Nuclear magnetic resonance cryoporometry

Nuclear Magnetic Resonance (NMR) cryoporometry is a technique for non-destructively determining pore size distributions in porous media through the observation of the depressed melting point of a confined liquid. It is suitable for measuring pore diameters in the range 2 nm-1 mu m, depending on the absorbate. Whilst NMR cryoporometry is a perturbative measurement, the results are independent of spin interactions at the pore surface and so can offer direct measurements of pore volume as a function of pore diameter. Pore size distributions obtained with NMR cryoporometry have been shown to compare favourably with those from other methods such as gas adsorption, DSC thermoporosimetry, and SANS. The applications of NMR cryoporometry include studies of silica gels, bones, cements, rocks and many other porous materials. It is also possible to adapt the basic experiment to provide structural resolution in spatially-dependent pore size distributions, or behavioural information about the confined liquid

Magneto-x-ray effects in transition-metal alloys

We present a theory that combines the relativistic spin-polarized version of the Koringa-Kohn-Rostoker coherent-potential approximation theory and the macroscopic theory of magneto-optical effects enabling us to calculate magneto-x-ray effects from first principles. The theory is illustrated by calculation of Faraday and Kerr rotations and ellipticities for transition-metal alloys

Characterisation of porous solids using small-angle scattering and NMR cryoporometry

The characteristics of several porous systems have been studied by the use of small-angle neutron scattering [SANS] and nuclear magnetic resonance [NMR] techniques. The measurements reveal different characteristics for sol-gel silicas, activated carbons and ordered mesoporous silicas of the MCM and SBA type. Good agreement is obtained between gas adsorption measurements and the NMR and SANS results for pore sizes above 10 nm. Recent measurements of the water/ice phase transformation in SBA silicas by neutron diffraction are also presented and indicate a complex relationship that will require more detailed treatment in terms of the possible effects of microporosity in the silica substrate. The complementarity of the different methods is emphasised and there is brief discussion of issues related to possible future developments

Electronic structure and x-ray magnetic dichroism in random substitutional alloys of f-electron elements

The Koringa-Kohn-Rostoker —coherent-potential-approximation method combines multiple-scattering theory and the coherent-potential approximation to calculate the electronic structure of random substitutional alloys of transition metals. In this paper we describe the generalization of this theory to describe f-electron alloys. The theory is illustrated with a calculation of the electronic structure and magnetic dichroism curves for a random substitutional alloy containing rare-earth or actinide elements from first principles

Clathrate formation and dissociation in vapor/water/ice/hydrate systems in SBA-15, sol-gel and CPG porous media, as probed by NMR relaxation, novel protocol NMR cryoporometry, neutron scattering and ab initio quantum-mechanical molecular dynamics simulation

The Gibbs-Thomson effect modifies the pressure and temperature at which clathrates occur, hence altering the depth at which they occur in the seabed. Nuclear magnetic resonance (NMR) measurements as a function of temperature are being conducted for water/ice/ hydrate systems in a range of pore geometries, including templated SBA-15 silicas, controlled pore glasses and sol-gel silicas. Rotator-phase plastic ice is shown to be present in confined geometry, and bulk tetrahydrofuran hydrate is also shown to probably have a rotator phase. A novel NMR cryoporometry protocol, which probes both melting and freezing events while avoiding the usual problem of supercooling for the freezing event, has been developed. This enables a detailed probing of the system for a given pore size and geometry and the exploration of differences between hydrate formation and dissociation processes inside pores. These process differences have an important effect on the environment, as they impact on the ability of a marine hydrate system to re-form once warmed above a critical temperature. Ab initio quantum-mechanical molecular dynamics calculations are also being employed to probe the dynamics of liquids in pores at nanometric dimensions

Formation and properties of metal-oxygen atomic chains

Suspended chains consisting of single noble metal and oxygen atoms have been formed. We provide evidence that oxygen can react with and be incorporated into metallic one-dimensional atomic chains. Oxygen incorporation reinforces the linear bonds in the chain, which facilitates the creation of longer atomic chains. The mechanical and electrical properties of these diatomic chains have been investigated by determining local vibration modes of the chain and by measuring the dependence of the average chain-conductance on the length of the chain. Additionally, we have performed calculations that give insight in the physical mechanism of the oxygen-induced strengthening of the linear bonds and the conductance of the metal-oxygen chains.Comment: 10 pages, 9 fig

Observation of magnetic circular dichroism in Fe L_{2,3} x-ray-fluorescence spectra

We report experiments demonstrating circular dichroism in the x-ray-fluorescence spectra of magnetic systems, as predicted by a recent theory. The data, on the L_{2,3} edges of ferromagnetic iron, are compared with fully relativistic local spin density functional calculations, and the relationship between the dichroic spectra and the spin-resolved local density of occupied states is discussed

An embedding scheme for the Dirac equation

An embedding scheme is developed for the Dirac Hamiltonian H. Dividing space into regions I and II separated by surface S, an expression is derived for the expectation value of H which makes explicit reference to a trial function defined in I alone, with all details of region II replaced by an effective potential acting on S and which is related to the Green function of region II. Stationary solutions provide approximations to the eigenstates of H within I. The Green function for the embedded Hamiltonian is equal to the Green function for the entire system in region I. Application of the method is illustrated for the problem of a hydrogen atom in a spherical cavity and an Au(001)/Ag/Au(001) sandwich structure using basis sets that satisfy kinetic balance.Comment: 16 pages, 5 figure

Establishing Social Work Practices in England: The Early Evidence

Social Work Practices (SWPs) were established in England in 2009 to deliver social work services to looked after children and care leavers. The introduction of independent social work-led organisations generated controversy focused on issues such as the privatisation of children's services and social workers' conditions of employment. This paper reports early findings from the evaluation of four of these pilots, drawing on interviews with children and young people, staff, and local authority and national stakeholders. The SWPs assumed a variety of organisational forms. The procurement process was demanding, with protracted negotiations over matters such as budgetary control and providing a round-the-clock service. Start-up was facilitated by an established relationship between the SWP provider and the local authority. Once operational, SWPs continued to rely on local authorities for various functions; in most cases, local authorities retained control of placement budgets. Levels of consultation and choice offered to children and young people regarding the move to an SWP varied considerably. Children's understanding about SWPs was generally low except in the pilot where most children retained their original social worker. These early findings show some dilution of the original SWP model, while the pilots' diversity allows the benefits of particular models to emerge