High-resolution electron energy-loss spectroscopy of CO on an Ni(110) surface

High-resolution vibrational electron energy-loss spectra of CO on an Ni(110) surface were studied at 300 K with the in-situ combination of LEED, Auger electron spectroscopy and work-function change measurement. The observed peaks are at 436 cm^?1, 1855 cm^?1 (shifting to 1944 cm^?1 with increasing coverage) and at 1960 cm^?1 (shifting to 2016 cm^?1 with increasing coverage). The experimental results indicate that CO is adsorbed non-dissociatively at all coverages. Three adsorbed states of CO have been found. At fractional CO coverages less than θ ~ 0.9 where the disordered adsorbed structure dominates, CO is adsorbed in two inequivalent sites (short- and long-bridge sites) at random with its axis oriented perpendicular to the surface. At high coverages (θ > 0.9) where the (2 × 1) structure develops, our results indicate that the adsorbed CO molecules may occupy the distorted long-bridge sites forming zig-zag chains which lie essentially in the troughs of the (110) surface.     

The adsorption of ammonia on a Fe(110) single crystal surface studied by high resolution electron energy loss spectroscopy (EELS)

EELS spectra of ammonia adsorbed on a Fe(110) single crystal surface at 120 K reveal four different molecular adsorption states:1. At very low exposures (0.05 L) three vibrational losses at 345 cm^?1, 1170 and 3310 cm^?1 are observed which are attributed to the symmetric Fe-N stretching-, N-H₃ deformation and N-H₃ stretching modes of chemisorbed molecular ammonia, respectively. The observation of only three vibrational losses indicates an adsorption complex of high symmetry (C_3v).2. Further exposures up to 0.5 L cause the appearance of additional losses at 1450 cm^?1, 1640 cm^?1 and 3370 cm^?1. The latter two are interpreted as the degenerate NH₃ deformation and - stretching modes of molecularly adsorbed NH₃. The 1450 cm^?1 loss is a combination of the losses at 345 cm^?1 and 1105 cm^?1. The observation of 5 vibrational losses is consistent with an adsorption complex of C_s symmetry.3. In the exposure range from 0.5 to 2 L adsorption of molecular ammonia in a second layer is observed. This phase is characterized by a symmetric deformation mode at 1190 cm^?1 and by two additional very intense modes at 160 cm^?1 and 350 cm^?1 which are due to rotational and translational modes.4. Exposures above 2 L cause multilayer condensation of ammonia characterized by translational and rotational bands at 190 cm^?1, 415 cm^?1 and 520 cm^?1, and a symmetric deformation mode at 1090 cm^?1. A broad loss feature around 3300 cm^?1 is attributed to hydrogen bonding in the condensed layer.Thermal processing of a Fe(110) surface ammonia covered at 120 K leads to decomposition of the ammonia into hydrogen and nitrogen above 260 K. No vibrational modes due to adsorbed NH or HN₂ species were detected.     

Reflection-absorption infrared and thermal desorption studies of carbon monoxide and hydrogen adsorbed on rhodium

Reflection-absorption infrared spectroscopic and thermal desorption techniques have been used to study the interaction of mixtures of carbon monoxide and hydrogen with evaporated rhodium films. For equimolar mixtures near 10^?9 Torr, hydrogen adsorbed much more rapidly, but long exposure times or increases in CO pressures to 10^?6 Torr led to its partial, but never complete, displacement by adsorbed carbon monoxide. Hydrogen desorption spectra taken during the displacement process showed two peaks which was consistent with a cooperative interaction between adsorbed CO and H species. In contrast to previous transmission studies of CO adsorption on small rhodium particles, the present reflection—absorption infrared study of the film system showed a single absorption band at 2075 ±10 cm^?1. While explanations for the discrepancy in terms of particle size effects are possible it is considered more likely that all CO molecules are linearly bound to individual Rh atoms in the present situation. In our work, increases in CO pressure (especially above 10^?6 Torr) were accompanied by an upward frequency shift (from 2065 cm^?1 to 2085 cm^?1) and a narrowing in half width (from 25 to 17 cm^?1). Several possible explanations for the latter unusual effect are discussed.     

Vibrational characterization of carbon monoxide adsorption on sulfur modified Ni(100) surfaces

Carbon monoxide adsorption has been studied on a series of presulfided Ni(100) surfaces using vibrational spectroscopy. The sulfided Ni(100) surfaces were characterized using Auger electron spectroscopy and low energy electron diffraction, binding states were isolated by heating CO-dosed surfaces to prescribed temperatures, corresponding to the desorption temperatures of the CO. Adsorption of CO on Ni(100) with a p(2 × 2) array of sulfur lead to CO stretching frequencies of 1740 and 1930 cm^?1 corresponding to desorption temperatures of 370 and 290 K, respectively. Adsorption of CO into the c(2 × 2)S structure resulted in a CO stretching frequency of 2115 cm^?1 and a desorption peak near 140 K. The binding sites on the p(2 × 2)S structure were interpreted as metal four-fold hollows and bridging sites. The high frequency state was interpreted as weak bonding into the four-fold hollow with back donation into the π¹ orbital on CO restricted by stearic hindrance due to adsorbed sulfur. Both the thermal desorption and vibrational results indicated that local CO-sulfur interactions are dominant on the presulfided Ni(100) surface in the coverage range studied.     

Vibrational EELS,XPS and UPS study of CO chemisorbed on Pt10Ni90(111): Evidence for the existence of different sites

CO adsorption on the (111) face of a Pt₁₀Ni₉₀ alloy single crystal has been investigated at room temperature by vibrational electron energy loss spectroscopy (EELS) and photoelectron spectroscopy (XPS and UPS). Two well separated CO stretching modes develop at 2070 and 1820 ± 10 cm^?1, with their intensities reaching 64 and 36% respectively of the total intensity at saturation coverage. They are attributed to CO adspecies in terminal and bridge bonded configuration respectively. The UPS spectra of 4σ, 5σ and 1π molecular orbitais of adsorbed CO show complex features which may be resolved into two components having the main characteristics of CO adsorbed on pure Pt(111) and Ni(111) respectively. Such behaviour is also observed by XPS on C 1s on O 1s peaks. Their respective contributions, in both XPS and UPS spectra are about 64 and 36% of the whole spectrum. Finally compared to Ni(111) — on which CO adsorbs mainly in bridge configuration — the alloying with 10% Pt has generated the appearance of a large number of new sites for CO chemisorption associated with the presence of Pt atoms at the surface. The large amount of terminal CO adspecies is interpreted in terms of considerable surface enrichment of the alloy in platinum.     

The adsorption of CO on evaporated iridium films,studied with infrared reflection-absorption spectroscopy

The adsorption of ^12CO on Ir films evaporated under ultrahigh vacuum (UHV) conditions was studied using infrared reflection-absorption spectroscopy (IRAS). Only a single absorption band was observed at 300 K, shifting continuously from the “singleton” value ~2010 cm^?1 at very low coverages to 2093 cm^?1 at saturation coverage. This band is attributed to CO adsorbed on top of the surface atoms. Synchronously with this shift the bandwidth at half maximum intensity $\text{Δv}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ decreases from ~30 to 8 cm^?1. The integrated peak area increases linearly with coverage up to a relative coverage (θ_r) of approximately 0.4, then the increase levels off and a maximum is observed. Upon continuing adsorption the intensity decreases slightly. In addition results are presented on adsorption at 300 K of ¹²CO?¹³CO isotopic mixtures. The coverage induced frequency shift is discussed in terms of a dipole-dipole coupling mechanism and it is concluded that intermolecular coupling can explain the shift (~83 cm^?1) observed. The decrease in intensity at coverages > 0.4 is attributed to the formation of a compressed overlayer with part of the CO molecules adsorbed in a multicentre position with different spectral properties. No infrared bands of nitrogen adsorbed at 78 K could be detected at pressures up to 6.7 kPa (1 Pa = 0.0075 Torr, 1 Torr = 133.32 Pa).     

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

The cluster Ni₂CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm^?1) shows reasonable agreement with EELS data (1810, 1870 cm^?1), whereas the (Ni₂)C frequency of 495 cm^?1 is remarkably higher than the experimental values (380, 400 cm^?1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a₁orbital manifold exhibits strong antibonding effects.     

The adsorption sites of CO on Ni(111) as determined by infrared reflection-absorption spectroscopy

The adsorption of CO on Ni(111) has been studied using infrared reflection-absorption spectroscopy combined with LEED, Auger electron spectroscopy, thermal desorption spectroscopy and work function measurements. At low CO coverage (θ = 0.05) CO adsorbs on threefold sites with a strecthing frequency given by ω_CO = 1817 cm^?1. At θ = 0.30 all molecules have shifted to two-fold sites, and θ = 0.50, where a c(4 × 2) structure is observed, ω_CO = 1910 cm^?1. At θ = 0.57, with a (√7/2) × √7/2)R19.1° structure, one quarter of the molecules are adsorbed on top of the nickel atoms with the others in two-fold sites. Molecules bonded on the top sites give rise to a band at 2045 cm^?1. The frequency shift due to dipole-dipole interactions is small compared with the shift resulting from bonding to different crystallographic sites.     

Chemisorption of nitrogen on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-absorption infrared spectroscopy has been combined with thermal desorption and surface coverage measurements to study nitrogen adsorption on a {111}-oriented platinum ribbon under ultrahigh vacuum conditions. Desorption spectra show a single peak (at 180 K) after adsorption at 120 K, giving a coverage-independent activation energy for desorption'of ～40 kJmol^?1. The initial sticking probability at this temperature is 0.15, and the maximum uptake was ～1.1 × 10¹⁴ molecule cm^?2. The adsorbed nitrogen was readily displaced by CO, h₂ and O₂. An infrared absorption band was observed with a peak located at 2238 ± 1 cm^?1, and a halfwidth of 9 cm^?1, with a molecular intensity comparable to that reported for CO on Pt{111}. The results are compared with data for chemisorption on other group VIII metals. An earlier assignment of infrared active nitrogen to B₅ sites on these metals is brought into question by the present results.     

Vibrational spectra of a GaS single crystal

The Raman and infrared active long wavelength phonons of a GaS single crystal were studied at different temperatures in the 10–600 cm^?1 range. Properly polarized Raman spectra could be obtained with the 4880 Å exciting line and the previous assignment of the E_1g modes controversed recently could be confirmed. Infrared spectra were recorded in the 30–600 cm^?1 region. The vibrational frequencies of the crystal were also calculated using a method developed by Wieting and six new frequencies corresponding to infrared and Raman inactive modes have been proposed.We have observed that the degree of leakage of scattered intensity in unallowed polarizations increases when the wavelength of the exciting line moves off the exciton absorption front. The phonon at 74 cm^?1 was particularly sensitive and the question of the antiresonant behaviour of this compound is raised.     

Adsorption d'hydrogène entre 300 et 873 K sur un catalyseur Pt/MgO

Hydrogen adsorption on MgO-supported platinum was studied by thermal desorption and infrared spectroscopy at 300 and 800 K. For both temperatures, reversibly and irreversibly adsorbed species have been detected. At 300 K, reversible adsorption leads to the appearance of infrared bands at 2120 and 2060 cm^?1, attributed to terminal Pt-H species. Irreversibly adsorbed hydrogen has been detected by thermal desorption, whereas no infrared band was detected in the spectral range 4000–4750 cm^?1 for Pt/MgO sample. For hydrogen adsorption at 800 K, reversibly adsorbed hydrogen gave the same picture as for the 300 K adsorption. An additional form of irreversibly adsorbed hydrogen has been evidenced both by thermal desorption and infrared spectroscopy. This form corresponds to hydrogen strongly adsorbed on platinum and gives an infrared band at 950 cm^?1 which is characteristic of an hydrogen atom in interaction with more than one platinum atom (multicentered) species.     

A laser infrared source of nanosecond pulses tunable from 1.4 to 22 μm

A reliable source of coherent ns pulses of infrared radiation continuously tunable between 1.4 and 22 m has been designed and built with the aim of developing a time-resolved infrared vibrational spectroscopy for species adsorbed on surfaces. The system is based on a Nd: YAG-laser and dye-laser combination which drive difference mixing processes in a sequence of nonlinear optical crystals (two LiNbO₃, and a CdSe or AgGaS₂). The system operates at MW peak power levels above 2500 cm^–1, at kW power levels from 1000–2500 cm^–1 and at 10–100 W levels down to 450 cm^–1. These power levels are certainly sufficient for spectroscopic purposes, and at shorter wavelengths molecular pumping and applications requiring high-power should be possible. Vibrational spectra of a monolayer of CO adsorbed on Pt in an electrochemical cell have been obtained in an initial application of this source.     

Theoretical studies of CO/Ni(100): Geometry,vibrational frequencies and ionization potentials for the on-top site

The chemisorption of CO on the (100) surface of Ni has been studied using an Ni₁₄ cluster and generalized valence bond (GVB) methods. CO is found to bond perpendicular to the Ni surface with optimized NiC and CO bond distances of 1.94 and 1.15 Å, respectively. The calculated NiCO bond strength is 29.7 kcal (experimental values 30–32 kcal). Vibrational frequencies are calculated to be 401 cm^?1 for NiC stretch, 327 cm^?1 for NiCO bend, and 2129 cm^?1 for CO stretch. This decrease of the CO frequency by 71 cm^?1 from the free molecule value is consistent with experiment based on self-consistent calculations of the positive ion states. We propose a new explanation for the loss of one PES peak upon chemisorption.     

Infrared spectrum of the CO-OCS van der Waals complex in the carbon monoxide stretching band

The rotation-vibration band of the weakly bound OCS-CO complex which corresponds to the carbon monoxide CO vibrational mode has been detected using a pulsed supersonic slit-jet expansion and a tunable infrared diode laser probe. The band was found to have a parallel (δK _a = 0) structure, in good agreement with previous determinations of the structure of the complex. Its rotational structure appeared to be affected by numerous small (～ 0.01 cm^?1) perturbations in the upper state which probably are due to interactions with bound levels of a lower lying vibrational state of the complex. The band origin is located with a relatively small shift of + 1.23 cm^?1 from that of the free CO molecule.     

First far-infrared high-resolution analysis of the ν2 and ν4 bands of phosgene 35Cl2CO and 35Cl37ClCO

ABSTRACT

A Fourier transform spectrum of phosgene (Cl₂CO) has been recorded in the 17.3-μm spectral region at a temperature of 180 K and at a resolution of 0.00102 cm^?1 using a Bruker IFS125HR spectrometer coupled to synchrotron radiation, leading to the observation of the ν₂ and ν₄ vibrational bands of the two isotopologues ³⁵Cl₂CO and ³⁵Cl³⁷ClCO. The corresponding upper-state ro-vibrational levels were fit using a Hamiltonian model accounting for the A-type Coriolis interaction linking the rotational levels of the 2¹ and 4¹ vibrational states. In this way, it was possible to reproduce the upper-state ro-vibrational levels to within the experimental uncertainty, i.e. ～0.30 × 10^?3 cm^?1. Very accurate rotational and centrifugal distortion and interaction constants were derived from the fit, together with the following band centres: ν₀(ν_2, ³⁵Cl₂CO) = 572.526299(30) cm^?1, ν₀(ν_4, ³⁵Cl₂CO) = 582.089026(30) cm^?1, ν₀(ν_2, ³⁵Cl³⁷ClCO) = 568.951791(35) cm^?1 and ν₀(ν₄, ³⁵Cl³⁷ClCO) = 581.758279(35) cm^?1.     

Raman spectra of pyridine adsorbed on Ni(111)

We have measured the intensities of the 992 cm^?1 (ν₁) and 1032 cm^?1 (ν₁₂) lines in the Raman spectra of pyridine multilayers adsorbed on a Ni(111) surface, as a function of multilayer thickness. These experiments have been carried out in a standard ultra high vacuum chamber with Auger electron spectroscopy and mass spectroscopy capabilities. We find that the intensity of the 992 cm^?1 line decreases linearly with multilayer thickness down to ～ 5 layers. From these data and spectra of submonolayer quantities of Nitrobenzene on Ni(111) we predict an observable intensity for unenhanced spectra for monolayer amounts of pyridine on Ni(111). Attempts at observation of monolayer pyridine on this surface have been unsuccessful. We conclude that the scattering intensity of chemisorbed pyridine on Ni(111) is not enhanced and is likely less than would be predicted from the gas phase cross section.     

Co stretching vibration of carbon monoxide adsorbed on nickel(111) studied by high resolution electron loss spectroscopy

The frequency of the v-CO stretching vibration measured by HRELS has been followed as a function of the CO coverage and in the presence of coadsorbed hydrocarbons on the Ni(111) face. The v-CO frequency shifts continuously from 225 meV (1814 cm^?1) to 237 meV (1911 cm^?1) when the CO coverage increases from 0 to 0.41. Coadsorption of electron donor molecules, such as ethylene and benzene, generates a significant lowering of the v-CO frequency. Results are discussed in terms of the back donation of metallic electrons into the 2π ¹ antibonding orbitals of CO, the dipole-dipole coupling and the coordination number of the CO adsorbed molecules. The back donation is found to play the major role in the range of coverage explored but we cannot exclude some contribution of a dipole-dipole coupling effect.     

The reflection-absorption infrared spectrum of the dioxygen species adsorbed on platinum recorded by FT-IR spectroscopy

The reflection-absorption infrared spectrum of oxygen adsorbed on a recrystallized Pt foil at 80K shows a single band at 875 cm^?1 at saturation coverage. The spectrum produced by an equilibrated mixture of oxygen isotopes confirms that the adsorbate is molecular. The apparent effective charge, e*, calculated from the RAIR spectrum is in good agreement with that calculated from the electron energy loss (EEL) spectrum reported previously. The coverage dependent frequency shift can be accounted for by dipole-dipole coupling. The large inherent bandwidth is probably due to enhanced vibrational relaxation via electron-hole pair formation.     

Dehydration and recrystallization of radiation-damaged titanite under thermal annealing

Abstract

Dehydration of oriented sections of a radiation-damaged titanite crystal, CaTiSiO₅, at temperatures up to 1500K was analysed using infrared spectroscopy. The IR spectra of the untreated sample show only a very weak orientational dependence. The absence of sharp absorption peaks at wave number near 3486 cm^?1 in metamict titanite shows that the local environmental configurations of OH species in the metamict titanite differ strongly from that of crystalline titanite. The OH spectra of radiation-damaged titanite can be decomposed into two components: the first component shows anisotropic and sharp spectral features while the second component consists of a broad spectral feature like those observed in disordered silica glasses. It is proposed that the first component is related to the crystalline part of the titanite sample while the second is from the defected and disordered part which suffered strong radiation damage. With increasing annealing temperature, a decrease in the broad absorption between 2500 and 3200 cm^?1 is accompanied by a recovery of sharp IR bands near 3486 cm^?1 which display the same orientational dependence as undamaged single crystals. Annealing the sample at 1000K leads to the line profiles and orientational dependence of the main OH stretching bands near 3486cm^?1 that are virtually identical with those of crystalline, undamaged titanites. At temperatures above 1500 K, the crystal starts to melt and the orientational dependence of the IR absorption is destroyed. The recrystallization processes are quantified and discussed in terms of a percolation behaviour of amorphous and crystalline titanite. It is proposed that hydrogen transport is strongly enhanced during recrystallization.     

Schwingungsspektrum von Magnesiumsulfat-Heptahydrat (Epsomit) und Cäsiumsulfat

As in the preceding paper [1], infrared reflection spectra of single crystals of orthorhombic MgSO₄·7H₂O and MgSO₄·7D₂O have been obtained at 300°K, 80°K, and at about 14°K in the region between 4000 cm^?1 and 400 cm^?1. By a Kronig-Kramers analysis, the frequencies of the infrared active transitions have been determined. The spectra and their temperature dependence are contrasted with reflection spectra of anhydrous, orthorhombic Cs₂SO₄, which show practically no temperature dependence. The spectra of the magnesium compounds show two prominent features: 1. In the region below 700 cm^?1, the low-temperature experiments show the existence of many distinct vibrational modes arising mainly from the coupled translational and librational motions of the water molecules. These observations will be discussed in the light of the results of the preceding paper [1]. 2. The internal vibrations of the SO₄-ions at about 1100 cm^?1 present a very interesting combination of two solid-state effects on vibrational states of molecules in crystals: a) The threefold degeneracy of this mode is lifted by the deformation of the molecule due to the asymmetric crystal field, and b) the coupling of four molecules in the unit cell (resonance or correlation-field coupling) results in a further splitting of each mode into four clearly separated states of which three are infrared active. The magnitude of this splitting is calculated with the Davydov-theory (Coulomb-interaction of the transition-dipoles), making use of the crystal structure and the experimentally determined strength of the transition dipoles. Considering the limitation of the model, fairly good agreement with the experiment is obtained.