Phonons from neutron powder diffraction

The spherically averaged structure function \soq obtained from pulsed neutron powder diffraction contains both elastic and inelastic scattering via an integral over energy. The Fourier transformation of \soq to real space, as is done in the pair density function (PDF) analysis, regularizes the data, i.e. it accentuates the diffuse scattering. We present a technique which enables the extraction of off-center phonon information from powder diffraction experiments by comparing the experimental PDF with theoretical calculations based on standard interatomic potentials and the crystal symmetry. This procedure (dynamics from powder diffraction(DPD)) has been successfully implemented for two systems, a simple metal, fcc Ni, and an ionic crystal, CaF$_{2}$. Although computationally intensive, this data analysis allows for a phonon based modeling of the PDF, and additionally provides off-center phonon information from powder neutron diffraction

Electronic structure, phase stability and chemical bonding in Th2_2Al and Th2_2AlH4_4

We present the results of theoretical investigation on the electronic structure, bonding nature and ground state properties of Th$_2$Al and Th$_2$AlH$_4$ using generalized-gradient-corrected first-principles full-potential density-functional calculations. Th$_2$AlH$_4$ has been reported to violate the "2 \AA rule" of H-H separation in hydrides. From our total energy as well as force-minimization calculations, we found a shortest H-H separation of 1.95 {\AA} in accordance with recent high resolution powder neutron diffraction experiments. When the Th$_2$Al matrix is hydrogenated, the volume expansion is highly anisotropic, which is quite opposite to other hydrides having the same crystal structure. The bonding nature of these materials are analyzed from the density of states, crystal-orbital Hamiltonian population and valence-charge-density analyses. Our calculation predicts different nature of bonding for the H atoms along $a$ and $c$. The strongest bonding in Th$_2$AlH$_4$ is between Th and H along $c$ which form dumb-bell shaped H-Th-H subunits. Due to this strong covalent interaction there is very small amount of electrons present between H atoms along $c$ which makes repulsive interaction between the H atoms smaller and this is the precise reason why the 2 {\AA} rule is violated. The large difference in the interatomic distances between the interstitial region where one can accommodate H in the $ac$ and $ab$ planes along with the strong covalent interaction between Th and H are the main reasons for highly anisotropic volume expansion on hydrogenation of Th$_2$Al.Comment: 14 pages, 9 figure

Beta interferon production is regulated by P38 mitogen-activated protein kinase in macrophages via both MSK1/2-and tristetraprolin-dependent pathways

Autocrine or paracrine signaling by beta interferon (IFN-β) is essential for many of the responses of macrophages to pathogen-associated molecular patterns. This feedback loop contributes to pathological responses to infectious agents and is therefore tightly regulated. We demonstrate here that macrophage expression of IFN-β is negatively regulated by mitogen- and stress-activated kinases 1 and 2 (MSK1/2). Lipopolysaccharide (LPS)-induced expression of IFN-β was elevated in both MSK1/2 knockout mice and macrophages. Although MSK1 and -2 promote the expression of the anti-inflammatory cytokine interleukin 10, it did not strongly contribute to the ability of MSKs to regulate IFN-β expression. Instead, MSK1 and -2 inhibit IFN-β expression via the induction of dual-specificity phosphatase 1 (DUSP1), which dephosphorylates and inactivates the mitogen-activated protein kinases p38 and Jun N-terminal protein kinase (JNK). Prolonged LPS-induced activation of p38 and JNK, phosphorylation of downstream transcription factors, and overexpression of IFN-β mRNA and protein were similar in MSK1/2 and DUSP1 knockout macrophages. Two distinct mechanisms were implicated in the overexpression of IFN-β: first, JNKmediated activation of c-jun, which binds to the IFN-β promoter, and second, p38-mediated inactivation of the mRNA-destabilizing factor tristetraprolin, which we show is able to target the IFN-β mRNA

Multi-phonon Raman scattering in semiconductor nanocrystals: importance of non-adiabatic transitions

Multi-phonon Raman scattering in semiconductor nanocrystals is treated taking into account both adiabatic and non-adiabatic phonon-assisted optical transitions. Because phonons of various symmetries are involved in scattering processes, there is a considerable enhancement of intensities of multi-phonon peaks in nanocrystal Raman spectra. Cases of strong and weak band mixing are considered in detail. In the first case, fundamental scattering takes place via internal electron-hole states and is participated by s- and d-phonons, while in the second case, when the intensity of the one-phonon Raman peak is strongly influenced by the interaction of an electron and of a hole with interface imperfections (e. g., with trapped charge), p-phonons are most active. Calculations of Raman scattering spectra for CdSe and PbS nanocrystals give a good quantitative agreement with recent experimental results.Comment: 16 pages, 2 figures, E-mail addresses: [email protected], [email protected], [email protected], accepted for publication in Physical Review