The production of water-cluster positive ions in the quiet daytime D region

In the quiet daytime D region, the primary positive-ion species is thought to be NO⁺, produced by solar Lyman-alpha ionization of NO. Below the altitude of the mesopause, however, the dominant ambient species observed are water-cluster ions of the general type H⁺(H₂O)_n. No satisfactory reaction scheme for producing these cluster ions from NO⁺ has yet been proposed. Following earlier suggestions, a model calculation has been carried out in which successive hydrations of NO⁺ take place through clustering with N₂ and CO₂, followed by “switching” reactions with H₂O. The third hydrate of NO⁺ is then converted into the water-cluster species H⁺(H₂O)₃, and the other water-cluster species are produced by successive clustering and thermal breakup reactions. Many of the reactions involved have not been measured in the laboratory, but reasonable estimates of their rates can be made on the basis of existing measurements of other species. Since both temperature and water-vapor content are of major importance in the model, calculations were carried out for two temperature profiles and two water-vapor profiles. It is shown that the results are in reasonably good agreement with observations as far as the water-cluster species are concerned. Under low-temperature conditions, the model predicts relatively large concentrations of various clusters of NO⁺, in agreement with some observations but in disagreement with others. The importance of sampling breakup of these weakly bound clusters, and their relevance to the free electron concentrations are discussed.