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. Carbonyls are among the most abundant volatile organic compounds in theatmosphere. They are central to atmospheric photochemistry as absorption ofnear-UV radiation by the C=O chromophore can lead to photolysis. Ifphotolysis does not occur on electronic excited states, non-radiativerelaxation to the ground state will form carbonyls with extremely highinternal energy. These “hot” molecules can access a range of ground statereactions. Up to nine potential ground state reactions are investigatedat the B2GP-PLYP-D3/def2-TZVP level of theory for a test set of 20representative carbonyls. Almost all are energetically accessible undertropospheric conditions. Comparison with experiment suggests the mostsignificant ground state dissociation pathways will be concerted triplefragmentation in saturated aldehydes, Norrish type III dissociation toform another carbonyl, and H2 loss involving the formyl H atomin aldehydes. Tautomerisation, leading to more reactive unsaturatedspecies, is also predicted to be energetically accessible and is likely tobe important when there is no low-energy ground state dissociation pathway,for example in α,β-unsaturated carbonyls and some ketones. Theconcerted triple fragmentation and H2-loss pathways have immediateatmospheric implications for global H2 production, and tautomerisation hasimplications for the atmospheric production of organic acids.

An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls