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

Abstract Experimental studies have shown that a sharp, high-frequency IR band at ~3615 cm -1 (in H 2 O form) and at ~2685 cm -1 (in D 2 O 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 H 2 O 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 H 2 O 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 H 2 O 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 H 2 O 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 H 2 O 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 H 2 O in monodentate and bidentate orientation.