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

Abstract

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.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [5];  [5]; ORCiD logo [6]
  1. Center for Research and Advanced Studies of the National Polytechnic Institute (CINVESTAV-IPN), Mexico City (Mexico)
  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)
Publication Date:
Research Org.:
West Virginia Univ., Morgantown, WV (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); CONACyT; National Science Foundation (NSF); eDARI
OSTI Identifier:
1594015
Alternate Identifier(s):
OSTI ID: 1455083
Grant/Contract Number:  
SC0016176; 152153; 1434897; 1740111; TKII-R2018-SLM1; ACI-1053575; A0011006368
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; equation-of-state; ABINIT software package; augmented-wave method; initio total-energy; high-pressure phase; magnesium-hydroxide; neutron-diffraction; thermal-expansion; Hartree-Fock; brucite

Citation Formats

Treviño, P., Garcia-Castro, A. C., López-Moreno, S., Bautista-Hernández, A., Bobocioiu, E., Reynard, B., Caracas, R., and Romero, A. H. Anharmonic contribution to the stabilization of Mg(OH)2 from first principles. United States: N. p., 2018. Web. doi:10.1039/c8cp02490a.
Treviño, P., Garcia-Castro, A. C., López-Moreno, S., Bautista-Hernández, A., Bobocioiu, E., Reynard, B., Caracas, R., & Romero, A. H. Anharmonic contribution to the stabilization of Mg(OH)2 from first principles. United States. doi:10.1039/c8cp02490a.
Treviño, P., Garcia-Castro, A. C., López-Moreno, S., Bautista-Hernández, A., Bobocioiu, E., Reynard, B., Caracas, R., and Romero, A. H. Tue . "Anharmonic contribution to the stabilization of Mg(OH)2 from first principles". United States. doi:10.1039/c8cp02490a. https://www.osti.gov/servlets/purl/1594015.
@article{osti_1594015,
title = {Anharmonic contribution to the stabilization of Mg(OH)2 from first principles},
author = {Treviño, P. and Garcia-Castro, A. C. and López-Moreno, S. and Bautista-Hernández, A. and Bobocioiu, E. and Reynard, B. and Caracas, R. and Romero, A. H.},
abstractNote = {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.},
doi = {10.1039/c8cp02490a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 26,
volume = 20,
place = {United States},
year = {2018},
month = {6}
}

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