PHOTODISSOCIATION OF (OCS)2 AND (CS2)2: COMPETING PHOTOCHEMICAL PATHWAYS

Article abstract of DOI:10.1021/j100342a029

The photochemistry of (OCS)2 and (CS2)2 is investigated by using resonance-enhanced multiphoton ionization.The competition between van der Waals and covalent bond chemistry occurring upon electronic excitation of the dimers is probed, and the energetic and kinetic factors affecting this competition are examined.Photodissociation of the ¹Σ⁺ state of OCS in a dimer is investigated and found to produce a significant amount of S2.Photodissotiation of the ¹B₂(¹Σ_u⁺) state of CS2 in a dimer leads to the production of S2 and C2S2 photoproducts.These fragments are obtained as a result of covalent bond photochemistry of the respective dimers.There appears to be a greater tendency toward van der Waals bond dissociation in (CS2)2 compared with (OCS)2, in agreement with expectations based on differences in energetics and excited-state dynamics of the two dimers.