  We use molecular dynamics as a tool to understand the structure and phase
transitions [Osman et. al. J. Phys. Chem. B 2000, 104, 4433; 2002, 106, 653] in
alkylammonium micas. The consistent force field 91 is extended for accurate
simulation of mica and related minerals. We investigate mica sheets with 12
octadecyltrimethylammonium (C18) ions or 12 dioctadecyldimethylammonium (2C18)
ions, respectively, as single and layered structures at different temperatures
with periodicity in the xy plane by NVT dynamics. The alkylammonium ions reside
preferably above the cavities in the mica surface with an aluminum-rich
boundary. The nitrogen atoms are 380 to 390 pm distant to the superficial
silicon-aluminum plane. With increasing temperature, rearrangements of C18 ions
on the mica surface are found, while 2C18 ions remain tethered due to geometric
restraints. We present basal-plane spacings in the duplicate structures, tilt
angles of the alkyl chains, and gauche-trans ratios to analyze the chain
conformation. Also, the individual phase transitions of the two systems on
heating are explained. Where experimental data are available, the agreement is
very good. We propose a geometric parameter lamba for the saturation of the
surface with alkyl chains, which determines the preferred self-assembly
pattern, i.e., islands, intermediate, or continuous. Lambda also determines the
tilt angles in continuous layers on mica or other surfaces. The thermal
decomposition appears to be a Hofmann elimination with mica as a base-template.
