Biomedical subjects

Alexander F Goncharov

Publications and source records attributed to Alexander F Goncharov.

9 recordsLinked to original sources

PubMed2006

Probing hydrogen-rich molecular systems at high pressures and temperatures.

Information on the behavior of hydrogen-containing simple molecular systems at high pressures and temperatures is central to many problems in chemistry and allied sciences. The combination of increasing pressure and temperature causes a redistribution of the electronic density, and the resulting alterations in interatomic interactions give rise to changes in macroscopic properties. Experimental studies of hydrogen-rich systems under extreme conditions have advanced considerably in recent years as a result of improvements in diamond anvil cell technology in combination with resistive- and laser-heating techniques. These experimental methods are combined with spectroscopic and diffraction techniques, and the results interpreted with the aid of molecular simulations. In this tutorial review we discuss recent findings in hydrogen, water, and other selected hydrogen-rich systems including compounds formed from these materials. The results are examined in terms of the evolution of effective potentials and interatomic vibrational coupling, molecular dissociation and recombination, ionization and polymerization, quantum effects, and order-disorder phenomena.

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PubMed2006

Reduced radiative conductivity of low-spin (Mg,Fe)O in the lower mantle.

Optical absorption spectra have been measured at pressures up to 80 gigapascals (GPa) for the lower-mantle oxide magnesiowüstite (Mg,Fe)O. Upon reaching the high-spin to low-spin transition of Fe2+ at about 60 GPa, we observed enhanced absorption in the mid- and near-infrared spectral range, whereas absorption in the visible-ultraviolet was reduced. The observed changes in absorption are in contrast to prediction and are attributed to d-d orbital charge transfer in the Fe2+ ion. The results indicate that low-spin (Mg,Fe)O will exhibit lower radiative thermal conductivity than high-spin (Mg,Fe)O, which needs to be considered in future geodynamic models of convection and plume stabilization in the lower mantle.

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PubMed2006

Synthesis and characterization of the nitrides of platinum and iridium.

Transition metal nitrides are of great technological and fundamental importance because of their strength and durability and because of their useful optical, electronic, and magnetic properties. We have evaluated a recently synthesized platinum nitride (PtN) that was shown to have a large bulk modulus, and we propose a structure that is isostructural with pyrite and has the stoichiometry PtN2. We have also synthesized a recoverable nitride of iridium under nearly the same conditions of pressure and temperature as PtN2. Although it has the same stoichiometry, it exhibits much lower structural symmetry. Preliminary results suggest that the bulk modulus of this material is also very large.

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PubMed2006

Raman spectroscopy of hot compressed hydrogen and nitrogen: implications for the intramolecular potential.

Raman measurements of molecular hydrogen ( and ) and nitrogen () have been made under simultaneous conditions of high temperature and high static pressure. Measurements have been made on H2 and D2 to 50 GPa and 1600 K, and on to 50 GPa and 2000 K. In all three materials the familiar molecular stretching mode (vibron) is accompanied in the high-temperature Raman spectra by one or more lower-frequency peaks due to transitions from excited vibrational states. We find that the frequency differences between these bands decreases with pressure, implying that the anharmonicity of the corresponding part of the intramolecular potential also decreases. This is accompanied by an increase in the measured linewidths of the bands that is consistent with a decrease of the depth of the potential and an approaching molecular dissociation.

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PubMed2005

Dynamic ionization of water under extreme conditions.

Raman spectroscopy in a laser heated diamond anvil cell and first principles molecular dynamics simulations have been used to study water in the temperature range 300 to 1500 K and at pressures to 56 GPa. We find a substantial decrease in the intensity of the O-H stretch mode in the liquid phase with pressure, and a change in slope of the melting line at 47 GPa and 1000 K. Consistent with these observations, theoretical calculations show that water beyond 50 GPa is "dynamically ionized" in that it consists of very short-lived (<10 fs) H2O, H3O+, and OH- species, and also that the mobility of the oxygen ions decreases abruptly with pressure, while hydrogen ions remain very mobile. We suggest that this regime corresponds to a superionic state.

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PubMed2005

Polymerization of formic acid under high pressure.

We report Raman, infrared, and x-ray diffraction (XRD) measurements, along with ab initio calculations on formic acid (FA) under pressure up to 50 GPa. We find an infinite chain Pna2(1) structure to be a high-pressure phase at room temperature. Our data indicate the symmetrization and a partially covalent character of the intrachain hydrogen bonds above approximately 20 GPa. Raman spectra and XRD patterns indicate a loss of long-range order at pressures above 40 GPa, with a large hysteresis upon decompression. We attribute this behavior to a three-dimensional polymerization of FA.

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PubMed2004

Elastic and vibrational properties of cobalt to 120 GPa.

Impulsive stimulated light scattering and Raman spectroscopy measurements have been made on hcp cobalt to a static pressure of 120 GPa. We find that at pressures above 60 GPa the shear elastic modulus and the Raman frequency of the E(2g) transverse optical phonon exhibit a departure from a linear dependence on density. We relate this behavior to a collapse of the magnetic moment under pressure that has been predicted theoretically, but until now not observed experimentally.

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PubMed2003

Raman spectroscopy of hot dense hydrogen.

High P-T Raman measurements of solid and fluid hydrogen to above 1100 K at 70 GPa and to above 650 K in 150 GPa range, conditions previously inaccessible by static compression experiments, provide new insight into the behavior of the material under extreme conditions. The data give a direct measure of the melting curve that extends previous optical investigations by up to a factor of 4 in pressure. The magnitude of the vibron frequency temperature derivative (dnu/dT)(P) increases by a factor of approximately 30 over the measured pressure range, indicating an increase in intrinsic anharmonicity and weakening of the molecular bond.

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PubMed2002

Hydrogen clusters in clathrate hydrate.

High-pressure Raman, infrared, x-ray, and neutron studies show that H2 and H2O mixtures crystallize into the sII clathrate structure with an approximate H2/H2O molar ratio of 1:2. The clathrate cages are multiply occupied, with a cluster of two H2 molecules in the small cage and four in the large cage. Substantial softening and splitting of hydrogen vibrons indicate increased intermolecular interactions. The quenched clathrate is stable up to 145 kelvin at ambient pressure. Retention of hydrogen at such high temperatures could help its condensation in planetary nebulae and may play a key role in the evolution of icy bodies.

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