Excitation and correlation of N-14 overtone transitions and measurement of heteronuclear dipolar coupling using DAPT

For studying systems containing nitrogen, limited use of N-14 NMR spectroscopy has been made because of the large quadrupolar interaction experienced by the N-14 nucleus and the absence of a central transition. To overcome the above problem, use of overtone spectroscopy has been suggested. Though this approach has limited applicability for powder samples due to second order quadrupole broadening, it is useful for studying oriented samples and single crystals. Here, we demonstrate the use of the recently proposed dipolar assisted polarization transfer (DAPT) pulse scheme for exciting the overtone transitions. The pulse sequence may also be utilized as a two-dimensional experiment to obtain H-1-N-14 dipolar couplings and H-1 chemical shifts. (C) 2010 Elsevier B.V. All rights reserved.

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.

Intensity of a Raman Overtone Band

Placzek [1] was the first to derive general expressions for the intensities of overtones in case of Raman scattering. He assumed electrical anharmonicity. However, he left the expressions for the derivations of the polarizability tensor undetermined. In 1941, a classical and semiempirical theory was developed by Wolkenstein [2]. He assumed the validity of the additivity of bond polarizabilities. However, the expressions derived by him for the intensities of overtones remain yet to be verified. It is the purpose of this paper to derive a formula for Raman polarizability tensor for overtones of (intramolecular) vibrational spectra along the lines of Kondilenko et al. [3,4].

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Studies on glass transition and starch re-crystallization in wheat bread during staling using electrical impedance spectroscopy

Bread staling is a very complex phenomenon that is not yet completely understood. The present work explains how the electrical impedance spectroscopy technique can be utilized to investigate the effect of staling on the physicochemical properties of wheat bread during storage. An instrument based on electrical impedance spectroscopy technique is developed to study the electrical properties of wheat bread both at its crumb and crust with the help of designed multi-channel ring electrodes. Electrical impedance behavior, mainly capacitance and resistance, of wheat bread at crust and crumb during storage (up to 120 h) is investigated. The variation in capacitance showed the glass transition phenomenon at room temperature in bread crust after 96 h of storage with 18% of moisture in it. The resistance changes at bread crumb showed the starch recrystallization during staling.

Identification of the nature of platinum related midgap state in silicon by deep level transient spectroscopy

In this article, we present the detailed investigations on platinum related midgap state corresponding to E-c -0.52 eV probed by deep level transient spectroscopy. By irradiating the platinum doped samples with high-energy (1.1 MeV) gamma rays, we observed that the concentration of the midgap state increases and follows a square dependence with irradiation dose. However, the concentration of the acceptor corresponding to E-c -20.28 eV remained constant. Furthermore, from the studies on passivation by atomic hydrogen and thermal reactivation, we noticed that the E-c -0.52 eV level reappears in the samples annealed at high temperatures after hydrogenation. The interaction of platinum with various defects and the qualitative arguments based on the law of mass action suggest that the platinum related midgap defect might possibly correspond to the interstitial platinum-divacancy complex (V-Pt-V).

Ultrafast Raman loss spectroscopy

This paper deals with a new form of nonlinear Raman spectroscopy called `ultrafast Raman loss spectroscopy (URLS)'. URLS is analogous to stimulated Raman spectroscopy (SRS) but is much more sensitive than SRS. The signals are background (noise) free unlike in coherent anti-Stokes Raman spectroscopy (CARS) and it provides natural fluorescence rejection, which is a major problem in Raman spectroscopy. In addition, being a self-phase matching process, the URLS experiment is much easier than CARS, which requires specific phase matching of the laser pulses. URLS is expected to be alternative if not competitive to CARS microscopy, which has become a popular technique in applications to materials, biology and medicine.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Theoretical Description of Time-Resolved Photoemission Spectroscopy: Application to Pump-Probe Experiments

The theory for time-resolved, pump-probe, photoemission spectroscopy and other pump-probe experiments is developed. The formal development is completely general, incorporating all of the nonequilibrium effects of the pump pulse and the finite time width of the probe pulse, and including possibilities for taking into account band structure and matrix element effects, surface states, and the interaction of the photoexcited electrons with the system leading to corrections to the sudden approximation. We also illustrate the effects of windowing that arise from the finite width of the probe pulse in a simple model system by assuming the quasiequilibrium approximation.

Determination of beta-turn conformation by laser Raman spectroscopy

To correlate the Raman frequencies of the amide I and III bands to beta-turn structures, three peptides shown to contain beta-turn structure by x-ray diffraction and NMR were examined. The compounds examined were tertiary (formula: see text). The amide I band of these compounds is seen at 1,668, 1,665, and 1,677 cm-1, and the amide III band appears at 1,267, 1,265, and 1,286 cm-1, respectively. Thus, it is concluded that the amide I band for type III beta-turn structure appears in the range between 1,665 and 1,677 cm-1 and the amide III band between 1,265 and 1,286 cm-1.

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Molecular conformation of N,N -diarylthioureas: An assessment by 1H NMR and infrared spectroscopy

Several N,N -dipyridyl- and N-phenyl-N -pyridyl-thioureas were examined in different solvents at various temperatures by 1H NMR in order to study their conformational properties. The influence of concentration and the methyl substituent in the pyridine ring on the chemical shifts of the NH and pyridine groups was investigated. The observed chemical shifts are analysed in terms of the conformational properties of the molecules. Free energy barriers to the internal rotation about the C N bonds have been determined. Infrared spectra have been measured to supplement the NMR studies. Intramolecular hydrogen bonding played a major role in the preferred conformation of pyridylthioureas. The data further revealed an interesting dynamic exchange phenomenon occurring in symmetric N,N -dipyridylthioureas between two intramolecularly hydrogen bonded conformers.

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.