We model the deposition and growth of MgF(2) on a sapphire substrate as it occurs in a low-temperature atom-beam-deposition experiment. In the experiment, an (X-ray) amorphous film of MgF(2) is obtained at low temperatures of 170-180 K, and upon heating, this transforms to the expected rutile phase via the CaCl(2)-type structure. We confirm this from our simulations and propose a mechanism for this transformation. The growth process is analyzed as a function of the synthesis parameters, which include the substrate temperature, deposition rate of clusters, and types of clusters deposited. Upon annealing an initially amorphous deposit, we observe the formation of two competing nanocrystalline modifications during this process, which exhibit the CaCl(2) and CdI(2) structure types, respectively. We argue that this joint growth of the two nanocrystalline polymorphs stabilizes the kinetically unstable CaCl(2)-type structure on the macroscopic level long enough to be observed in the experiment.
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http://dx.doi.org/10.1021/ic501499k | DOI Listing |
Inorg Chem
November 2015
Institute of Solid State Physics, TU Wien , A-1040 Vienna, Austria.
On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.
View Article and Find Full Text PDFJ Chem Phys
June 2014
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India.
Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here.
View Article and Find Full Text PDFJ Phys Condens Matter
April 2013
Departamento de Física, Facultad de Ciencias Exactas y Naturales y Agrimensura UNNE, Corrientes, Argentina.
The pressure dependences of the structural, thermoelastic and vibrational properties of SnO2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl2-type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO2.
View Article and Find Full Text PDFJ Phys Chem B
June 2007
Departament de Química Física i Analítica, Universitat Jaume I, Campus de Riu Sec, Castelló E-12080, Spain.
Theoretical investigations concerning the high-pressure polymorphs, the equations of state, and the phase transitions of SnO2 have been performed using density functional theory at the B3LYP level. Total energy calculations and geometry optimizations have been carried out for all phases involved, and the following sequence of structural transitions from the rutile-type (P42/mnm) driven by pressure has been obtained (the transition pressure is in parentheses): --> CaCl2-type, Pnnm (12 GPa) --> alpha-PbO2-type, Pbcn (17 GPa) --> pyrite-type, Pa (17 GPa) --> ZrO2-type orthorhombic phase I, Pbca (18 GPa) --> fluorite-type, Fmm (24 GPa) --> cotunnite-type orthorhombic phase II, Pnam (33 GPa). The highest bulk modulus values, calculated by fitting pressure-volume data to the second-order Birch-Murnaghan equation of state, correspond to the cubic pyrite and the fluorite-type phases with values of 293 and 322 GPa, respectively.
View Article and Find Full Text PDFActa Crystallogr B
December 2003
Department of Earth Sciences, Kanazawa University, Kakuma-machi, Kanazawa-shi, Ishikawa 920-1165, Japan.
Recently, there has been substantial interest in the new high-pressure polymorphs of GeO2 synthesized in the laboratory. Previous investigators reported the synthesis of 'CaCl2-type', 'alpha-PbO2-type' and 'pyrite-type (modified-fluorite-type)' GeO2 at pressures of 30-130 GPa in laser-heated diamond anvil cells. In order to provide definitive information about the new high-pressure polymorphs, we performed Rietveld refinements of the structures.
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