@article{discovery1545201, month = {January}, volume = {142}, title = {Effects of the surroundings and conformerisation of n-dodecane molecules on evaporation/condensation processes.}, note = {This is the published version of record. For information on re-use, please refer to the publisher's terms and conditions.}, journal = {Journal of Chemical Physics}, year = {2015}, number = {3}, author = {Gun'ko, VM and Nasiri, R and Sazhin, SS}, abstract = {The evaporation/condensation coefficient ({\ensuremath{\beta}}) and the evaporation rate ({\ensuremath{\gamma}}) 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 {\ensuremath{\omega}}B97X-D with the cc-pVTZ and cc-pVDZ basis sets) and in liquid phase (solvation method: SMD/{\ensuremath{\omega}}B97X-D). It is shown that {\ensuremath{\beta}} 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 {\ensuremath{\beta}} for n-dodecane molecules. These values are shown to be similar (at reduced temperatures T/Tc {\ensuremath{<}} 0.8) or slightly larger (at T/Tc {\ensuremath{>}} 0.8) than the values of {\ensuremath{\beta}} calculated by the molecular dynamics force fields (MD FF) methods. This endorses the reliability of the previously developed classical approach to estimation of {\ensuremath{\beta}} by the MD FF methods, except at temperatures close to the critical temperature.}, issn = {1089-7690}, url = {http://dx.doi.org/ 10.1063/1.4905496} }