Reexamination of ionospheric chemistry: high temperature kinetics, internal energy dependences, unusual isomers, and corrections.

A number of aspects of ionospheric chemistry are revisited. The review discusses in detail only work performed at AFRL, but other work is mentioned. A large portion of the paper discusses measurements of the kinetics of upper ionospheric reactions at very high temperatures, i.e. the upper temperature range has been extended to at least 1400 K and in some cases to 1800 K. These temperatures are high enough to excite vibrations in O2, N2, and NO and comparing them to drift tube data allows information on the rotational temperature and vibrational level dependences to be derived. Rotational and translational energy are equivalent in controlling the kinetics in most reactions. Vibrational energy in O2 and N2 is often found to promote reactivity which is shown to cause ionospheric density depletions. NO vibrations do not significantly affect the reactivity. In a number of cases, detailed calculations accompanied the experimental studies and elucidated details of the mechanisms. Kinetics of two peroxide isomers important in the lower ionospheric have been measured for the first time, i.e. NOO+ and ONOO-. Finally, two examples are shown where errors in previous data are corrected.