A photo-chemical method for the production of olivine nanoparticles as cosmic dust analogues |
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| Authors: | Russell W Saunders John MC Plane |
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| Institution: | 1. Department of Mechanical Engineering, University of Illinois at Chicago, Chicago, IL 60607, USA;2. Chemical and Biochemical Reference Data Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8320, USA;1. The European Synchrotron (ESRF), CS 40220, F-38043 Grenoble Cedex 9, France;2. Istituto Italiano di Tecnologia, Via Morego 30, Genova 16163, Italy;3. Department of Analytical Chemistry, Ghent University, Krijgslaan 281, S12B-9000 Ghent, Belgium;4. LAMS (Laboratoire d?Archéologie Moléculaire et Structurale), UMR-8220, 3 rue Galilée 94200 Ivry-sur-Seine, France;5. Physical Science and Engineering Divisions, KAUST (King Abdullah University of Science and Technology), Jeddah, Saudi Arabia;6. BIONEM lab University of Magna Graecia, Campus Salvatore Venuta, Viale Europa Germaneto, Catanzaro 88100, Italy;7. Institute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos 138669, Singapore;1. Space Science Division, Naval Research Laboratory, Washington DC, USA;2. Remote Sensing Division, Naval Research Laboratory, Washington DC, USA;3. Laboratory for Atmospheric and Space Physics and Department of Atmospheric and Oceanic Sciences, University of Colorado, Boulder, CO, USA;4. GATS Inc., Driggs ID, USA;5. Computational Physics Inc., USA;6. Bradley Department of Electrical and Computer Engineering, Center for Space Science and Engineering, Virginia Tech, Blacksburg, VA, USA;7. Center for Atmsopheric Sciences, Hampton Univ, Hampton, VA, USA;3. Program in Biophysics;5. Department of Biological Chemistry, University of Michigan, Ann Arbor, Michigan 48109-5606;4. Small-Angle X-ray Scattering Core Facility, Frederick National Laboratory for Cancer Research, Leidos Biomedical Research Inc., Frederick, Maryland 21702 |
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| Abstract: | This paper describes a new experimental method to synthesise metal silicate particles in the laboratory with compositions and structures which reflect those likely to form in planetary atmospheres and in relatively cool regions of oxygen-rich stellar outflows. Fe–Mg-silicate nanoparticles of olivine composition were produced by the photo-oxidation of a mixture of Fe(CO)5, Mg(OC2H5)2 and Si(OC2H5)4 vapours in the presence of O3 at room temperature and atmospheric pressure. Transmission electron microscope X-ray and electron energy loss analysis of the particles from a number of experiments run with different precursor vapour mixture ratios show that Mg2xFe2?2xSiO4 particles can be produced ranging from x = 0 to 1, where x is linearly proportional to the ratio of Mg(OC2H5)2/(Fe(CO)5 + Mg(OC2H5)2). Electronic structure calculations with hybrid density functional/Hartree–Fock theory are then used to explore the pathways involved in producing olivine particles from the FeO3, MgO3 and SiO2 produced from the photolysis of the organometallic precursors in O3. These calculations indicate that highly exothermic reactions lead to the formation of Mg2SiO4, MgFeSiO4 and Fe2SiO4 molecules, which then polymerize. An alternative pathway, also strongly favoured thermodynamically, is the polymerization of MgSiO3 and FeSiO3 to form pyroxenes, which then undergo structural rearrangement to olivine and silica phases. The implications for metal silicate formation in planetary atmosphere and stellar outflows are then discussed. |
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