Efficient low-temperature oxidation of carbon-cluster anions by so ₂

Carbon-cluster anions, CN ^-, are very reactive toward SO ₂ (sticking probability of 0.012 ± 0.005 for C ₂₇ at 25 °C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO ₂ by the carbon cluster anions, N = 4-60, yields C _NSO ₂ or C _N-1S ^-. The inferred elimination of neutral CO ₂ is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO ₂ with nascent carbon clusters yields C _N-1SO ^- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO ₂.