When ZAA applied MDSRS to VOAG-generated water droplets, they found that the relative heights of the water 3245 cm -l and 3450 cm -1 Raman bands were different from a reference bulk water sample. These differences were interpreted by ZAA as resulting from VOAG-induced hydrogen bonding changes occurring in the water droplets. Hydrogen bonding ratios, as defined by ZAA and normally having a value of 0.95, were reported to have decreased to 0.56. Since most currently accepted mass accommodation coefficients on aerosols were measured using VOAG technology, ZAA conclude that such values are invalid. This claim has such wide ranging implications that it required critical review and experimental confirmation from other laboratories.This paper is not subject to U.S. copyright. Published in 1996 by the American Geophysical Union.
Paper number 96JD02158.This comment is divided into four sections. First, we discuss possible systematic spectral artifacts which could appear under operating conditions used by ZAA. Second, we describe VOAG experiments in which we perform a similar spectroscopic study under conditions that avoid the aforementioned problems. We find that there are no changes in Raman spectra, either between the surface and the droplet interior or between droplet and a bulk liquid reference sample. Third, we critically examine the validity of several of the VOAG-related mechanisms the authors have proposed. We show that these cannot lead to extensive changes in the hydrogen bonding ratio as reported.
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