Longitudinal spin relaxation in simple stochastic models for disordered systems

The relaxation of single probe spins was investigated for simple models of systems with quenched disorder. The spin relaxation was calculated for a two-site model with arbitrarily oriented magnetic fields and the result was averaged over various distributions of the fields, and of the hopping rates of the spin. On an intermediate time scale, a modified Kubo-Toyabe behavior is obtained for large hopping rates, in agreement with recent SR experiments. A stretched-exponential decay of the spin polarization is obtained at longer times. The Kohlrausch exponent is found to be field and hopping-rate dependent, in qualitative agreement with recent NMR and -NMR experiments. The resulting longitudinal relaxation rate still does not show the significant deviations from the Bloembergen-Purcell-Pound (BPP) behavior that are typical for glassy systems. Therefore, the random two-frequency model was extended to include time-dependent renewals of the environment. This modification may yield asymmetric peaks for the longitudinal relaxation rate in the BPP plot for very large renewal rates. © 1995 The American Physical Society

Diffusion in infinite and semi-infinite lattices with long-range coupling

We prove that for a one-dimensional infinite lattice, with long-range coupling among sites, the diffusion of an initial delta-like pulse in the bulk, is ballistic at all times. We obtain a closed-form expression for the mean square displacement (MSD) as a function of time, and show some cases including finite range coupling, exponentially decreasing coupling and power-law decreasing coupling. For the case of an initial excitation at the edge of the lattice, we find an approximate expression for the MSD that predicts ballistic behavior at long times, in agreement with numerical results.Comment: 4 pages, 5 figures, submitted for publicatio

High-resolution 27Al MAS NMR spectroscopic studies of the response of spinel aluminates to mechanical action

The response of the local structure of various types of spinel aluminates, ZnAl2O4 (normal spinel), MgAl2O4 (partly inverse spinel), and Li0.5Al2.5O4 (fully inverse spinel), to mechanical action through high-energy milling is investigated by means of 27Al MAS NMR. Due to the ability of this nuclear spectroscopic technique to probe the local environment of Al nuclei, valuable quantitative insight into the mechanically induced changes in the spinel structure, such as the local cation disorder and the deformation of the polyhedron geometry, is obtained. It is revealed that, independent of the ionic configuration in the initial oxides, the mechanical action tends to randomize cations over the two non-equivalent cation sublattices provided by the spinel structure. The response of the spinels to mechanical treatment is found to be accompanied by the formation of a non-uniform core-shell nanostructure consisting of an ordered crystallite surrounded by a structurally disordered interface/surface shell region. Based on the comparative NMR studies of the non-treated and mechanically treated spinels, an attempt is made to separate the surface effects from the bulk effects in spinel nanoparticles. The non-equilibrium cation distribution and the deformed polyhedra are found to be confined to the near-surface layers of spinel nanoparticles with the thickness extending up to about 0.7 nm. The cation inversion parameter of the mechanically treated spinel is compared with that of the non-treated material at non-ambient conditions. © 2011 The Royal Society of Chemistry

Quantitative Chemically-Specific Coherent Diffractive Imaging of Buried Interfaces using a Tabletop EUV Nanoscope

Characterizing buried layers and interfaces is critical for a host of applications in nanoscience and nano-manufacturing. Here we demonstrate non-invasive, non-destructive imaging of buried interfaces using a tabletop, extreme ultraviolet (EUV), coherent diffractive imaging (CDI) nanoscope. Copper nanostructures inlaid in SiO2 are coated with 100 nm of aluminum, which is opaque to visible light and thick enough that neither optical microscopy nor atomic force microscopy can image the buried interfaces. Short wavelength (29 nm) high harmonic light can penetrate the aluminum layer, yielding high-contrast images of the buried structures. Moreover, differences in the absolute reflectivity of the interfaces before and after coating reveal the formation of interstitial diffusion and oxidation layers at the Al-Cu and Al-SiO2 boundaries. Finally, we show that EUV CDI provides a unique capability for quantitative, chemically-specific imaging of buried structures, and the material evolution that occurs at these buried interfaces, compared with all other approaches.Comment: 12 pages, 8 figure

Nonequilibrium structure of Zn 2SnO 4 spinel nanoparticles

Zinc stannate (Zn 2SnO 4) nanoparticles with an average size of about 26 nm are synthesized via single-step mechanochemical processing of binary oxide precursors (ZnO and SnO 2) at ambient temperature, without the need for the subsequent calcination, thus making the synthesis route very simple and cost-effective. The mechanically induced phase evolution of the 2ZnO + SnO 2 mixture is followed by XRD and by a variety of spectroscopic techniques including 119Sn MAS NMR, Raman spectroscopy, 119Sn Mössbauer spectroscopy, and XPS. High-resolution TEM studies reveal a non-uniform structure of mechanosynthesized Zn 2SnO 4 nanoparticles consisting of a crystalline core surrounded by a structurally disordered surface shell. Due to the ability of the applied solid-state spectroscopies to probe the local environment of Sn cations, valuable complementary insight into the nature of the local structural disorder of mechanosynthesized Zn 2SnO 4 is obtained. The findings hint at a highly nonequilibrium state of the as-prepared stannate characterized by its partly inverse spinel structure and the presence of deformed polyhedra in the surface shell of nanoparticles. © 2012 The Royal Society of Chemistry

Crystallite size dependent cation distribution in nanostructured spinels studied by nmr, mössbauer spectroscopy and XPS

Owing to the structural flexibility of spinels, providing a wide range of physical and chemical behavior, these materials have been considered as a convenient model system for the investigation of the size dependent properties of complex ionic systems. In this work, quantitative formation is obtained on the crystallite size dependent ionic configuration in nanosized spinel oxides prepared by mechanochemical processing of the corresponding bulk materials. Experimentally determined values of the crystallite size and of the mean degree of inversion of nanostructured spinels are used to calculate the volume fraction of interfaces/surfaces and their thickness in the nanomaterials