Reactive scattering of small molecules from platinum crystal surfaces: D2CO,CH3OH,HCOOH, and the nonanomalous kinetics of hydrogen atom recombination

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 $\text{kcal}\text{gmol}$ · RT) s^?1, and from Pt(S)-[9(111) × (100)] it was 1 × 10¹⁵ exp(?36.2 $\text{kcal}\text{gmol}\text{·RT}$) s^?1. On Pt(110) the rate constant for hydrogen formation was 10^{0 ± 1}exp(?24 $\text{kcal}\text{gmol}\text{·RT}$) $\text{m}\text{?}{}^2\text{atom}$ · s. On Pt(S)-[9(111) × (100)] two pathways for H₂ formation existed with rate constants of 8.7 × 10^?2exp( ?24.9 $\text{kcal}\text{gmol}\text{· RT}$) $\text{cm}{}^2\text{atom}$· s and 3.2 × 10^?3 exp(?19.5 $\text{kcal}\text{gmol}\text{·RT}$) $\text{cm}{}^2\text{atom}\text{·}$ 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.     

The interaction of oxygen with the Rh(111) surface a

The adsorption of oxygen on Rh(111) at 100 K has been studied by TDS, AES, and LEED. Oxygen adsorbs in a disordered state at 100 K and orders irreversibly into an apparent (2 × 2) surface structure upon heating to T? 150 K. The kinetics of this ordering process have been measured by monitoring the intensity of the oxygen $\text{(1,}\text{1}\text{2}\text{) LEED}$ beam as a function of time with a Faraday cup collector. The kinetic data fit a model in which the rate of ordering of oxygen atoms is proportional to the square of the concentration of disordered species due to the nature of adparticle interactions in building up an island structure. The activation energy for ordering is $\text{13.5 ± 0.5}\text{kcal}\text{mole}$. At higher temperatures, the oxygen undergoes a two-step irreversible disordering (T? 280 K) and dissolution (T?400K) process. Formation of the high temperature disordered state is impeded at high oxygen coverages. Analysis of the oxygen thermal desorption data, assuming second order desorption kinetics, yields values of 56 ± 2 kcal/ mole and 2.5 ± 10^?3 cm² s^?1 for the activation energy of desorption and the pre-exponential factor of the desorption rate coefficient, respectively, in the limit of zero coverage. At non-zero coverages the desorption data are complicated by contributions from multiple states. A value for the initial sticking probability of 0.2 was determined from Auger data at 100 K applying a mobile precursor model of adsorption.     

Search for radiation damage in heavy ion implanted thin layer single crystal SnS22

Single crystal platelets of stannic sulfide (SnS₂, trigonal) mounted with the easy cleavage plane normal to the incident ion beam, were implanted at 100 K with 150 and 350 KeV O⁺ ions to a total dose of $\text{\$}\text{?}$2.5 × 10¹⁷ cm^?2, and subsequently examined by ¹¹⁹Sn Mossbauer spectroscopy in transmission geometry. Despite the expectation that a hot zone of $\text{\$}\text{?}$300 Å radius is created near the end of the ion track, no evidence for the thermal decomposition of SnS₂ to SnS + S is observed for thermally well clamped samples. Data for the lattice temperature of oxygen implanted SnS₂ are compared to that for unirradiated single crystal and randomly oriented powder samples.     

Chemical shifts in auger electron spectra from silicon in silicon nitride

The chemisorption of nitric oxide on (110) nickel has been investigated by Auger electron spectroscopy, LEED and thermal desorption. The NO adsorbed irreversibly at 300 K and a faint (2 × 3) structure was observed. At 500 K this pattern intensified, the nitrogen Auger signal increased and the oxygen signal decreased. This is interpreted as the dissociation of NO which had been bound via nitrogen to the surface. By measuring the rate of the decomposition as a function of temperature the dissociation energy is calculated at 125 kJ mol^?1. At ～860 K nitrogen desorbs. The rate of this desorption has been measured by AES and by quantitative thermal desorption. It is shown that the desorption of N₂ is first order and that the binding energy is 213 kJ mol^?1. The small increase in desorption temperature with increasing coverage is interpreted as due to an attractive interaction between adsorbed molecules of ～14 kJ mol^?1 for a monolayer. The (2 × 3) LEED pattern which persists from 500–800 K is shown to be associated with nitrogen only. The same pattern is obtained on a carbon contaminated crystal from which oxygen has desorbed as CO and CO₂. The (2 × 3) pattern has spots split along the (0.1) direction as $\text{(m,}\text{n}\text{3}\text{)}$ and $\text{(}\text{m}\text{2, n}\text{)}$. This is interpreted as domains of (2 × 3) structures separated by boundaries which give phase differences of $\text{2π}\text{3}$ and π. The split spots coalesce as the nitrogen starts to desorb. A (2 × 1) pattern due to adsorbed oxygen was then observed to 1100 K when the oxygen dissolved in the crystal leaving the nickel (110) pattern.     

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.     

Adsorption of oxygen on Pt(111)

Oxygen adsorbed on Pt(111) has been studied by means of temperature programmed thermal desorption spectroscopy (TPDS). high resolution electron energy loss spectroscopy (EELS) and LEED. At about 100 K oxygen is found to be adsorbed in a molecular form with the axis of the molecule parallel to the surface as a peroxo-like species, that is, the OO bond order is about 1. At saturation coverage (θ_mol= 0.44) a $\text{(}\text{3}\text{2}\text{×}\text{3}\text{2}\text{)R15°}$ diffraction pattern is observed. The sticking probability S at 100 K as a function of coverage passes through a maximum at θ = 0.11 with S = 0.68. The shape of the coverage dependence is characteristic for adsorption in islands. Two coexisting types of adsorbed oxygen molecules with different OO stretching vibrations are distinguished. At higher coverages units with v-OO = 875 cm^?1 are dominant. With decreasing oxygen coverages the concentration of a type with v-OO = 700 cm^?1 is increased. The dissociation energy of the OO bond in the speices with v-OO = 875 cm^?1 is estimated from the frequency shift of the first overtone to be ~ 0.5 eV. When the sample is annealed oxygen partially desorbs at ~ 160K, partially dissociates and orders into a p(2×2) overlayer. Below saturation coverage of molecular oxygen, dissociation takes place already at92 K. Atomically adsorbed oxygen occupies threefold hollow sites, with a fundamental stretching frequency of 480 cm^?1. In the non-fundamental spectrum of atomic oxygen the overtone of the E-type vibration is observed, which is “dipole forbidden” as a fundamental in EELS.     

Effect of surface states on the amphoteric behavior of Sn in vapor epitaxial GaAs

The amphoteric behavior of Sn, a commonly-used dopant in AsCl₃GaH₂ vapor epitaxy, is examined for Sn concentration from 5 × 10¹⁴ to 5 × 10¹⁷cm^?3. The compensation ratio $\text{(}\text{N}{}_{\mathrm{A}}\text{N}{}_{\mathrm{D}}\text{)}$ remains constant at 0.23 for low concentrations and begins to increase in the 10¹⁶cm^?3 range. This behavior can be explained quantitatively with non-equilibrium impurity incorporation model which takes into account 3 × 10¹¹ cm^?2 surface states.     

Search for long-lived particles in 200 GeV/c proton-nucleon collisions

A search for long-lived particles (τ ? 10^?8 sec), with changes $\text{±}\text{2}\text{3}\text{, ± 1, ±}\text{4}\text{3}\text{and}\text{± 2}$, produced in 200 GeV pN collisions was performed at the CERN-SPS in a secondary beam equipped with superconducting r.f. separators. Upper limits were obtained for the production of long-lived hadrons and leptons. For charge - 1 particles the limits are at the level of 10^?7 of the pions at a mass m = 0.2 GeV and reach the 10^?11 level from $\text{3}\text{to}\text{8}\text{GeV}$. The production of light antinuclei was measured. The cross sections for ³He production are (1.3 ± 0.3) and (1.9 ± 0.3) × 10^?34 cm²/sr · GeV/c at 21 and 47.4 GeV/c respectively; for t the cross section is (7.6 ± 0.9) × 10^?34 cm²/sr · GeV/c at 23.7 GeV/c.     

AES study of nickel carburization: Electron beam-induced effects

A preliminary study of the CO/CO₂ carburization of (111) Ni at 217°C and 1 × 10^?6 Torr total pressure by Auger electron spectroscopy was undertaken. It was found that electron beam (～20 μA, ～2500 μA/cm², 3 kV) induced effects were significant for CO and CO₂ adsorbed on the nickel surface; these effects could be factored out by using delayed beam techniques. The electron-induced reactions were similar in both cases and plots of normalized carbon peak height versus time could be characterized by the equation $\text{C = A(1-}\text{e}{}^{\mathrm{<mtext>?</mtext><mtext>t</mtext><mtext>\tau </mtext>}}$) were τ_CO = 32.0 min , A_CO = 206.2, τ_CO2 = 39.8 min, A_CO2 = 176.2. Observed oxygen peaks were smaller than expected. The evidence of several researchers suggests electron beam induced dissociation of CO and CO₂ followed by electron beam induced desorption of the resulting oxygen. Reactant gas interaction with the electron gun cathode was significant with resulting beam movements causing scatter in AES peak height measurements.     

The GaP(001) surface and the adsorption of Cs

GaP(001) cleaned by argon-ion bombardment and annealed at 500°C showed the Ga-stabilized GaP(001)(4 × 2) structure. Only treatment in 10^?5 Torr PH₃ at 500°C gave the P-stabilized GaP(001)(1 × 2) structure. The AES peak ratio $\text{P}\text{Ga}$ is 2 for the (4 × 2) and 3.5 for the (1 × 2) structure. Cs adsorbs with a sticking probability of unity up to 5 × 10¹⁴ Cs atoms cm^?2 and a lower one at higher coverages. The photoemission measured with uv light of 3660 Å showed a maximum at the coverage of 5 × 10¹⁴ atoms cm^?2. Cs adsorbs amorphously at room temperature, but heat treatment gives ordered structures, which are thought to be reconstructed GaP(001) structures induced by Cs. The LEED patterns showed the GaP(001)(1 × 2) Cs structure formed at 180°C for 10 h with a Cs coverage of 5 × 10¹⁴ atoms cm^?2, the GaP(001)(1 × 4) Cs formed at 210°C for 10 hours with a Cs coverage of 2.7 × 10¹⁴ atoms cm^?2, the GaP(001)(7 × 1) and the high temperature GaP(001)(1 × 4), the latter two with very low Cs content. Desorption measurements show three stability regions: (a) between 25–150°C for coverages greater than 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.2 eV; (b) between 180–200°C with a coverage of 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.8 eV; (c) between 210–400°C with a coverage of 2.7 × 10¹⁴ atoms cm^?2, and an activation energy of 2.5 eV.     

The adsorption of acetylene on W(100) at room temperature: An electron spectroscopic study

The adsorption of acetylene on W(100) at room temperature has been studied by AES, ELS, thermal desorption, mass spectrometry, work function and LEED in one vacuum chamber. AES line profile analysis shows that there are at least two adsorption processes occurring at room temperature. Further, it is possible to explain all the AES results by assuming non-sequential adsorption into just two states, denoted by α and β. This picture was substantiated and embellished by comparison with other standard surface techniques. The α-state comprises either a C₂H₂ unit with an activation energy for desorption of $\text{2.3}\text{eV}\text{molecule}\text{(53}\text{kcal mole}{}^{\mathrm{?1}}\text{)}$ or CH units bounded through the carbon of the β-state. Saturation coverage for the α-state is 3 × 10¹⁴ molecules cm^?2. The β-state is dissociative at low acetylene exposures and comparison between a carbon covered surface and the β-state suggest the latter to be dissociative up to saturation. There also appears to be ca. 10¹⁴ hydrogen atoms cm^?2 on W(100) on room temperature acetylene saturation, the carbon content of the β-state being 9 × 10¹⁴ atoms cm^?2. The residual C?C bond from the molecule in the β-state remains unknown. No sign of ordering in the adsorbed species was detected, save the possibility of (1 × 1) in the β-state. Acetylene adsorption at 580 K showed hydrogen from the β-state to block acetylene adsorption by 15% at saturation. A two-site adsorption model for the β-state is proposed to explain the results. The α-state is bonded through the carbon of the β-state and it is speculated that the former adsorbs onto “β” domains where there is a critical minimum size for the latter.     

Ionic transport in the lithium nitride bromides,Li6NBr3 and Li1 3N4Br

The ionic and electronic conductivities of the lithium nitride bromides Li₆NBr₃ and Li_{1 3}N₄Br have been studied in the temperature range from 50 to 220°C and 120 to 450°C, respectively. Both compounds are practically pure lithium ion conductors with negligible electronic contribution. Li₆NBr₃ has an ionic conductivity Ω of 2 × 10^-6Ω^-1cm^-1 at 100°C and an activation enthalpy for σT of 0.46 eV. Li_{1 3}N₄Br shows a phase transition at about 230°C. The activation enthalpy for σT is 0.73 eV below and 0.47 eV above this temperature. The conductivities at 150 and 300°C were found to be 3.5 × 10^-6 Ω^-1cm^-1 and 1.4 × 10^-3Ω^-1cm^-1, respectively. The crystal structure is hexagonal at room temperature with $\text{a = 7.415 (1)}\text{A}\text{?}$ and $\text{c = 3.865 (1)}\text{A}\text{?}$.     

High resolution studies of NiSi2 ultrathin film formation by ion scattering and cross-section tem

Ultrathin epitaxial NiSi₂ films (0–40 Å) have been grown on Si(111) surfaces. Medium energy ion shadowing and blocking has been used to determine the orientation, morphology and interfacial order of these films. For the whole coverage range studied ((0–1) × 10¹⁶ Ni $\text{atoms}\text{cm}{}^2$) the films are found to be rotated 180° about the surface normal with respect to the Si(111) substrate. Using the high depth resolution of the technique the annealed films are shown to consist initially of islands, which coalesce into continuous films for coverages above ≈ 5 × 10¹⁵ Ni $\text{atoms}\text{cm}{}^2$. High resolution cross-section transmission electron microscopy shows the NiSi₂Si interface to be atomically abrupt. This interface has been probed directly using the ion channeling technique, and the number of disordered Ni atoms at the interface is found to be less than 7.5 × 10¹³$\text{atoms}\text{cm}{}^2$.     

Reexamination of the I2 spectrum near the B(3Π0u+) state dissociation limit

The disagreement of Danyluk and King's (Chem. Phys.25, 343 (1977)) rotational constants for levels lying near the dissociation limit of B-state I₂ with the mechanical behavior predicted by near-dissociation theory is investigated. The discrepancies are shown to be much too large to be explained by either the neglect of centrifugal distortion effects in the original analysis or by rotational or spin-rotation coupling to a nearby repulsive 1_u state. These differences are therefore attributed to experimental error, a conclusion which is confirmed by more recent experimental results. A reanalysis of the best available data for levels near the dissociation limit of B-state I₂ then yields improved values for the B-state dissociation limit $\text{D}$ = 20 043.16 (±0.02) cm^?1 of the vibrational index at dissociation v_$\text{D}$ = 87.32 (±0.04) and of the long-range potential constant $\text{C}{}_5\text{= 2.88 (±0.03) × 10}{}^5\text{cm}{}^{\mathrm{?1}}\text{A}\text{?}{}^5$. This in turn implies a slightly improved ground-state dissociation energy of $\text{D}$₀ = 12 440.18 (±0.02) cm^?1.     

Quantum efficiency and radiative lifetime in degenerate n-type GaAs

The hole lifetime, the radiative lifetime, the non-radiative lifetime, and the internal quantum efficiency in degenerate n-type GaAs crystals have been investigated with a simplified model of degenerate semiconductors, in which the recombination constant B is approximately proportional to the$\text{?13}\text{8}$ power of the electron density.In n-type GaAs at 77 K, the radiative lifetime reaches a minimum equal to 4 × 10^?9 sec. at 6 × 10¹⁷ cm^?3, and the internal quantum efficiency exhibits a maximum equal to 50% at 8 × 10¹⁷cm^?3, in good agreement with the theoretical prediction of Dumke and the experiments of Cusano. At high impurity concentrations, the polytropy effect is taken into account in the case of GaAs crystals doped with tellurium and selenium. Finally, it is suggested that, for a given high concentration, the internal quantum efficiency increases with increasing temperature, in accordance with the observed results.     

Co desorption and adsorption on Pt(111)

The kinetics of the desorption of CO from a Pt(111) crystal between 419 and 505 K is reported using a Low-Energy Molecular-Beam-Scattering (LEMS) technique with a helium probe beam and a CO dosing beam. The resulting first-order Arrhenius rate constant is $\text{k = 2.7 × 10}{}^{13}\text{exp(?31.1}\text{kcal}\text{mole}\text{· RT) s}{}^{\mathrm{?1}}$. We also report a study of the equilibriumadsorbed CO between 400 and 600 K using LEMS. These results, fitted to a Temkin isotherm model, indicate that the adsorption energy decreases linearly with surface coverage with the average value equal to $\text{31.1 + 1.2}\text{kcal}\text{mole}$ over the coverage range 0 < θ ? 0.5. The average harmonic oscillator frequency of the adsorbed CO molecules is 191 ± 76 cm^?1.     

Adsorption of sulfur dioxide and the interaction of coadsorbed oxygen and sulfur on Pt(111)

The adsorption of sulfur dioxide and the interaction of adsorbed oxygen and sulfur on Pt(111) have been studied using flash desorption mass spectrometry and LEED. The reactivity of adsorbed sulfur towards oxygen depends strongly on the sulfur surface concentration. At a sulfur concentration of 5 × 10¹⁴ S atoms cm^?2 ($\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ structure) oxygen exposures of 5 × 10^?5 Torr s do not result in the adsorption of oxygen nor in the formation of SO₂. At concentrations lower than 3.8 × 10¹⁴ S stoms cm^?2 ((2 × 2) structure) the thermal desorption following oxygen dosing at 320 K yields SO₂ and O₂. With decreasing sulfur concentration the amount of desorbing O₂ increases and that of SO₂ passes a maximum. This indicates that sulfur free surface regions, i.e. holes or defects in the (2 × 2) S structure, are required for the adsorption of oxygen and for the reaction of adsorbed sulfur with oxygen. SO₂ is adsorbed with high sticking probability and can be desorbed nearly completely as SO₂ with desorption maxima occurring at 400, 480 and 580 K. The adsorbed SO₂ is highly sensitive to hydrogen. Small H₂ doses remove most of the oxygen and leave adsorbed sulfur on the surface. After adsorption of SO₂ on an oxygen predosed surface small amounts of SO₃ were desorbed in addition to SO₂ and O₂ during heating. Preadsorbed oxygen produces variations of the SO₂ peak intensities which indicate stabilization of an adsorbed species by coadsorbed oxygen.     

Preparation and semiconducting properties of Th3As4

The resistivity, thermoelectric power and Hall constant in the temperature range of 78–830 K were determined for polycrystalline Th₃As₄ samples obtained by annealing thin thorium slabs in arsenic vapour. The samples examined were n-type semiconductors with a carrier concentration ranging from 1.0 × 10¹⁸cm^?3 to 2.8 × 10¹⁸ cm^?3 for which the effective mass was found to be equal to 0.55–0.76m₀. The Hall mobility, about 450cm²V^?1s^?1 at room temperature, obeys a $\text{T}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$ law at high temperatures. On the basis of the electrical measurements the forbidden gap of Th₃As₄ was found to be equal to 0.43 eV.     

Evidence for charmed baryon “elastic” production in neutrino reactions at the CERN SPS

Evidence for charmed baryon “elastic” production is found in a sample of 55 000 charged-current neutrino interactions in the bubble chamber Gargamelle exposed to the SPS wide-band neutrino beam. The product of the average cross section times the branching ratio into modes including a Λ⁰ or a $\text{K}$⁰p system is found to be α·B=(14.3 ± 7.4) × 10^?40 cm² for ν+n reactions and α · B<3.3×10^?40 cm² (90% CL) for ν+p reactions.     

Composition,structure, surface states,and O2 sticking coefficient for differently prepared GaAs(1&#x0304;1&#x0304;1&#x0304;)As surfaces

The polar GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface can be prepared in three stable and ordered states: two by molecular beam epitaxy (MBE), namely the As-stabilized and the Ga-stabilized states and one simply by ion bombardment and annealing at 770 K. The respective LEED structures are $\text{(2 × 2), (}\text{19}\text{×}\text{19}\text{)}\text{R}\text{23.4°}$, and (1 × 1) with a diffuse faint (3 × 3) superstructure. Auger measurements and the comparison with the stoichiometric cleaved (110) surface show that there are different As concentrations in the first atomic layer associated with each of these three surfaces. Whereas about 10 to 15% of the first As layer appears to be missing on the (2 × 2) surface, about 50% is missing on the $\text{19}$ surface. On the (1 × 1) surface the first As layer is removed completely. The intensity of emission from the surface sensitive states between 1 and 4 eV below the valence band edge, as seen by angular resolved UPS, roughly corresponds to the amount of As at the surface thus confirming their interpretation as As-derived surface states. The inital sticking coefficent for oxygen depends strongly on the surface structure: ～10^?8 for the (2 × 2), ～10^?7 for the $\text{19}$, and ～10^?4 for the (1 × 1) surface. The sticking coefficient does not depend on the surface concentration of As but rather on the degree of saturation of dangling bonds on Ga atoms.