Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study.
- Resource Type
- Academic Journal
- Authors
- Sosulin IS; Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia. feldman@rad.chem.msu.ru.; Shiryaeva ES; Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia. feldman@rad.chem.msu.ru.; Tyurin DA; Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia. feldman@rad.chem.msu.ru.; Feldman VI; Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia. feldman@rad.chem.msu.ru.
- Source
- Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 100888160 Publication Model: Electronic Cited Medium: Internet ISSN: 1463-9084 (Electronic) Linking ISSN: 14639076 NLM ISO Abbreviation: Phys Chem Chem Phys Subsets: PubMed not MEDLINE; MEDLINE
- Subject
- Language
- English
The investigation of the reactions of oxygen atoms with fluoroform (CHF 3 ) molecules and products of their degradation present significant interest for better understanding of the impact of chemically inert fluorinated compounds on atmospheric chemistry and may provide a deeper insight into mechanisms of chemical processes occurring under the action of hard UV and ionizing radiation. In the present study we applied a matrix isolation technique with FTIR spectroscopic detection combined with ab initio calculations to address this issue. It was found that the reactions of "hot" (translationally excited) O( 1 D) atoms produced by X-ray or UV radiation from appropriate precursors (N 2 O or H 2 O) resulted in the formation of carbonyl fluoride (COF 2 ) and its complex with HF. The complex was detected and characterized for the first time. Singlet oxygen atoms also probably react with the products of radiation-induced degradation of fluoroform (CF 3 and CF 2 ). Additionally, the reaction of "hot" O( 3 P) atoms with fluoroform may occur to a certain extent yielding the CF 3 radical. No evidence for the reactions of thermal O( 3 P) atoms with CHF 3 or products of its degradation was found under the experimental conditions used. The implications of the results of this model study for understanding the evolution of fluoroform in the upper layers of the stratosphere and ionosphere are discussed.