Thermodynamics of xenon adsorption on Pd(s)[8(100) × (110)]: From steps to multilayers

The thermodynamic properties of the adsorption of xenon on the stepped Pd(s)[8(100)×(110)] surface have been studied over a wide range of pressure (5×10^?11 to 1×10^?4 Torr) and temperature (40–140 K). We have measured adsorption isobars using AES in order to evaluate the surface coverage. By choosing pressure and temperature we have studied under equilibrium conditions, the successive adsorption of xenon on the steps and on the terraces until the first layer is formed, the condensation of the second layer as well as the formation of xenon multilayers. For a small range of pressure and temperature, adsorption takes place only on the atomic steps. The LEED pattern shows that only every other site along the steps is occupied. The extrapolated initial heat of adsorption for steps is E_ad^S = 10.2 kcal/mol, decreasing monotonically by about 2 kcal/mol as the relative coverage of the step sites increases. The dipole moment of the Xe atoms adsorbed on steps is 1.12 D. During adsorption on the terraces the LEED observations suggest that the xenon adlayer is non-localized up to completion of the hexagonally close packed monolayer. The initial heat of adsorption on the terraces, E_ad^T is 8.2 kcal/mol and decreases continuously to a value of 6.9 kcal/mol for a complete monolayer due to lateral repulsive interactions between the adsorbed xenon atoms. The induced dipole moment of Xe on terraces is reduced to 0.49 D. The 5p_{$\text{1}\text{2}$} binding energy of Xe adsorbed on terrace sites is 0.3 eV smaller than that of Xe occuping step sites. The differential molar entropy of the adsorbed layer on the terraces as a function of coverage compares fairly well with the calculated value for an ideally mobile two-dimensional gas. No indication of the growth of two-dimensional xenon islands has been found under these conditions. The isosteric heat of adsorption for the second layer is E_ad^sec = 5.8 kcal/mol independently of the coverage. The condensation of the second layer is a first order two-dimensional gas ? two-dimensional solid phase transition in opposition to the continuous nature of the adsorption of the first layer (extending over a wide range of temperature for a given pressure). The induced dipole moment is further reduced for the Xe second layer to a value of 0.11 D. Finally, the condensation of multilayers proceeds with a latent heat of transformation of E_cond = 3.8 kcal/mol in excellent agreement with the known bulk value for the heat of sublimation of xenon. The line shape of the NVV low energy Auger transitions of xenon or the UPS binding energies of the Xe 5p_{$\text{3}\text{2}$,$\text{1}\text{2}$} spectra allow a clear distinction between first, second and higher layer Xe atoms. We have also established the temperature/pressure conditions for equilibrium between first, second and bulk xenon layers, i.e. a so-called “roughening point”.     

Interaction of inert gases with a nickel (100) surface: I. Adsorption of xenon

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 $\text{Xe 5p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{5p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ orbitals show up as intense peaks at 5.56 and 6.83 eV below E_f 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.     

X-ray photoelectron spectroscopic study of the physical adsorption of xenon and the chemisorption of oxygen on tungsten (111)

X-ray photoelectron spectroscopy (ESCA) has been used to study the physical adsorption of Xe and the chemisorption of oxygen by W (111). An ultrahigh vacuum ESCA spectrometer has been modified such that thermal desorption behavior from the W (111) crystal can be directly compared with ESCA spectra of the adsorbed species. In addition, since the work function of a W (111) crystal covered with one monolayer of Xe is accurately known from previous work, the binding energy of the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ adsorbate level can be accurately compared to the gaseous $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ level.When Xe is physisorbed to 1 monolayer the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ level exhibits a binding energy (relative to the vacuum level) which is 2.1 eV below that found for Xe (g). At lower Xe coverages the shift becomes monotonically greater, approaching 2.6 eV at a Xe coverage of 0.05. This 0.5 eV shift downward is accompanied by an increase of only 0.05 eV in adsorption energy as coverage decreases, and may be partially caused by the presence of ~ 10–20 % of extraneous adsorption sites other than W (111) which adsorb Xe with higher adsorption energy. The adsorption energy of Xe may also be increased by coadsorption of oxygen and the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ binding energy exhibits a corresponding shift downward as adsorbed oxygen coverage is increased to θ_o = 0.5. Electronic relaxation processes affecting the final state are dominant factors in determining the magnitude of the chemical shift upon adsorption, in agreement with the predictions of Shirley. The magnitude of the relaxation effect seems to be very sensitive to small changes in Xe adsorption energy. Similar effects have been seen for chemisorption of CO.The adsorption of O₂ at 120 K by W (111) yields a single broad O(1s) peak whose line-width decreases with increasing coverage. The final spectra at θ_o = 1 monolayer are very similar to those obtained at temperatures of 300 K or above on polycrystalline tungsten.     

Photoemission of Xe and Kr adsorbed on the W(110) plane

The UPS and XPS spectra of Xe adsorbed on clean, O, CO, and Xe covered W(110) surfaces and the UPS spectrum for Kr on clean and O covered W(110) surfaces have been investigated. On clean W, Xe and Kr show a splitting of the $\text{5p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{4p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ hole states respectively. For Xe the coverage dependence of this splitting was investigated in detail; neither the positions nor the intensity ratio of the substates are coverage dependent for θ ? 0.04, suggesting that splitting is due to differences in the image interaction of the $\text{m}{}_{\mathrm{j}}\text{= ±}\text{3}\text{2}$ and $\text{m}{}_{\mathrm{j}}\text{= ±}\text{1}\text{2}$ components. For Xe equal shifts, relative to vacuum, of ~1.0 eV were observed for 5p, 4d, and 3d levels, suggesting that initial state effects are small. Image interaction for Xe and Kr on clean W could best be fitted by assuming an increase, rather than a decrease in the effective hole-image separation from the nominal value, suggesting that the image plane is moved back into the metal by a screening length. For Xe adsorbed on $\text{Xe}\text{W}$(110), or on virgin-$\text{CO}\text{W}\text{(110)}$ polarization of the intermediate layers was found to contribute significantly to relaxation. Coadsorbed oxygen broadened Xe 5p and Kr 4p peaks. There was an almost linear relation between O 2p UPS intensity at the energies of the various peaks and the amounts of broadening, suggesting that the latter results from resonance neutralization by electrons from the O 2p states.     

Photoemission (XPS,UPS) studies of Pd-Si metallic glasses

The valence bands of glassy $\text{Pd}{}_{\mathrm{100?x}}\text{Si}{}_{\mathrm{x}}\text{(15?x?21)}$ and pure Pd were studied by XPS and UPS. The valence band spectra of the alloys show a strongly reduced density of states at the Fermi energy E_F compared to Pd. From the measured relative photoelectric cross sections for the different excitation energies we conclude that the electron states near E_F of the glassy alloys have mainly d-character. This is in good agreement with recent measurements of the low-temperature specific heat, the magnetic susceptibility and the optical reflectivity.     

Formation of Xe12 by collision pair absorption at 158 nm

Pair absorption from colliding Xe atoms of the molecular fluorine laser radiation is reported. The absorption coefficient for this process at 300 K was found to be α = (4.32 ± 0.1) × 10^-9Torr^-2cm^-1. Fluorescence at 172 nm originating predominantly from the ${}^1\text{Σ}{}^{\mathrm{+}}{}_{\mathrm{u}}$ state of Xe¹₂ indicates that by this mechanism the Xe dimer laser can be pumped optically.     

Spectroscopic information on ground-state Ar2, Kr2, and Xe2 from interatomic potentials

Calculations of vibrational and rotational level spacings of homonuclear inert gas diatomic molecules by numerical integration of the radial Schrödinger equation are presented. The potentials which were used for the ground states of Ar₂, Kr₂, and Xe₂ were obtained from accurate fits to the molecular beam scattering data. From the calculated $\text{Δ}\text{G}{}_{\mathrm{<mtext>v+</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{'}\text{s}$ and B_v's, the following spectroscopic constants (in cm^?1) were fitted: for Ar₂ω_e = 31.92, ω_ex_e = 3.31, ω_ey_e = 0.11, B_e = 0.060, α_e = 0.004; for $\text{Kr}{}_2\text{ω}{}_{\mathrm{e}}\text{? 23.99}$, $\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}\text{? 1.30}$, $\text{ω}{}_{\mathrm{e}}\text{y}{}_{\mathrm{e}}\text{? 0.021}$, $\text{B}{}_{\mathrm{e}}\text{? 0.024}$, $\text{α}{}_{\mathrm{e}}\text{? 0.001}$; for $\text{Xe}{}_2\text{ω}{}_{\mathrm{e}}\text{? 21.26}$, $\text{ω}{}_{\mathrm{e}}\text{x}{}_{\mathrm{e}}\text{? 0.75}$, $\text{ω}{}_{\mathrm{e}}\text{y}{}_{\mathrm{e}}\text{? 0.008}$, $\text{B}{}_{\mathrm{e}}\text{? 0.013}$, $\text{α}{}_{\mathrm{e}}\text{? 0.0004}$.     

The surface structure of V(100)

The structure of the clean V(100)?(1×1) surface is determined, based on an r-factor comparison of experimental LEED intensity-energy spectra with the results of multiple-scattering model calculations. Minimization of the r-factor with respect to the calculational variables leads to optimum values of the first and second interlayer spacings of $\text{d}{}_1\text{=1.41 ± 0.01}\text{A}\text{?}$ and $\text{d}{}_2\text{=1.53 ±0.01}\text{A}\text{?}$, corresponding respectively to a contraction of 7% and an expansion of 1% with respect to the bulk value of $\text{d}{}_{\mathrm{<mtext>B</mtext>}}\text{=1.5141}\text{A}\text{?}$. Preliminary studies of the adsorption of O₂ and CO confirm that the V(100)?(5×1) structure observed during the process of cleaning the crystal is not characteristic of the clean surface, as suggested recently by Davies and Lambert (Surface Science 107 (1981) 391), but rather is associated with the presence of a significant concentration of oxygen in the surface region.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Holtzmark electric field distribution in a two-dimensional electron fluid

The Holtzmark distribution for the thermal electric field at a neutral point in a two-dimensional and uncorrelated electron fluid is given by $\text{β(1 + β}{}^2\text{)}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$, with $\text{β =}\text{E}\text{E}{}_0$, and E₀ = πnZ_pe in terms of the density n and perturber Z_pe.     

Band structural properties of MoS2 (molybdenite)

Semiconductivity and superconductivity in MoS₂ (molybdenite) can be understood in terms of the band structure of MoS₂. We present here the band structural properties of MoS₂. The energy dependence of n_eff and ε_xeff is investigated. Using calculated values of n_eff and ε_xeff, the Penn gap has been determined. The value thus obtained is shown to be in good agreement with the reflectivity data and also with the value obtained from the band structure. The Ravindra and Srivastava formula has been shown to give values for the isobaric temperature gradient of $\text{E}{}_{\mathrm{G}}\text{[}\text{(?E}{}_{\mathrm{G}}\text{?T)}{}_{\mathrm{P}}\text{]}$, which are in agreement with the experimental data, and the contribution to $\text{(}\text{?E}{}_{\mathrm{G}}\text{?T)}{}_{\mathrm{P}}$ due to the electron lattice interaction has been evaluated. In addition, the electronic polarizability has been calculated using a modified Lorentz-Lorenz relation.     

Stark mixing spectroscopy in cesium

We present a new technique for selectively populating excited states which are inaccessible by dipole excitation from the ground state. The method uses a static electric field to introduce a component of a dipole-allowed state into the state of interest. We have applied the method to cesium to measure lifetimes and a Stark mixing coefficient. The results are $\text{τ(6}{}^2\text{D}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)=64(2) ns}$, $\text{τ(7}{}^2\text{D}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)=92.5(15) ns}$, and <6²D_{$\text{5}\text{2}$}|;ez |7²P_{$\text{3}\text{2}$}>/(E_7P?E_6D)=0.7(3)×10^?3 where is in kV/cm. 141     

Stress-induced optical dichroism of V−-centers in MgO

The stress-induced optical dichroism and optical absorption spectra of the V^?-centers in electron irradiated MgO are reported. The dichroism spectrum can be largely attributed to a paraelastic alignment of inherently-dichroic V^?-centers. A curve-fit analysis of the lower-energy portions of the dichroism and absorption spectra yields the ratio of the transition dipole strengths, $\text{D}{}_{\mathrm{\parallel }}\text{D}{}_{\mathrm{\perp }}\text{= 1.55 ± 0.2}$, and the energy splitting, E_∥ ? E_⊥ = 0.22 ± 0.07 eV, for light polarized parallel (∥) and perpendicular (⊥) to the defect symmetry axis. The spectra also have considerable intensity in their high-energy tails, and it is speculated that a portion of this intensity is due to the V-center. The implications of the results with regard to the electronic structure of the center are discussed.     

The co-adsorption of copper and oxygen on a tungsten {100} surface

The co-adsorption of Cu on O₂ and a W{100}surface is studied by Auger electron spectroscopy (AES), thermal desorption (TD), low energy electron diffraction (LEED) and by work function change (δø) measurements. It is shown that the presence of Cu on the surface initially decreases s_O, the sticking coefficient of O₂. For longer oxygen exposures and for higher adsorption temperatures, θ_O reaches values larger than those on the clean surface for the same O₂ exposure. Except at the highest θ_O values and temperatures, the sticcking coefficient for copper, s_Cu, is unity and is independent of the oxygen coverage θ_O in the range studied (0 ? θ_O ? 2). Co-adsorption at room temperatures does not produce any long range order while co-adsorption at elevated temperature leads to the ordered structures (1 × 1), p(2 × 1), p(2 × 2) and c(2 × 2). The saturation coverage of the two dimensional co-adsorbate at 800 K is given by the relation $\text{θ}{}_{\mathrm{Cu}}\text{+}\text{8}\text{5}\text{θ}{}_{\mathrm{O}}\text{= 2}$. The work function is a complicated function of θ_O and θ_Cu and is determined predominantly by the temperature at which oxygen is adsorbed. At high temperatures the sequence of adsorption has no influence, in contrast to the room temperature behavior.     

Anomalous stoner enhancements in amorphous systems

An n-orbital model describing both elastic impurity scattering and exchange interaction is examined near its instability for itinerant ferromagnetism. At the critical point and at zero temperature, long range spin fluctuations cause anomalous enhancements of the density of states near the Fermi energy with $\text{?(E) - ?(E}{}_{\mathrm{F}}\text{) ∝ |E ? E}{}_{\mathrm{F}}\text{|}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$ in three-dimensions (3D) and with ln²|E ? E_F| in 2D. An estimation of the conductivity $\text{σ(Ω)}$ in a continuum analog model reveals Ω^{$\text{1}\text{4}$} -and ln²$\text{|Ω}{}_{\mathrm{\tau }}\text{|}$-corrections in 3D and 2D respectively.     

Structure determination of the clean Co(112&#x0304;0) surface by LEED

The atomic structure of the (112&#x0304;0) surface of cobalt has been determined by LEED using six intensity spectra at normal incidence. The surface exhibits the truncated bulk structure with a contraction of the first interlayer spacing by about 8.5% with respect to the bulk value. Quantitative evaluation of the LEED spectra was done using Zanazzi and Jona's and Pendry's r-factors. The minimum averaged r-factors are $\text{r}{}_{\mathrm{<mtext>ZJ</mtext>}}\text{= 0.09}$ and $\text{r}{}_{\mathrm{<mtext>P</mtext>}}\text{= 0.22}$. No change of the interatomic distances within the plane could be detected and no rearrangement of the surface structure takes place up to temperatures shortly below the transition temperature.