Effect of flexibility on surface tension and coexisting densities of water.

Molecular dynamics simulations of pure water at the liquid-vapor interface are performed using direct simulation of interfaces in a liquid slab geometry. The effect of intramolecular flexibility on coexisting densities and surface tension is analyzed. The dipole moment profile across the liquid-vapor interface shows different values for the liquid and vapor phases. The flexible model is a polarizable model. This effect is minor for liquid densities and is large for surface tension. The liquid densities increase from 2% at 300 K to 9% at 550 K when the force field is changed from a fully rigid simple point charge extended (SPCE) model to that of a fully flexible model with the same intermolecular interaction parameters. The increases in surface tension at both temperatures are around 11% and 36%, respectively. The calculated properties of the flexible models are closer to the experimental data than those of the rigid SPCE. The effect of the maximum number of reciprocal vectors (h(z) (max)) and the surface area on the calculated properties at 300 K is also analyzed. The coexiting densities are not sensitive to those variables. The surface tension fluctuates with h(z) (max) with an amplitude larger than 10 mN m(-1). The effect of using small interfacial areas is slightly larger than the error in the simulations.