State-Specific Reactions of Cu+(1S,3D,1D) with the Super Greenhouse Gas SF5CF3

State-specific reactions of the potent greenhouse gas SF5CF3 with Cu+ were carried out in a selected ion drift cell apparatus. Copper ions were prepared in a glow discharge utilizing Ne as the working gas. Analysis of these ions using ion mobility mass spectrometry (IMS) indicated the presence of both Cu+(3d10) and Cu+(3d94s1) configurations. Subsequent analysis indicates that the 3d10 configuration consists of Cu+(1S) exclusively whereas the 3d94s1configuration is composed primarily of Cu+(3D) with small contributions from Cu+(1D). State-specific product formation in reactions of these ions with SF5CF3 was determined using IMS along with the known energetic requirements for product formation. These experiments reveal that Cu+ excited states initiate fragmentation of SF5CF3 to yield SF2 +, SF3 +, SF5 +, and CF3 +, where SF3 + represents the largest branching fraction at 90% of the total bimolecular product formation. The energetics associated with the formation of these ions suggest that molecular Cu-containing products must also be formed in all cases, indicating that the governing reaction mechanisms are more complicated than simple dissociative charge transfer. Production of SF2 + and SF3 + are shown to proceed via Cu+(3D) and can be rationalized with a two-step mechanism proceeding through the common intermediate SF3CF3 +. Production of CF3 + can be explained using this same mechanism but is also energetically possible from Cu+(1D) in a more direct process. Energetic requirements indicate that Cu+(1D) is the sole source of SF5 + with concomitant formation of CuCF3. Cu+(1S) exhibits adduct formation exclusively, but IMS spectra of the resulting Cu+·SF5CF3 suggest that as many as three association structures are formed.