BaHg[sub2]TI[sub2] An Unusual Polar Intermetallic Phase with Strong Differentiation between the Neighboring Elements Mercury and Thallium.
High yields of the novel BaHg[sub2]TI[sub2] are achieved from reactions of the appropriate cast alloys at ∼400°C. (Isotypic SrHg[sub2]TI[sub2] also exists.) The tetragonal barium structure (P4[sub2]/mnm, a + 10.606 Å, c= 5.159 Å) was refined from both single crystal X-ray and neutron powder diffract...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 24; pp. 8677 - 8683 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
6/24/2009
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=43018145&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 43018145 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/24/2009 vid: 131 iid: 24 pid: 997 pub: American Chemical Society artinfo: ui: 43018145 10.1021/ja901865d ppf: 8677 ppct: 6 formats: tig: atl: BaHg[sub2]TI[sub2] An Unusual Polar Intermetallic Phase with Strong Differentiation between the Neighboring Elements Mercury and Thallium. aug: au: Jing-Cao Dai Gupta, Shalabh Gourdont, Olivier Hyun-Jeong Kim Corbett, John D. affil: Ames Laboratory and Department of Chemistry, Iowa State University, Ames, Iowa 50011 Neutron Scattering Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 Lujan Neutron Scattering Center, Los Alamos National Laboratory, Los Alamos, New Mexico su: Physical & theoretical chemistry Mercury (Element) Thallium Intermetallic compounds X-ray diffraction Polyhedra Barium sug: subj: Physical & theoretical chemistry Mercury (Element) Thallium Intermetallic compounds X-ray diffraction Polyhedra Barium ab: High yields of the novel BaHg[sub2]TI[sub2] are achieved from reactions of the appropriate cast alloys at ∼400°C. (Isotypic SrHg[sub2]TI[sub2] also exists.) The tetragonal barium structure (P4[sub2]/mnm, a + 10.606 Å, c= 5.159 Å) was refined from both single crystal X-ray and neutron powder diffraction data in order to ensure the atom site assignments although distances and calculated atom site population also support the results. The Hg and TI network atoms are distinctive in their functions and bonding. Parallel chains of Hg hexagons and of TI network atoms are distinctive in their functions and bonding. Parallel chains of hexagons and of TI tetrahedra along c are constructed from polyhedra that share opposed like edges, and these are in turn interconnected by Hg—TI bonds. Overall, the number of TI—TI bonds per cell exceeds the Hg-Hg type by 20:12, but these are ∼1:2 each in bonding according to their average -ICOHP values (related to overlap populations). Barium is bound within a close 15-atom polyhedron, 12 atoms of which are the more electronegative Hg. LMTO-ASA calculations show that scalar relativistic effects are particularly important for Hg 5d-6s mixing in Hg—Hg and Hg—TI bonding, whereas relatively separate TI 6s and 6p states are more important in TI—TI interactions. The 6p states of Hg and TI and 5d of Ba define a dominant conduction band around E[subF], and the phase is metallic and Pauli-like paramagnetic. The thallium characteristics here are close to those in numerous alkali-metal—TI cluster systems. Other active metal—mercury phrases that have been studied theoretically are all distinctly electron-richer and more reduced, and without appreciable net 5d, 6s contributions to Hg—Hg bonding. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
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