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81.
Karla J. Moreno Miroslaw Maczka Ulises Amador 《Journal of solid state chemistry》2006,179(12):3805-3813
The structural and microstructural characteristics of metastable Gd2(Ti1−yZry)2O7 powders prepared by mechanical milling have been studied by a combination of XRD and Raman spectroscopy. Irrespective of their Zr content, as-prepared powder phases present an anion-deficient fluorite-type of structure as opposed to the pyrochlore equilibrium configuration obtained for the same solid solution by other synthetic routes. These fluorites are stable versus thermal activation, at least up to temperatures of 800 °C. For the Ti-rich compositions, thermal treatments at higher temperatures facilitate the rearrangement of the cation and anion substructures and the relaxation of mechanochemically induced defects whereas for compositions with high Zr content, the fluorite crystal structure is retained even at temperatures as high as 1200 °C. Interestingly enough, transient pyrochlores showing a very unusual cation distribution were observed during the thermally induced defect-recovery process. 相似文献
82.
Dinesh Topwal U. Manju Sugata Ray S. Raj D. D. Sarma S. R. Krishnakumar M. Bertolo S. La Rosa G. Cautero 《Journal of Chemical Sciences》2006,118(1):87-92
Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function
of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of
such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish
that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is
responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with
composition fluctuations of the type Sr2Fe1+x
Mo1-x
O6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.
Dedicated to Prof J Gopalakrishnan on his 62nd birthday. 相似文献
83.
Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DSTos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DSTos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DSMA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DSTos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and 13C CP/MAS NMR spectroscopy. 13C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DSMA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out. 相似文献
84.
XPS measurement revealed that the original state of TiO2 was changed to Ti2O3 and TiO by ion bombardment. TiO2 decreased and Ti2O3 increased at the initial stage. TiO increased at a later stage than Ti2O3. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO2 to Ti2O3 and from Ti2O3 to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO2 to Ti2O3 is about ten times larger than that from Ti2O3 to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment. 相似文献
85.
The electronic states of the Cr overlayers on TiO2(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO2(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti3+ (3d1) ions and Cr3+ (3d3) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO2(0 0 1) at this stage. 相似文献
86.
Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule. 相似文献
87.
Milind V. Kulkarni Annamraju Kasi Viswanath R. Marimuthu Tanay Seth 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):2043-2049
Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004 相似文献
88.
Eduardo Rissi Roberto Rivelino Sylvio Canuto 《International journal of quantum chemistry》2003,91(4):575-585
Density functional theory (DFT), using the most common functionals, and ab initio quantum chemistry methods are used to calculate the rotational constants and dipole moments of the astrophysically important molecules HCN, CH3CN, CH3CNH+, HCCCN, and HCCNC. As far as millimeter‐wave spectroscopy is of interest the DFT methods performed well with most functionals, giving results within ±1% of experiments for rotational constants and ±3% for dipole moments. Analyzing the results obtained with all theoretical models, it may be concluded that the Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Paar (B3LYP) and Becke's three‐parameter functional with Perdew–Wang correlational functional [B3PW91/6‐31G(d, p)] give the best performances. A detailed analysis of the electron correlation effects shows that HCCCN is more stable than is HCCNC, by 1.16 eV, with important contribution arising from triple excitations. This result is also compared with those obtained with DFT methods. Despite occasional difficulties, DFT with the currently available functionals are of great utility in quickly assessing spectroscopic parameters of astrophysical interest. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
89.
The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested. 相似文献
90.
The detailed characterization of multifunctional hybrid organosilazane/organosilylamine telechelic oligomers by IR and 1H, 13C and 29Si NMR spectroscopy in one and two dimenions has been undertaken. The specific multifunctional oligomers, comprising NH/NH2 or SiCl functionalities depending on the monomer feed-ratio, were prepared from mono- and di-functionally reacted dichlorodimethylsilane (DDS) and mono-, di-, tri- and tetra-functionally reacted ethylenediamine (EDA). Varying the feed-ratio afforded control of the microstructures of the oligomers and the preparation of oligomers with, in some cases, conterminously located silicon–chlorine (SiCl) groups. The combination of the NMR methods with the IR technique has enabled the detailed microstructural characterization of the oligomers and the identification of the functionalities therein. This approach and the knowledge gained from the DDS/EDA system has been applied to the microstructural characterization of other hybrid organosilazane/silylamine preceramic telechelic oligomers. 相似文献