The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.     

HREELS of H/GaN(0001): evidence for Ga termination

Two issues relevant to the growth and processing of GaN are the termination of the GaN(0001) surface and its reaction with hydrogen. We have used high-resolution electron energy loss spectroscopy (HREELS), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES) to study the adsorption of hydrogen on MOCVD-grown GaN(0001). LEED of the sputtered and annealed surface shows evidence of facetting. No adsorbate vibrations are observed on the clean surface by HREELS, only Fuchs–Kliewer phonons at intervals of 700 cm⁻¹. Following exposure of the clean GaN surface to hydrogen atoms, HREEL spectra show adsorbate loss peaks at 2580, 3280, and 3980 cm⁻¹. The Ga–H stretching vibration at 1880 cm⁻¹ becomes evident when the HREEL spectrum is deconvoluted to remove the phonon multiple-loss peaks. We assign the 2580, 3280, and 3980 cm⁻¹ peaks to combination modes of the Ga–H stretch and phonon(s). Upon dosing with deuterium, the Ga–D bending mode is observed at 400 cm⁻¹. No vibrational peaks due to N–H (N–D) species are observed after H (D) exposure. We conclude that sputtered and annealed GaN(0001) is Ga-terminated.     

Preparation of high purity spherical γ-alumina using a reduction-magnetic separation process

A purified alumina hydrosol has been prepared by removing metal impurities using a new reduction-magnetic separation process. The amount of iron in the alumina hydrosol was reduced by over 78% from 0.0094% to 0.0020%. As a result of co-crystallization, the copper content was simultaneously reduced from 0.0003% to 0.0001%. Spherical γ-alumina granules were prepared by the oil-drop method using the purified alumina hydrosol as starting material. The γ-alumina granules had a bulk density of about 0.50 g cm⁻³, crush strength of around 90N per granule, specific surface area of about 200 m² g⁻¹ and pore volume of about 0.75 cm³ g⁻¹. The purification process employed during the preparation of the alumina hydrosol had no effect on the physical properties, pore structure and crystal structure of the final spherical alumina granules.     

Femtosecond laser micro-structuring of aluminium under helium

The interaction of 180 fs, 775 nm laser pulses with aluminium under a flowing stream of helium at ambient pressure have been used to study the material re-deposition, ablation rate and residual surface roughness. Threshold fluence F_th0.4 J cm⁻² and the volume ablation rate was measured to be 30<V<450 μm³ per pulse in the fluence range 1.4<F<21 J cm⁻². The presence of helium avoids gas breakdown above the substrate and leads to improved surface micro-structure by minimising surface oxidation and debris re-deposition. At 1 kHz rep. rate, with fluence F>7 J cm⁻² and >85 W cm⁻² average power density, residual thermal effects result in melt and debris formation producing poor surface micro-structure. On the contrary, surface micro-machining at low fluence F1.4 J cm⁻² with low power density, 3 W cm⁻² produces much superior surface micro-structuring with minimum melt and measured surface roughness R_a1.1±0.1 μm at a depth D50 μm. By varying the combination of fluence/scan speed during ultra-fast ablation of aluminium at 1 kHz rep. rate, results suggest that maintaining average scanned power density to <5 W cm⁻² combined with single pulse fluence <4 J cm⁻² produces near optimum micro-structuring. The debris under these conditions contains pure aluminium nanoparticles carried with the helium stream.     

Vibrational study of silicon oxidation: H2O on Si(100)

The vibrational spectrum of water dissociatively adsorbed on Si(100) surfaces is obtained with surface infrared absorption spectroscopy. Low frequency spectra (< 1450 cm⁻¹ are acquired using a buried CoSi₂ layer as an internal mirror to perform external reflection spectroscopy. On clean Si(100), water dissociates into H and OH surface species as evidenced by EELS results [1] in the literature which show a Si---H stretching vibration (2082 cm⁻¹), and SiO---H vibrations (O---H stretch at 3660 cm⁻¹ and the Si---O---H bend and Si---O stretch of the hydroxyl group centered around 820 cm⁻¹). In this paper, infrared (IR) measurements are presented which confirm and resolve the issue of a puzzling isotopic shift for the Si---O mode of the surface hydroxyl group, namely, that the Si---O stretch of the O---H surface species formed upon H₂O exposure occurs at 825 cm⁻¹, while the Si---O stretch of the ---OD surface species formed upon D₂O exposure shifts to 840 cm⁻¹, contrary to what is expected for simple reduced mass arguments. The higher resolution of IR measurements versus typical EELS measurements makes it possible to identify a new mode at 898 cm⁻¹, which is an important piece of evidence in understanding the anomalous frequency shift. By comparing the results of measurements for adsorption of H¹⁶₂O, H¹⁸₂O and D₂O with the results from recently performed first-principles calculations, it can be shown that a strong vibrational interaction between the Si---O stretching and Si---O---H bending functional group vibrations of the hydroxyl group accounts for the observed isotopic shifts.     

NIR-FT-SERS of 4″-trimethylsilylethylsulfanyl-4,4′-di(phenyleneethynylene)benzenethiol on Au nanospheres

Oligo(phenyleneethynylene) (OPE) compounds have been identified as promising molecular electronic bridges. Self-assembled monolayers of 4″-trimethylsilylethylsulfanyl-4,4′-phenyleneethynylenebenzene thiol (OPE′) on Au were characterized by surface-enhanced Raman scattering (SERS). The FT-Raman spectrum of OPE′ shows three C–S bands at 834, 1086, and 1131 cm⁻¹. From the FT-Raman to the SERS spectra, the 1086 cm⁻¹ band exhibits a 9 cm⁻¹ red shift. Chemisorption of OPE′ to the gold surface occurs via oxidative cleavage of the disulfide bond and the formation of the Au–S bond. The Au–S vibration is visible in the SERS spectra at 257 cm⁻¹. Peaks due to the S–S and S–H stretch are observed at 544 and 2519 cm⁻¹, respectively, in the FT spectrum, but are unobserved in the surface-enhanced spectra. The C–H stretching region (2700–3350 cm⁻¹) in the spectrum of neat OPE′ shows three distinct bands, whereas the SERS spectra show a single broad band. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.52 was obtained for the non-CH stretching frequencies.     

Surface chemistry of alkyl and perfluoro ethers: a FTIR and ab initio study of adsorption and decomposition of CF3OCF3 on an Al2O3 surface

The adsorption and thermal decomposition of perfluorodimethyl ether, (CF₃)₂O, on a high-surface-area Al₂O₃ surface was investigated by FTIR under both vacuum and pressure conditions. IR spectra in the 4000-1050 cm⁻¹ range were collected and the spectral assignments were assisted by quantum chemical ab initio calculations. The spectral evidence indicated that (CF₃)₂O decomposed to form adsorbed fluoroformate, FCOO (ads). Increases of temperature (up to 525 K) caused the FCOO (ads) to convert to hydrogen formate, HCOO (ads). Surface hydroxyl groups participated in the decomposition of (CF₃)₂O and the conversion of FCOO (ads) to HCOO (ads). A decomposition mechanism is proposed.     

ATR–SEIR study of anions and water adsorbed on platinum electrode

Adsorbed species on bare Pt, and UPD-Pb or UPD-Cu/Pt electrodes were characterized in HClO₄ or H₂SO₄ solutions at various potentials using attenuated total reflection (ATR)–surface enhanced infrared absorption (SEIRA) spectroscopy. On the bare Pt electrode, anions were observed at 1120–1095 cm⁻¹ at +0.0 < E < +0.6 V, solvated by water molecules with OH stretching absorption at 3600 cm⁻¹ and HOH bending mode at 1610–1620 cm⁻¹. In addition to the S–OH totally symmetric mode at 950 cm⁻¹, adsorbed sulfate species gave two bands at 1230–1100 cm⁻¹ between 0.0 V < E < +0.8 V that are assigned to ν₃ (symmetric stretch of S–O in SO₃) of ions with different coordination based on the peak shift by isotope substitution. At more negative potential, solely water molecules adsorb on the bare Pt surfaces. In contrast, it was found that electrolyte anions such as bisulfate and with hydrating water molecules adsorb onto the UPD-Pb/Pt and UPD-Cu/Pt electrodes even at much negative potentials, e.g. −0.2 V for UPD-Pb.     

Highly sintered nickel oxide: surface morphology and FTIR investigation of CO adsorbed at low temperature

The monolayer of CO molecules adsorbed at low temperature on highly sintered nickel oxide, gives rise to a very symmetric IR absorption band at 2136 cm⁻¹ (θ_max) with a full-width at half-maximum (FWHM) of 3.7 cm⁻¹. This band shifts to higher frequenc upon decreasing the coverage, reaching the 2152 cm⁻¹ value for θ→0. The observed shift is due to changes in the lateral interactions (dynamic and static) among the adsorbed molecules. The observed spectral simplicity implies that most of the adsorbed CO molecules occupy crystallographically identical sites with a similar environment. Moreover, the remarkably small half-width indicates that inhomogeneous broadening effects, due to surface defects, are very small and that NiO microcrystals behave as single crystals. The morphology of microcrystals has been studied by SEM, AFM and HRTEM techniques: it was concluded that the surface termination of the sample is mainly represented by the (100) and (111) faces.     

The adsorbate-induced removal of the Pt{100} surface reconstruction Part I: NO

The molecular adsorption of NO on both the reconstructed (hex) and unreconstructed (1 × 1) surfaces of Pt{100} has been studied using a combination of infrared reflection-absorption spectroscopy (IRAS) and low energy electron diffraction (LEED) at temperatures between 90 and 300 K. On the (1 × 1) surface at 300 K adsorbed NO gives rise to an N-O stretching band at initially 1596 cm⁻¹ shifting to 1641 cm⁻¹ at a coverage of θ = 0.5. The LEED pattern at this coverage is interpreted in terms of a c(4 × 2) structure in which all the molecules occupy a single type of adsorption site between the on-top and bridge positions. At temperatures below 300 K, a higher coverage disordered phase is observed, giving rise to an N-O stretching band at 1680 cm⁻¹ associated with an on-top NO species. On the (hex) phase surface above 210 K, NO adsorption gives rise to bands characteristic of adsorption on the (1 × 1) phase indicating that the reconstruction is immediately lifted. Below 200 K initial adsorption actually occurs directly on the (hex) phase, resulting in a band at 1680 cm⁻¹, which is assigned to on-top NO. This band increases in intensity until, at a critical coverage dependent on temperature, the (hex) → (1 × 1) surface phase transition is induced. This is indicated by the disappearance of the band at 1680 cm⁻¹ and its replacement by bands characteristic of adsorption on islands of the (1 × 1) structure.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Vibrational spectroscopy of ordered oxygen adiayers on Ni/Cu(001) and Co/Cu(001) thin film systems

We report surface vibrations in c(2 × 2) oxygen adlayers on Ni and Co thin films on a Cu(001) substrate measured at gG by high resolution EELS. For the Ni thin film surface, one phonon peak is measured for varying film thicknesses from 1.3 ML (monolayer) to 6 ML with a constant energy of 221 cm⁻¹. For the Co thin film surface, three loss peaks are found, whose relative intensities change as the film thicknesses are varied. One loss peak at ˜520 cm⁻¹ is tentatively assigned to the Fuchs-Kliewer mode of cobalt oxide (CoO). The other two peaks at 317 and 376 cm⁻¹ are likely related to different bonding sites. Surface phonons on the p(2 × 2) Co thin film (389 cm⁻¹) and a bulk resonance mode (115 cm⁻¹) are also reported.     

Far-infrared and millimeter wave spectroscopy of superionic copper conductors

Far-infrared and millimeter wave spectra of copper ion conducting crystal RbCu₄Cl_3+xI_2−x, which has the same structure as the room temperature silver ion conductor RbAg₄I₅, were investigated. Broad absorption peaks observed around 40, 80, and 110–200 cm⁻¹ at room temperature show doublet structures at low temperature; this may be attributed to the difference of local structure by chlorine and iodine ion. The 110–200 cm⁻¹ bands seem to be symmetric breathing modes of CuX₄ (X = Cl or I) tetrahedron and the frequency shift coincides with the square root of the mass ratio of conduction ions. The 80 cm⁻¹ band seems to be Rb-X vibration in RbX₆ octahedron. The 40 cm⁻¹ band seems to be the attempt mode which is an outward motion of the mobile ion in halogen cage. The increase of the absorption intensity at the low energy side with temperature corresponds to an increase of the DC conductivity. Plasmon fitting in energy loss function spectra was attempted.     

The chemistry of iodomethane on MoAl alloy thin films formed on dehydroxylated alumina: Formation and reaction of surface methyl species

The surface chemistry of iodomethane is studied in ultrahigh vacuum using X-ray and Auger spectroscopies and temperature-programmed desorption, on a MoAl alloy film formed by reacting molybdenum hexacarbonyl with dehydroxylated alumina. The alloy is grown by reacting Mo(CO)₆ with a thin alumina film on a molybdenum substrate at 700 K and heating to 1500 K. A portion of the iodomethane dissociates following adsorption at 150 K. Heating to 220 K desorbs molecular iodomethane from the surface leaving adsorbed methyl species and iodine, where the iodine appears to adsorb preferentially on the aluminum. The resulting methyl species can either decompose to deposit carbon and evolve hydrogen, hydrogenate to yield methane or oligomerize yielding predominantly ethylene and propylene, and a small amount of ethane is formed. Both methyl and ethyl radicals are found to desorb from the surface suggesting that the ethylene is formed by methylene insertion into the methyl surface bond to form an ethyl intermediate, which forms ethylene by β-hydride elimination, or hydrogenates to yield ethane. Propylene is likely to form by further methylene insertion into the ethyl-surface bond.     

Infrared spectra of oxalate, malonate and succinate adsorbed on the aqueous surface of rutile, anatase and lepidocrocite measured with in situ ATR-FTIR

The adsorption of oxalate, malonate and succinate on anatase, rutile and lepidocrocite, was studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) at aqueous concentrations of 200 μM between pH 9 and 3. Clear spectral differences between the aqueous species and the surface adsorbed species for all three dicarboxylates are taken as strong evidence for inner-sphere adsorption. The characteristically different spectra on each oxide reveal surface specific interactions and could be used as a diagnostic tool, e.g., to probe the relative abundance of anatase and rutile on the surface of TiO₂ samples. Spectral changes between pH 7.0 and 3.0 show that two to three different surface complexes of oxalate and one to three surface complexes of malonate and succinate are formed on each of the three surfaces. While the exact structures of each complex can currently not be derived, important differences between the dicarboxylates can be identified. Only adsorbed oxalate exhibits two strong bands above 1670 cm⁻¹, as expected for a five- (bidentate chelating) or six-membered (bidentate bridging) ring structure with one oxygen of each carboxylic group coordinated to surface sites and two CO double bonds pointing away from the surface. The absence of clear CO double bond vibrations above 1620 cm⁻¹ show that malonate and succinate adsorb differently, with one or both of the carboxylic groups independently forming monodentate hydrogen bonded, bidentate chelating (four-ring) or bidentate bridging (five-ring) structures. Oxalate is the only one of the three dicarboxylates that formed additional surface complexes at low pH on rutile and anatase and lead to rapid dissolution of lepidocrocite below pH 5.0.     

Theoretical study of the Cl-passivated Si(111) surface

The Cl-passivated Si(111) surface is studied using density functional theory, in conjunction with the B3LYP functional and the cluster model. We compute the Si–Cl frequency and the Si–Cl bond energy for R₃SiCl, and the abstraction barrier for the reaction R₃SiCl+H→R₃Si+HCl using the B3LYP approach. We calibrate the B3LYP bond energy and the abstraction barriers using the values obtained using the G2MP2, G2 and CCSD(T) approaches. Our computed B3LYP Si–Cl frequency of 555 cm⁻¹ is in good agreement with the experimental value of 588 cm⁻¹. The shift in the Si–Cl frequency as surface chlorine is added to the cluster agrees with experimental observations.     

Identification of a vibrational Stark shift within an adsorbate layer: NH3 on Ru(001)

Using high-resolution electron energy loss spectroscopy we investigated the coverage-dependent vibrational properties of ammonia chemisorbed on Ru(001). With increasing coverage we find a drastic red shift of 100 cm⁻¹ for the ammonia symmetric deformation mode. Based on results for ammonia layers containing different isotopic species, such as NH₃ as well as partially and totally deuterated ND_xH_3−x, this red shift can be identified as a dominantly static shift (no dynamical coupling). Based on DFT model calculations, the origin of this shift can be understood as a Stark shift due to the electric fields produced by the static NH₃ dipoles within the adlayer. Calculations for isolated ammonia and for ammonia adsorbed on small Ru clusters, both in the fields of neighboring electric dipoles, can well reproduce the sign and magnitude of the observed red shift and for this molecular system allow a clear distinction between pure electrostatic and adsorption-induced (chemical) effects. We show that as a consequence of the electric field, the ammonia molecule opens the H–N–H angle and a softening of the symmetric deformation mode occurs.     

Adsorption of carbon monoxide on Pt{100} surfaces: dependence of the CO stretching vibrational frequency on surface coverage

We have used the ab initio cluster model approach to study the dependence of the CO stretching frequency on CO surface coverage. We have also investigated the relative importance of the various factors that can affect the position of the CO stretching band as coverage increases. Two effects can change the CO stretching frequency: the adsorbate–adsorbate dipole coupling, which is a purely physical effect, and the changes in the 2π^* CO molecular orbitals, due to the different chemical environment at higher coverages. From our vibrational analysis, we conclude that CO–CO dipole coupling is the main cause of the upward shift of the CO stretching band when the CO coverage is increased. The population of the 2π^* CO molecular orbitals does not change at any coverage within the region considered. We have also estimated the ¹²CO–¹³CO dipole coupling, which previous studies have assumed to be weak. Our results demonstrate that the ¹²CO–¹³CO dipole coupling is indeed weak compared with the ¹²CO–¹²CO dipole coupling. At a CO surface coverage of 0.5 monolayers (ML), we have calculated a band shift of 40 cm⁻¹ to higher frequency. However, we should point out that when one ¹²CO molecule is surrounded by a ¹³CO environment, the ¹²CO stretching band shifts 10 cm⁻¹ upwards. We have also computed the heat of adsorption of CO on Pt{100}-(1×1) as a function of CO coverage. The initial heat of adsorption is calculated to be about 192 kJ mol⁻¹ and then drops to 180 kJ mol⁻¹ at 0.5 ML. These results agree quite well with recent calorimetric measurements. Besides that, we have estimated that the CO–CO interaction energy at 0.5 ML is repulsive and has a value of 5 kJ mol⁻¹.     

A theoretical study of CHx chemisorption on the Ni(100) and Ni(111) surfaces

Cluster model calculations have been performed for CH_x, x = 0−3, chemisorbed on Ni(100) and Ni(111). The predicted chemisorption energies, at the present level of theory, based on bond-prepared clusters for Ni(100) are for carbon 150 kcal/mol, for CH 136 kcal/mol, for CH₂ 91 kcal/mol and for CH₃ 46 kcal/mol. The corresponding energies for Ni(111) are for CH 120 kcal/mol, for CH₂ 88 cal/mol and for CH₃ 49 kcal/mol. These chemisorption energies lead to similar stabilities for all CH_x fragments on both Ni(100) and Ni(111). Large basis sets and multi-reference correlation treatments are found to be very important in particular for the multiply bonded species. The vibrational C-H stretching frequencies predicted for CH_x on Ni(111) are for CH 3054 cm⁻¹ (2980 cm⁻¹), for CH₂ 3204 cm⁻¹ and for CH₃ 2709 cm⁻¹ (2680 cm⁻¹), where the available experimental values are given in parent The predicted ionization spectra of adsorbed CH_x are also in general agreement with experimental findings.     

Infrared spectra of edge-shared silicate tetrahedra

Dehydroxylated silica exhibits two well-defined infrared bands at 888 and 907 cm⁻¹ previously assigned to a highly reactive strained surface defect. Comparisons of the spectra of dehydroxylated silica to frequencies and intensities calculated using molecular orbital (MO) calculations and to spectra obtained for cyclodisiloxanes suggest that the strained surface defect consists of an edge-shared silicate tetrahedral ring. Changes in vibrational frequencies and peak intensities with ¹⁸O labeling for both the surface defect and the cyclodisiloxanes are consistent with those expected for ring vibrational modes. The IR bands associated with the strained edge-shared ring disappear when either the surface defects or the cyclodisiloxanes react with water. Reactions of the surface defect can be used to study how strain enhances the reactivity of Si-O-Si bonds for modeling phenomena such as stress corrosion cracking.