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.
Similar content being viewed by others
References
Allen, M.P. and Tildesley, D.J. (1987) Computer Simulation of Liquids. Oxford University Press, New York, 385 pp.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Kalinichev, A.G. (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Pp. 83–129 in: Molecular Modeling Theory: Applications in the Geosciences (R.T. Cygan and J.D. Kubicki, editors). Reviews in Mineralogy and Geochemistry, 42, Mineralogical Society of America, Washington, D.C.
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.
Kuligiewicz, A., Derkowski, A., Szczerba, M., Gionis, V., and Chryssikos, G.D. (2015a) Water-smectite interface by infrared spectroscopy, Clays and Clay Minerals, 63, 15–29.
Kuligiewicz, A., Derkowski, A., Emmerich, K., Christidis, G.E., Tsiantos, C., Gionis, V., and Chryssikos, G.D. (2015b) Measuring the layer charge of dioctahedral smectite by O-D vibrational spectroscopy. Clays and Clay Minerals, 63, 443–456.
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.
Lee, J.H. and Guggenheim, S. (1981) Single crystal X-ray refinement of pyrophyllite-1Tc. American Mineralogist, 66, 350–357.
Libowitzky, E. (1999) Correlation of O-H stretching frequencies and O-H…O bond lengths in minerals. Monatshefte für Chemie, 130, 1047–1059.
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.
Loganathan, N., Yazaydin, A.O., Bowers, G.M., Kalinichev, A.G., and Kirkpatrick, R.J. (2016a) 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.
Loganathan, N., Yazaydin, A.O., Bowers, G.M., Kalinichev, A.G., and Kirkpatrick, R.J. (2016b) 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.
Löwenstein, W. (1954) The distribution of aluminum in the tetrahedra of silicates and aluminates. American Mineralogist, 39, 92–96.
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.
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.
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.
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.
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.
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
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.
Plimpton, S. (1995) Fast parallel algorithms for short-range molecular dynamics. Journal of Computational Physics, 117, 1–19.
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.
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, Mexico City, 351–359.
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.
Russell, J.D. and Farmer, V.C. (1964) Infrared spectroscopic study of the dehydration of montmorillonite and saponite. Clay Minerals Bulletin, 5, 443–464.
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.
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.
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.
Šolc, R., Gerzabek, M.H., Lischka, H., and Tunega, D. (2011) Wettability of kaolinite (001) surfaces — molecular dynamic study. Geoderma, 169, 47–54.
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.
Sposito, G. and Prost, R. (1982) Structure of water adsorbed on smectites. Chemical Reviews, 82, 554–573.
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.
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.
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.
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.
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.
Szczerba, M., Kłapyta, Z., and Kalinichev, A.G. (2014) Ethylene glycol intercalation in smectites. Molecular dynamics simulation studies. Applied Clay Science, 91, 87–97.
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.
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.
Toukan, K. and Rahman, A. (1985) Molecular-dynamics study of atomic motions in water. Physical Review B, 31, 2643–2648.
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.
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.
Wang, J.W., Kalinichev, A.G., and Kirkpatrick, R.J. (2005a) Structure and decompression melting of a novel, highpressure nanoconfined 2-D ice. Journal of Physical Chemistry B, 109, 14308–14313.
Wang, J., Kalinichev, A.G., Kirkpatrick, R.J., and Cygan, R.T. (2005b) 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.
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.
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.
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.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Szczerba, M., Kuligiewicz, A., Derkowski, A. et al. Structure and Dynamics of Water-Smectite Interfaces: Hydrogen Bonding and the Origin of the Sharp O-Dw/O-Hw Infrared Band From Molecular Simulations. Clays Clay Miner. 64, 452–471 (2016). https://doi.org/10.1346/CCMN.2016.0640409
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.2016.0640409