Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy

Our knowledge of actinide chemical bonds lags far behind our understanding of the bonding regimes of any other series of elements. This is a major issue given the technological as well as fundamental importance of f-block elements. Some key chemical differences between actinides and lanthanides—and between different actinides—can be ascribed to minor differences in covalency, that is, the degree to which electrons are shared between the f-block element and coordinated ligands. Yet there are almost no direct measures of such covalency for actinides. Here we report the first pulsed electron paramagnetic resonance spectra of actinide compounds. We apply the hyperfine sublevel correlation technique to quantify the electron-spin density at ligand nuclei (via the weak hyperfine interactions) in molecular thorium(III) and uranium(III) species and therefore the extent of covalency. Such information will be important in developing our understanding of the chemical bonding, and therefore the reactivity, of actinides

Ultrafast control of a surface plasmon resonance via the insulator to metal transition in VO2 nanoparticles

We report on the study of the ultrafast insulator-to-metal transition in nanoparticles of strongly correlated VO2. The particles are grown by ion-implantation and self-assembly in a Silica matrix and can be switched between the insulating and metallic phase within less than 100 fs. The prompt formation of the metallic state results in the appearance of a surface-plasmon resonance that is absent in the bulk and can be further tailored by controlling the particle shape

Effect of local dipole moments on the structure and lattice dynamics of K0.98Li0.02TaO3

We present high energy x-ray (67 keV) and neutron scattering measurements on a single crystal of K$_{1-x}$Li$_x$TaO$_3$ for which the Li content ($x=0.02$) is less than $x_c = 0.022$, the critical value below which no structural phase transitions have been reported in zero field. While the crystal lattice does remain cubic down to T=10 K under both zero-field and field-cooled ($E \le 4$ kV/cm) conditions, indications of crystal symmetry lowering are seen at $T_C=63$ K where the Bragg peak intensity changes significantly. A strong and frequency-dependent dielectric permittivity is observed at ambient pressure, a defining characteristic of relaxors. However an extensive search for static polar nanoregions, which is also widely associated with relaxor materials, detected no evidence of elastic neutron diffuse scattering between 300 K and 10 K. Neutron inelastic scattering methods were used to characterize the transverse acoustic and optic phonons (TA1 and TO1 modes) near the (200) and (002) Bragg peaks. The zone center TO1 mode softens monotonically with cooling but never reaches zero energy in either zero field or in external electric fields of up to 4 kV/cm. These results are consistent with the behavior expected for a dipolar glass in which the local polar moments are frozen and exhibit no long-range order at low temperatures.Comment: 7 pages, 7 figure

Photoinduced phase transition in VO2 nanocrystals: ultrafast control of surface-plasmon resonance.

We study the ultrafast insulator-to-metal transition in nanoparticles of VO2, obtained by ion implantation and self-assembly in silica. The nonmagnetic, strongly correlated compound VO2 undergoes a reversible phase transition, which can be photoinduced on an ultrafast time scale. In the nanoparticles, prompt formation of the metallic state results in the appearance of surface-plasmon resonance. We achieve large, ultrafast enhancement of optical absorption in the near-infrared spectral region that encompasses the wavelength range for optical-fiber communications. One can further tailor the response of the nanoparticles by controlling their shape