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Title: Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms

Abstract

Molecular scale understanding of the structure and properties of aqueous interfaces with clays, metal (oxy-) hydroxides, layered double hydroxides, and other inorganic phases is strongly affected by significant degrees of structural and compositional disorder of the interfaces. ClayFF was originally developed as a robust and flexible force field for classical molecular simulations of such systems. However, despite its success, multiple limitations have also become evident with its use. One of the most important limitations is the difficulty to accurately model the edges of finite size nanoparticles or pores rather than infinitely layered periodic structures. Here we propose a systematic approach to solve this problem by developing specific metal–O–H (M–O–H) bending terms for ClayFF, E bend = k (θ – θ 0) 2 to better describe the structure and dynamics of singly protonated hydroxyl groups at mineral surfaces, particularly edge surfaces. On the basis of a series of DFT calculations, the optimal values of the Al–O–H and Mg–O–H parameters for Al and Mg in octahedral coordination are determined to be θ 0,AlOH = θ 0,MgOH = 110°, k AlOH = 15 kcal mol –1 rad –2 and k MgOH = 6 kcal mol –1 rad –2. Molecular dynamics simulations were performedmore » for fully hydrated models of the basal and edge surfaces of gibbsite, Al(OH) 3, and brucite, Mg(OH) 2, at the DFT level of theory and at the classical level, using ClayFF with and without the M–O–H term. The addition of the new bending term leads to a much more accurate representation of the orientation of O–H groups at the basal and edge surfaces. Finally, the previously observed unrealistic desorption of OH 2 groups from the particle edges within the original ClayFF model is also strongly constrained by the new modification.« less

Authors:
 [1];  [2];  [2]; ORCiD logo [1]
  1. Institut Mines-Telecom Atlantique, Nantes (France)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1367350
Report Number(s):
SAND-2017-6270J
Journal ID: ISSN 1932-7447; 654478
Grant/Contract Number:
AC04-94AL85000; NA0003525
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 27; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pouvreau, Maxime, Greathouse, Jeffery A., Cygan, Randall T., and Kalinichev, Andrey G.. Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b05362.
Pouvreau, Maxime, Greathouse, Jeffery A., Cygan, Randall T., & Kalinichev, Andrey G.. Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms. United States. doi:10.1021/acs.jpcc.7b05362.
Pouvreau, Maxime, Greathouse, Jeffery A., Cygan, Randall T., and Kalinichev, Andrey G.. 2017. "Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms". United States. doi:10.1021/acs.jpcc.7b05362.
@article{osti_1367350,
title = {Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms},
author = {Pouvreau, Maxime and Greathouse, Jeffery A. and Cygan, Randall T. and Kalinichev, Andrey G.},
abstractNote = {Molecular scale understanding of the structure and properties of aqueous interfaces with clays, metal (oxy-) hydroxides, layered double hydroxides, and other inorganic phases is strongly affected by significant degrees of structural and compositional disorder of the interfaces. ClayFF was originally developed as a robust and flexible force field for classical molecular simulations of such systems. However, despite its success, multiple limitations have also become evident with its use. One of the most important limitations is the difficulty to accurately model the edges of finite size nanoparticles or pores rather than infinitely layered periodic structures. Here we propose a systematic approach to solve this problem by developing specific metal–O–H (M–O–H) bending terms for ClayFF, Ebend = k (θ – θ0)2 to better describe the structure and dynamics of singly protonated hydroxyl groups at mineral surfaces, particularly edge surfaces. On the basis of a series of DFT calculations, the optimal values of the Al–O–H and Mg–O–H parameters for Al and Mg in octahedral coordination are determined to be θ0,AlOH = θ0,MgOH = 110°, kAlOH = 15 kcal mol–1 rad–2 and kMgOH = 6 kcal mol–1 rad–2. Molecular dynamics simulations were performed for fully hydrated models of the basal and edge surfaces of gibbsite, Al(OH)3, and brucite, Mg(OH)2, at the DFT level of theory and at the classical level, using ClayFF with and without the M–O–H term. The addition of the new bending term leads to a much more accurate representation of the orientation of O–H groups at the basal and edge surfaces. Finally, the previously observed unrealistic desorption of OH2 groups from the particle edges within the original ClayFF model is also strongly constrained by the new modification.},
doi = {10.1021/acs.jpcc.7b05362},
journal = {Journal of Physical Chemistry. C},
number = 27,
volume = 121,
place = {United States},
year = 2017,
month = 6
}

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