Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

• Published in: Chemical physics letters Vol. 619; pp. 236 - 240
• Main Authors: Knap, Hasse C., Jørgensen, Solvejg, Kjaergaard, Henrik G.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05.01.2015
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2014.11.056

[Display omitted] •The atmospheric decomposition of 3-methyl-3-buten-1-ol is studied.•3-Methyl-3-buten-1-ol undergo a 1,5-CH H-shift reaction in the atmosphere.•F12, wB97X-D and M06-2X methods calculate similar barrier heights.•F12 energies had similar barrier height when calculated on different DFT optimized structures. The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHandHLYP, wB97X-D and M06-2X) with the aug-cc-pVTZ basis set. We found that the single-point CCSD(T)-F12A/VDZ-F12 energies calculated at the different DFT geometries had very similar barrier heights. The wB97X-D, M06-2X and CCSD(T)-F12A/VDZ-F12 barrier heights are comparable. The atmospheric decomposition of the MBO331 peroxy radical was found to undergo a 1,5-CH H-shift reaction with a reaction rate constant of about 1s−1.