Mapping the Complete Reaction Path of a Complex Photochemical Reaction

Abstract

We probe the dynamics of dissociating CS${}_2$ 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.

References in corpus (4)

• X-ray diffraction from isolated and strongly aligned gas-phase molecules with a free-electron laser
• Time-resolved photoelectron spectroscopy of non-adiabatic dynamics in polyatomic molecules
• Photoionization of the $3s^{2}3p^4{}^{3}P$ and the $3s^{2}3p^4{}^{1}D,{}^{1}S$ states of sulfur: experiment and theory
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