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Theoretical Prediction of Ion Clusters Relevant to the Atmosphere: Size and Mobility

S. H. SuckDepartment of Physics and Graduate Center for Cloud Physics Research, University of Missouri, Rolla 65401

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J. L. Kassner Jr.Department of Physics and Graduate Center for Cloud Physics Research, University of Missouri, Rolla 65401

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R. E. ThurmanDepartment of Physics and Graduate Center for Cloud Physics Research, University of Missouri, Rolla 65401

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P. C. YueDepartment of Physics and Graduate Center for Cloud Physics Research, University of Missouri, Rolla 65401

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R. A. AndersonDepartment of Physics and Graduate Center for Cloud Physics Research, University of Missouri, Rolla 65401

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Abstract

The clustering of water vapor about ions is important because of its relevance to atmospheric electrical processes. For this reason we have placed our emphasis particularly on the description of the size distribution (concentrations) and mobilities of the small ion clusters at various humidities. From our present theoretical study, we find that most of the hydronium ions H3O+ tend to associate with a small number of water molecules to form a hydrated ion cluster even at extremely low humidities in the range of 5 × 10−3 to 1%. At atmospherically more realistic humidities and at the room temperature, our computed number of water molecules in the hydrated ion clusters is predicted to be relatively small. It is then conjectured that ion-induced nucleation process (if it occurs) starts rather from the small hydrated ion clusters which initially existed even at extremely low humidities in the atmosphere. In addition, we also find that, in general, the hydrated ion clusters of small sizes corresponding to the mass range of 2–5 water molecules are responsible for the ion mobility range of 2–2.5 cm−2 (V s)−1. For reduced mobility below 2.0 cm2 (V s)−1, the mass of the hydrated ion cluster is predicted to be greater than that of approximately five water molecules. The simultaneous estimation of size distribution and mobility aids us in better understanding observed mobility spectra and the nature of atmospherically important prenucleation clusters, including the information of their electric conductivities in the atmosphere.

Abstract

The clustering of water vapor about ions is important because of its relevance to atmospheric electrical processes. For this reason we have placed our emphasis particularly on the description of the size distribution (concentrations) and mobilities of the small ion clusters at various humidities. From our present theoretical study, we find that most of the hydronium ions H3O+ tend to associate with a small number of water molecules to form a hydrated ion cluster even at extremely low humidities in the range of 5 × 10−3 to 1%. At atmospherically more realistic humidities and at the room temperature, our computed number of water molecules in the hydrated ion clusters is predicted to be relatively small. It is then conjectured that ion-induced nucleation process (if it occurs) starts rather from the small hydrated ion clusters which initially existed even at extremely low humidities in the atmosphere. In addition, we also find that, in general, the hydrated ion clusters of small sizes corresponding to the mass range of 2–5 water molecules are responsible for the ion mobility range of 2–2.5 cm−2 (V s)−1. For reduced mobility below 2.0 cm2 (V s)−1, the mass of the hydrated ion cluster is predicted to be greater than that of approximately five water molecules. The simultaneous estimation of size distribution and mobility aids us in better understanding observed mobility spectra and the nature of atmospherically important prenucleation clusters, including the information of their electric conductivities in the atmosphere.

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