X-ray and neutron scattering

Abstract:

The thermal expansion behavior of isostructural variants of the colossal thermal expansion material Ag3[CoIII(CN)6] has been investigated using variable temperature X-ray and neutron powder diffraction. It was found that substitution at the octahedral transition metal site did not strongly affect the thermal expansion behavior, giving Ag3[FeIII(CN)6] as a new colossal thermal expansion material. Substitution at the Ag site (by D) was shown to reduce the thermal expansion coefficients by an order of magnitude. It was proposed that this correlation between the presence of argentophilic interactions and extreme thermal expansion behavior may explain a variety of thermal effects in flexible framework materials containing metallophilic interactions.

Abstract:

Local structure in the colossal thermal expansion material Ag 3[Co(CN)6] is studied here using a combination of neutron total scattering and reverse Monte Carlo (RMC) analysis. We show that the large thermal variations in cell dimensions occur with minimal distortion of the [Co(CN)6 ] coordination polyhedra, but involve significant flexing of the Co-CN-Ag-NC-Co linkages. We find real-space evidence in our RMC configurations for the importance of low-energy rigid unit modes (RUMs), particularly at temperatures below 150K. Using a reciprocal-space analysis we present the phonon density of states at 300K and show that the lowest-frequency region is dominated by RUMs and related modes. We also show that thermal variation in the energies of Ag...Ag interactions is evident in both the Ag partial pair distribution function and in the Ag partial phonon density of states. These findings are discussed in relation to the thermodynamic properties of the material. © 2008 IOP Publishing Ltd.

Abstract:

We have investigated charge dynamics in the static stripe ordered phase of La2-x Srx Ni O4+δ at lattice temperatures below the charge ordering transition, via optical conductivity measurements at low energies (1-10 meV). The thermally activated dynamic response of the charge stripes is found to be characteristic of a collective mode such as a pinned charge density wave. At incommensurate doping levels, the pinning energy is reduced, owing to the presence of real-space defects in the stripe order, and a pronounced increase in the oscillator strength is seen. The results provide compelling evidence for the existence of low-energy collective modes of the charge stripes. © 2008 The American Physical Society.

Abstract:

Polarized- and unpolarized-neutron scattering was used to study the temperature evolution of the magnetic excitations of charge ordered La5/3Sr1/3NiO4. We studied two features in detail: (i) the resonance-like scattering at 27 meV in the quasi-two-dimensional magnetic excitations from the ordered Ni2+ (S = 1) spins, and (ii) the diffuse scattering associated with quasi-one-dimensional antiferromagnetic correlations along the stripes. Although both these features persist up to at least similar to 125 K, their temperature dependences are found to be quite different. We argue from the results that the resonance- like feature observed in La2-xSrxNiO4 (x similar to 1/3) is not caused by a coupling between the spin dynamics of the two magnetic sub-systems.