Abstract
Density functional theory (DFT) calculations at the MPWB1K/ 6-311+G(3df,2p) level were performed to study OH-initiated atmospheric oxidation reactions of 6-chlorobenzo[a]pyrene (6-ClBaP). The rate constants for key elementary reactions were estimated by means of transition state theory. The computed results demonstrate that only four of the twelve possible intermediates (INT1, INT3, INT4, and INT12) can be generated kinetically. The principal atmospheric oxidation products of 6-ClBaP, benzo[a]pyrenols, can be produced by subsequent reactions of INT1, INT3, INT4, and INT12, although their hydrogen abstraction mechanism is not exactly the same. For peroxy radical intermediates formed by O2 addition toward INT4 intramolecular hydrogen transfer from −OH to −OO was found to be a highly non-spontaneous process and hence difficult to proceed. The rate-controlling steps for subsequent reactions of INT1, INT3, INT4, and INT12 involving NO2 or NO were found to be very slow kinetically.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
