TY - JOUR
T1 - Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)
AU - Knap, Hasse Christian
AU - Jørgensen, Solvejg
AU - Kjærgaard, Henrik Grum
PY - 2015
Y1 - 2015
N2 - 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 1 s-1.
AB - 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 1 s-1.
U2 - 10.1016/j.cplett.2014.11.056
DO - 10.1016/j.cplett.2014.11.056
M3 - Journal article
AN - SCOPUS:84920725720
SN - 0009-2614
VL - 619
SP - 236
EP - 240
JO - Chemical Physics Letters
JF - Chemical Physics Letters
ER -