N+NO reaction on Rh(111) surfaces studied with fast near-edge X-ray absorption fine structure spectroscopy: role of NO dimer as an extrinsic precursor

We studied the mechanism of the N+NO reaction on Rh(111) surfaces by means of fast near-edge X-ray absorption fine structure spectroscopy. This reaction is important as a basis of NOx reduction reactions on platinum-group metal surfaces. Atomic nitrogen layers on Rh(111) were titrated with NO at various temperatures. N2O is exclusively formed and desorbs into the gas phase below 350 K. The consumption rate of atomic nitrogen exhibits strange temperature dependence between 100 and 350 K; the reaction proceeds slower with increasing temperature. Reaction kinetics analyses and isotope-controlled experiments have revealed that the surface N atoms do not react with chemisorbed NO molecules but with NO dimers weakly bound on top of the chemisorbed layer, which play a role as an extrinsic precursor. The present results may support the possibility that NO dimers participate in various NO-related synthetic, biochemical, and surface reactions as an intermediate.     

Mechanism of the CO oxidation reaction on O-precovered Pt(111) surfaces studied with near-edge x-ray absorption fine structure spectroscopy

The mechanism of CO oxidation reaction on oxygen-precovered Pt(111) surfaces has been studied by using time-resolved near-edge x-ray absorption fine structure spectroscopy. The whole reaction process is composed of two distinct paths: (1) a reaction of isolated oxygen atoms with adsorbed CO, and (2) a reaction of island-periphery oxygen atoms after the CO saturation. CO coadsorption plays a role to induce the dynamic change in spatial distribution of O atoms, which switches over the two reaction paths. These mechanisms were confirmed by kinetic Monte Carlo simulations. The effect of coadsorbed water in the reaction mechanism was also examined.     

Dipole-induced structure in aromatic-terminated self-assembled monolayers: a study by near edge x-ray absorption fine structure spectroscopy

The structure of self-assembled monolayers presenting aromatic rings at a surface is studied by near edge x-ray absorption fine structure spectroscopy (NEXAFS). Fluorine substitution at asymmetric positions in the aromatic rings is used to generate a layer of dipoles at the surface of the monolayer. We find that fluorine substituted aromatic rings are more ordered than unsubstituted aromatic rings by a factor of two based on the polarization dependence of the lowest C 1s to pi* transition, which is associated with transitions from phenyl carbons attached to hydrogens. This result is consistent with the influence of dipole-dipole interactions and quadrupolar interactions between the aromatic groups due to the substitution of fluorine atoms. The work also serves to illustrate how subtle variations in the orientation of an end group of a self-assembled monolayer can be determined by using NEXAFS.     

Orientation and bonding of ethylene and ethylidyne on Pt(111) by means of near-edge x-ray absorption fine structure spectroscopy

Near-edge X-ray absorption fine structure (NEXAFS) spectra have been measured for ethylene chemisorbed on Pt(111) at 90 and 300 K. From the polarization dependence of the spectra at 90 K, ethylene is found to lie down with a π bond to the surface. The spectra collected at 300 K indicate a CC bond normal to the surface in ethylidyne, and a SCF Xα calculation was carried out to assign the K-edge transitions in this species. The ethylidyne carboncarbon bond (which is nominally a single bond) appears to be shorter (≈0.03 A) than that for chemisorbed ethylene.     

CO adsorption and CO and O coadsorption on Rh(111) studied by reflection absorption infrared spectroscopy and density functional theory

The adsorption of carbon monoxide on Rh(111) and on oxygen modified Rh(111) was investigated using thermal desorption spectroscopy, reflection absorption infrared spectroscopy (RAIRS), and density functional theory. The results show that CO adsorbs on Rh(111) in on top sites at low coverages. With increasing coverage hollow sites and bridge sites get occupied according to the RAIRS results. A new vibrational feature at high wave numbers was found in the on top region of the CO stretching frequency. This feature can be explained by a local high density CO structure where two CO molecules are adsorbed in the ( radical3x radical3)R30 degrees structure. The coadsorption of oxygen and carbon monoxide leads to a shift of the CO stretching frequency to higher wave numbers with increasing O to CO ratio. CO adsorption on a (2x1) oxygen layer is possible and RAIRS shows that the CO adsorbs in on top and most likely in bridge sites in this case.     

Pressure-dependent electronic structures in multiferroic DyMnO(3): A combined lifetime-broadening-suppressed x-ray absorption spectroscopy and ab initio electronic structure study

Variations in the electronic structure and structural distortion in multiferroic DyMnO(3) were probed by synchrotron x-ray diffraction, lifetime-broadening-suppressed x-ray absorption spectroscopy (XAS), and ab initio electronic structure calculations. The refined x-ray diffraction data enabled an observation of a diminished local Jahn-Teller distortion of Mn sites within MnO(6) octahedra in DyMnO(3) on applying the hydrostatic pressure. The intensity of the white line in Mn K-edge x-ray absorption spectra of DyMnO(3) progressively increased with the increasing pressure. With the increasing hydrostatic pressure, the absorption threshold of an Mn K-edge spectra of DyMnO(3) shifted toward a greater energy, whereas the pre-edge line slightly shifted to a smaller energy. We provide the spectral evidence for the pressure-induced bandwidth broadening for manganites. The intensity enhancement of the white line in Mn K-edge spectra is attributed to a diminished Jahn-Teller distortion of MnO(6) octahedra in compressed DyMnO(3). A comparison of the pressure-dependent XAS spectra with the ab initio electronic structure calculations and full calculations of multiple scattering using the code FDMNES shows the satisfactory agreement between experimental and calculated Mn K-edge spectra.     

Thermal and mechanical aging of self-assembled monolayers as studied by near edge X-ray absorption fine structure

Self-assembled monolayers (SAMs) enable significant changes in the surface energy and/or specific interactions of surfaces, which are desirable for microelectromechanical systems (MEMS), superhydrophobic coatings, sensors, and other applications. However, SAMs often exhibit poor durability and rapid degradation upon mechanical, thermal, or moisture exposure. The chemical and orientational changes in SAMs due to mechanical and thermal degradation were investigated using near-edge X-ray absorption fine structure (NEXAFS) and the water contact angle. SAMs were based on unfluorinated or fluorinated linear hydrocarbons that form highly oriented and densely packed structures on silicon substrates. Complex chemical and orientational changes were observed via NEXAFS following degradation. Under heating in a dry, oxygen-rich environment, unfluorinated SAMs tended to cleave at C-C bonds on the main chain; below 250 °C, CH(3) groups were sequentially cleaved toward the surface, whereas above 250 °C, remaining hydrocarbon groups were converted to a graphitic coating dominated by C═C bonds. Under similar conditions, fluorinated SAMs began their chemical degradation at 350 °C and above, although the orientation decreased steadily from 150 to 300 °C; at and above 350 °C, the preferential removal of F occurred and the SAM was slowly converted to a graphitic layer. By contrast, under vacuum the fluorinated molecules were very thermally stable, showing good stability up to 550 °C; when degradation occurred, entire molecules were removed. Mechanical degradation followed two routes; both unfluorinated and fluorinated SAMs that were mechanically rubbed with smooth surfaces exhibited severe chemical degradation of the molecules, leading to an amorphous and poorly defined layer with C═C, C-C, C-H, and C-F bonds. Unfluorinated and fluorinated surfaces that were mechanically rubbed in the presence of free silicon particulates showed the rapid and complete destruction of both the molecular orientation and the protective SAM layer, even for short exposure periods. The resulting NEXAFS spectra were very similar to those produced by heating to 550 °C, suggesting that the friction created by granular particles may lead to extreme local heating.     

Characterization of protein immobilization at silver surfaces by near edge X-ray absorption fine structure spectroscopy

Ribonuclease A (RNase A) is immobilized on silver surfaces in oriented and random form via self-assembled monolayers (SAMs) of alkanethiols. The immobilization process is characterized step-by-step using chemically selective near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the C, N, and S K-edges. Causes of imperfect immobilization are pinpointed, such as oxidation and partial desorption of the alkanethiol SAMs and incomplete coverage. The orientation of the protein layer manifests itself in an 18% polarization dependence of the NEXAFS signal from the N 1s to pi* transition of the peptide bond, which is not seen for a random orientation. The S 1s to C-S sigma* transition exhibits an even larger polarization dependence of 41%, which is reduced to 5% for a random orientation. A quantitative model is developed that explains the sign and magnitude of the polarization dependence at both edges. The results demonstrate that NEXAFS is able to characterize surface reactions during the immobilization of proteins and to provide insight into their orientations on surfaces.     

Dysprosium compounds studied by resonant inelastic X-ray scattering and high-resolution X-ray absorption near edge structure spectroscopy

A set of resonant inelastic X-ray scattering (RIXS) studies focusing on the 2p64f(n)-->2p54f(n)5d1(2p54f(n+1)5d0)-->2p63d94f(n)5d1(2p63d94f(n+1)5d0) channel of dysprosium in Dy metal, Dy2O3, DyNi3 and Dy25Fe18 compounds have been carried out. Data showed with high statistics and resolution, the different delocalization degree of the 5d band of dysprosium in these compounds, e.g., decreasing from Dy metal to DyNi3, Dy25Fe18 and to dysprosium oxide, in agreement with the high-resolution XANES (HRXANES) spectra. Band structure calculations performed on Dy metal and Dy2O3 confirm both RIXS and HRXANES results in the increasing delocalization of the dysprosium 5d band in Dy metal with respect to Dy2O3. The 5d orbital occupancies of DyNi3 and Dy25Fe18 alloys have been also studied by comparison of the HRXANES white line (WL) area with the behavior of the final states energy position in RIXS spectra and we show that DyNi3 has a higher 5d orbital occupancy than Dy25Fe18.     

Matrix effects in the carbon 1s near edge x-ray absorption fine structure spectra of condensed alkanes

The carbon 1s near edge x-ray absorption fine structure (NEXAFS) spectra of simple gaseous alkane molecules differ from the spectra of the same alkane molecules in the condensed phase. The origin of these large, systematic differences is poorly understood. The NEXAFS spectra of gaseous alkanes are interpreted as a progression of core-->Rydberg transitions with distinctive vibronic structure. The interpretation of the NEXAFS spectra of condensed phase alkanes is varied. Specifically, the degree of Rydberg character in the pre-edge core excited states of condensed alkanes is controversial. We determined the character of core excited states in condensed alkanes with a combination of experiment and computational study. From this, we have determined the nature of matrix effects for these species. The high-resolution carbon 1s NEXAFS spectrum of gaseous neopentane is dramatically different from its condensed phase spectrum, a striking illustration of the dramatic spectroscopic changes that occur upon condensation. High quality ab initio calculations of a cluster designed to model the solid phase environment provide definitive evidence for the reduction of Rydberg character and support the assignment of sigma*C-H) valence character in the pre-edge features in the NEXAFS spectra of condensed alkanes.     

X-ray absorption near edge structure and extended X-ray absorption fine structure analysis of Fe(II) aqueous and acetone solutions

X-ray absorption spectroscopy measurements were used to determine the structure of the first coordination shell of Fe(II) ions in aqueous and acetone based solutions. Extended X-ray absorption fine structure analysis coupled with ab initio X-ray absorption near edge structure calculations confirms the octahedral coordination of the iron ion in water based solution. Data collected for acetone rich solutions can be reproduced assuming coexistence of the octahedral Fe(H(2)O)(6)(2+) and tetrahedral [FeCl(4)](2-) complexes. Distortion of the tetrahedral coordination of ion was detected in some of the acetone based solutions.     

sp hybridization in free carbon nanoparticles--presence and stability observed by near edge X-ray absorption fine structure spectroscopy

The presence and stability of sp hybridized atoms in free carbon nanoparticles was investigated by NEXAFS spectroscopy. The experiments show that a predominant fraction of carbon atoms is found in linear sp-chains and that conversion into sp(2) structures proceeds already at low temperature and in the gas phase.     

Soft x-ray photoreactions of CF3Cl adsorbed on Si(111)-7x7 studied by continuous-time photon-stimulated desorption spectroscopy near F(1s) edge

The continuous-time core-level photon-stimulated desorption (PSD) spectroscopy was employed to monitor the monochromatic soft x-ray-induced reactions of CF3Cl adsorbed on Si(111)-7x7 near the F(1s) edge (681-704 eV). Sequential F+ PSD spectra were measured as a function of photon exposure at the CF3Cl-covered surface (dose=0.3x10(15) molecules/cm2, approximately 0.75 ML). The F+ PSD and total electron yield (TEY) spectra of molecular solid CF3Cl near the F(1s) edge were also measured. Both F+ PSD and TEY spectra show two features at the energy positions of 690.2 and 692.6 eV, and are attributed to the excitations of F(1s) to 11a1[(C-Cl)*] and (8e+12a1)[(C-F)*] antibonding orbitals, respectively. Following Auger decay, two holes are created in the F(2p) lone pair and/or C-F bonding orbitals forming the 2h1e final state which leads to the F+ desorption. This PSD mechanism, which is responsible for the F+ PSD of solid CF3Cl, is employed to interpret the first F+ PSD spectrum in the sequential F+ PSD spectra. The variation of spectrum shapes in the sequential F+ PSD spectra indicates the dissipation of adsorbed CF3Cl molecules and the formation of surface SiF species as a function of photon exposure. From the sequential F+ PSD spectra the photolysis cross section of the adsorbed CF3Cl molecules by photons with varying energy (681-704 eV) is determined to be approximately 1.0x10(-17) cm2.     

A reflection absorption infrared spectroscopy and density-functional theory investigation of methanol dehydrogenation on Rh(111)V alloy surfaces

The dehydrogenation reaction of methanol on a Rh(111) surface, a Rh(111)V subsurface alloy, and on a Rh(111)V islands surface has been studied by thermal-desorption spectroscopy, reflection absorption infrared spectroscopy, and density-functional theory calculations. The full monolayer of methanol forms a structure with a special geometry with methanol rows, where two neighboring molecules have different oxygen-rhodium distances. They are close enough to form a H-bonded bilayer structure, with such a configuration, where every second methanol C-O bond is perpendicular to the surface on both Rh(111) and on the Rh(111)V subsurface alloy. The Rh(111)V subsurface alloy is slightly more reactive than the Rh(111) surface which is due to the changes in the electronic structure of the surface leading to slightly different methanol species on the surface. The Rh(111)V islands surface is the most reactive surface which is due to a new reaction mechanism that involves a methanol species stabilized up to about 245 K, partial opening of the methanol C-O bond, and dissociation of the product carbon monoxide. The latter two reactions also lead to a deactivation of the Rh(111)V islands surface.     

NO adsorption and dissociation on Rh(111): PM-IRAS study

We have used in situ polarization-modulation infrared reflection absorption spectroscopy to study the adsorption/dissociation of NO on Rh(111). While these studies have not been conclusive regarding the detailed surface structures formed during adsorption, they have provided important new information on the dissociation of NO on Rh(111). At moderate pressures (< or =10(-6) Torr) and temperatures (<275 K), a transition from 3-fold hollow to atop bonding is apparent. Data indicate that this transition is not due to the migration of the 3-fold hollow NO but rather to the adsorption of gas-phase NO that is directed toward the atop position due to the presence of NO decomposition products, particularly chemisorbed atomic O species at the hollow sites. These results indicate that NO dissociation occurs at temperatures well below the temperature previously reported. Additionally, high pressure (1 Torr) NO exposure at 300 K results in only atop NO, calling into question the surface structures previously proposed at these adsorption conditions consisting of atop and 3-fold hollow sites.     

Local structure of Pt and Pd ions in Ce(1-x)TixO2: x-ray diffraction, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure

Ce(1-x-y)Ti(x)Pt(y)O(2-delta) (x=0.15; y=0.01) and Ce(1-x-y)Ti(x)Pd(y)O(2-delta) (x=0.25; y=0.02 and 0.05) are found to be good CO oxidation catalysts [T. Baidya et al., J. Phys. Chem. B 110, 5262 (2006); T. Baidya et al., J. Phys. Chem. C 111, 830 (2007)]. A detailed structural study of these compounds has been carried out by extended x-ray absorption fine structure along with x-ray diffraction and x-ray photoelectron spectroscopy. The gross cubic fluorite structure of CeO(2) is retained in the mixed oxides. Oxide ion sublattice around Ti as well as Pt and Pd ions is destabilized in the solid solution. Instead of ideal eight coordinations, Ti, Pd, and Pt ions have 4+3, 4+3, and 3+4 coordinations creating long and short bonds. The long Ti-O, Pd-O, and Pt-O bonds are approximately 2.47 A (2.63 A for Pt-O) which are much higher than average Ce-O bonds of 2.34 A.     

Temperature effect of the local structure in liquid Sb studied with x-ray absorption spectroscopy

The temperature dependence of the local structure of liquid Sb has been studied by x-ray absorption spectroscopy. It is shown that about 10% of the atoms with coordination of 3 and weak Peierls distortion exist in liquid Sb just above its melting point. The Peierls distortion weakens gradually with increasing temperature and vanishes at about 750 degrees C. This structural variation in liquid Sb is different from the normal liquid-liquid phase transition. This work reveals the relationship between the variation in the local structure and the change in the physical properties, such as the electrical resisitvity of liquid Sb, with temperature. The complete agreement between the measured electrical resistivity values during heating and cooling processes suggests that the structural units with the features of a rhombohedron appear above the melting point of Sb during solidification.     

Characterization of calcium carbonate polymorphs with Ca K edge X-ray absorption fine structure spectroscopy

Ca K edge X-ray absorption fine structure (XAFS) spectroscopy was utilized for the characterization and quantification of calcium carbonate polymorphs and their mixtures. The advantage of the XAFS is the small sample quantity required for measurements, and a flexible sample environment. The near-edge XAFS spectra of calcite, aragonite and vaterite were measured with the conversion electron yield (CEY) method, and the obtained spectra showed characteristic features that can be utilized as fingerprints. The quantification of mixed polymorphs was examined by using a linear combination fitting of reference XAFS spectra. Though the quality of the fits was satisfactory, discrepancies in the evaluated values were observed between those with X-ray diffraction (XRD) and XAFS. The nonuniformity of samples may be enhanced by the surface sensitivity of the CEY method.     

Comparative study of water dissociation on Rh(111) and Ni(111) studied with first principles calculations

The dissociation and formation of water on the Rh(111) and Ni(111) surfaces have been studied using density functional theory with generalized gradient approximation and ultrasoft pseudopotentials. Calculations have been performed on 2x2 surface unit cells, corresponding to coverages of 0.25 ML, with spot checks on 3x3 surface unit cells (0.11 ML). On both surfaces, the authors find that water adsorbs flat on top of a surface atom, with binding energies of 0.35 and 0.25 eV, respectively, on Rh(111) and Ni(111), and is free to rotate in the surface plane. Barriers of 0.92 and 0.89 eV have to be overcome to dissociate the molecule into OH and H on the Rh(111) and Ni(111) surfaces, respectively. Further barriers of 1.03 and 0.97 eV need to be overcome to dissociate OH into O and H. The barriers for the formation of the OH molecule from isolated adsorbed O and H are found to be 1.1 and 1.3 eV, and the barriers for the formation of the water molecule from isolated adsorbed OH and H are 0.82 and 1.05 eV on the two surfaces. These barriers are found to vary very little as coverage is changed from 0.25 to 0.11 ML. The authors have also studied the dissociation of OH in the presence of coadsorbed H or O. The presence of a coadsorbed H atom only weakly affects the energy barriers, but the effect of O is significant, changing the dissociation barrier from 1.03 to 1.37 and 1.15 eV at 0.25 or 0.11 ML coverage on the Rh(111) surface. Finally, the authors have studied the dissociation of water in the presence of one O atom on Rh(111), at 0.11 ML coverage, and the authors find a barrier of 0.56 eV to dissociate the molecule into OH+OH.