Formation of Carbonic Acid in Impact of CO2 on Ice and Water

A new mode of formation is proposed for carbonic acid in the atmosphere. It involves impact of vibrationally excited gas-phase CO2 molecules on water or ice particles. This is a first mechanism that supports formation on ice as well as on liquid water surfaces. Results of ab initio molecular dynamics simulations are presented on collisions of CO2 with (H2O) n clusters (n = 1, 4, 8, 12). Efficient formation of carbonic acid is seen with product lifetimes exceeding 100 ps. The reaction is feasible even for collision of CO2 with a single water molecule but in a different mechanism than for larger clusters. For clusters, the transition state shows charge separation into H3O+···HCO3 –, which transforms into neutral carbonic acid as the product, hydrated by the remaining waters. Possible atmospheric implications of the results are discussed.