X-ray photoelectron spectroscopic study of the adsorption of N2 and NO on tungsten

X-ray photoelectron spectroscopy (ESCA) has been used in a study of N₂ and NO adsorbed on a polycrystalline tungsten ribbon. The sample was flash cleaned under ultrahigh vacuum conditions, and cooled to either 300 K or 100 K for the adsorption studies. Large chemical shifts, as great as 8 eV, were observed between the N (1s) spectra associated with the weakly chemisorbed γ-nitrogen states and the strongly chemisorbed β-nitrogen states. Chemical shifts in both the N(1s) and O(1s) spectra suggest that NO is largely non-dissociatively chemisorbed at 100 K. In general, the binding energies of N(1s) and O(1s) electrons in the adsorbed layers are smaller than the binding energies for the same atoms in small gaseous molecules. In addition, the binding energies associated with the weakly-bound states of NO and N₂ are invariably greater than the binding energies associated with strongly chemisorbed species.     

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.     

Interaction of NO with a Ni (111) surface

The interaction of NO with a Ni (111) surface was studied by means of LEED, AES, UPS and flash desorption spectroscopy. NO adsorbs with a high sticking probability and may form two ordered structures (c4 × 2 and hexagonal) from (undissociated) NO_ad. The mean adsorption energy is about 25 $\text{kcal}\text{mole}$. Dissociation of adsorbed NO starts already at ?120°C, but the activation energy for this process increases with increasing coverage (and even by the presence of preadsorbed oxygen) up to the value for the activation energy of NO desorption. The recombination of adsorbed nitrogen atoms and desorption of N₂ occurs around 600 °C with an activation energy of about 52 $\text{kcal}\text{mole}$. A chemisorbed oxygen layer converts upon further increase of the oxygen concentration into epitaxial NiO. A mixed layer consisting of N_ad + O_ad (after thermal decomposition of NO) exhibits a complex LEED pattern and can be stripped of adsorbed oxygen by reduction with H₂. This yields an N_ad overlayer exhibiting a 6 × 2 LEED pattern. A series of new maxima at ≈ ?2, ?8.8 and ?14.6 eV is observed in the UV photoelectron spectra from adsorbed NO which are identified with surface states derived from molecular orbitals of free NO. N_ad as well as O_ad causes a peak at ?5.6 eV which is derived from the 2p electrons of the adsorbate. The photoelectron spectrum from NiO agrees closely with a recent theoretical evaluation.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.     

Tunable diode laser measurements of the band strength and collision halfwidths of nitric oxide

The strength of the fundamental absorption band of nitric oxide at 5.3 μm and collision halfwidths of nitric oxide lines broadened by nitrogen, argon, and combustion gases were measured in absorption cell, flat flame and shock tube experiments using a tunable diode laser. Room temperature absorption measurements were made in an absorption cell filled with NO/N₂ or NO/Ar mixtures or with probe-extracted combustion gases. High temperature (to 2500 K) absorption measurements were performed for NO in N₂ and NO in Ar using a shock tube, and for NO in combustion gases using a flat flame burner.Absorption measurements were made on lines from 1860–1925 cm^?1, ($\text{Ω=}\text{1}\text{2}$ and $\text{3}\text{2}$,P($\text{5}\text{2}$-R ($\text{29}\text{2}$)) resulting in a band strength of 123±8 cm^-2 atm^?1 at 273.2 K. Collision halfwidth dependencies for each broadening species were examined as a function of rotational quantum number and temperature.     

Adsorption,coadsorption, and reactivity of sodium and nitric oxide on Ag(111)

The adsorption, desorption, and surface structural properties of Na and NO on Ag(111), together with their coadsorption and surface reactivity, have been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption of NO into the a-state occurs at 300 K with an initial sticking probability of ~0.1, saturation occurring at a coverage of $\text{~}\text{1}\text{20}$. Desorption occurs reversibly without decomposition and is characterised by a desorption energy of E_d ~ 103 kJ mol^?1. In the coverage regime 0 < θ_Na < 1, sodium adsorbs in registry with the Ag surface mesh and the desorption spectra show a single peak corresponding to E_d ~ 228 kJ mol^?1. For multilayer coverages (1 < θ _Na < 5) a new low temperature peak appears in the desorption spectra with E_d ~ 187 kJ mol^?1. This is identified with Na desorption from an essentially Na surface, and the desorption energy indicates that Na atoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The LEED results show that Na multilayers grow as a (√7 × √7) R19.2° overlayer, and are interpreted in a way which is consistent with the above conclusion. Coadsorption of Na and NO leads to the appearance of a more strongly bound and reactive chemisorbed state of NO (β-NO) with E_d ~ 121 kJ mol^?1. β-NO appears to undego surface dissociation to yield adsorbed O and N atoms whose subsequent reactions lead to the formation of N₂, N₂O, and O₂ as gaseous products. The reactive behaviour of the system is complicated by the effects of Na and O diffusion into the bulk of the specimen, but certain invariant features permit us to postulate an overall reaction mechanism, and the results obtained here are compared with other relevant work.     

Adsorption of NO and CO on a Ru(1010) surface

A combination of modern surface measurement techniques such as LEED, AES and Thermal Desorption Spectroscopy were used to study the chemisorptive behavior of NO and CO on a $\text{(10}\text{1}\text{0)Ru}$ surface. The experimental evidence strongly favors a model in which NO adsorbs and rapidly dissociates into separate nitrogen and oxygen adsorbed phases, each exhibiting ordered structures: the C(2 × 4) and (2 × 1) structures at one-half and full saturation coveilage, respectively. At temperatures as low as 200°C, the nitrogen phase begins to desorb, and continuous exposure to NO in this temperature range results in an increasing oxygen coverage until the surface is saturated with oxygen and no further NO dissociation can take place. The nitrogen desorption spectrum depends strongly on coverage and exhibits several peaks which are related to structure of the adsorbed phase. There is evidence that once the surface is saturated with the dissociated NO phase further NO adsorption occurs in a molecular state. Carbon monoxide adsorbs in a molecular state and does not exhibit an ordered structure. The implications of the results with respect to the catalytic reduction of NO by H₂ and CO and the N₂ selectivity of Ru catalysts are discussed.     

An X-ray photoelectron spectroscopic study of the adsorption of N2, NH3, NO,and N2O on dysprosium

The adsorption of N₂, NH₃, NO, and N₂O onto clean polycrystalline dysprosium at 300 and 115 K and the changes undergone by the adsorbed species upon heating from 115 K have been investigated using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). At 115 K, N₂ adsorbs dissociatively, vielding two peaks in the N 1s region at 396.2 and 398.2 eV corresponding respectively to a nitride and to chemisorbed nitrogen N(a). No peaks corresponding to molecularly adsorbed N₂ (BE 400.2 eV [10]) were observed. Upon heating the sample the N(a) is converted into the nitride species, as evidenced by a decrease in the 398.2 eV peak and a corresponding increase in the 396.2 eV peak. At a warm-up temperature of 300 K, the N(a) species accounts for only ～10% of the total nitrogen on the surface. Ammonia adsorbed at 115 K shows three distinct peaks, at 401.7, 399.3 and 396.2 eV, corresponding to molecular, partly dissociated, and completely dissociated (nitride) ammonia. Upon heating multilayer ammonia to 175 K, it desorbs to leave predominantly the peak corresponding to the partly dissociated species. Upon further heating the molecular and partly dissociated ammonia is converted into the nitride species. At 400 K only nitride-type nitrogen remains on the surface. The adsorption of NO and N₂O at 115 K is predominantly dissociative. NO has N 1s peaks at 403.1 and 396.3 eV corresponding possibly to molecularly adsorbed NO, and to nitride species. After N₂O adsorption there is very little nitrogen on the surface. Adsorption of N₂ and NO at 300 K yields only the peak at 396.2 eV, whereas NH₃ yields, in addition to this peak, a small intensity (～20%) of the peak at 398.2 eV (partly dissociated ammonia).     

Chemisorption and surface reactivity of nitric oxide on clean and sodium-dosed Ag(110)

The chemisorption of NO on clean and Na-dosed Ag(110) has been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption into the α-state occurs at 300 K with an initial sticking probability of ～0.1, and the surface is saturated at a coverage of about $\text{1}\text{25}$. Desorption occurs without decomposition, and is characterised by an enthalpy of E_d ～104 kJ mol^?1 — comparable with that for NO desorption from transition metals. Surface defects do not seem to play a significant role in the chemistry of NO on clean Ag, and the presence of surface Na inhibits the adsorption of αNO. However, in the presence of both surface and subsurface Na, both the strength and the extent of NO adsorption are markedly increased and a new state (β₁NO) with E_d ～121 kJ mol^?1 appears. Adsorption into this state occurs with destruction of the Ag(110)-(1 × 2)Na ordered phase. Desorption of β₁NO occurs with significant decomposition, N₂ and N₂O are observed as geseous products, and the system's behaviour towards NO resembles that of a transition metal. Incorporation of subsurface oxygen in addition to subsurface Na increases the desorption enthalpy (β₂NO), maximum coverage, and surface reactivity of NO still further: only about half the adsorbed layer desorbs without decomposition. The bonding of NO to Ag is discussed, and comparisons are made with the properties of α and βNO on Pt(110).     

Adsorption of carbon monoxide on polycrystalline nickel films

The adsorption states of carbon monoxide on polycrystalline nickel films have been investigated by measuring the thermal desorption, the heat of adsorption, the change in resistivity, and the change in work function in dependence on coverage and temperature. It can be shown that there are two chemisorbed (β₂, β₂) and one weakly bound (γ) species. Desorption peaks appear at 170K, 310–360 K, and 460–490 K. The differential heat of adsorption is $\text{30}\text{kcal}\text{mole}$ at low coverages and approximately $\text{25}\text{kcal}\text{mole}$ between 0.3 and 0.6 monolayers. The resistivity of the nickel film is characteristically changed with increasing coverage, and there is a maximum of resistivity at half a monolayer. At low coverages the increase in the work function is proportional to the amount adsorbed; at a monolayer the total increase is 1.26 eV at 77 K and 1.46 eV at 273 K. The two chemisorbed species differ only in the structures they form in the adsorption phase, β₂ being the species that is stable at low coverages, β₁ being the species that is stable at high coverages. These results are in good agreement with those recently found for CO adsorption on single crystal surfaces.     

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.     

Properties of pp annihilations into strange particles at 702 and 757 MeV/c

$\text{p}\text{p}$ annihilations, leading to the production of at least one neutral K meson in the final state, have been studied in the incident momentum region of 700–760 MeV/c. Topological cross sections and cross sections for the various exclusive final states are presented. Detailed analyses of the different final states have been carried out to study the importance of resonance production and of quasi two-body and quasi three-body processes. A detailed study of the $\text{K}\text{K}\text{π}$ system in the four-body final states shows that the F₁ meson is a spurious effect due to systematic biases. In the momentum range investigated, the C = +1 final states are strongly suppressed.     

Adsorption of nitrogen and ammonia by polycrystalline iron surfaces in the temperature range 80–290 K studied by electron spectroscopy

X-ray and uv induced photoelectron spectroscopy have provided information on the various molecular states of nitrogen formed on polycrystalline iron surfaces from dinitrogen and ammonia. At 85 K two distinct states are observed with N₂(g) which have N(1s) binding energy values of 405.3 and 400.2 eV. These are in equilibrium with N₂(g), are weakly held, and are desorbed on warming to 290 K leaving a nitrogen free surface. The two states are assigned to a molecularly adsorbed

and linear

species the former characterised by an N(1s) value of 400.2 eV and the latter by 405.3 eV. At 290 K nitrogen is adsorbed with a very low sticking probability (?10^?6) giving rise to an N(1s) value of 397.2 eV. This is undoubtedly the dissociatively chemisorbed

species. At a nitrogen pressure of l Torr adsorption is “instantaneous” and the N(1s) value is 397 eV. No evidence for the unstable bridged and linear forms of nitrogen is obtained at 290 K although they may well be precursors to the formation of the strongly chemisorbed nitrogen species. Shifts in the N(1s) binding energy induced by subsequent oxygen adsorption are discussed briefly. At 85 K ammonia adsorbs largely in the molecular form with a broad N(1s) peak centred at about 400 eV but on warming to 290 K this splits to give two peaks one at 397 eV and the other at 400 eV. Interaction at 290 K leads to a dominant peak at 397.2 eV and a subidiary one at 400 eV. Helium (1) spectra support the assignment of the 397.2 eV peak to dissociated species (N, NH) and the 400 eV peak to molecular adsorption. The conclusions with N₂ and NH₃ are substantiated further by comparing the data with results for nitric oxide. The concentration of nitrogen adatom species formed from NO at 290 K and 10^?6 Torr is some ten times that formed from N₂ at 1 Torr and three times that from NH₃ at 10^?6 Torr and the same temperature.     

A structural and kinetic study of chlorine and silver chloride on Ag(100): The transition from overlayer to bulk halide

Adsorption of chlorine on Ag(100) at 298 K leads to the formation of a chemisorbed over layer of Cl atoms with Δφ = 1.4 eV and exhibiting a sharp c(2 × 2) LEED pattern. This layer is impervious to electron stimulated desorption (ESD). At 430 K (well below the desorption temperature) Δφ decreases quite rapidly to +0.9 eV, the LEED pattern deteriorates and ESD is observed. The temperature dependence of the ($\text{1}\text{2}$, $\text{1}\text{2}$) LEED beam indicates that an irreversible change in surface Debye temperature has occurred. On raising the temperature further, evaporation of the adiayer occurs with AgCl as the sole desorption product. These results suggest that an overlayer → silver chloride transition has occurred, a conclusion which is supported by studying the properties of AgCl dosed surfaces. Chlorine dosing never leads to halide growth beyond the monolayer stage. Multilayer growth of AgCl is investigated by dosing with AgCl(g). It is found that the desorption spectra evolve in an unusual way and the observed energetics of AgCl evaporation are accounted for in terms of the reduced lattice energy of small adsorbed crystallites. LEED shows that these crystallites re-orient from (100) to (111) as their size increases.     

Interaction of NO and O2 with Pd(111) surfaces. II

At least three different types of oxygen atoms may be present in the surface region of Pd(111) which may be distinguished by their thermal, chemical, structural and electronic properties. Exposure to O₂ at low temperatures causes the formation of 2 × 2 and $\text{3}\text{×}\text{3}\text{R30°}$ structures from chemisorbed oxygen, the latter being probably stabilized by small amounts of H_ab or CO_ab on the surface. The initial sticking coefficient was estimated to be about s₀ ≈ 0.3, the adsorption energy ~55 kcal/mole. The photoelectron spectrum exhibits an additional maximum at 5 eV below E_F. During thermal desorption dissolution of oxygen in the bulk strongly competes; on the other hand absorbed oxygen may diffuse to the surface giving rise to high temperature peaks in the flash desorption spectra. High temperature (~1000 K) treatment of the sample with O₂ causes the formation of a more tightly bound surface species also characterized by a 2 × 2 LEED pattern which is chemically rather stable and which is considered to be a transition state to PdO. The latter compound is only formed by interaction with NO at about 1000 K via the reaction $\text{Pd}\text{+}\text{NO}\text{→}\text{PdO}\text{+}\text{1}\text{2N}{}_2$ which offers a rather high “virtual” oxygen pressure. This reaction leads to drastic changes of the photoelectron spectrum and is also identified within the LEED pattern.     

Energy loss mechanisms in low energy electron scattering from W(100) and their use as a surface sensitive spectroscopy

The energy loss spectrum of low energy (0 < E_p < 200 eV) electrons scattered from W(100) has been experimentally investigated, and mechanisms giving rise to the fine structure analyzed using a dielectric response formalism. The dielectric medium is characterized by available optical data and energy band calculations for tungsten. All of the structure for loss energies, w, less than 18 eV is attributed to intra- and interband transitions involving the bulk valence and conduction bands. The surface and bulk plasmon excitations are observed at w = 21 eV and w = 25.5 eV respectively which is in reasonable agreement with the optical data. A very narrow peak in the density of conduction d-band states apparently functions strongly in well defined excitations involving the $\text{5p}\text{3}\text{2}$ and 4f tungsten orbitais and the 2s and 2p orbitais of adsorbed oxygen. These conduction band states form a “window” with which to measure the electronic orbital structure of both the substrate and adsorbate during adsorption and reaction. We demonstrate this for the room temperature adsorption of oxygen on W(100) in which we observe the sequential filling of two electronically inequivalent binding states. The stability of the “d-band window” during thermally activated reaction, and the likelihood of its existence in other transition metals makes this an attractive surface sensitive spectroscopy.     

Deposition of nickel from Ni(CO)4 on palladium and iron surfaces studied by X-ray photoelectron spectroscopy

The interaction of nickel carbonyl, Ni(CO)₄, with evaporated palladium and iron surfaces has been studied at 90 and 290 K by X-ray photoelectron spectroscopy. The carbonyl is weakly adsorbed in molecular form at 90 K on the metals giving a $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak at 854.6 eV, a C 1s at 287.2 eV and an O 1s at 533.8 eV. Some fraction of the carbonyl decomposes even at 90 K on iron to give deposited nickel atoms. In the interaction with palladium at 290 K, deposited nickel atoms $\text{(Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{= 852.9 eV)}$ and chemisorbed CO are observed. A satellite feature of the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak varies depending on the quantity of the deposited nickel atoms; the main peak-satellite separation increases with increase in the quantity. The same variation is observed for evaporated nickel-palladium alloys. This can be ascribed to the difference in the electronic states of the nickel atoms. The difference is reflected in the reactivity of the atoms with O₂. With iron the deposited nickel atoms show an increase in binding energy of 0.4 eV in the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ Peak and no satellite when the number of nickel atoms is small. The oxidation of the surface is also studied.     

Shallow acceptor bound exciton and free exciton states in high-purity zinc telluride

We investigated excitons bound to shallow acceptors in high-purity ZnTe and measured excitation spectra of two-hole luminescence lines at 1.6 K using a tunable dye-laser. The electron-hole coupling in the bound exciton (BE) states appears to be very different for the various acceptors even for almost identical exciton localisation energies. Three different types of BE are reported. For the Li-acceptor BE we observe three sub-components separated by 0.22 and 0.17 meV and interpreted as J = $\text{1}\text{2}$, $\text{3}\text{2}$, $\text{5}\text{2}$ states. The Ag-acceptor BE exhibits a strong ground state and a weak excited state at 1.3 meV higher energy. For the as yet unidentified k-acceptor we observe a single BE level, degenerate with the Ag-acceptor BE ground state. Dips in the excitation spectra due to absorption into free exciton 1S, 2S, and 3S states yield an exciton Rydberg R₀ = 12.8±0.3 meV and a free exciton binding energy FE(1S) = 13.2±0.3 meV.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

Nitric oxide chemisorption on Re(0001) at 100 and 300 K: Evolution of the adsorbed layer during annealing from 100 to 700 K; XPS,UPS, TDS and work function measurements

At 100 K NO is molecularly adsorbed on Re(0001). Bridge bonded and linear species have been identified by XPS and UPS measurements. Moreover a weakly bonded species reversibly adsorbed at 100 K has been found, but not precisely identified. As the temperature of the surface is increased a complex transformation of the layer occurs: the weakly bonded molecules are probably transformed into a more strongly bonded state and desorb between 100 and 300 K. One part of the linear species desorbs between 300 and 500 K giving the α₂ molecular state, the other part dissociates and desorbs between 600 and 700 K giving the β₁ nitrogen molecules. In the same temperature range the bridge bonded molecules dissociate into nitrogen and oxygen atoms, but nitrogen desorbs into the gas phase between 700 and 1100 K as β₂ and β₃ states with a second order process. Oxygen is adsorbed as atoms and desorbs at higher temperature. If adsorption takes place at room temperature, NO is mainly dissociated and nitrogen desorbs as β₂ and β₃ states with a second order process.