Mapping the Complete Reaction Path of a Complex Photochemical Reaction

Physical Review Letters
Adam D SmithRussell S Minns

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

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Feb 4, 2012·The Journal of Chemical Physics·M BrouardW-H Yuen
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Citations

Jun 8, 2018·Physical Chemistry Chemical Physics : PCCP·Maria TudorovskayaAdam Kirrander
Nov 13, 2018·Physical Chemistry Chemical Physics : PCCP·Jaime SuárezI Rabadán
Dec 13, 2018·Physical Chemistry Chemical Physics : PCCP·Darren BellshawAdam Kirrander
May 17, 2019·Physical Chemistry Chemical Physics : PCCP·Emily M WarneRussell S Minns
Mar 9, 2019·Physical Review Letters·Mats SimmermacherAdam Kirrander
Nov 5, 2020·Physical Chemistry Chemical Physics : PCCP·Emily M WarneRussell S Minns
Jan 28, 2021·The Journal of Chemical Physics·Emily M WarneRussell S Minns
Apr 29, 2021·Physical Chemistry Chemical Physics : PCCP·Nikoleta Kotsina, Dave Townsend
Mar 21, 2019·The Journal of Physical Chemistry. a·Thomas Northey, Adam Kirrander
Dec 2, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Yifan GongLiangliang Zhu

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