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The Under-Explored Possibilities of Ground State Carbonyl Photochemistry

preprint
submitted on 14.09.2020, 05:34 and posted on 15.09.2020, 06:54 by Keiran Rowell, Scott Kable, Meredith J. T. Jordan
Carbonyls are among the most abundant volatile organic compounds in the atmosphere, and their C=O chromophores allow them to photolyse. However, carbonyl photolysis reactions are not restricted to the excited state: the C=O chromophore allows relaxation to, and reaction on, the ground state, following photon absorption.

In this paper, the energetic thresholds for eight ground state reactions across twenty representative carbonyl species are calculated using double-hybrid density functional theory. Most reactions are found to be energetically accessible within the maximum photon energy available in the troposphere, but are absent in contemporary atmospheric chemistry models.

Structure–activity relationships are then elucidated so that the significance of each reaction pathway for particular carbonyl species can be predicted based upon their class. The calculations here demonstrate that ground state photolysis pathways are ubiquitous in carbonyls and should not be ignored in the analysis of carbonyl photochemistry.

Funding

DP160101792

History

Email Address of Submitting Author

krow4060@sydney.edu.au

Institution

The University of Sydney

Country

Australia

ORCID For Submitting Author

0000-0001-6955-1167

Declaration of Conflict of Interest

None

Version Notes

First versio, pre-print upload

Exports