The photodissociation dynamics of jet-cooled trifluoroacetaldehyde (CF3CHO) into radical products, CF3 + HCO, was explored using velocity mapped ion imaging over the wavelength range 297.5 nm 342.8 nm (33 613–29 172 cm−1) covering the entire section of the absorption spectrum accessible with solar actinic wavelengths at the ground level. After initial excitation to the first excited singlet state, S1, the radical dissociation proceeds largely via the first excited triplet state, T1, at excitation energies above the T1 barrier. By combining velocity-mapped ion imaging with high-level theory, we place this barrier at 368.3 ± 2.4 kJ mol−1 (30 780 ± 200 cm−1). After exciting to S1 at energies below this barrier, the dissociation proceeds exclusively via the ground electronic state, S0. The dissociation threshold is determined to be 335.7 ± 1.8 kJ mol−1 (28 060 ± 150 cm−1). Using laser-induced fluorescence spectroscopy, the origin of the S1 ← S0 transition is assigned at 28 903 cm−1. The S0 dissociation channel is active at the S1 origin, but the yield significantly increases above 29 100 cm−1 due to enhanced intersystem crossing or internal conversion.
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28 November 2021
Research Article|
November 23 2021
Photodissociation dynamics of CF3CHO: C–C bond cleavage
Special Collection:
2021 JCP Emerging Investigators Special Collection
Jyoti S. Campbell
;
Jyoti S. Campbell
School of Chemistry, University of New South Wales
, Sydney, NSW, Australia
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Klaas Nauta
;
Klaas Nauta
School of Chemistry, University of New South Wales
, Sydney, NSW, Australia
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Scott H. Kable
;
Scott H. Kable
School of Chemistry, University of New South Wales
, Sydney, NSW, Australia
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Christopher S. Hansen
Christopher S. Hansen
a)
School of Chemistry, University of New South Wales
, Sydney, NSW, Australia
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the 2021 JCP Emerging Investigators Special Collection.
J. Chem. Phys. 155, 204303 (2021)
Article history
Received:
October 05 2021
Accepted:
November 03 2021
Citation
Jyoti S. Campbell, Klaas Nauta, Scott H. Kable, Christopher S. Hansen; Photodissociation dynamics of CF3CHO: C–C bond cleavage. J. Chem. Phys. 28 November 2021; 155 (20): 204303. https://doi.org/10.1063/5.0073974
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