The origin of enhanced [Formula: see text] production from photoionized CO 2 clusters.

CO 2 -rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO 2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO 2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of [Formula: see text] from photoionized CO 2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing [Formula: see text]. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres.