气候变化领域集成服务门户(CCPortal): An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls

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DOI	10.5194/acp-22-929-2022
	An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls
	Rowell, Keiran N.; Kable, Scott H.; Jordan, Meredith J. T.
发表日期	2022
ISSN	1680-7316
EISSN	1680-7324
起始页码	929
结束页码	949
卷号	22 期号:2 页码:21
英文摘要	Carbonyls are among the most abundant volatile organic compounds in the atmosphere. They are central to atmospheric photochemistry as absorption of near-UV radiation by the C=O chromophore can lead to photolysis. If photolysis does not occur on electronic excited states, non-radiative relaxation to the ground state will form carbonyls with extremely high internal energy. These hot molecules can access a range of ground state reactions. Up to nine potential ground state reactions are investigated at the B2GP-PLYP-D3/def2-TZVP level of theory for a test set of 20 representative carbonyls. Almost all are energetically accessible under tropospheric conditions. Comparison with experiment suggests the most significant ground state dissociation pathways will be concerted triple fragmentation in saturated aldehydes, Norrish type III dissociation to form another carbonyl, and H-2 loss involving the formyl H atom in aldehydes. Tautomerisation, leading to more reactive unsaturated species, is also predicted to be energetically accessible and is likely to be important when there is no low-energy ground state dissociation pathway, for example in alpha, beta-unsaturated carbonyls and some ketones. The concerted triple fragmentation and H-2-loss pathways have immediate atmospheric implications for global H-2 production, and tautomerisation has implications for the atmospheric production of organic acids.
学科领域	Environmental Sciences; Meteorology & Atmospheric Sciences
语种	英语
WOS研究方向	Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
WOS记录号	WOS:000747495000001
来源期刊	ATMOSPHERIC CHEMISTRY AND PHYSICS
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/273028
作者单位	University of Sydney; University of New South Wales Sydney
推荐引用方式 GB/T 7714	Rowell, Keiran N.,Kable, Scott H.,Jordan, Meredith J. T.. An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls[J],2022,22(2):21.
APA	Rowell, Keiran N.,Kable, Scott H.,&Jordan, Meredith J. T..(2022).An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(2),21.
MLA	Rowell, Keiran N.,et al."An assessment of the tropospherically accessible photo-initiated ground state chemistry of organic carbonyls".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.2(2022):21.