Monte Carlo simulations have been used to predict the interlayer basal separations of sodium-saturated Wyoming clays at constant stress (NP zz T ensemble͒ and at constant chemical potential (VT ensemble͒. These simulations use the Ewald summation technique to incorporate long-range Coulombic interactions in the calculation of the total potential energy and the pressure tensor. A comparison is made between the use of one, two, and three sheets of clay. It is shown that, for small separations, at least two separate clay sheets must be used to avoid system-size effects. The stable interlamellar separations are determined by combining results from isostress-isothermal and grand canonical simulations. It is shown that, consistent with experiments, at the temperature and pressure studied here, the cations in the interlayer are hydrated, except at the smallest basal separations.

Clay minerals are considered important to chemical evolution processes due to their properties, ancient origin, and wide distribution. To extend the knowledge of their role in the prebiotic epoch, the adsorption sites of adenine, adenosine, AMP, ADP, ATP, Poly A, uracil, uridine, UMP, UDP, UTP and Poly U on sodium montmorillonite are investigated. X-ray diffraction, ultraviolet and infrared spectroscopy studies indicate that these molecules distribute into the interlamellar channel and the edge of the clay crystals. Monomers are adsorbed predominantly in the interlamellar channel, whereas polymers adsorb along the crystal edges. Such behavior is discussed mainly in terms of bulk pH, pK(a) of the adsorbate, and Van der Waals interactions.

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The hydration of Na-saturated Wyoming-type montmorillonite is investigated by Monte Carlo simulations at constant stress in the NP(zz)T ensemble and at constant chemical potential in the microVT ensemble, at the sedimentary basin temperature of 353 K and pressure of 625 bar, equivalent to 2-4 km depth. The simulations use procedures established in Chavez-Paez et al. [J. Chem. Phys. 114, 1405 (2001)]. At these conditions, simulations predict a single stable form of 1,2-water layer Na-montmorillonite, containing 164.38 mg/g or 53.37 molecules/layer of adsorbed water and having a spacing of 12.72 A. The corresponding density is 0.32 g/ml. Sodium ions are coordinated with six molecules of water separated 2.30-2.33 A. Water molecules are closer to the central interlayer plane and the spacing is larger than that at 300 K and 1 bar. The interlayer configuration consists of two symmetrical layers of oriented water molecules 1.038 A from the central plane, with the hydrogen atoms in two outermost layers, 3.826 A apart, and the sodium ions on the central plane located between the water layers. The interlayer configuration can be considered to be a stable two-layer intermediate between the one- and two-layer hydrates. Our simulations do not predict formation of other hydrates of Na-montmorillonite at 353 K and 615 bar.

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Nanocrystalline cobalt spinels were synthesized under hydrothermal conditions, starting from metal chlorides. The color properties in these systems mainly depend upon the preparative method and cation distributions, which have been determined by X-ray powder diffraction using Rietveld refinements and visible near infrared absorption spectra. We observe the influence of tetrahedral and octahedral preference of cations such as Co 2+ , Cr 3+ , Mn 3+ upon the formation and the color development of cobalt spinel pigments. All the samples prepared revealed the formation of single spinel with particle size at about 0.8-2.1 mm; CoAl 2 O 4 reveals king's blue, CoMn 2 O 4 dark blue and CoCr 2 O 4 bluish green. Cobalt blues developed giving deep absorption characteristic of tetrahedral Co 2+ ions at about 550-680 nm; therefore, color changed from king's blue to bluish green in CoCr 2 O 4 , showing the absorption band of octahedral Cr 3+ ions owing to the large excess octahedral crystal field stabilization energy.

Monte Carlo grand canonical molecular simulations on the hydration of Na-, K-, and Ca-montmorillonite show that between 333 and 533 K and 300-1300 bar Na-montmorillonite forms stable one-layer hydrates of d(001) spacings 12.64-12.38 Angstroms, K-montmorillonite of 12.78-12.59 Angstroms, and Ca-montmorillonite of 12.48-12.32 Angstroms. A two-layer hydrate of 14.80 Angstroms occurs for Na-montmorillonite at 533 K and 1300 bar, for K-montmorillonite of 15.32 Angstroms at 533 K and 1300 bar and of 14.74 Angstroms at 533 K and 2000 bar, and for Ca-montmorillonite of 13.83 Angstroms at 473 K and 1000 bar. Three-layer hydrates may possibly form within these same ranges. Outside of them, one-layer hydrates simulate as the only stable hydrates. In sedimentary basins, the two-layer hydrate of Ca-montmorillonite will locate at 6.7 km depth and those of Na- and K-montmorillonite at 8.7 km depth; above and below these depths, the one-layer hydrates are the stable phases.