Molecular dynamics study of the stabilization of the silica hexamer Si6O15(6-) in aqueous and methanolic solutions.

We use molecular dynamics simulations to study the stabilization of the hexameric, cagelike silicate with double three-ring structure in aqueous and methanolic solutions. We find that in purely aqueous environments its stabilization requires the presence of both tetramethylammonium and tetraethylammonium (TEA) cations and involves the formation of a stable TMA layer which leads to a water-silicate heteronetwork clathrate. We also find that TEA alone can facilely stabilize the hexamer when methanol cosolvent is added, in accordance with experiment. The mechanism of this stabilization, however, differs from that in purely aqueous environments. Because of the unique properties of water-methanol mixtures, the organosilicate complex does not participate in heteronetwork clathrates but resides in a large solvent cavity; that is, it is forced out of true solution.

Potential of mean force for tetramethylammonium binding to cagelike oligosilicates in aqueous solution.

We have carried out free energy calculations to compute the potential of mean force for the cagelike silicate polyion-TMA+ cation ion pair interaction in aqueous solution. We also have studied solvent reorganization-related entropic effects. We conclude that the organocations, as opposed to, for example, alkali-metal ions, play a pivotal role in reorganizing the solvent around the cagelike silicates in a manner conducive to the formation of heteronetwork clathrates that are stable both thermodynamically and kinetically. In the case of stable cagelike polysilicate anions, this solvent reorganization correlates with entropic losses. We also infer that transient cagelike polysilicate species, that may indeed form but participate in floppy clathrates, eventually have to give way to cagelike polysilicates that lead to more rigid structures.

Molecular dynamics studies on the role of tetramethylammonium cations in the stability of the silica octamers Si8O20(8-) in solution.

The stability of silica octamers, Si(8) observed in tetramethylammonium (TMA) solutions by Kinrade et al. is investigated in connection with the TMA concentration by performing equilibrium molecular dynamics simulations of Si(8)-TMA-water mixture at two concentrations. At the experimental concentration at which the silica octamers have been observed spectroscopically, we find that, on the average, six TMA molecules surround the silica octamer, coordinated so that each cation occupies a face of the cubic octamer. We also find that upon TMA adsorption, water molecules associated with the siloxane oxygens leave the silica surface, whereas the hydrogen-bond network of the silanol oxygens with water molecules remains intact. No TMA adsorption is observed at the concentration at which the octamers have not been observed.