Desorption of halogens from some Nb,Mo, Ta and W single crystal surfaces

A systematic investigation of the thermal desorption of halogens from well characterized (111), (100) and (110) 4d (Nb, Mo) and 5d (Ta, W) transition metal surfaces has been carried out under low coverage conditions (θ < 10^?2 of a monolayer). Characterization of the surfaces was achieved by LEED, AES and work function determinations while the desorption kinetics were recorded in a large temperature range (1700–2300 K) using a pulsed ionic beam method. The new data concerning some Ta and W surfaces are presented and the results of this systematic study are discussed. It is shown that the halogen desorption parameters, e.g., desorption energies and preexponential factors, are independent of both surface structure and d bond filling of the substrate; E(F) ～4.75 eV, E(Cl) ～4.1 eV, E(Br) ～3.7 eV and τ₀ ～10^?13 ?10^?14 S. The halogen behaviour is compared with that of other adsorbates and with the predictions of a general chemisorption model.     

A study of the γ-ray decays from single particle states in 91Zr and 93Mo

Lifetimes have been measured in ⁹¹Zr and ⁹³Mo by the Doppler shift attenuation method through the ⁹⁰Zr(¹³C, ¹²C)⁹¹Zr and the ⁹²Mo(¹³C, ¹²C)⁹³Mo reactions. Gamma rays were observed in coincidence with the back scattered particles and the reactions took place at sub-Coulomb energies. The lifetimes measured in ⁹¹Zr are τ(1205) = 250⁺⁹⁰_?70 fs, τ(1467) = 280⁺¹⁶⁰_?110 fs, τ(2042) < 30 fs, τ(2558) = 180⁺⁹⁰_?60 fs. The lifetimes measured in ⁹³Mo are τ(1361) = 170⁺⁸⁰_?40 fs, τ(1494) = 60 ± 40 fs, τ(1697) = 440⁺²³⁰_?130 fs, τ(2705)=160⁺⁸⁰_?60fs These results are compared with the expectations of the shell model and the $\text{3}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→ 2}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{E}\text{2}$ transition is shown to be very enhanced.     

Energies of Cu1+ ions sputtered from Cu by very low energy (50 eV < E < 1 keV) Inert gas ions

He⁺, Ne⁺ and Ar⁺ ions with energies E₁ between 50 and 1000 eV were used to bombard a polycrystalline Cu target at an angle of 45°. The energies, E₂, of the Cu₁⁺ ions sputtered at 90° to the primary beam were investigated using a UHV magnetic sector mass spectrometer. The maxima of the energy distributions as measured by the instrument, were at values of E₂ of about 4 eV (±1 eV), nearly independent of e₁ and primary ion mass. Plots of log N(E₂) versus log E₂ displayed limited linear portions over which the functional dependence of N(E₂) is proportional to E₂^?0.5. Plots of the average secondary ion energy, ē₂, versus the energy transferred by the primary ion to a Cu atom in a direct collision $\text{([}\text{4m}{}_1\text{m}{}_2\text{(m}{}_1\text{+ m}{}_2\text{)}{}^2\text{]E}{}_1\text{)}$, indicate that ē₂ increases linearly with transfer energy up to a transferred energy of about 200 eV, independent of primary ion mass. Above about 200 eV transferred energy, ē₂ asymptotically approaches values which depend upon primary ion mass. At transferred energies below about 200 eV, the collision kinematics in the fust few collisions appears to dominate the emission process.     

Superlattices formed by interaction of hydrogen bromide and hydrogen chloride with Pt(111) and Pt(100) studied by LEED,Auger and thermal desorption mass spectroscopy

HBr and HCl react with Pt(111) and Pt(100) surfaces to form adsorbed layers consisting of specific mixtures of halogen atoms and hydrogen halide molecules. Exposure of Pt(111) to HBr yielded a (3×3) LEED pattern beginning at $\text{Θ}{}_{\mathrm{Br}}\text{=}\text{2}\text{9}$ and persisting at the maximum coverage which consisted of $\text{Θ}{}_{\mathrm{<mtext>Br</mtext>}}\text{=}\text{1}\text{3}$ plus $\text{Θ}{}_{\mathrm{<mtext>HBr</mtext>}}\text{=}\text{1}\text{9}$. The most probable structure at maximum coverage, Pt(111)[c(3 × 3)]-(3 Br + HBr), nas a rhombic unit cell encompassing nine surface Pt atoms, and containing three Br atoms and one HBr molecule. On Pt(100) the structure at maximum coverage appears to be Pt(100)[c(2√2 × √2)]R45°-(Br + HBr), $\text{Θ}{}_{\mathrm{<mtext>Br</mtext>}}\text{= Θ}{}_{\mathrm{<mtext>HBr</mtext>}}\text{=}\text{1}\text{4}$; the rectangular unit cell involves four Pt atoms, one Br atom and one HBr molecule. Each of these structures consists of an hexagonal array of adsorbed atoms or molecules, excepting slight distortion for best fit with the substrate in the case of Pt(100). Treatment of Pt(100) with HCl produced a diffuse Pt(100)(2 × 2)-(Cl + HCl) structure at the maximum coverage of Θ_Cl = 0.13, Θ_HCl = 0.11. Exposure of Pt(111) to HCl produced a disordered overlayer. Thermal desorption, Auger spectroscopy and mass spectroscopy provided coverage data. Thermal desorption data reveal prominent rate maxima associated with the structural transitions observed by LEED. Br and HBr, Cl and HCl were the predominant thermal desorption products.     

Desorption of halogens from Nb,Mo, Ta and W polycrystalline surfaces

The desorption kinetics of halogens from Nb, Ta, Mo and W polycrystalline surfaces are studied, at low coverage (Θ ? 10^?2 of a monolayer) and high temperature (1800–2400 K), using a pulsed ionic beam method. For a relatively high energy incident positive ion beam (? = 2500 eV), the diffusion kinetics of implanted Br and I ions towards the surface are observed. At low energy (? < 500 eV), a first order kinetic corresponding to the desorption of halogens from these surfaces is found. Preliminary results are given on the desorption energy and the preexponential factor of halogens adsorbed on Nb, Mo, Ta and W polycrystalline surfaces. The main result of this systematic study is that the mean adsorption lifetime for a given temperature, as the desorption energy decreases for F through I on all of the studied surfaces. A similarity between Nb and Ta, as between Mo and W surfaces for the desorption energies of halogens is also found.     

Coverage and adsorption-site dependence of core-level binding energies for tin and lead on Al(111) and Ni(111)

Thin layers (0.2–10 monolayers) of Pb and Sn were prepared on Al(111) and Ni(111) surfaces and characterized by means of LEED, AES, UPS and work-function measurements. The binding energy of the shallow Sn 4d and Pb 5d core-levels was investigated with respect to coverage and adsorption-site-dependent changes. On Al(111) the Sn and Pb monolayers exhibit ordered, two-domain, aligned but not in registry structures. For these layers core-level binding energies were found identical to those of the bulk metals. On Ni(111), Pb gives rise to a 3 × 3 structure, followed then by a 4 × 4 structure at higher coverages. The Pb 5d core-level binding energies shift continuously to higher values. A final shift of 0.42 eV is reached after about 2 monolayers. Sn on Ni(111) exhibits two welll separated peaks lying at 23.70 and 23.97 eV for the $\text{4d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ line. These two lines can be correlated with two different adsorption sites which have to be assumed for the $\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ and the (2 × 2) structure found at different coverages. The binding energy shifts are discussed in a model based on a Born-Haber cycle.     

Site-selective adsorption of xenon on a stepped Ru(0001) surface

The adsorption of xenon has been studied with UV photoemission (UPS), flash desorption (TDS) and work function measurements on differently conditioned Ru(0001) surfaces at 100 K and at pressures up to 3 × 10^?5 Torr. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) served to ascertain the surface perfectness. On a perfect Ru(0001) surface only one Xe adsorption state is observed, which is characterized by$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 5.40 and 6.65 eV, an adsorption energy of E_ad≈ 5 kcal/mole and dipole moment of μ'_T ≈ 0.25 D. On a stepped-kinked Ru(0001) surface, the terrace-width, the step-height and step-orientation of which are well characterized with LEED, however, two coexisting xenon adsorption states are distinguishable by an unprecedented separation in$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 800 meV, by their different UPS intensities and line shapes, by their difference in adsorption energy ofΔE_ad ≈ 3 kcal/mole and finally by their strongly deviating dipole moments of μ_S = 1.0 D and μ_T = 0.34 D. The two xenon states (which are also observed on a slightly sputtered surface) are identified as corresponding to xenon atoms being adsorbed at step and terrace sites, respectively. Their relative concentrations as deduced from the UPS intensities quantitatively correlate with the abundance of step and terrace sites of the ideal TLK surface structure model as derived from LEED. Furthermore, ledge-sites and kink-sites are distinguishable via E_ad. The E_ad heterogeneity on the stepped-kinked Ru(0001) surface is interpreted in terms of different coordination and/or different charge-transfer-bonding at the various surface sites. The enormous increase in Xe 5p electron binding energy of 0.8 eV for Xe atoms at step sites is interpreted as a pure surface dipole potential shift. —The observed effects suggest selective xenon adsorption as a tool for local surface structure determination.     

Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

A study of the (00) LEED beam intensity at normal incidence from CdS(0001), Cu(001), Cu(111), and Ni(111)

A Faraday cage apparatus is used for the measurement of the (00) LEED beam intensity, I₍₀₀₎, and the total secondary emission coefficient, δ(E_k), for angles of incidence from 0° ± 2° to 8° ± 2°, with an energy resolution of ± 0.037 of the incident beam energy, in the energy range 1 to 200 eV. The data are normalized and expressed as a fraction of the incident beam intensity. The basic principle of operation is the separation of the incident and specularly diffracted beams in a uniform magnetic field. Monolayer, or in-plane, resonances associated with the emergence of nonspecular beams, as well as beam threshold minima, are observed in I₍₀₀₎ at normal incidence from clean CdS(0001), Cu(111), and Ni(111). Some major differences are observed in the I₍₀₀₎ profiles for the clean (111) surfaces of nickel and copper. All secondary Bragg peaks, except the 2$\text{2}\text{3}$ order, have greater intensities for Ni(111) in the energy range 50–150 eV, thus indicating that the atomic scattering cross-section for electrons in this energy range is larger for nickel than for copper. For the (111) surface of nickel, the (11) resonance is missing, but the (10) resonance and all $\text{1}\text{3}$ order secondary Bragg peaks between the second and fifth orders are observed. For Cu(111) both the (10) and (11) resonances are observed, but the $\text{1}\text{3}$, $\text{2}\text{3}$, 1$\text{2}\text{3}$, and 3$\text{1}\text{3}$ order secondary Bragg peaks are missing in this energy range. These data indicate that multiple scattering with evanescent intermediate waves, or “shadowing”, is predominate on the (111) surfaces on nickel and copper for energies above 30 eV, and that below 30 eV multiple scattering with propagating intermediate waves is predominate on Cu(111). Correlation of the (00) beam intensity profiles from clean Ni(111) at 0°, 2°, and 6° with the intensity profiles of the (10). (1&#x0304;0), and (11) non-specular beams is nearly one-to-one from 30 eV to 100 eV, thus supporting the dynamical theories of LEED in which peaks in the (00) beam are expected to occur at nearly the same energies as peaks in the non-specular beams.     

Study of Ag/Si(111) submonolayer interface: I. Electronic structure by angle-resolved UPS

Angle-resolved ultraviolet photoelectron spectra have been measured for well defined Ag/Si(111) submonolayer interfaces of (1) $\text{Si(111)(}\text{3}\text{×}\text{3}\text{)R30°-Ag}$, (2) “Si(111)(6 × 1)-Ag”, and (3) Ag/Si(111) as deposited at room temperature. Non-dispersive and very narrow (FWHM ～ 0.4–0.5 eV) Ag 4d derived peaks are found at 5.6 and 6.5 eV below the Fermi level for surface (1) and at 5.3 and 6.0 eV for surface (2). Dispersions of sp “binding” states in the energy range between E_F and Ag 4d states have been precisely determined for surface (1). Electronic structures similar to those of the Ag(111) surface, including the surface state near E_F, have been observed for surface (3).     

Oxygen adsorption on the LaB6(100), (110) and (111) surfaces

Oxygen adsorption on the LaB₆(100), (110) and (111) clean surfaces has been studied by means of UPS, XPS and LEED. The results on oxygen adsorption will be discussed on the basis of the structurs and the electronic states on the LaB₆(100), (110) and (111) clean surfaces. The surface states on LaB₆(110) disappear at the oxygen exposure of 0.4 L where a c(2 × 2) LEED pattern disappears and a (1 × 1) LEED pattern appears. The work function on LaB₆(110) is increased to ～3.8 eV by an oxygen exposure of ～2 L. The surface states on LaB₆(111) disappear at an oxygen exposure of ～2 L where the work function has a maximum value of ～4.4 eV. Oxygen is adsorbed on the surface boron atoms of LaB₆(111) until an exposure of ～2 L. Above this exposure, oxygen is adsorbed on another site to lower the work function from ～4.4 to ～3.8 eV until an oxygen exposure of ～100L. The initial sticking coefficient on LaB₆(110) has the highest value of ～1 among the (100), (110) and (111) surfaces. The (100) surface is most stable to oxygen among these surfaces. It is suggested that the dangling bonds of boron atoms play an important role in oxygen adsorption on the LaB₆ surfaces.     

High accuracy energy-level calculations of the rotational-vibrational weakly bound states of ddμ and dtμ mesic molecules

Calculations are performed of the nonrelativistic energies $\text{E}{}_{\mathrm{JV}}$ of rotational-vibrational weakly bound states J = ν = 1 of ddμ and dtμ mesic molecules: $\text{E}{}_{11}\text{(}\text{dd}\text{μ) = ? 1.956}\text{eV}$ and $\text{E}{}_{11}\text{(}\text{dt}\text{μ) = ? 0.656}\text{eV}$ with an accuracy of 0.001 eV. With the relativistic effects and nuclear finite size corrections taken into account the result is: $\text{E}{}_{11}\text{(}\text{dd}\text{μ) = ? 1.946}\text{eV}$ and $\text{E}{}_{11}\text{(}\text{dt}\text{μ) = ? 0.634}\text{eV}$.     

Electroabsorption in TlInS2

Electroabsorption spectra of single crystals have been studied near the fundamental absorption edge at 77 and 300 K. At 300 K two positive peaks (2.34 and 2.42 eV) and a negative peak (2.38 eV) are observed in the electroabsorption spectrum. At liquid-nitrogen temperature a fine structure corresponding to the formation of a parabolic exciton (2.503 eV) is observed.Values of the width of the forbidden gap E_g, the n = 1 exciton positions, the exciton activation energy ΔE_b, the effective Bohr radius a_exc, the reduced effective mass of an electron-hole pair μ, and the exciton ionization field F(E_g = 2.535 eV, E_exc = 2.503 eV, E_b = 32 meV, $\text{a}{}_{\mathrm{<mtext>exc</mtext>}}\text{=}\text{28}\text{A}\text{A;}\text{;}$;, μ = 0.15 m₀, and F = 1.2 × 10⁵ V cm^-1) have been determined from the electroabsorption spectrum.     

Anomalous temperature dependence of third-order elastic constants in NH4Cl and NH4Br near the λ point

Second order elastic constants of NH₄Cl and NH₄Br crystals were measured under hydrostatic and uniaxial pressures near the λ-type phase transitions. Third order elastic constants were calculated from the pressure derivatives of the second order elastic constants. Results show that the temperature dependences of the third order elastic constants of NH₄Cl differ from those of NH₄Br dramatically. In addition, it is found that the coefficients $\text{1}\text{54}\text{(C}{}_{111}\text{+ 6C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ and $\text{(}\text{1}\text{24}\text{√3)(C}{}_{111}\text{? 3C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ of strains in the free energy of NH₄Cl show quite different temperature dependences from those of NH₄Br.     

Study of the 45Sc(n, γ) reaction

Primary and secondary γ-rays from the ⁴⁵Sc(n, γ) reaction were measured at four resonances, two of them of p-wave (460.6 and 1060.4 eV) and the others of s-wave (3290 and 4330 eV) character. High accuracy measurements at near the thermal region (0.14-7.65 eV) resulted in an improved set of primary γ-ray energies and level energies above 1 MeV. We obtain a neutron binding energy $\text{B}{}_{\mathrm{<mtext>n</mtext>}}\text{(}{}^{45}\text{Sc}\text{) = 8760.5(2)}\text{keV}$. Absolute intensities of primary capture γ-rays were derived by comparison to the resonance capture in gold at 4.91 eV. El and Ml radiation strengths were observed to be about equal. No correlation of any kind [either between (n, γ) or (d, p) strengths or between adjacent s- and p-wave capture] was observed. The primary γ-ray spectrum following the capture of polarized neutrons in oriented and unoriented ⁴⁵Sc nuclei was studied. A combined χ² analysis of these two experiments resulted in 21 unique spin assignments and many spin restrictions. The fraction of spin J = 3^? in thermal capture was determined to be (92 + 5)%. From the observed transition rates to final states of known spin, J = 3 assignments result for the two p-wave resonances studied.     

Coupled mode behavior of the soft E(TO) phonon of Pb(Ti1-x,Zrx)O3 and (Pb1-3x2, Lax)TiO3

We report the temperature dependence of the low frequency part (ω < 100 cm^?1) of the Raman spectra of the Pb(Ti_1-x, Zr_x)O₃ and $\text{(}\text{Pb}{}_{\mathrm{<mtext>1-</mtext><mtext>3x</mtext><mtext>2</mtext>}}$, La_x)TiO₃ systems. The spectra indicate a coupled mode behavior between the soft E(TO) phonon and a mode which produces an additional band in the spectra. We discuss the possibility that the additional band might be due to zone boundary tranverse acoustical phonons which couple to the q ～ 0 soft E(TO) mode because of the disorder existing in the systems.     

Multiple coulomb excitation of 167Er

The ground-state rotational band in ¹⁶⁷Er has been investigated through multiple Coulomb excitation with a 160 MeV ³⁵Cl beam. Excited states up to $\text{25}\text{2}{}^{\mathrm{+}}$ were established by measuring γγ coincidences and γ-ray angular distributions. Gamma-gamma angular correlations were also measured. Nuclear lifetimes of levels up to spin $\text{23}\text{2}$ have been determined from Doppler-broadened γ-ray lineshapes, and B(M1) and B(E2) values of intra-band transitions deduced. Considerable signature dependence was observed for level energies and M1 transition probabilities. A Coriolis band-mixing calculation was carried our for comparison with the experimental results. The measured M1 transition probabilities are compared to calculations based on a particle-rotor model, a cranking model, and a microscopic model with quantum-number projection.     

Multiple scattering features in neon ion scattering spectra (ISS) from polycrystalline materials

A systematic investigation of multiple scattering from polycrystalline materials in ion scattering spectrometry was carried out using Ne⁺ at a scattering angle of 90° over the energy range of 100 to 2500 eV. It was found that the intensity of multi scattering shoulders increased with ion beam energy. The intensity at a given energy could be predicted on the basis of interatomic distances of the target. The larger the interatomic distance, the more intense the multi scattering shoulder. The separation of the double scattering shoulder from the binary peak decreased linearly with increasing mass, and the maximum of the shoulder to higher energies from the binary peak could be calculated by the relationship $\text{ΔE}\text{E}{}_0\text{= 0.166 ?(0.00064)M}$, where M is the mass of the target atom.     

Polarization of 12B in deep-inelastic heavy-ion reaction 100Mo(14N, 12B)

Spin polarization of ¹²B was measured for ¹⁰⁰Mo(¹⁴N, ¹²B) at $\text{E}{}_{\mathrm{<mtext>i</mtext>}}\text{(}{}^{14}\text{N}\text{) ? 200}\text{MeV}$ as a function of $\text{Q}$ value down to $\text{Q ? ?150}\text{MeV}$, and was found anti-parallel to $\text{k}{}_{\mathrm{f}}\text{×}\text{k}{}_{\mathrm{i}}$ in the deep-inelastic region. The data together with those at lower incident energies show a systematic trend in $\text{Q}$-value dependence of the polarization.