A study of the reactions of Al + ions with O 3 , N 2 , O 2 , CO 2 and H 2 O: influence on Al + chemistry in planetary ionospheres

The reactions between Al+(31S) and O3, O2, N2, CO2 and H2O were studied using the pulsed laser ablation at 532 nm of an aluminium metal target in a fast flow tube, with mass spectrometric detection of Al+ and AlO+. The rate coefficient for the reaction of Al+ with O3 is k(293 K) = (1.4 ± 0.1) × 10-9 cm3 molecule-1 s-1; the reaction proceeds at the ion-dipole enhanced Langevin capture frequency with a predicted T-0.16 dependence. For the recombination reactions, electronic structure theory calculations were combined with Rice-Ramsperger-Kassel-Markus theory to extrapolate the measured rate coefficients to the temperature and pressure conditions of planetary ionospheres. The following low-pressure limiting rate coefficients were obtained for T = 120-400 K and He bath gas (in cm6 molecule-2 s-1, uncertainty ±σ at 180 K): log10(k, Al+ + N2) = -27.9739 + 0.05036 log10(T) - 0.60987(log10(T))2, σ = 12%; log10(k, Al+ + CO2) = -33.6387 + 7.0522 log10(T) - 2.1467(log10(T))2, σ =13%; log10(k, Al+ + H2O) = -24.7835 + 0.018833 log10(T) - 0.6436(log10(T))2, σ = 27%. The Al+ + O2 reaction was not observed, consistent with a D°(Al+-O2) bond strength of only 12 kJ mol-1. Two reactions of AlO+ were also studied: k(AlO+ + O3, 293 K) = (1.3 ± 0.6) × 10-9 cm3 molecule-1 s-1, with (63 ± 9)% forming Al+ as opposed to OAlO+; and k(AlO+ + H2O, 293 K) = (9 ± 4) × 10-10 cm3 molecule-1 s-1. The chemistry of Al+ in the ionospheres of Earth and Mars is then discussed.