Peroxy and alkoxy radicals from 2-methyl-3-buten-2-ol.
Quantum mechanical calculations were used to determine the structure and energetics of peroxy radicals (P1 and P2) and alkoxy radicals (A1-A3) formed in the atmospheric degradation of 2-methyl-3-buten-2-ol. At the level of theory employed (B3LYP/6-31G(d,p)) low energy conformers were identified with zero, one, or two hydrogen bonds. The beta C-C scission (decomposition) reactions are computed to occur with low barriers, and the 1,5 H-shift (isomerization) reaction of A2 is computed to be of negligible importance. Scission 2 of A2 is computed to be about 93% of the fate of A2, with the balance being scission 1. The new BB1K functional of Truhlar was employed to investigate activation barriers for single intramolecular H-atom transfers across the OH...O* hydrogen bonds, but the barriers to these reactions appear to be too high for these reactions to be important. Extensive searches for transition states for simultaneous double intramolecular H-atom transfer across OH...OH...O* hydrogen bond pairs were unsuccessful.
Chemistry Department, State University of New York, Environmental Science and Forestry, Syracuse, NY 13210, USA. tsdibble@syr.edu
Theodore S
TS
Dibble
Trang
T
Pham
D000438:Alcohols / Q000737:chemistry*; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D000439:Pentanols / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D011789:Quantum Theory
D000438:Alcohols; D005609:Free Radicals; D000439:Pentanols; D010545:Peroxides; C059688:alkoxyl radical; C027250:3-hydroxy-3-methylbutene