Cluster Ions and Atmospheric Processes
Abstract
We investigate the properties and possible roles of naturally occurring ions under at- mospheric conditions. Among other things, the formation of stable charged molecular clusters represents the initial stages of aerosol nucleation [e.g., Keesee and Castle- man, 1982], while the conversion of vapor to aggregates is the first step in certain atmospheric phase transitions [e.g. Hamill and Turco, 2000]. We analyze the stability and size distributions of common ionic clusters by solving the differential equations describing their growth and loss. The necessary reaction rate coefficients are deter- mined using kinetic and thermodynamic data. The latter are derived from direct labo- ratory measurements of equilibrium constants, from the classical charged liquid drop model applied to large aggregates (i.e., the Thomson model [Thomson, 1906]), and from quantum mechanical calculations of the thermodynamic potentials associated with the cluster structures. This approach allows us to characterize molecular clusters across the entire size range from true molecular species to larger aggregates exhibiting macroscopic behavior [D'Auria, 2001]. Cluster systems discussed in this talk include the proton hydrates (PHs) and nitrate-water and nitrate-nitric acid series [D'Auria and Turco, 2001]. These ions have frequently been detected in the stratosphere and tropo- sphere [e.g., Arnold et al., 1977; Viggiano and Arnold, 1981]. We show how the pro- posed hybrid cluster model can be extended to a wide range of ion systems, including non-proton hydrates (NPHs), mixed-ligand clusters such as nitrate-water-nitric acid and sulfate-sulfuric acid-water, as well as more exotic species containing ammonia, pyridine and other organic compounds found on ions [e.g., Eisele, 1988; Tanner and Eisele, 1991].
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EGS General Assembly Conference Abstracts
- Pub Date:
- 2002
- Bibcode:
- 2002EGSGA..27.2591D