Molecular dynamics simulation of a smectic liquid crystal with atomic detail

Abstract

A molecular dynamics simulation of a sodium–decanoate/decanol/water system is reported. The system is treated in full atomic detail, with the exception of CH2 and CH3 groups that are considered to be ‘‘united atoms,’’ and is a refinement of a previous model membrane [Mol. Phys. 11, 1 (1983)]. The long-range Coulomb interactions were included specifically. The order parameters of the chain units of the lipids and diffusion constants of components in the system calculated from the simulation agree well with those reported in experiments on this model membrane. The overall structure of the membrane shows considerable disorder, with a broad lipid–water interface, extending over approximately 1 nm. The distribution of the components is such that an almost complete charge cancellation occurs throughout the system, which is in contradiction with the generally assumed electrical double layer structure for membranes. A counterion condensation of 70% is observed. Both the translational and the rotational motions of water are slowed down compared to bulk water. The penetration of water into the hydrocarbon region of the membrane is substantial. Pair correlations of various atom pairs, and dihedral statistics and transition rates of the dihedrals in the lipids are reported. The distributions of chain segments of the lipids, of water molecules, and of sodium ions are compared with theoretical predictions.