The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

A simple theoretical expression for the evaporation/condensation coefficient in equilibrium has been proposed by Nagayama and Tsuruta based on the transition state theory and molecular dynamics simulations in 2003. It is not clear, however, whether this approach can be applied to complex molecules such as n-dodecane with long chain structures.In this study, molecular dynamics (MD) simulations have been performed to investigate the evaporation/condensation coefficients of n-dodecane in equilibrium systems. It is found that the evaporation coefficient of n-dodecane primarily depends on the translational energy and the surface temperature similar to simple molecules like argon and water, while the molecular orientation of long chain n-dodecane has less effect. Also, the MD data of n-dodecane agree well with the theoretical expression based on the transition state theory. We conclude that the evaporation coefficient can be predicted by the translational length ratio of liquid to vapor in general even for the long-chain molecules.