Water nucleation at extreme supersaturation

We report water cluster formation in the uniform postnozzle flow of a Laval nozzle at low temperatures of 87.0 and 47.5 K and high supersaturations of InS similar to 41 and 104, respectively. Cluster size distributions were measured after soft single-photon ionization at 13.8 eV with mass spectrometry. Critical cluster sizes were determined from cluster size distributions recorded as a function of increasing super-saturation, resulting in critical sizes of 6-15 and 1, respectively. Comparison with previous data for propane and toluene reveals a systematic trend in the nucleation behavior, i.e., a change from a steplike increase to a gradual increase of the maximum cluster size with increasing supersaturation. Experimental nucleation rates of 5.10(15) cm(-3) s(-1) and 2.10(15) cm(-3) s(-1) for 1nS similar to 41 and 104, respectively, were retrieved from cluster size distributions recorded as a function of nucleation time. These lie 2-3 orders of magnitude below the gas kinetic collision limit assuming unit sticking probability, but they agree very well with a recent prediction by a master equation model based on ab initio transition state theory. The experimental observations are consistent with barrierless growth at 47.5 K, but they hint at a more complex nucleation behavior for the measurement at 87.0 K. Published by AIP Publishing.