Direct dioxygen evolution in collisions of carbon dioxide with surfaces

The intramolecular conversion of CO 2 to molecular oxygen is an exotic reaction, rarely observed even with extreme optical or electronic excitation means. Here we show that this reaction occurs readily when CO 2 ions scatter from solid surfaces in a two-step sequential collision process at hyperthermal incidence energies. The produced O 2 is preferentially ionized by charge transfer from the surface over the predominant atomic oxygen product, leading to direct detection of both O 2 + and O 2 − . First-principles simulations of the collisional dynamics reveal that O 2 production proceeds via strongly-bent CO 2 configurations, without visiting other intermediates. Bent CO 2 provides dynamic access to the symmetric dissociation of CO 2 to C+O 2 with a calculated yield of 1 to 2% depending on molecular orientation. This unexpected collision-induced transformation of individual CO 2 molecules provides an accessible pathway for generating O 2 in astrophysical environments and may inspire plasma-driven electro- and photo-catalytic strategies for terrestrial CO 2 reduction.