Transition element-like chemistry for potassium under pressure

Science

Volumn 273, Issue 5271, 1996, Pages 95-97

  Parker, L J ^a   Atou, T ^a   Badding, J V ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLOY; POTASSIUM;

ARTICLE; CHEMICAL ANALYSIS; HYPERBARISM; MOLECULAR DYNAMICS; PHASE TRANSITION; PRIORITY JOURNAL;

EID: 0030036969     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.273.5271.95     Document Type: Article

References (38)

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8. + ions and interstitial electrons (H. G. von Schnering and R. Nesper, Angew. Chem. Int. Ed. Engl. 26, 1059 (1987)], The other heavy alkali metals, K and Rb, also exhibit large changes in electronic structure and bonding under pressure (1).
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24. 3 were found.
25. m, are the bulk modulus (in gigapascals) and molar volume (in cubic centimeters), respectively, at a given pressure (12). Because the Miedema charge density parameters are adjusted empirically from experimental values (12), we estimated the charge densities at high pressure by adding a shift in charge density under pressure determined from this equation to the Miedema value at ambient pressure.
26. Use of a single-crystal sapphire, which has great thermal and chemical stability, greatly retards or eliminates reaction between transition metals and the insulating medium in laser-heating experiments [G. Shen, P. Lazor, S. K. Saxena, Phys. Chem. Minerals 20, 91 (1993); R. Boehler, Nature 363, 534 (1993)]. Reaction between elemental K and clean sapphire plates can also be ruled out on thermodynamic grounds.
27. Use of a single-crystal sapphire, which has great thermal and chemical stability, greatly retards or eliminates reaction between transition metals and the insulating medium in laser-heating experiments [G. Shen, P. Lazor, S. K. Saxena, Phys. Chem. Minerals 20, 91 (1993); R. Boehler, Nature 363, 534 (1993)]. Reaction between elemental K and clean sapphire plates can also be ruled out on thermodynamic grounds.
28. 2O). Before loading, the diamond cell, gasket, and sapphire crystals were heated to drive off any water or other adsorbed contaminants, then quickly loaded into the glove box while hot.
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30. T Atou and J. V. Badding, Rev. Sci. Instrum. 66, 4496 (1995). This x-ray diffraction system provides exceptional resolution, accuracy, and signal-to-noise ratio for a laboratory-based system, facilitating the experiments presented here.
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32. Other, much weaker diffraction lines were also observed, indicating the presence of a small amount of at least one more phase. The diffraction lines of Ni became weaker after laser heating but did not disappear. The presence of three phases violates the phase rule, indicating that thermodynamic equilibrium was not achieved. Equilibrium was not achieved because there were temperature gradients in the laser-heated sample, which arise because of the large thermal conductivity of the diamonds. Laser heating of the sample simultaneously from both sides would allow thermodynamic equilibrium to be reached
33. 2, which would involve bonding to electrons in a noble gas configuration octet, should be favored under high pressure (J. V. Badding, unpublished data). The availability of the d-electron bonding state of the alkali metals should also allow new chemistry with many of the nonmetallic elements.
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38. Supported by the National Science Foundation, a National Science Foundation Young Investigator award, the donors of the Petroleum Research Fund (administered by the American Chemical Society), and a David and Lucile Packard Foundation Fellowship. We thank R. J. Hemley for valuable discussions.