Evaporation sampled by stationary molecular dynamics simulation

A nonequilibrium method is developed to sample evaporation of a liquid across a planar interface in a stationary scenario by molecular dynamics. The method does not rely on particle insertions which are challenging when they are used to maintain mass conservation. Its algorithm has a low complexity and is well suited for massively parallel simulations that may yield results with an excellent statistical accuracy. Spatially resolved classical profiles, e.g., for temperature, density, and force, are sampled with a high resolution for a varying hydrodynamic velocity of the evaporation flow. Relatively large systems are simulated, allowing for a detailed study of velocity distribution functions. Varying the hydrodynamic velocity from zero to the speed of sound, it is found that the evaporation flux increases asymptotically, reaching about 90% of its maximum value when the hydrodynamic velocity is about half of its maximum value. A deviation from the Maxwell distribution is identified for the transversal particle velocity near the interface which selectively hinders the migration of individual particles from liquid to vapor with its potential well, allowing only the faster ones to escape. The vapor region in the vicinity of the interface exhibits a spread between the transversal and longitudinal temperature, but equipartition is reattained through particle interactions such that Maxwell distributions are found at a certain distance from the interface. A detailed discussion of the atomistic mechanisms during evaporation is provided, facilitating understanding of this ubiquitous process.