skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Lithium hydroxide, LiOH, at elevated densities

Abstract

We discuss the high-pressure phases of crystalline lithium hydroxide, LiOH. Using first-principles calculations, and assisted by evolutionary structure searches, we reproduce the experimentally known phase transition under pressure, but we suggest that the high-pressure phase LiOH-III be assigned to a new hydrogen-bonded tetragonal structure type that is unique amongst alkali hydroxides. LiOH is at the intersection of both ionic and hydrogen bonding, and we examine the various ensuing structural features and their energetic driving mechanisms. At P = 17 GPa, we predict another phase transition to a new phase, Pbcm-LiOH-IV, which we find to be stable over a wide pressure range. Eventually, at extremely high pressures of 1100 GPa, the ground state of LiOH is predicted to become a polymeric structure with an unusual graphitic oxygen-hydrogen net. However, because of its ionic character, the anticipated metallization of LiOH is much delayed; in fact, its electronic band gap increases monotonically into the TPa pressure range.

Authors:
; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1385821
DOE Contract Number:  
SC0001057
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Related Information: EFree partners with Carnegie Institution of Washington (lead); California Institute of Technology; Colorado School of Mines; Cornell University; Lehigh University; Pennsylvania State University
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous), solar (photovoltaic), phonons, thermoelectric, energy storage (including batteries and capacitors), hydrogen and fuel cells, superconductivity, charge transport, mesostructured materials, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Hermann, Andreas, Ashcroft, N. W., and Hoffmann, Roald. Lithium hydroxide, LiOH, at elevated densities. United States: N. p., 2014. Web. doi:10.1063/1.4886335.
Hermann, Andreas, Ashcroft, N. W., & Hoffmann, Roald. Lithium hydroxide, LiOH, at elevated densities. United States. doi:10.1063/1.4886335.
Hermann, Andreas, Ashcroft, N. W., and Hoffmann, Roald. Mon . "Lithium hydroxide, LiOH, at elevated densities". United States. doi:10.1063/1.4886335.
@article{osti_1385821,
title = {Lithium hydroxide, LiOH, at elevated densities},
author = {Hermann, Andreas and Ashcroft, N. W. and Hoffmann, Roald},
abstractNote = {We discuss the high-pressure phases of crystalline lithium hydroxide, LiOH. Using first-principles calculations, and assisted by evolutionary structure searches, we reproduce the experimentally known phase transition under pressure, but we suggest that the high-pressure phase LiOH-III be assigned to a new hydrogen-bonded tetragonal structure type that is unique amongst alkali hydroxides. LiOH is at the intersection of both ionic and hydrogen bonding, and we examine the various ensuing structural features and their energetic driving mechanisms. At P = 17 GPa, we predict another phase transition to a new phase, Pbcm-LiOH-IV, which we find to be stable over a wide pressure range. Eventually, at extremely high pressures of 1100 GPa, the ground state of LiOH is predicted to become a polymeric structure with an unusual graphitic oxygen-hydrogen net. However, because of its ionic character, the anticipated metallization of LiOH is much delayed; in fact, its electronic band gap increases monotonically into the TPa pressure range.},
doi = {10.1063/1.4886335},
journal = {Journal of Chemical Physics},
number = 2,
volume = 141,
place = {United States},
year = {Mon Jul 14 00:00:00 EDT 2014},
month = {Mon Jul 14 00:00:00 EDT 2014}
}