Hydrogen-bond formation in sodium and potassium hydrosulfides at high pressure

Haines, J and Christy, AG (1992) Hydrogen-bond formation in sodium and potassium hydrosulfides at high pressure. Physical Review B, 46 14: 8797-8805. doi:10.1103/PhysRevB.46.8797


Author Haines, J
Christy, AG
Title Hydrogen-bond formation in sodium and potassium hydrosulfides at high pressure
Journal name Physical Review B   Check publisher's open access policy
ISSN 0163-1829
Publication date 1992-01-01
Sub-type Article (original research)
DOI 10.1103/PhysRevB.46.8797
Open Access Status
Volume 46
Issue 14
Start page 8797
End page 8805
Total pages 9
Language eng
Subject 3104 Condensed Matter Physics
Abstract Sodium and potassium hydrosulfide were investigated at high pressure using a combination of infrared and Raman spectroscopy and energy dispersive x-ray powder diffraction. NaSH was found to undergo an ordering transition below 9 kbar to yield a cell equivalent to that of the low-temperature phase, but reduced in size. A hydrogen-bonded phase was formed above 83 kbar, the diffraction pattern of which could be fitted using a TlI-type structural model. The refined cell parameters at 130 kbar are a=7.362(60), b=3.698(38), c=5.615(50), β=104.50(51)°, Z=4. The space group would be P21/a with bifurcated hydrogen-bonded chains running along b. KSH underwent two transitions on compression at 19 and 23 kbar, respectively. The first transition involved only a small volume change. The diffraction data for this phase could be indexed based on a TlI-type model structure, resulting in the following cell at 20 kbar: a=9.129(41), b=4.181(18), c=6.781(18), β=106.47(27)°, Z=4. A large decrease in frequency, increase in bandwidth, and strongly negative dν/dp values for the infrared and Raman active S-H stretching vibrations indicated that strong hydrogen bonds were formed at the 23-kbar transition. A unit cell was obtained from the x-ray powder data with a=7.448(22), b=7.328(26), c=8.110(22), β=97.46(36)°, Z=8 at 31 kbar. A structure model with a distorted CsCl structure, related to the hydrogen-bonded, low-temperature phase of CsSD containing four-membered, hydrogen-bonded S4D44- units, is proposed. These and other recently reported results indicate that TlI-type structures are more common than previously believed and are, in fact, the favored intermediates between the NaCl- and CsCl-based structures for systems with nonspherical atoms or ions.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
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