Coordination changes in crystalline and vitreous GeO2

Abstract

High pressure x ray absorption spectroscopy (XAS) has been performed up to 29 GPa on crystalline and amorphous GeO₂. The modification of the x ray absorption near edge structure (XANES) as well as the variation of the Ge-O distance, indicate that the coordination of Ge changes from 4 to 6 above 6.5 GPa. The transition is confirmed by Raman spectroscopy.     

Pressure-induced transformations in crystalline and vitreous PbGeO3

Structural transitions in crystalline and vitreous PbGeO₃ were studied at pressures up to 20 GPa. Crystalline PbGeO₃ was observed to undergo a pressure-induced amorphization between 12–18 GPa. Vitreous PbGeO₃ was found to exhibit an amorphous-to-amorphous transition in a similar pressure range. The structural and thermal properties of the pressure-cycled PbGeO₃ materials were further studied with high-energy x-ray diffraction and differential scanning calorimetry. The properties were then compared to those of thermally quenched glass and ball-milled PbGeO₃ samples. The structure of pressure-amorphized PbGeO₃ was found to closely resemble that of ball-milled PbGeO₃. However, the thermal properties probed by differential scanning calorimetry exhibited significant differences to those of thermally quenched PbGeO₃ glass.     

Pressure-induced structural transition in amorphous GeO2: a molecular dynamics simulation

We studied the structural and dynamical properties of amorphous germanium dioxide (GeO₂) from low to high pressure by means of the classical molecular dynamics technique. The simulations were done in the micro-canonical ensemble, with systems at densities ranged from 3.16 to 6.79 g/cm³, using a pairwise potential. The network topology of the systems is analyzed at atomic level through partial pair correlations, coordination number and angular distributions. The dynamic properties were characterized by means of the vibrational density of states. According the density increases, a structural transformation from a short-range order, defined by a building block composed by a basic (GeO₄) tetrahedron, to a basic (GeO₆) octahedron is observed. The vibrational density of states also presents important changes when the density increases, with a low frequency band lessened, and a high density band wider and flatter.     

Pressure-induced intermolecular interactions in crystalline silane-hydrogen

The structure and dynamics of a recently discovered solid silane-hydrogen complex under high pressure are elucidated with first-principles molecular dynamics calculations. A structure with orientationally disordered silane and hydrogen with their centers of mass arranged in a distinctive manner are found. Natural bond orbital analysis reveals that perturbative donor-acceptor interactions between the two molecular species are enhanced by pressure. The experimentally observed anticorrelated pressure-frequency dependency is a consequence of these novel interactions. Moreover, the experimentally observed multiple Raman peaks of H2 can be explained by temporal changes in the environment due to deviations of the lattice parameters from the ideal cubic lattice.     

Neutron interactions with germanium isotopes and amorphous and crystalline GeO2

Coherent neutron scattering lengths and total cross sections have been measured on elemental and oxide samples of ordinary Ge and of isotopically enriched substances. From the experimental results the following values were obtained:

the coherent scattering lengths (in fm) of the bound atoms Ge(8.185±0.020);⁷⁰Ge(10.0±0.1);⁷²Ge(8.51±0.10);⁷³Ge(5.02±0.04);⁷⁴Ge(7.58±0.10) and⁷⁶Ge(8.2 ±1.5);

the absorption cross sections at 0.0253 eV (in barn) for Ge(2.20±0.04);⁷⁰Ge(2.9±0.2);⁷²Ge(0.8±0.2);⁷³Ge(14.4±0.4) and⁷⁴Ge(0.4±0.2);

the free cross sections for epithermal neutrons and the zero energy scattering cross sections.

On the basis of this data, the isotopic- and spin-incoherent cross sections and thes-wave resonance contributions to the coherent scattering lengths have been determined and discussed. Transmission measurements at 0.57 meV on amorphous and crystalline GeO₂ yielded for the amorphous sample an inelastic cross section eight times larger than for the crystalline samples. This effect corresponds to a clearly higher density of low energy states in the amorphous than in the crystalline substances.     

Pressure-induced sharp coordination change in liquid germanate

Local structures around germanium in liquid germanate have been investigated by means of in situ x-ray absorption measurements up to 9 GPa at 1273 K. Liquid germanate consisting of tetrahedrally coordinated germanium contracts with increasing pressure without significant changes in the local structure up to 2.5 GPa and then shows an abrupt fourfold-to-sixfold coordination change around 3 GPa. The coordination change is completed below 4 GPa where upon a high-density liquid consisting of octahedrally coordinated germanium becomes stable. The GeO6 octahedron in the high-density liquid is more compressible than that in solids.     

Quantum chemical modelling of the structure and properties of hypervalent defects in vitreous SiO2 and GeO2

A cluster approximation using a semiempirical MNDO-PM3 scheme is used to study the structure and properties of the defect structures which develop in vitreous SiO₂ and GeO₂ during the interaction of the previously discovered most probable defects (two-member cycles, fragments with double bonds O=A<(A=Si, Ge) and open chains) with valence-saturated segments of a fracture surface. During the interaction of open chains with such a surface, defects with a large dipole moment (up to 15–20 D) are formed, which may create anisotropic highly polarized regions in the glass. The bonds around hypervalent centers are weakened, and the characteristics of the newly formed and already existing bonds approach one another; that is, in a grouping of this sort, other decay paths may exist that change the direction of fracture. In structures formed by the interaction of O=A< defects and two-member cycles with the surface, hypervalent bonds are easily broken; that is, the hypervalent configuration is transformed into an ordinary one. In a number of cases, the potential surface contains two or three minima with similar energies, separated by low or moderate potential barriers. Fiz. Tverd. Tela (St. Petersburg) 41, 1419–1423 (August 1999)     

Four to sixfold coordination changes in crystalline silicates at high pressure

MgSiO₃ exists in a variety of polymorphs which can be largely divided into two subclasses: (a) low pressure modifications in which Si is coordinated to four oxygens and (b) high pressure modifications in which Si is coordinated to six oxygens. The coordination change usually requires an accompanying high temperature. We present a four to six coordination change in MgSiO₃ orthoenstatite at high pressure and ambient temperature in an argon pressure medium, using Raman spectroscopic measurements in a diamond cell. CO₂ laser-heating experiments indicate that the four to sixfold coordination change is facilitated by defects in the structure which may serve as nucleation sites for the formation of the octahedrally coordinated silicate phase.     

Pressure-induced valence changes in EuS and SmTe

Abstract

X-ray absorption spectroscopy was applied to study the pressure-induced valence changes in EuS and SmTe, which are divalent semiconductors of NaCl-type structure at ambient pressure. In both systems the Eu-L_III and Sm-L_III thresholds exhibit the onset of intermediate valencies of the rare earth ions at 15 GPa and 4 GPa, respectively. In EuS, one observes only a small increase of the valency within the investigated pressure range (36 GPa), while in SmTe a full transition to trivalency is observed above 20 GPa. The transition to the CsCl-Type high-pressure phase has no significant influence on the valence in both systems.     

Pressure-induced structural changes in liquid SiO2 from Ab initio simulations

First-principles molecular dynamics simulations at constant pressure have been used to investigate the mechanisms of compression of liquid SiO2. Liquid SiO2 is found to become denser than quartz at a pressure of about 6 GPa, in agreement with extrapolations of lower pressure experimental data. The high compressibility of the liquid is traced to medium-range changes in the topology of the atomic network. These changes consist in an increase of network connectivity caused by the pressure-induced appearance of coordination defects.     

Influence of radiation damage on lattice vibration parameters in crystalline and vitreous SiO2

The influence of radiation damage on a number of lattice vibration parameters in two SiO₂ modifications was investigated using IR reflectance spectroscopy. The radiation kinetics of changes in spectral characteristics of SiO₂ fundamental vibrations in crystalline and glassy states were determined. The reflectivity coefficient and the frequency of degenerate vibrations as functions of dose showed minima, the locations of which were governed by the type of sample. At high neutron irradiation doses (10²¹ cm⁻²), certain characteristics of the bands had the same values for both modified materials. Features of the radiation kinetics of sample dynamic parameters were determined. It was deduced that the specific character of the observed radiation-induced changes in spectral and dynamic parameters of vibrations near degenerate modes was due to both the accumulation of radiation damage and a change in the force field surrounding bridging bonds, which is related to a change in the SiO₂ structure. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 354–358, May–June, 2008.     

Luminescence kinetics of crystalline and vitreous silicon dioxide

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 5, pp. 800–805, November, 1991.     

Theoretical investigations of the spin Hamiltonian parameters and local tetragonal distortions for Cu2+ in crystalline and amorphous TeO2 and GeO2

The spin Hamiltonian parameters (i.e., anisotropic g factors and hyperfine structure constants) and local tetragonal distortions for Cu²⁺ in crystalline and amorphous TeO₂ and GeO₂ are theoretically investigated using the high-order perturbation formulas of these parameters for a tetragonally elongated octahedral 3d⁹ cluster. The impurity Cu²⁺ occupying the octahedral sites are found to experience the relative tetragonal elongation ratios of about 11.4% and 9.5% for crystalline TeO₂ and GeO₂ and 10.8% and 6.6% for amorphous TeO₂ and GeO₂, respectively, along the C₄ axis due to the Jahn–Teller effect. This reveals the larger tetragonal elongation distortions for the Cu²⁺ centres in crystalline than amorphous systems (especially TeO₂). The theoretical spin Hamiltonian parameters show good agreement with the experimental data. The results are discussed.     

Pressure-induced phase transition of crystalline and amorphous silicon and germanium at low temperatures

Abstract

X-ray diffraction has been measured for crystalline silicon, crystalline germanium, amorphous silicon and amorphous germanium at temperatures down to 100 K and pressures up to 20 GPa using a diamond anvil cell and synchrotron radiation. The structural phase transitions, including amorphization, take place in the pressure-temperature range. It has been found that the structures after the phase transitions strongly depend on the path in the pressure-temperature diagram through which the system undergoes the phase transitions. For any of the aforementioned four materials, the high-pressure phase with the p-Sn structure is quenched during a release of pressure at 100 K, and transforms into an amorphous state when heated up to around 2 GPa. The path dependence of the states is discussed in relation to the pressure dependence of the heights of the energy barriers which have to be overcome when phase transitions occur. The effect of a structural disorder on the phase transition is also discussed by comparing the experimental results for the crystalline and amorphous materials.     

Pressure-induced phase transition in ThO2 and PuO2

Abstract

Thorium and plutonium dioxides were studied under pressure by the energy dispersive X-ray diffraction method. A double conical slit assembly was used to collect simultaneously the diffracted radiation at five and seven degrees.

ThO₂ undergoes a phase transformation at 40 GPa. The high-pressure phase remains stable up to 55 GPa, the highest pressure reached in the experiment. For PuO₂, a structural transformation occurs near 39 GPa. The observed high-pressure phases of ThO₂ and PuO₂ exhibit similar diffraction spectra. Like for some other fluorite type compounds, the ThO₂ and PuO₂ high-pressure phase has been indexed in the PbCl₂-type structure. The bulk modulus has been calculated as B₀= 262 GPa with a pressure derivative of B₀' = 6.7 for ThO₂ and as B₀ = 379 GPa with B₀' = 2.4 for PuO₂. The volume decrease at the transition is 12% for PuO₂ and 8% for ThO₂.