This paper presents a classical molecular dynamics (MD) and metadynamics investigation of the relationships between the structure, energetics, and dynamics of Na-hydroxyhectorite and serves to provide additional, molecular-scale insight into the interlayer hydration of this mineral. The computational results support a model for interlayer H2O structure and dynamics based on 2H NMR spectroscopy and indicate that H2O molecules undergo simultaneous fast librational motions about the H2O C2 symmetry axis and site hopping with C3 symmetry with respect to the surface normal. Hydration energy minima occur at one-, one-and-one-half-, and two-water-layer hydrates, which for the composition modeled correspond to 3, 5.5, and 10 H2O/Na+, respectively. Na+ ions are coordinated by basal O atoms (OMIN) at the lowest hydration levels and by H2O molecules (OH2O) in the two-layer hydrate, and H2O molecules have an average of three H-bonds at the greatest hydration levels. The metadynamics calculations yield activation energies for site hopping of H2O molecules of ~6.0 kJ/mol for the one-layer structure and ~3.3 kJ/mol for hopping between layers in the two-layer structure. Computed diffusion coefficients for water and Na+ are substantially less than in bulk liquid water, as expected in a nanoconfined environment, and are in good agreement with previous results.
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 (Cygan, R. T.; Liang, J.-J.; Kalinichev, A. G. J. Phys. Chem. B 2004, 108, 1255-1266). 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 (theta - theta0)**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 theta0(AlOH) = theta0(MgOH) = 110°, k(AlOH) = 15 kcal mol(-1) rad(-2) and k(MgOH) = 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. 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.
Toward the development of classical force fields for the accurate modeling of clay mineral-water systems, we have extended the use of metalâ€“Oâ€“H (Mâ€“Oâ€“H) angle bending terms to describe surface Siâ€“Oâ€“H bending for hydrated kaolinite edge structures. Kaolinite, comprising linked octahedral Al and tetrahedral Si sheets, provides a rigorous test by combining aluminol and silanol groups with water molecules in hydrated edge structures. Periodic density functional theory and classical force fields were used with molecular dynamics to evaluate the structure, dynamics, hydrogen bonding, and power spectra for deriving optimum bending force constants and optimal equilibrium angles. Cleavage energies derived from density functional theory molecular dynamics calculations indicate the relative stabilities of both AC1 and AC2 edge terminations of kaolinite where Siâ€“OH and Alâ€“(OH2) or Siâ€“OH, Alâ€“OH, and Alâ€“(OH2) groups exist, respectively. Although not examined in this study, the new Siâ€“Oâ€“H angle bending parameter should allow for improved modeling of hydroxylated surfaces of silica minerals such as quartz and cristobalite, as well as amorphous silica-based surfaces and potentially those of other silicate and aluminosilicate phases.