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Mechanism of Atmospheric Photooxidation of Aromatics: A Theoretical Study

Andino, Jean M. and Smith, James N. and Flagan, Richard C. and Goddard, William A., III and Seinfeld, John H. (1996) Mechanism of Atmospheric Photooxidation of Aromatics: A Theoretical Study. Journal of Physical Chemistry, 100 (26). pp. 10967-10980. ISSN 0022-3654. doi:10.1021/jp952935l.

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The mechanisms of atmospheric photooxidation of aromatic compounds are of seminal importance in the chemistry of the urban and regional atmosphere. It has been difficult to experimentally account for the full spectrum of oxidation products in laboratory studies. In an effort to fully elucidate the atmospheric reaction pathways for the aromatic−OH reaction, we have conducted theoretical calculations on aromatic intermediates. Energies have been determined for these intermediates by using semiempirical UHF/PM3 geometry optimizations combined with ab initio calculations using density functional theory (DFT). A hybrid DFT model, the Becke3 parameter function with the nonlocal correlation function of Lee, Yang, and Parr, was used in conjunction with the 6-31G(d,p) basis set to study the intermediate structures. Full mechanisms for the OH-initiated photooxidation of toluene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, and m-ethyltoluene are developed. The lowest energy intermediates have been determined, and predicted products from these structures are compared to available experimental product data. These studies serve to refine proposed mechanisms currently available for toluene, m-xylene, and p-xylene, while providing new information on the 1,2,4-trimethylbenzene and m-ethyltoluene reaction pathways.

Item Type:Article
Related URLs:
URLURL TypeDescription
Smith, James N.0000-0003-4677-8224
Flagan, Richard C.0000-0001-5690-770X
Goddard, William A., III0000-0003-0097-5716
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 1996 American Chemical Society. Received: October 3, 1995; In Final Form: December 13, 1995. This work was supported by the U.S. Environmental Protection Agency Center for Airborne Organics (R-819714-01-0), National Science Foundation Grant ATM-9307603, the Coordinating Research Council (A-5-1), and the Chevron Corporation. The authors thank J. K. Perry and T. Jungkamp for helpful discussions.
Funding AgencyGrant Number
Environmental Protection Agency (EPA)R-819714-01-0
Coordinating Research CouncilA-5-1
Chevron CorporationUNSPECIFIED
Issue or Number:26
Record Number:CaltechAUTHORS:20160607-114130563
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Official Citation:Mechanism of Atmospheric Photooxidation of Aromatics:  A Theoretical Study Jean M. Andino, James N. Smith, Richard C. Flagan, William A. Goddard, and John H. Seinfeld The Journal of Physical Chemistry 1996 100 (26), 10967-10980 DOI: 10.1021/jp952935l
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67727
Deposited By: George Porter
Deposited On:08 Jun 2016 14:28
Last Modified:18 Apr 2023 18:51

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