2 × 10¹⁵ molecules cm^?2. A replacement process between the β- and α-states has been observed where each atom in the (β-state excludes two molecules from the α-state.     

Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

Diffusion and compressibility of sodium on the (110) plane of tungsten

The surface diffusion parameters and the compressibility of sodium on the (110) plane of tungsten have been measured using the field emission fluctuation method for sodium coverages from 0.2 to 3 × 10¹⁴ atoms cm^?2 and for temperatures from 170 to 500 K. Two temperature regimes can be defined. In the high temperature regime (? 300 K) the diffusion is essentially normal with an activation energy ranging from 0.28 to 0.58 eV and a preexponential coefficient D₀ from 10^?8.1 to 10^?2.7 cm² s^?1. In this regime the compressibility increases with temperature indicating an effective repulsive adatoms interaction. In the low temperature regime (? 300 K) the diffusion coefficient decreases with temperature at high coverage and slowly increases with temperature at lower coverage. The transition between both regimes appears on the compressibility versus temperature curve as an inflection point. The comparison of the present results with slow electron diffraction results furnishes strong evidence that the observed transition corresponds to a continuous short-range order-disorder transition.     

Chemically driven diffusion of Pd in the surface region of Zn(0001): An ultraviolet photoemission investigation

The diffusion of deposited Pd through the (0001) surface region of zinc has been studied with photoemission at hν = 21.2 eV by following the time evolution of the Zn 3d and Pd 4d peaks for a Pd initial coverage of 1, 3, 10 and 15 monolayers. The time decay of the Pd 4d signal is explained with a model where the diffusion coefficient D is not constant; it is (4.6 ± 0.5) × 10^?19 cm² s^?1 for t?7000s, then decreases to (5.5 ± 1) × 10^?20 cm² s^?1 for t ? 15,000 s. The D values correlate well with the spectroscopic results on the valence state evolution during diffusion. At short times (higher D) the spectra show an electron energy gain of Pd atoms during diffusion while at higher time (lower D) this gain is negligible. The initial diffusion is chemically driven while at longer times the diffusion becomes gradually entropic.     

Absolute coverages of CO and O on Pt(111); Comparison of saturation CO coverages on Pt(100), (110) and (111) surfaces

Nuclear microanalysis (NMA) has been used to determine the absolute coverages of oxygen and CO adsorbed on Pt(111). The saturation oxygen coverage at 300 K is 3.9 ± 0.4 × 10¹⁴ O atoms cm^?2 (θ = 0.26 ± 0.03), confirming the assignment of the LEED pattern as p(2 × 2). The saturation CO coverage at 300 K is 7.4 ± 0.3 × 10¹⁴ CO cm^?2 (θ = 0.49 ± 0.02). The low temperature saturation CO coverages on Pt(100), (110) and (111) surfaces are compared.     

Chromium tracer diffusion in NiO crystals

Diffusion of ⁵¹Cr in NiO single crystals in air has been studied by the tracer-sectioning technique. In the temperature range 1192–1642°C, the diffusion coefficient can be expressed by the Arrhenius expression D=D_oexp(-Q/RT), with D_o=(8·6±1·2)×10^?3 cm²/sec and Q=67·4±1·1 kcal/mole. The use of a high specific-activity tracer and a special configuration for the diffusion anneal prevented the self-dopling effect found by Seltzer and the evaporation of chromium from the sample surface. The present results, in conjunction with published results on nickel self-diffusion in NiO and interdiffusion in the NiO?Cr₂O₃ system, are used to determine a chromium ion-vacancy binding energy of about 5 kcal/mole in pure NiO.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

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.     

EHD-photoluminescence kinetics in doped Ge

Measurements of the LA-phonon assisted line kinetics of the EHD photoluminescence in As- and Sb-doped germanium with impurity concentrations n_D = 10¹⁵ ? 10¹⁷ cm^?3 are presented. These kinetics are found to be strongly dependent on the excitation level at 4.2 K. From the experimental results and a simplified kinetic equation the EHD “diffusion length” in Ge:As sample with n_D = 2 × 10¹⁶ cm^?3 is estimated to be L_D ? 0.34 mm which is consistent with previous results.     

Analysis of the ν6(A″2) band of cyclopropane-d6 recorded under high resolution

The parallel band ν₆(A″₂) of C₃D₆ near 2336 cm^?1 has been studied with high resolution (Δν = 0.020 – 0.024 cm^?1) in the infrared. The band has been analyzed using standard techniques and the following parameters have been determined: B″ = 0.461388(20) cm^?1, D″_J = 3.83(17) × 10^?7 cm^?1, ν₀ = 2336.764(2) cm^?1, α^B = (B″ ? B′) = 8.823(12) × 10^?4 cm^?1, β^J = (D″_J ? D′_J) = 0, and α^C = (C″ ? C′) = 4.5(5) × 10^?4 cm^?1.     

The analysis of symmetric rotor Raman spectra: The pure rotational spectrum of 11BF3

The pure rotational Raman spectrum of ¹¹BF₃ has been photographed. Great care was taken in the analysis to consider all the unresolved components under each observed Raman line profile. If this is ignored, systematic errors result. The final set of molecular constants obtained was B₀ = 0.34502(±3 × 10^?5)cm^?1, D_J = 4.38(±0.10) × 10^?7cm^?1, and D_JK = ?9.1(±1.0) × 10^?7cm^?1.     

Heterodiffusion of chromium and cobalt in liquid iron

The heterodiffusion has been studied by the method of stationary diffusion source. In that method the saturated radioactive vapour of the diffusing element comes into contact with the liquid in which diffusion is being studied. Two variants of that method were applied and the diffusion coefficients of chromium and cobalt in liquid iron were determined, i.e.D _{(Cr→Fe, 1860K)}= =4·9×10^?5cm²/s andD _{(Co→Fe, 1820K)}=5×10^?5cm²/s, respectively. The values of maximum concentration of chromium in Fe-samples after diffusion were of the order of 10^?1 to 10^?2 wt-%, those of cobalt of 10^?4 wt-%. This experimental method is rather simple and the results obtained are in good conformity with other measurements.     

The adsorption and desorption of oxygen on the Pt(110) surface; A thermal desorption and LEED/AES study

The interaction of oxygen with a Pt(110) crystal surface has been investigated by thermal desorption mass spectroscopy, LEED and AES. Adsorption at room temperature produces a β-state which desorbs at ~800 K. Complete isotopic mixing occurs in desorption from this state and it populates with a sticking probability which varies as (1 ? θ)², both observations consistent with dissociative adsorption. The desorption is second order at low coverage but becomes first order at high coverage. The saturationcoverage is 3.5 × 10¹⁴ mol cm^?2. The spectra have been computer analysed to determine the fraction desorbing by first (β₁) and second (β₂) order kinetics as a function of total fractional coverage θ using this fraction as the only adjustable parameter. The β₁ desorption commences at θ ～ 0.25 and β₁ and β₂ contribute equally to the desorption at saturation. The kinetic parameters for β₁ desorption were calculated from the variation of peak temperature with heating rate as ν₁ = 1.7 × 10⁹ s^?1 and E^≠₁ = 32 kcal mole^?1 whereas two different methods of analysis gave consistent parameters ν₂ = 6.5 × 10^?7 cm² mol^?1 s^?1 and E^≠₂ = 29 and 30 kcal mole^?1 for β₂ desorption. The kinetics of desorptior are discussed in terms of the statistics for occupation of near neighbour sites. While many fea tures of the results are consistent with this picture, it is concluded that simple models considering either completely mobile or immobile adlayers with either strong or zero adatom repulsion are not completely satisfactory. The thermal desorption surface coverage has been correlated with the AES measurements and it has been possible to use the AES data for PtO as an internal standard for calibration of the AES oxygen coverage determination. At low temperature (170 K) oxygen populates an additional molecular α-state. Adsorption into the α- and β-states is competitive for the same sites and pre-saturation of the β-state at 300 K excludes the α-state. This, together with the AES observation that the adsorption is enhanced and faster at 450 than 325 K suggests a low activation energy for adsorption into the β-state.     

A high-resolution study of the 14.4-μm infrared band of deuterofluoroform

The FT-IR spectrum of the ν₃ parallel band of deuterofluoroform has been recorded at a resolution of 0.0045 cm^?1. Nine independent spectral parameters were determined which reproduce some 650 observed wavenumbers with a standard error of 3 × 10^?4 cm^?1. The constants derived for the ν₃ band are (in cm^?1): ν₀ = 694.2822(3); B₀ = 0.3309321(9); B₃ = 0.3302464(11); α^B = 6.859(10) × 10^?4; α^C = 1.429 × 10^?4; D₃^J = 3.168(3) × 10^?7; D₀^J = 3.188(3) × 10^?7; D_JK³ = 4.766 × 10^?7; D_JK⁰ = 4.864 × 10^?7; and D_K⁰ ? D_K³ = 2 × 10^?10.     

Vibration-rotation spectra of ethane and deuteroethanes: The ν2 band of CH3CD3

The ν₂ band of CH₃CD₃ has been measured under an effective resolution of 0.04 cm^?1. About 400 transitions observed in the region from 2130 to 2060 cm^?1 have been identified as due to the ν₂ fundamental band. The least-squares analysis of these transitions yields the band constants: ν₀ = 2089.957, B′ = 0.548937, D_J′ = 6.97 × 10^?7, D_JK′ = 1.92 × 10^?6, A′ - A″ = ?0.01158, and D_K′ - D_K″ = 1.30 × 10^?6 cm^?1. The ground-state constants B″, D_J″, and D_JK″ are fixed to the values obtained from microwave spectroscopy.     

Analysis of the 2ν3 band of 12CD3F at 5.06 μm recorded under high resolution

The 2ν₃(A₁) band of ¹²CD₃F near 5.06 μm has been recorded with a resolution of 20–24 × 10^?3 cm^?1. The value of the parameter (α^B ? α^A) for this band was found to be very small and, therefore, the K structure of the R(J) and P(J) manifolds was unresolved for J < 15 and only partially resolved for larger J values. The band was analyzed using standard techniques and values for the following constants determined: ν₀ = 1977.178(3) cm^?1, B″ = 0.68216(9) cm^?1, D″_J = 1.10(30) × 10^?6 cm^?1, α^B = (B″ ? B′) = 3.086(7) × 10^?3 cm^?1, and β^J = (D″_J ? D′_J) = ?3.24(11) × 10^?7 cm^?1. A value of α^A = (A″ ? A′) = 2.90(5) × 10^?3 cm^?1 has been obtained through band contour simulations of the R(J) and P(J) multiplets.     

A monte-carlo/molecular dynamics study of the diffusional recombination kinetics of C(a) + O(a) → CO(g) on Pt(111)

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 D_C(T)=(3.4 × 10^?3e^{$\text{?13156}\text{T}$})cm²s^?1 for carbon and D_O(T) = (1.5×10^?3 e^{$\text{?9089}\text{T}$}) 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^{$\text{?9089}\text{T}$}) cm² s^?1.     

The adsorption of CO on the (100) plane of tungsten; thermal and work function measurements

Thermal desorption and work function measurements indicate that a largely molecular layer, with some dissociation, is formed at 80–100 K, with an increase in work function of 0.55 eV. The coverage in this layer is 11.5 × 10¹⁴ molecules/cm², or CO/W = 1.15. On heating, equal amounts of a β precursor, possibly dissociated, and a molecular α species are formed at ≈300 K, with abundances of 5 × 10¹⁴ molecules/cm² each. The α desorption is complete at 360 K. The β precursor evolves on heating without desorption in the range 400–700 K as indicated by work function decreases, to β-CO, which is almost certainly dissociated. This change occurs at lower temperatures for low coverages. Thermal desorption shows 3 peaks, which have been traditionally labelled β_{1, β2}, and β₃ at 930, 1070, and 1375 K. Of these only β₃ corresponds to a well defined state. Readsorption after heating to 950 or 1150 K results in a doubly peaked spectrum at 1070 and 1375 K. The β₁ and β₂ peaks obey complex desorption kinetics, probably corresponding to desorption and rearrangement. The coverage of β₃ is 2.5 × 10¹⁴ molecules/cm², suggesting that the c(2 × 2) LEED pattern corresponds to occupany of every other unit cell by a C or an O atom. For coverages ? 1.5 × 10¹⁴ molecules/cm² β₃ desorption obeys second order kinetics with an activation energy of 83 ± 3 kcal/mole. For β₃ the work function decreases from the clean W value by 0.1 eV, suggesting adsorption of C and O in the center of the W unit mesh, below the surface layer of W atoms. Readsorption on β and β precursor layers leads to formation of electropositive α-CO, with a multiply peaked thermal desorption spectrum, indicating the existence of different binding sites. Adsorption-heatingreadsorption, -heating-readsorption sequences indicate that additional changes in the α desorption spectrum occur, suggesting reconstruction in the β layer.