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Title: Stability of numerous novel potassium chlorides at high pressure

Journal Article · · Scientific Reports
DOI:https://doi.org/10.1038/srep26265· OSTI ID:1259765
 [1];  [2];  [3];  [4];  [5];  [6]
  1. China Agricultural Univ., Beijing (China); State Univ. of New York, Stony Brook, NY (United States)
  2. State Univ. of New York, Stony Brook, NY (United States); Skolkovo Institute of Science and Technology, Moscow (Russia); Moscow Institute of Physics and Technology, Moscow Region (Russia)
  3. Carnegie Institution of Washington, Washington, D.C. (United States); V.S. Sobolev Institute of Geology and Mineralogoy, Novosibirsk (Russia)
  4. Carnegie Institution of Washington, Washington, D.C. (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  5. Carnegie Institution of Washington, Washington, D.C. (United States); Institute of Solid State Physics, Hefei (China); Univ. of Science and Technology of China, Hefei (China)
  6. State Univ. of New York, Stony Brook, NY (United States)
+ Show Author Affiliations

K-Cl is a simple system displaying all four main types of bonding, as it contains (i) metallic potassium, (ii) elemental chlorine made of covalently bonded Cl2 molecules held together by van der Waals forces, and (iii) an archetypal ionic compound KCl. The charge balance rule, assigning classical charges of “+1” to K and “–1” to Cl, predicts that no compounds other than KCl are possible. However, our quantum-mechanical variable-composition evolutionary simulations predict an extremely complex phase diagram, with new thermodynamically stable compounds K3Cl, K2Cl, K3Cl2, K4Cl3, K5Cl4, K3Cl5, KCl3 and KCl7. Of particular interest are 2D-metallic homologs Kn+1Cln, the presence of positively charged Cl atoms in KCl7, and the predicted stability of KCl3 already at nearly ambient pressures at zero Kelvin. We have synthesized cubic Pm3¯n -KCl3 at 40–70 GPa and trigonal P3¯cl -KCl3 at 20–40 GPa in a laser-heated diamond anvil cell (DAC) at temperature exceeding 2000 K from KCl and Cl2. These phases were identified using in situ synchrotron X-ray diffraction and Raman spectroscopy. Lastly, upon unloading to 10 GPa, P3¯cl -KCl3 transforms to a yet unknown structure before final decomposition to KCl and Cl2 at near-ambient conditions.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1259765
Report Number(s):
LLNL-JRNL-691558
Journal Information:
Scientific Reports, Vol. 6; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

References (25)

Generalized Gradient Approximation Made Simple journal October 1996
High-pressure synthesis of lithium hydride journal August 2012
Anharmonic phonons of NaZr 2 (PO 4 ) 3 studied by Raman spectroscopy, first-principles calculations, and x-ray diffraction journal October 2012
Unexpected Stable Stoichiometries of Sodium Chlorides journal December 2013
Projector augmented-wave method journal December 1994
Ab initio molecular dynamics study of pressure-induced phase transformation in KCl journal May 2010
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
New developments in evolutionary structure prediction algorithm USPEX journal April 2013
How Evolutionary Crystal Structure Prediction Works—and Why journal March 2011
Thermodynamics and mechanism of the B 1 - B 2 phase transition in group-I halides and group-II oxides journal May 1998
Reaction kinetics of CO2 absorption in to phosphonium based anion-functionalized ionic liquids journal January 2013
The electronic structure of the lithium trimer anion and cation journal June 1980
A little bit of lithium does a lot for hydrogen journal October 2009
Structural properties of NaCl journal March 1984
Infrared and Raman spectra of the M + Cl 3 − ion pairs and their chlorine–bromine counterparts isolated in argon matrices journal June 1976
Low- and high-pressure ab initio equations of state for the alkali chlorides journal September 1993
Evolutionary Crystal Structure Prediction as a Method for the Discovery of Minerals and Materials journal January 2010
IR spectroscopy of alkali halides at very high pressures: Calculation of equations of state and of the response of bulk moduli to the B 1 − B 2 phase transition journal September 1997
High-pressure–high-temperature equation of state of KCl and KBr journal June 2012
Stable magnesium peroxide at high pressure journal September 2015
Pressure-Stabilized Sodium Polyhydrides: NaH n ( n > 1 ) journal June 2011
Structural aspects of dense solid halogens under high pressure studied by x-ray diffraction—Molecular dissociation and metallization journal October 1995
Crystal structure prediction using ab initio evolutionary techniques: Principles and applications journal June 2006
Pressure‐Induced Phase Transformation in NaCl journal January 1968
STM3: a chemistry visualization platform journal May 2005

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Correspondence: Reply to ‘Strongly-driven Re+CO2 redox reaction at high-pressure and high-temperature’ journal November 2016

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