HO x Regeneration in the Oxidation of Isoprene III: Theoretical Study of the key Isomerisation of the Z -Δ-hydroxy-peroxy Isoprene Radicals
dc.contributor.author | Nguyen, Thanh Lam | en_US |
dc.contributor.author | Vereecken, Luc | en_US |
dc.contributor.author | Peeters, Jozef | en_US |
dc.date.accessioned | 2011-01-04T16:24:52Z | |
dc.date.available | 2011-03-01T16:26:48Z | en_US |
dc.date.issued | 2010-12-17 | en_US |
dc.identifier.citation | Nguyen, Thanh Lam; Vereecken, Luc; Peeters, Jozef (2010). "HO x Regeneration in the Oxidation of Isoprene III: Theoretical Study of the key Isomerisation of the Z -Δ-hydroxy-peroxy Isoprene Radicals." ChemPhysChem 11(18): 3996-4001. <http://hdl.handle.net/2027.42/78501> | en_US |
dc.identifier.issn | 1439-4235 | en_US |
dc.identifier.issn | 1439-7641 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/78501 | |
dc.description.abstract | As a sequel to our communication on a proposed new isoprene oxidation mechanism aiming to rationalize the unexpectedly high OH and HO 2 levels observed in isoprene-rich areas (J. Peeters, T. L. Nguyen, L. Vereecken, Phys. Chem. Chem. Phys. 2009 , 11 , 5935), we report herein the detailed quantum chemical and statistical kinetics characterization of the crucial 1,6-H shifts in the two Z -Δ-hydroxy-peroxy radicals from isoprene. Geometries, energies and vibration frequencies of all conformers of the reactant radicals and transition states are computed at the B3LYP/6-31+G(d,p) level of theory and the energies of the lowest-lying conformers are then refined at various higher levels of theory, including CBS-QB3, IRCMax(CBS-QB3//B3LYP) and CBS-APNO. The rate coefficients over a wide temperature range are calculated using multi-conformer transition state theory with WKB tunneling factors evaluated for the barrier shape found by CBS-QB3//B3LYP IRC analyses. The WKB tunneling factors for these allyl-stabilisation-assisted reactions are about 25 at ambient temperatures. The rate coefficients can be represented by Arrhenius expressions over the 250–350 K range: k ( T )=1.4×10 9 exp(−6380/ T ) s −1 for the Z-1-OH-4-OO ⋅ -isoprene radical, and k ( T )=0.72×10 9 exp(−5520/ T ) s −1 for Z-1-OH-4-OO ⋅ -isoprene. With the k (1,6-H) of order 1 s −1 at ambient temperatures, these isomerisations can compete with and even outrun the traditional peroxy reactions at low and moderate NO levels. The importance of these reactions as key processes in the newly proposed, OH-regenerating isoprene oxidation scheme is discussed. | en_US |
dc.format.extent | 195896 bytes | |
dc.format.extent | 3118 bytes | |
dc.format.mimetype | application/pdf | |
dc.format.mimetype | text/plain | |
dc.publisher | WILEY-VCH Verlag | en_US |
dc.subject.other | Chemistry | en_US |
dc.title | HO x Regeneration in the Oxidation of Isoprene III: Theoretical Study of the key Isomerisation of the Z -Δ-hydroxy-peroxy Isoprene Radicals | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Heverlee-Leuven (Belgium), Fax: (+32) (0)16327992 ; Current address: Department of Atmospheric, Oceanic and Space Sciences, 1218 Space Research Building, University of Michigan Ann Arbor, 2455 Hayward Street Ann Arbor, MI 48109-2143 (USA) | en_US |
dc.contributor.affiliationother | Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Heverlee-Leuven (Belgium), Fax: (+32) (0)16327992 | en_US |
dc.contributor.affiliationother | Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Heverlee-Leuven (Belgium), Fax: (+32) (0)16327992 ; Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Heverlee-Leuven (Belgium), Fax: (+32) (0)16327992 | en_US |
dc.identifier.pmid | 20865719 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/78501/1/cphc_201000480_sm_miscellaneous_information.pdf | |
dc.identifier.doi | 10.1002/cphc.201000480 | en_US |
dc.identifier.source | ChemPhysChem | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
Files in this item
Remediation of Harmful Language
The University of Michigan Library aims to describe library materials in a way that respects the people and communities who create, use, and are represented in our collections. Report harmful or offensive language in catalog records, finding aids, or elsewhere in our collections anonymously through our metadata feedback form. More information at Remediation of Harmful Language.
Accessibility
If you are unable to use this file in its current format, please select the Contact Us link and we can modify it to make it more accessible to you.