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Structure and Dynamics of Water—Smectite Interfaces: Hydrogen Bonding and the Origin of the Sharp O-Dw/O—Hw Infrared Band From Molecular Simulations

Published online by Cambridge University Press:  01 January 2024

Marek Szczerba ,
Artur Kuligiewicz ,
Arkadiusz Derkowski ,
Vassilis Gionis ,
Georgios D. Chryssikos  and
Andrey G. Kalinichev
Marek Szczerba*
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, Kraków, Poland
Artur Kuligiewicz
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, Kraków, Poland
Arkadiusz Derkowski
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, Kraków, Poland
Vassilis Gionis
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece
Georgios D. Chryssikos
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece
Andrey G. Kalinichev
Affiliation:
Laboratoire SUBATECH (UMR 6457), Ecole des Mines de Nantes, Nantes, France
*
*E-mail address of corresponding author: ndszczer@cyf-kr.edu.pl
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Abstract

Experimental studies have shown that a sharp, high-frequency IR band at ~3615 cm-1 (in H2O form) and at ~2685 cm-1 (in D2O form) is a common feature for all smectites, and its position correlates with layer charge. In order to explain the molecular origin of this band in terms of total layer charge, charge localization, as well as nature of interlayer cations influencing the position and intensity of this peak, a series of classical molecular dynamics (MD) simulations was performed for several smectite models. The smectite layers were described using a modified CLAYFF force field, where the intramolecular vibrations of H2O were described more accurately by the Toukan-Rahman potential. The power spectra of molecular vibrations of hydrogens were calculated for selected sub-sets of interlayer H2O to analyze quantitatively their contribution to the observed spectral features. The statistics of hydrogen bonds in the smectite interlayers were also analyzed to support the spectral calculations.

The simulation results demonstrated clearly that only the H2O molecules in close proximity to the smectite surface are responsible for the sharp vibrational band observed. Other hypotheses for the possible origins of this band were considered carefully and eventually rejected. Two orientations of H2O molecules donating one or two H bonds to the basal oxygens of the smectite surface (monodentate and bidentate orientations, respectively) were observed. In both orientations, these H bonds are quite weak, pointing to a generally hydrophobic character of the smectite surface. Both orientations contributed to the high-frequency band, but the monodentate orientation provided the predominant contribution because surface H2O molecules in this orientation were much more abundant. In good agreement with experiment, only a small difference in the peak position was observed between smectites with different charge localization. The effect of the total layer charge, i.e. the red-shift for higher-charge smectites, was also confirmed. This shift arose from the decrease in the H-bonding distances of H2O in monodentate and bidentate orientation.

Keywords

Adsorbed WaterClay—Water InterfaceInfrared SpectroscopyMolecular DynamicsSmectite
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016 , pp. 452 - 471
Copyright
Copyright © The Clay Minerals Society 2016

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Footnotes

This paper is published as part of a special issue on the subject of ‘Computational Molecular Modeling.’ Some of the papers were presented during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.

References

Allen, M.P. and Tildesley, D.J., 1987 Computer Simulation of Liquids New York Oxford University Press 385 pp..Google Scholar
Arab, M. Bougeard, D. and Smirnov, K.S., 2003 Structure and dynamics of the interlayer water in an uncharged 2:1 clay Physical Chemistry Chemical Physics 5 4699–4707.CrossRefGoogle Scholar
Boek, E.S. and Sprik, M., 2003 Ab initio molecular dynamics study of the hydration of a sodium smectite clay Journal of Physical Chemistry B 107 3251–3256.CrossRefGoogle Scholar
Boek, E.S. Coveney, P.V. and Skipper, N.T., 1995 Monte Carlo molecular modeling studies of hydrated Li-, Na-, and K-smectites: Understanding the role of potassium as a clay swelling inhibitor Journal of the American Chemical Society 117 12608–12617.CrossRefGoogle Scholar
Bridgeman, C.H. and Skipper, N.T., 1997 A Monte Carlo study of water at an uncharged clay surface Journal of Physics-Condensed Matter 9 4081–4087.CrossRefGoogle Scholar
Cariati, F. Erre, L. Micera, G. Piu, P. and Gessa, C., 1981 Water molecules and hydroxyl groups in montmorillonites as studied by near infrared spectroscopy Clays and Clay Minerals 29 157–159.CrossRefGoogle Scholar
Cariati, F. Erre, L. Micera, G. Piu, P. and Gessa, C., 1983 Polarization of water molecules in phyllosilicates in relation to exchange cations as studied by near infrared spectroscopy Clays and Clay Minerals 31 155–157.CrossRefGoogle Scholar
Cases, J.M. Berend, I. Francois, M. Uriot, J.P. Michot, L.J. and Thomas, F., 1997 Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite. 3. The Mg2+, Ca2+, Sr2+ and Ba2+ exchanged forms Clays and Clay Minerals 45 8–22.CrossRefGoogle Scholar
Chang, F.R.C. Skipper, N.T. and Sposito, G., 1995 Computer simulation of interlayer molecular structure in sodium montmorillonite hydrates Langmuir 11 2734–2741.CrossRefGoogle Scholar
Churakov, S.V., 2006 Ab initio study of sorption on pyrophyllite: Structure and acidity of the edge sites Journal of Physical Chemistry B 110 4135–4146.CrossRefGoogle ScholarPubMed
Cygan, R.T. Liang, J.J. and Kalinichev, A.G., 2004 Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field Journal of Physical Chemistry B 108 1255–1266.CrossRefGoogle Scholar
Dazas, B. Ferrage, E. Delville, A. and Lanson, B., 2014 Interlayer structure model of tri-hydrated low-charge smectite by X-ray diffraction and Monte Carlo modeling in the Grand Canonical ensemble American Mineralogist 99 1724–1735.CrossRefGoogle Scholar
Dazas, B. Lanson, B. Delville, A. Robert, J.L. Komarneni, S. Michot, L.J. and Ferrage, E., 2015 Influence of tetrahedral layer charge on the organization of interlayer water and ions in synthetic Na-saturated smectites Journal of Physical Chemistry C 119 4158–4172.CrossRefGoogle Scholar
Efimov, Y.Y. and Naberhukhin, Y.I., 2002 On the interrelation between frequencies of stretching and bending vibrations in liquid water Spectrochimica Acta A 58 519–524.CrossRefGoogle ScholarPubMed
Farmer, V.C. and Russell, J.D., 1971 Interlayer complexes in layer silicates: The structure of water in lamellar ionic solutions Transactions of the Faraday Society 67 2737–2749.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. and Drits, V.A., 2005 Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties American Mineralogist 90 1358–1374.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. Geoffroy, N. Jacquot, E. and Drits, V.A., 2007 Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: Influence of layer charge and charge location American Mineralogist 92 1731–1743.CrossRefGoogle Scholar
Ferrage, E. Sakharov, B.A. Michot, L.J. Delville, A. Bauer, A. Lanson, B. Grangeon, S. Frapper, G. Jiménez-Ruiz, M. and Cuello, G.J., 2011 Hydration properties and interlayer organization of water and ions in synthetic Nasmectite with tetrahedral layer charge. Part 2. Toward a precise coupling between molecular simulations and diffraction data Journal of Physical Chemistry C 115 1867–1881.CrossRefGoogle Scholar
Greathouse, J.A. and Sposito, G., 1998 Monte Carlo and molecular dynamics studies of interlayer structure in Li(H2O)3-smectites Journal of Physical Chemistry B 102 2406–2414.CrossRefGoogle Scholar
Greathouse, J.A. Durkin, J.S. Larentzos, J.P. and Cygan, R.T., 2009 Implementation of a Morse potential to model hydroxyl behavior in phyllosilicates Journal of Chemical Physics 130 134713.CrossRefGoogle ScholarPubMed
Greathouse, J.A. Hart, D.B. Bowers, G.M. Kirkpatrick, R.J. and Cygan, R.T., 2015 Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores Journal of Physical Chemistry C 119 17126–17136.CrossRefGoogle Scholar
Guillot, B., 2002 A reappraisal of what we have learnt during three decades of computer simulations on water Journal of Molecular Liquids 101 219–260.CrossRefGoogle Scholar
Jaynes, W.F. and Boyd, S.A., 1991 Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water Clays and Clay Minerals 39 428–436.CrossRefGoogle Scholar
Kalinichev, A.G., 2001 Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding Molecular Modeling Theory: Applications in the Geosciences 42 83–129.CrossRefGoogle Scholar
Kleinhesselink, D. and Wolfsberg, M., 1992 The evaluation of power spectra in molecular dynamics simulations of anharmonic solids and surfaces Surface Science 262 189–207.CrossRefGoogle Scholar
Kuligiewicz, A. Derkowski, A. Szczerba, M. Gionis, V. and Chryssikos, G.D., 2015 Water-smectite interface by infrared spectroscopy Clays and Clay Minerals 63 15–29.CrossRefGoogle Scholar
Kuligiewicz, A. Derkowski, A. Emmerich, K. Christidis, G.E. Tsiantos, C. Gionis, V. and Chryssikos, G.D., 2015 Measuring the layer charge of dioctahedral smectite by O-D vibrational spectroscopy Clays and Clay Minerals 63 443–456.CrossRefGoogle Scholar
Kumar, R. Schmidt, J.R. and Skinner, J.L., 2007 Hydrogen bonding definitions and dynamics in liquid water Journal of Chemical Physics 126 204107–204112.CrossRefGoogle ScholarPubMed
Lee, J.H. and Guggenheim, S., 1981 Single crystal X-ray refinement of pyrophyllite-1Tc American Mineralogist 66 350–357.Google Scholar
Libowitzky, E., 1999 Correlation of O-H stretching frequencies and O-H…O bond lengths in minerals Monatshefte für Chemie 130 1047–1059.CrossRefGoogle Scholar
Loganathan, N. and Kalinichev, A.G., 2013 On the hydrogen bonding structure at the aqueous interface of ammonium-substituted mica: A molecular dynamics simulation Zeitschrift für Naturforschung A 68 91–100.CrossRefGoogle Scholar
Loganathan, N. Yazaydin, A.O. Bowers, G.M. Kalinichev, A.G. and Kirkpatrick, R.J., 2016 Structure, energetics, and dynamics of Cs+ and H2O in hectorite: Molecular dynamics simulations with an unconstrained substrate surface Journal of Physical Chemistry C 120 10298–10310.CrossRefGoogle Scholar
Loganathan, N. Yazaydin, A.O. Bowers, G.M. Kalinichev, A.G. and Kirkpatrick, R.J., 2016 Cation and water structure, dynamics, and energetics in smectite clays: A molecular dynamics study of Ca-hectorite Journal of Physical Chemistry C 120 12429–12439.CrossRefGoogle Scholar
Löwenstein, W., 1954 The distribution of aluminum in the tetrahedra of silicates and aluminates American Mineralogist 39 92–96.Google Scholar
Madejová, J. Janek, M. Komadel, P. Herbert, H.-J. and Moog, H.C., 2002 FTIR analyses of water in MX-80 bentonite compacted from high salinary salt solution systems Applied Clay Science 20 255–271.CrossRefGoogle Scholar
Marry, V. Rotenberg, B. and Turq, P., 2008 Structure and dynamics of water at a clay surface from molecular dynamics simulation Physical Chemistry Chemical Physics 10 4802–4813.CrossRefGoogle Scholar
Marry, V. Dubois, E. Malikova, N. Breu, J. and Haussler, W., 2013 Anisotropy of water dynamics in clays: Insights from molecular simulations for experimental QENS analysis Journal of Physical Chemistry C 117 15106–15115.CrossRefGoogle Scholar
Michot, L.J. Villieras, F. Francois, M. Yvon, J. Le Dred, R. and Cases, J.M., 1994 The structural microscopic hydrophilicity of talc Langmuir 10 3765–3773.CrossRefGoogle Scholar
Morrow, C.P. Yazaydin, A.O. Krishnan, M. Bowers, G.M. Kalinichev, A.G. and Kirkpatrick, R.J., 2013 Structure, energetics, and dynamics of smectite clay interlayer hydration: molecular dynamics and metadynamics investigation of Na-hectorite Journal of Physical Chemistry C 117 5172–5187.CrossRefGoogle Scholar
Ngouana Wakou, B.F. and Kalinichev, A.G., 2014 Structural arrangements of isomorphic substitutions in smectites: Molecular simulation of the swelling properties, interlayer structure, and dynamics of hydrated Cs-montmorillonite revisited with new clay models Journal of Physical Chemistry C 118 12758–12773.CrossRefGoogle Scholar
Ortega-Castro, J. Hernández-Haro, N. Dove, M.T. Hernández-Laguna, A. and Saínz-Diaz, C.I., 2010 Density functional theory and Monte Carlo study of octahedral cation ordering of Al/Fe/Mg cations in dioctahedral 2:1 phyllosilicates American Mineralogist 95 209–220.CrossRefGoogle Scholar
Plimpton, S., 1995 Fast parallel algorithms for short-range molecular dynamics Journal of Computational Physics 117 1–19.CrossRefGoogle Scholar
Praprotnik, M. Janezic, D. and Mavri, J., 2004 Temperature dependence of water vibrational spectrum: A molecular dynamics simulation study Journal of Physical Chemistry A 108 11056–11062.CrossRefGoogle Scholar
Prost, R., 1975 Interactions between adsorbed water molecules and the structure of clay minerals: Hydration mechanism of smectites Proceedings of the International Clay Conference of The Clay Minerals Society MexicoCity 351–359.Google Scholar
Rotenberg, B. Patel, A.J. and Chandler, D., 2011 Molecular explanation for why talc surfaces can be both hydrophilic and hydrophobic Journal of the American Chemical Society 133 20521–20527.CrossRefGoogle ScholarPubMed
Russell, J.D. and Farmer, V.C., 1964 Infrared spectroscopic study of the dehydration of montmorillonite and saponite Clay Minerals Bulletin 5 443–464.CrossRefGoogle Scholar
Sato, T. Watanabe, T. and Otsuka, R., 1992 Effects of layer charge, charge location, and energy change on expansion properties of dioctahedral smectites Clays and Clay Minerals 40 103–113.CrossRefGoogle Scholar
Skipper, N.T. Soper, A.K. and McConnell, J.D.C., 1991 The structure of interlayer water in vermiculite Journal of Chemical Physics 94 5751–5760.CrossRefGoogle Scholar
Sobolev, O. Favre Buivin, F. Kemner, E. Russina, M. Beuneu, B. Cuello, G.J. and Charlet, L., 2010 Water-clay surface interaction: A neutron scattering study Chemical Physics 374 55–61.CrossRefGoogle Scholar
Šolc, R. Gerzabek, M.H. Lischka, H. and Tunega, D., 2011 Wettability of kaolinite (001) surfaces — molecular dynamic study Geoderma 169 47–54.CrossRefGoogle Scholar
Sovago, M. Kramer Campen, R.K. Bakker, H.J. and Bonn, M., 2009 Hydrogen bonding strength of interfacial water determined with surface sum-frequency generation Chemical Physics Letters 470 7–12.CrossRefGoogle Scholar
Sposito, G. and Prost, R., 1982 Structure of water adsorbed on smectites Chemical Reviews 82 554–573.CrossRefGoogle Scholar
Sposito, G. Prost, R. and Gaultier, J.-P., 1983 Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li-montmorillonites Clays and Clay Minerals 31 9–16.CrossRefGoogle Scholar
Sposito, G. Skipper, N.T. Sutton, R. Park, S.-H. Soper, A.K. and Greathouse, J.A., 1999 Surface geochemistry of clay minerals Proceedings of the National Academy of Science USA 96 3358–3364.CrossRefGoogle ScholarPubMed
Suquet, H. Prost, R. and Pezerat, H., 1977 Etude par la spectroscopie infrarouge de l’eau adsorbée par la saponitecalcium Clay Minerals 12 113–125.CrossRefGoogle Scholar
Suzuki, S. and Kawamura, K., 2004 Study of vibrational spectra of interlayer water in sodium beidellite by molecular dynamics simulations Journal of Physical Chemistry B 108 13468–13474.CrossRefGoogle Scholar
Środoń, J. and McCarty, D.K., 2008 Surface area and layer charge of smectite from CEC and EGME/H2O retention measurements Clays and Clay Minerals 56 155–174.CrossRefGoogle Scholar
Szczerba, M. Kłapyta, Z. and Kalinichev, A.G., 2014 Ethylene glycol intercalation in smectites Molecular dynamics simulation studies. Applied Clay Science 91 87–97.CrossRefGoogle Scholar
Tay, K. and Bresme, F., 2006 Hydrogen bond structure and vibrational spectrum of water at a passivated metal nanoparticle Journal of Materials Chemistry 16 1956–1962.CrossRefGoogle Scholar
Teich-McGoldrick, S.L. Greathouse, J.A. Jové-Colón, C.F. and Cygan, R.T., 2015 Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature, interlayer cation, and charge location effects Journal of Physical Chemistry C 119 20880–20891.CrossRefGoogle Scholar
Toukan, K. and Rahman, A., 1985 Molecular-dynamics study of atomic motions in water Physical Review B 31 2643–2648.CrossRefGoogle ScholarPubMed
Tunega, D. Gerzabek, M.H. and Lischka, H., 2004 Ab initio molecular dynamics study of a monomolecular water layer on octahedral and tetrahedral kaolinite surfaces Journal of Physical Chemistry B 108 5930–5936.CrossRefGoogle Scholar
Wang, J.W. Kalinichev, A.G. and Kirkpatrick, R.J., 2004 Molecular modeling of the 10-angstrom phase at subduction zone conditions Earth and Planetary Science Letters 222 517–527.CrossRefGoogle Scholar
Wang, J.W. Kalinichev, A.G. and Kirkpatrick, R.J., 2005 Structure and decompression melting of a novel, highpressure nanoconfined 2-D ice Journal of Physical Chemistry B 109 14308–14313.CrossRefGoogle ScholarPubMed
Wang, J. Kalinichev, A.G. Kirkpatrick, R.J. and Cygan, R.T., 2005 Structure, energetics, and dynamics of water adsorbed on the muscovite (001) surface: a molecular dynamics simulation The Journal of Physical Chemistry B 109 15893–15905.CrossRefGoogle ScholarPubMed
Wang, J. Kalinichev, A.G. and Kirkpatrick, R.J., 2009 Asymmetric hydrogen bonding and orientational ordering of water at hydrophobic and hydrophilic surfaces: A comparison of water/vapor, water/talc, and water/mica interfaces Journal of Physical Chemistry C 113 11077–11085.CrossRefGoogle Scholar
Xu, W. Johnston, C.T. Parker, P. and Agnew, S.F., 2000 Infrared study of water sorption on Na-, Li-, Ca- and Mg-exchanged (SWy-1 and SAz-1) montmorillonite Clays and Clay Minerals 48 120–131.CrossRefGoogle Scholar
Zaunbrecher, L.K. Cygan, R.T. and Elliott, W.C., 2015 Molecular models of cesium and rubidium adsorption on weathered micaceous minerals Journal of Physical Chemistry A 119 5691–5700.CrossRefGoogle ScholarPubMed