Mapping the Complete Reaction Path of a Complex Photochemical Reaction

Adam D. Smith, Emily M. Warne, Darren Bellshaw, Daniel A. Horke, Maria Tudorovskya, Emma Springate, Alfred J. H. Jones, Cephise Cacho, Richard T. Chapman, Adam Kirrander, Russell S. Minns

Research output: Contribution to journalArticlepeer-review


We probe the dynamics of dissociating CS2 molecules across the entire reaction pathway upon excitation. Photoelectron spectroscopy measurements using laboratory-generated femtosecond extreme ultraviolet pulses monitor the competing dissociation, internal conversion, and intersystem crossing
dynamics. Dissociation occurs either in the initially excited singlet manifold or, via intersystem crossing, in the triplet manifold. Both product channels are monitored and show that, despite being more rapid, the singlet dissociation is the minor product and that triplet state products dominate the final yield. We explain this by a consideration of accurate potential energy curves for both the singlet and triplet states.We propose that rapid internal conversion stabilizes the singlet population dynamically, allowing for singlet-triplet relaxation via intersystem crossing and the efficient formation of spin-forbidden dissociation products on longer timescales. The study demonstrates the importance of measuring the full reaction pathway for defining accurate reaction mechanisms.
Original languageEnglish
JournalPhysical Review Letters
Issue number18
Early online date4 May 2018
Publication statusE-pub ahead of print - 4 May 2018


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