X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

Determination of acidities of zeolites by photoacoustic spectroscopy

Photoacoustic spectroscopy is found to be a useful technique for determining the acidity of zeolites. The acidity so determined correlates well with temperature programmed vdesorption studies of ammonia and product distribution.

Use of 45° pulse pair as a filter for pure-phase two-dimensional NMR spectroscopy

Conventionally two-dimensional NMR spectra are recorded in the absolute-intensity mode (1-4). It has recently been demonstrated that absorption-mode 2D spectra have much higher resolution and are the preferred mode of presentation, especially for 2D spectra of biomolecules (5-7). Indeed, any experimental scheme which yields phasemixed lineshapes is subject to modification to yield pure-phase spectra, even at the expense of intensity and anomalous multiplet structure (8-10). For this purpose two types of filters are already known: the z filter (9, 20) and the purging pulse (8, 10). In this note, we propose a 45” pulse pair as a filter for obtaining pure-phase 2D spectra, mainly for experiments in which the above filters do not yield pure-phase spectra.

Conformation of antibiotic X-537A (lasalocid-A) and its calcium complex in acetonitrile solvent using circular dichroism spectroscopy

The calcium binding characteristics of antibiotic X-537A (lasalocid-A) in a lipophilic solvent, acetonitrile (CH3CN), have been studied using circular dichroism (CD) spectroscopy. The analysis of the data indicated that in this medium polar solvent, X-537A forms predominantly the charged complexes of stoichiometries 2:1 and 1:1, the relative amounts of the two being dependent on [Ca2+]. The conformation of the complexes, arrived at on the basis of the data, seem to indicate a rigid part encompassing Ca2+, liganded to 3 oxygens of the molecule, viz., the carbonyl, the substituted tetrahydrofuran ring and the substituted pyran ring oxygens (apart from possibly, the liganding provided by nitrogen atoms of the solvent molecules), and a flexible part consisting of the salicylic acid group of the molecule.

Ce CORE level X-ray photo electron spectroscopy of CeX2Si2 (X = Fe, Co, Ni and Cu)

Ce(3d) and (4d) core level XPS spectra of CeX = Fe, Co, Ni and Cu) suggest that the mean valence of Ce was as well as 4f hybridization strength decrease systematically from Fe to Cu. This observation is in agreement with the results of Bremstrahlung Isochromat Spectroscopy (BIS), but in disagreement with LIII-edge data reported earlier.

Coherence transfer via longitudinal spin order generalized pulse pair filtering for pure phase two-dimensional NMR spectroscopy

A generalized pulse pair has been suggested in which the longitudinal spin order is retained and the transverse components cancelled by random variation of the interval between pulses, in successive applications of the two-dimensional NMR algorithm. This method leads to pure phases and has been exploited to provide a simpler scheme for two-spin filtering and for pure phase spectroscopy in multiple-quantum-filtered two-dimensional NMR experiments.

Study of strontium compounds and minerals by X-ray absorption spectroscopy. I. K-edge shifts

The chemical shifts in the X-ray K-absorption edge of strontium in various compounds and in six minerals are measured using a single crystal X-ray spectrometer. Besides valence, the shifts are found to be governed by ionic charges on the absorbing ions, which are calculated employing Pauling's method. For the minerals the plot of chemical shift against the theoretically calculated ionic charges is used to determine the charges on the strontium ions.

Study of surface acidity of oxide catalysts by photoacoustic spectroscopy

Photoacoustic spectroscopy has been employed to estimate quantitatively the acid sites on oxide catalysts. The technique involves the measurement of the ratio of intensities of absorption bands due to conjugate bases and acids of indicators adsorbed on the catalyst surface as a function of the amount of added n-butylamine. Basic sites in sodium-impregnated alumina samples have been examined by adsorbing phenolphthalein on these surfaces.

Renormalization of the phonon spectrum in semiconducting single-walled carbon nanotubes studied by Raman spectroscopy

In situ Raman experiments together with transport measurements have been carried out in single-walled carbon nanotubes as a function of electrochemical top gate voltage (Vg). We have used the green laser (EL=2.41 eV), where the semiconducting nanotubes of diameter ~1.4 nm are in resonance condition. In semiconducting nanotubes, the G−- and G+-mode frequencies increase by ~10 cm−1 for hole doping, the frequency shift of the G− mode is larger compared to the G+ mode at the same gate voltage. However, for electron doping the shifts are much smaller: G− upshifts by only ~2 cm−1 whereas the G+ does not shift. The transport measurements are used to quantify the Fermi-energy shift (EF) as a function of the gate voltage. The electron-hole asymmetry in G− and G+ modes is quantitatively explained using nonadiabatic effects together with lattice relaxation contribution. The electron-phonon coupling matrix elements of transverse-optic (G−) and longitudinal-optic (G+) modes explain why the G− mode is more blueshifted compared to the G+ mode at the same Vg. The D and 2D bands have different doping dependence compared to the G+ and G− bands. There is a large downshift in the frequency of the 2D band (~18 cm−1) and D (~10 cm−1) band for electron doping, whereas the 2D band remains constant for the hole doping but D upshifts by ~8 cm−1. The doping dependence of the overtone of the G bands (2G bands) shows behavior similar to the dependence of the G+ and G− bands.

3d and 4d core level X-ray photoelectron spectroscopy of mixed-valence CePd3

3d and 4d core-level XPS spectra for CePd3, a mixed-valence system, have been measured. Each spectrum exhibits two sets of structures, each corresponding to one of the valence states of cerium. Thus the usefulness of XPS, which has so far not been used extensively to investigate the mixed-valence cerium systems, is pointed out.

Studies of Solids and Surfaces by Auger Electron Spectroscopy

Although the applications of Auger electron spectroscopy in surface analysis have by far outweighed its use as a tool to investigate electron states of solids and surfaces, there are a variety of situations where Auger spectroscopy provides unique information. Apart from the chemical shifts, Auger intensities are useful in determining the number of d-electron states in transition metal systems. Auger spectroscopy is a good probe to investigate the surface oxidation of metals. In addition to the intra-atomic Auger transitions, inter-atomic transitions observed in oxides and other systems reveal the nature of electron states of surfaces. Charge-transfer and hybridization effects in alloys are also usefully studied by Auger spectroscopy. Auger electron spectroscopy has not been a popular technique to investigate adsorption of molecules on surfaces, but the technique is useful to obtain fingerprints of surface species.

Electron energy loss spectroscopy (EELS) of H2O, H2S, H2Se and H2Te

Electronic excitation in H2O, H2S, H2Se and H2Te molecules has been studied by the EELS technique. Spectra of H2S and H2Se are remarkably similar with the 1b1-nd transition most intense. The intensity of the first transition 1b1-nsa1 decreases through H2O to H2Se and this transition is absent in H2Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.

Surface oxidation of cadmium, indium, tin and antimony by photoelectron and Auger spectroscopy

Surface oxidation of Cd, In, Sn and Sb has been investigated by employing valence bands, metal 4d levels and plasmon bands in X-ray photoelectron spectra. O(KLL), metal M4N45N45, and plasmon transitions in electron-induced Auger spectra as well as Auger transitions due to the metal (metal oxide) and plasmons in X-ray-induced Auger spectra. The surface oxides are In2O4, CdO and a mixture of SnO and SnO2 in the case of In. Cd and Sn respectively. The facility of surface oxidation is found to vary as In>Cd>Sn>Sb. Inter-atomic Auger transitions involving oxygen valence bands have been identified on oxidized surfaces of Cd and In.

A novel investigation of vapor-phase charge-transfer complexes of halogens with n-donors by electron energy loss spectroscopy

Complexes of I2 with diethyl ether and triethylamine and of Br, with diethyl ether have been investigated in the vapor phase for the first time by employing electron energy loss spectroscopy. Besides the CT bands, blue-shifted vacuum-UV bands of the halogens have been assigned; the amine-I, system appears to exhibit two CT bands,associated with two different excited states of the complex.

Electron-Energy Loss Spectroscopy (Eels) Of Organic-Molecules In Vapor-Phase - Design And Fabrication Of An Indigenous Eel Spectrometer

An indigenous electron energy loss spectrometer has been designed and fabricated for the study of free molecules. The spectrometer enables the recording of low-resolution electronic spectra of molecules inthe vapour phase with ready access to the vacuum ultraviolet region. Electron energy loss spectra of aliphatic alcohols and carbonyl compounds as wellas of benzene derivatives have been recorded with the indigenous spectrometer and the electronic transitions in these molecules discussed.