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Anharmonic contribution to the stabilization of Mg(OH)2 from first principles

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c8cp02490a· OSTI ID:1594015
 [1];  [2];  [3];  [4];  [5];  [5];  [5];  [6]
  1. Center for Research and Advanced Studies of the National Polytechnic Institute (CINVESTAV-IPN), Mexico City (Mexico); West Virginia University
  2. Univ. of Liege, (Belgium); Univ. Industrial de Santander, Bucaramanga (Colombia)
  3. San Luis Potosí Institute of Scientific Research and Technology (IPICyT), San Luis Potosí (Mexico)
  4. Benemerita Universidad Autónoma de Puebla (BUAP) (Mexico)
  5. Lab. de Gélogie de Lyon UMR CNRS (France)
  6. Benemerita Universidad Autónoma de Puebla (BUAP) (Mexico); West Virginia Univ., Morgantown, WV (United States)
+ Show Author Affiliations

Geometrical and vibrational characterization of magnesium hydroxide was performed using density functional theory. Four possible crystal symmetries were explored: P$$\bar{3}$$ (No. 147, point group -3), C2/m (No. 12, point group 2), P3m1 (No. 156, point group 3m) and P$$\bar{3}$$m1 (No. 164, point group -3m) which are the currently accepted geometries found in the literature. While a lot of work has been performed on Mg(OH)2, in particular for the PP$$\bar{3}$$m1 phase, there is still a debate on the observed ground state crystal structure and the anharmonic effects of the OH vibrations on the stabilization of the crystal structure. In particular, the stable positions of hydrogen are not yet defined precisely, which have implications in the crystal symmetry, the vibrational excitations, and the thermal stability. Previous work has assigned the P$$\bar{3}$$m1 polymorph as the low energy phase, but it has also proposed that hydrogens are disordered and they could move from their symmetric position in the P$$\bar{3}$$m1 structure towards P$$\bar{3}$$. Here, we examine the stability of the proposed phases by using different descriptors. We compare the XRD patterns with reported experimental results, and a fair agreement is found. While harmonic vibrational analysis shows that most phases have imaginary modes at 0 K, anharmonic vibrational analysis indicates that at room temperature only the C2/m phase is stabilized, whereas at higher temperatures, other phases become thermally competitive.

Research Organization:
West Virginia Univ., Morgantown, WV (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); CONACyT; National Science Foundation (NSF); eDARI
Grant/Contract Number:
SC0016176
OSTI ID:
1594015
Alternate ID(s):
OSTI ID: 1455083
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 26 Vol. 20; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

Effect of particle size on flame retardancy of Mg(OH)2-filled ethylene vinyl acetate copolymer composites journal January 2006
A highly efficient fire-retardant nanomaterial based on carbon nanotubes and magnesium hydroxide: A HIGHLY EFFICIENT FIRE-RETARDANT NANOMATERIAL journal January 2012
Ab initio total energy study of brucite, diaspore and hypothetical hydrous wadsleyite journal October 1995
Static compression and H disorder in brucite, Mg(OH)2, to 11 GPa: a powder neutron diffraction study journal April 1995
Thermal expansion of Mg(OH) 2 brucite under high pressure and pressure dependence of entropy journal October 2003
Structural and vibrational properties of solid Mg(OH)2 and Ca(OH)2 – performances of various hamiltonians journal June 2001
Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory journal June 1999
The polarized infra-red and Raman spectra of Mg(OH)2 and Ca(OH)2 journal July 1973
Atomistic simulation of defected magnesium hydroxide as flame retardants journal December 2015
Infrared emission spectroscopic study of brucite journal September 1999
D/H isotopic fractionation between brucite Mg(OH)2 and water from first-principles vibrational modeling journal May 2009
Materials properties of magnesium and calcium hydroxides from first-principles calculations journal December 2014
Dispersion, thermal and mechanical properties of polypropylene/magnesium hydroxide nanocomposites compatibilized by SEBS-g-MA journal September 2009
Recent developments in the ABINIT software package journal August 2016
Vibrational spectrum of brucite, Mg(OH)2: a periodic ab initio quantum mechanical calculation including OH anharmonicity journal October 2004
Simulation of magnesium hydroxide surface and interface journal November 2014
Synthesis of Magnesium Hydroxide and Oxide Nanoparticles Using a Spinning Disk Reactor journal August 2007
Synthesis and Characterization of Porous Magnesium Hydroxide and Oxide Nanoplates journal January 2004
Theoretical Study of the Reaction between HF Molecules and Hydroxyl Layers of Mg(OH) 2 journal June 2009
Static compression of Mg(OH) 2 to 78 GPa at high temperature and constraints on the equation of state of fluid H 2 O journal July 1993
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Solvothermal synthesis of Mg(OH) 2 nanotubes using Mg 10 (OH) 18 Cl 2 ·5H 2 O nanowires as precursors journal January 2003
First-principles study of pressure-induced structural phase transitions in MnF 2 journal January 2016
Anharmonic OH vibrations in Mg(OH)2 (brucite): Two-dimensional calculations and crystal-induced blueshift journal December 2009
Vibrational spectra of Mg(OH) 2 and Ca(OH) 2 under pressure journal November 1989
High-pressure phase of brucite stable at Earth’s mantle transition zone and lower mantle conditions journal November 2016
A molecular dynamics method for simulations in the canonical ensemble journal January 2002
A molecular dynamics method for simulations in the canonical ensemble journal June 1984
Canonical dynamics: Equilibrium phase-space distributions journal March 1985
Special points for Brillouin-zone integrations journal June 1976
Periodic Hartree-Fock study of a weakly bonded layer structure: Brucite Mg(OH ) 2 journal February 1993
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Nonlinear optical susceptibilities, Raman efficiencies, and electro-optic tensors from first-principles density functional perturbation theory journal March 2005
First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures journal October 2008
First-principles study of electronic, vibrational, elastic, and magnetic properties of FeF 2 as a function of pressure journal April 2012
Temperature dependent effective potential method for accurate free energy calculations of solids journal March 2013
Temperature-dependent effective third-order interatomic force constants from first principles journal October 2013
Pressure-induced phase-transition sequence in CoF 2 : An experimental and first-principles study on the crystal, vibrational, and electronic properties journal December 2013
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
Pressure-Induced Frustration and Disorder in Mg ( OH ) 2 and Ca ( OH ) 2 journal September 1999
Phonons and related crystal properties from density-functional perturbation theory journal July 2001
Crystal structure and profile fitting of Mg(OD)2 by time-of-flight neutron diffraction journal August 1994
Interlayer interactions in M(OH)2: a neutron diffraction study of Mg(OH)2 journal February 1996
High-pressure phase transition in brucite, Mg(OH) 2 journal April 1995
Equation of state of brucite; single-crystal Brillouin spectroscopy study and polycrystalline pressure-volume-temperature measurement journal February 1998
High-pressure proton disorder in brucite journal January 2006
The WURM project--a freely available web-based repository of computed physical data for minerals journal February 2011
Temperature dependent effective potential method for accurate free energy calculations of solids text January 2013

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABINIT software package
Hartree-Fock
augmented-wave method
brucite
equation-of-state
high-pressure phase
initio total-energy
magnesium-hydroxide
neutron-diffraction
thermal-expansion