  Evaporation and condensation at a liquid/vapor interface are ubiquitous
interphase mass and energy transfer phenomena that are still not well
understood. We have carried out large scale molecular dynamics simulations of
Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to
investigate these processes with molecular detail. For LJ monomers in contact
with a vacuum, the evaporation rate is found to be very high with significant
evaporative cooling and an accompanying density gradient in the liquid domain
near the liquid/vapor interface. Increasing the chain length to just dimers
significantly reduces the evaporation rate. We confirm that mechanical
equilibrium plays a key role in determining the evaporation rate and the
density and temperature profiles across the liquid/vapor interface. The
velocity distributions of evaporated molecules and the evaporation and
condensation coefficients are measured and compared to the predictions of an
existing model based on kinetic theory of gases. Our results indicate that for
both monatomic and polyatomic molecules, the evaporation and condensation
coefficients are equal when systems are not far from equilibrium and smaller
than one, and decrease with increasing temperature. For the same reduced
temperature $T/T_c$, where $T_c$ is the critical temperature, these two
coefficients are higher for LJ dimers and trimers than for monomers, in
contrast to the traditional viewpoint that they are close to unity for
monatomic molecules and decrease for polyatomic molecules. Furthermore, data
for the two coefficients collapse onto a master curve when plotted against a
translational length ratio between the liquid and vapor phase.
