Kinetics of O3 with Ca+ and Its Higher Oxides CaOn+ (n=1-3) and Updates to a Model of Meteoric Calcium in the Mesosphere and Lower Thermosphere

The room-temperature rate constants and product branching fractions of CaOn+ (n = 0-3) + O3 are measured using a selected ion flow tube apparatus. Ca+ + O3 produces CaO+ + O2 with k = 9 +/- 4 x 10-10 cm3 s-1, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values. Most likely, those values were underestimated due to the reformation of Ca+ from the sequential chemistry of higher calcium oxide cations with O3, as explored here. A rate constant of 8 +/- 3 x 10-10 cm3 s-1 is recommended. Both CaO+ and CaO2+ react near the capture rate constant with ozone. The CaO+ reaction yields both CaO2+ + O2 (0.80 +/- 0.15 branching) and Ca+ + 2O2. Similarly, the CaO2+ reaction yields both CaO3+ + O2 (0.85 +/- 0.15 branching) and CaO+ + 2O2. CaO3+ + O3 yield CaO2+ + 2O2 at 2 +/- 1 x 10-11 cm3 s-1, about 2% of the capture rate constant. The results are supported using density functional calculations and statistical modeling. In general, CaOn+ + O3 yield CaOn+1+ + O2, the expected oxidation. Some fraction of CaOn+1+ is produced with sufficient internal energy to further dissociate to CaOn-1+ + O2, yielding the same products as the oxidation of O3 by CaOn+. Mesospheric Ca and Ca+ concentrations are modeled as functions of day, latitude, and altitude using the Whole Atmosphere Community Climate Model (WACCM); incorporating the updated rate constants improves agreement with concentrations derived from lidar measurements.