A theoretical model of liquid water evaporation has been developed to interpret results from a recentexperimental investigation of isotope fractionation during free evaporation [Cappa et al.
J. Phys. Chem. B2005,
109 (51), 24391]. It is established that the free evaporation isotope fractionation factors (
evap) areprimarily influenced by the nature of the intermolecular interactions between water molecules, namely, thecondensed phase hindered translational and librational frequencies at the surface. The dependence of
evap onthe isotopic composition of the liquid can be understood in terms of small variations in these frequencieswith isotopic composition. This result suggests that the explicit nature of the solvation environment directlyinfluences evaporation rates from liquids. The sensitivity of the calculated evaporation coefficient for liquidwater to both temperature and isotope composition is also explored.