Growth Mechanism of Cadmium Sulfide Nanocrystals

We investigate the growth kinetics of CdS nanocrystals in the quantum confinement regime using time-resolved small-angle X-ray scattering. In contrast to earlier reports for similar systems, we establish that the growth kinetics in this case follows the Lifshitz-Slyozov-Wagner theory, for not only growth of the average diameter of the nanocrystals but also the time dependence of the size distribution and the temperature dependence of the rate constant. This is the first rigorous example of the coarsening process in the quantum confinement (< 5 nm)regime. Ab initio studies for the reaction pathways provide a microscopic understanding of this finding.

Nature of copper in the new cuprate superconductors Pb2Sr2Ca1-xLxCu3O8+δ

Based on Cu K-edge absorption spectroscopy as well as Cu(2p3/2) and Cu(LVV) Auger spectroscopies it is shown that the recently discovered Pb2Sr2Ca1-xLxCu3O8+δ (L=Y or Lu) superconductors contain well-defined Cu1+ species in admixture with Cu2+. The proportion of Cu1+ is small in the nonsuperconducting samples with x=1, a feature which is uniquely different from that in YBa2Cu3O7-δ.

Scaling behavior of plasmon coupling in Au and ReO3 nanoparticles incorporated in polymer matrices

Polymer nanocomposites containing different concentrations of Au nanoparticles have been investigated by small angle X-ray scattering and electronic absorption spectroscopy. The variation in the surface plasmon resonance (SPR) band of Au nanoparticles with concentration is described by a scaling law. The variation in the plasmon band of ReO3 nanoparticles embedded in polymers also follows a similar scaling law. Sistance dependence of plasmon coupling in polymer composites f metal nanoparticles. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative structural refinement of mn K edge XANES in LaMnO3 and CaMnO3 perovskites

The special magnetotransport properties of hole doped manganese perovskites originate from a complex interplay among structural, magnetic and electronic degree of freedom. In this picture the local atomic structure around Mn ions plays a special role and this is the reason why short range order techniques like X-ray absorption spectroscopy (XAS) have been deeply exploited for studying these compounds. The analysis of near edge region features (XANES) of XAS spectra can provide very fine details of the local structure around Mn, complementary to the EXAFS, so contributing to the full understanding of the peculiar physical properties of these materials. Nevertheless the XANES analysis is complicated by the large amount of structural and electronic details involved making difficult the quantitative interpretation.This work exploits the recently developed MXAN code to achieve a full structural refinement of the Mn K edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3, in which the Mn ions are present only in one charge state as Mn3+ and Mn4+ respectively. The good agreement between the results derived from the analysis of near edge and extended region of the XAS spectra demonstrates that a quantitative picture of the local structure call be obtained from structural refinement of Mn K edge XANES data in these crystalline compounds. The XANES analysis offers, in addition.. the possibility to directly achieve information on the topology of local atomic structure around the absorber not directly achievable from EXAFS.

A simple synthesis and characterization of CuS nanocrystals

Water-soluble CuS nanocrystals and nanorods were prepared by reacting copper acetate with thioacetamide in the presence of different surfactants and capping agents. The size of the nanocrystals varied from 3-20 nm depending on the reaction parameters such as concentration, temperature, solvent and the capping agents. The formation of nanocrystals was studied by using UV-visible absorption spectroscopy.

A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

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+xMo1-xO6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.

Nanoscale studies of materials using x-ray synchrotron radiation and mesoscopic modelling

X-ray synchrotron radiation was used to study the nanostructure of cellulose in Norway spruce stem wood and powders of cobalt nanoparticles in cellulose support. Furthermore, the growth of metallic clusters was modelled and simulated in the mesoscopic size scale. Norway spruce was characterized with x-ray microanalysis at beamline ID18F of the European Synchrotron Radiation Facility in Grenoble. The average dimensions and the orientation of cellulose crystallites was determined using x-ray microdiffraction. In addition, the nutrient element content was determined using x-ray fluorescence spectroscopy. Diffraction patterns and fluorescence spectra were simultaneously acquired. Cobalt nanoparticles in cellulose support were characterized with x-ray absorption spectroscopy at beamline X1 of the Deutsches Elektronen-Synchrotron in Hamburg, complemented by home lab experiments including x-ray diffraction, electron microscopy and measurement of magnetic properties with a vibrating sample magnetometer. Extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray diffraction were used to solve the atomic arrangement of the cobalt nanoparticles. Scanning- and transmission electron microscopy were used to image the surfaces of the cellulose fibrils, where the growth of nanoparticles takes place. The EXAFS experiment was complemented by computational coordination number calculations on ideal spherical nanocrystals. The growth process of metallic nanoclusters on cellulose matrix is assumed to be rather complicated, affected not only by the properties of the clusters themselves, but essentially depending on the cluster-fiber interfaces as well as the morphology of the fiber surfaces. The final favored average size for nanoclusters, if such exists, is most probably a consequence of these two competing tendencies towards size selection, one governed by pore sizes, the other by the cluster properties. In this thesis, a mesoscopic model for the growth of metallic nanoclusters on porous cellulose fiber (or inorganic) surfaces is developed. The first step in modelling was to evaluate the special case of how the growth proceeds on flat or wedged surfaces.

Field-tunable stochasticity in the magnetization reversal of a cylindrical nanomagnet

The nature of magnetization reversal in an isolated cylindrical nanomagnet has been studied employing time-resolved magnetoresistance measurement. We find that the reversal mode is highly stochastic, occurring either by multimode or single-step switching. Intriguingly, the stochasticity was found to depend on the alignment of the driving magnetic field to the long axis of the nanowires, where predominantly multimode switching gives way to single-step switching behavior as the field direction is rotated from parallel to transverse with respect to the nanowire axis.

A porphyrin bearing tetrahydrothiophene pickets; co-ordination behaviour and electron transfer

A novel ‘picket-fence’ porphyrin, 5,10,15,20-tetrakis[o-(tetrahydro-2-thenoylamino)phenyl]porphyrin (H2L) with ligating tetrahydrothiophene rings disposed perpendicular to the porphyrin plane has been synthesised. Its zinc(II) derivative, [ZnL], binds two silver(I) ions co-operatively with a dissociation constant of 4.8 × 10–8 dm3 mol–1. Time-resolved fluorescence lifetime measurements reveal the presence of intramolecular photoexcited electron transfer in this donor–acceptor system.

Temperature-dependent chirped coherent phonon dynamics in Bi2Te3 using high-intensity femtosecond laser pulses

Degenerate pump-probe reflectivity experiments have been performed on a single crystal of bismuth telluride (Bi2Te3) as a function of sample temperature (3 K to 296 K) and pump intensity using similar to 50 femtosecond laser pulses with central photon energy of 1.57 eV. The time-resolved reflectivity data show two coherently generated totally symmetric A(1g) modes at 1.85 THz and 3.6 THz at 296 K which blue-shift to 1.9 THz and 4.02 THz, respectively, at 3 K. At high photoexcited carrier density of similar to 1.7 x 10(21) cm(-3), the phonon mode at 4.02 THz is two orders of magnitude higher positively chirped (i.e the phonon time period decreases with increasing delay time between the pump and the probe pulses) than the lower-frequency mode at 1.9 THz. The chirp parameter, beta is shown to be inversely varying with temperature. The time evolution of these modes is studied using continuous-wavelet transform of the time-resolved reflectivity data. Copyright (C) EPLA, 2010

Electron Donor-Acceptor Complexes of the Fullerenes C60 and C70 with Amines

Based on electronic absorption spectroscopy, C60 is found to form complexes with aromatic amines with an enthalpy of association in the range 9-16 kJ mol-1. Interaction of C70 with the amines is negligible. Cyclic voltammetric measurements confirm these observations.

Phenomenological Ginzburg-Landau-like theory for superconductivity in the cuprates

We propose and develop here a phenomenological Ginzburg-Landau-like theory of cuprate high-temperature superconductivity. The free energy of a cuprate superconductor is expressed as a functional F of the complex spin-singlet pair amplitude psi(ij) equivalent to psi(m) = Delta(m) exp(i phi(m)), where i and j are nearest-neighbor sites of the square planar Cu lattice in which the superconductivity is believed to primarily reside, and m labels the site located at the center of the bond between i and j. The system is modeled as a weakly coupled stack of such planes. We hypothesize a simple form FDelta, phi] = Sigma(m)A Delta(2)(m) + (B/2)Delta(4)(m)] + C Sigma(< mn >) Delta(m) Delta(n) cos(phi(m) - phi(n)) for the functional, where m and n are nearest-neighbor sites on the bond-center lattice. This form is analogous to the original continuum Ginzburg-Landau free-energy functional; the coefficients A, B, and C are determined from comparison with experiments. A combination of analytic approximations, numerical minimization, and Monte Carlo simulations is used to work out a number of consequences of the proposed functional for specific choices of A, B, and C as functions of hole density x and temperature T. There can be a rapid crossover of from small to large values as A changes sign from positive to negative on lowering T; this crossover temperature T-ms(x) is identified with the observed pseudogap temperature T*(x). The thermodynamic superconducting phase-coherence transition occurs at a lower temperature T-c(x), and describes superconductivity with d-wave symmetry for positive C. The calculated T-c(x) curve has the observed parabolic shape. The results for the superfluid density rho(s)(x, T), the local gap magnitude , the specific heat C-v(x, T) (with and without a magnetic field), as well as vortex properties, all obtained using the proposed functional, are compared successfully with experiments. We also obtain the electron spectral density as influenced by the coupling between the electrons and the correlation function of the pair amplitude calculated from the functional, and compare the results successfully with the electronic spectrum measured through angle resolved photoemission spectroscopy (ARPES). For the specific heat, vortex structure, and electron spectral density, only some of the final results are reported here; the details are presented in subsequent papers.

Coherent phonons in pyrochlore titanates A(2)Ti(2)O(7) (A = Dy, Gd, Tb): A phase transition in Dy2Ti2O7 at 110 K

We study the generation of coherent optical phonons in spin-frustrated pyrochlore single crystals Dy2Ti2O7, Gd2Ti2O7, and Tb2Ti2O7 using femtosecond laser pulses (65 fs, 1.57 eV) in degenerate time-resolved transmission experiments as a function of temperature from 4 to 296 K. At 4 K, two coherent phonons are observed at similar to 5.3 THz (5.0 THz) and similar to 9.3 THz (9.4 THz) for Dy2Ti2O7 (Gd2Ti2O7), whereas three coherent phonons are generated at similar to 5.0, 8.6, and 9.7 THz for Tb2Ti2O7. In the case of spin-ice Dy2Ti2O7, a clear discontinuity is observed in the linewidths of both the coherent phonons as well as in the phase of lower-energy coherent phonon mode, indicating a subtle structural change at 110 K. Another important observation is a phase difference of pi between the modes in all the samples, thus suggesting that the driving forces behind the generation of these modes could be different in nature, unlike a purely impulsive or displacive mechanism.

Probing the structural changes in the phase transitions of a Bi2MoO6 catalyst: the nature of the intermediate-temperature phase

The nature of the phase transitions of Bi2MoO6 has been investigated by the combined use of X-ray diffraction and Xray absorption spectroscopy. The distorted MoO6 octahedra in the low-temperature form are shown to undergo further distortion in the intermediate-temperature form before transforming to MoO4 tetrahedra in the high-temperature phase. (C) 1995 Academic Press, Inc.

Spectroscopic, redox and photophysical properties of push-pull fluoroarylporphyrins

Novel fluoroarylporphyrins bearing electron donor dimethylamino groups in the meso-aryl positions and an electron acceptor nitro group on one of the pyrrole carbons exhibit significant solvent dependent fluorescence spectra and time-resolved emission properties. These effects are suggestive of intramolecular charge transfer (ICT) in the singlet excited state of these porphyrins. Electrochemical redox behaviour of these porphyrins showed the presence of substantial donor-acceptor interactions in the nitro-amino porphyrins.