%X The evaporation/condensation coefficient (β) and the evaporation rate (γ) for n-dodecane vs. temperature, gas pressure, gas and liquid density, and solvation effects at a droplet surface are analysed using quantum chemical density functional theory calculations of several ensembles of conformers of n-dodecane molecules in the gas phase (hybrid functional ωB97X-D with the cc-pVTZ and cc-pVDZ basis sets) and in liquid phase (solvation method: SMD/ωB97X-D). It is shown that β depends more strongly on a number of neighbouring molecules interacting with an evaporating molecule at a droplet surface (this number is estimated through changes in the surface Gibbs free energy of solvation) than on pressure in the gas phase or conformerisation and cross-conformerisation of molecules in both phases. Thus, temperature and the surrounding effects at droplet surfaces are the dominant factors affecting the values of β for n-dodecane molecules. These values are shown to be similar (at reduced temperatures T/Tc < 0.8) or slightly larger (at T/Tc > 0.8) than the values of β calculated by the molecular dynamics force fields (MD FF) methods. This endorses the reliability of the previously developed classical approach to estimation of β by the MD FF methods, except at temperatures close to the critical temperature.
%J Journal of Chemical Physics
%A VM Gun'ko
%A R Nasiri
%A SS Sazhin
%T Effects of the surroundings and conformerisation of n-dodecane molecules on evaporation/condensation processes.
%N 3
%C United States
%L discovery1545201
%V 142
%D 2015
%O This is the published version of record. For information on re-use, please refer to the publisher’s terms and conditions.