Evaporation of Lennard-Jones Fluids

TL;DR

This study uses molecular dynamics simulations to analyze evaporation and condensation in Lennard-Jones fluids, revealing how molecular structure influences evaporation rates, coefficients, and interphase profiles.

Contribution

It provides detailed molecular insights into evaporation processes of LJ fluids, highlighting the effects of chain length and temperature on evaporation and condensation coefficients.

Findings

Evaporation rate decreases with increasing chain length.

Evaporation and condensation coefficients are equal near equilibrium and less than one.

Coefficients decrease with temperature and vary with molecular structure.

Abstract

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.