Significance: The role of chlorine and bromine in Antarctic stratospheric ozone depletion is well known. However, the contribution of iodine to the ozone hole chemistry has not been assessed, mainly due to the negligible amounts of iodine previously reported to enter the stratosphere. New measurements demonstrate that the injection of iodine to the lower stratosphere is higher than previously assumed. Based on these observations, our modeling work shows that iodine chemistry can enhance spring ozone loss at the lower part of the Antarctic ozone hole, and even dominate the halogen-mediated ozone loss during summer. Iodine can also alter, by several days, the timing of the seasonal formation and closure of the ozone hole.

As of yet, unexamined aluminum bearing molecules may help elucidate aluminum chemistry and associated refractory atom reactions in the interstellar medium. The flexibility of modern quantum chemistry in the construction and analysis of novel molecules makes it perfectly suited to analyze molecules of astrochemical significance. In this paper, high level ab initio electronic structure calculations using the coupled cluster CCSD(T) and explicitly correlated coupled cluster CCSD(T)-F12 methods with large basis sets extrapolated to the complete basis set limit have been performed on the various [Al,N,C,O] isomers. The anharmonic rotational and vibrational spectroscopic parameters for all isomers are produced with these same levels of theory via quartic force fields and vibrational perturbation theory in order to aid in their potential laboratory or even astrophysical identification. The most stable isomer is determined here to be the aluminum isocyanate radical with linear equilibrium geometry AlNCO (X¹Σ⁺). The NCO antisymmetric stretch of AlNCO has an intensity of 1500 km/mol, which should greatly aid in its infrared detection in the region around 2305 cm⁻¹. Additionally, the AlOCN isomer is relatively low lying, possesses a 5.12 D dipole moment, and has a notable kinetic stability, making it a viable candidate for astronomical observation. All isomers are characterized by small frequencies, which indicates that these are floppy molecules. Isomers with a terminal aluminum atom are especially floppy, with bending modes less than 100 cm⁻¹.