Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals
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Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals. / Knap, Hasse Christian; Jørgensen, Solvejg.
I: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Bind 121, Nr. 7, 2017, s. 1470-1479.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals
AU - Knap, Hasse Christian
AU - Jørgensen, Solvejg
PY - 2017
Y1 - 2017
N2 - We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H-shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1 with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H-shift reactions are much faster than the reactions with NO and HO2 under most atmospheric conditions and must be included in the atmospheric models when hydroperoxy acyl peroxy radicals are oxidized. Finally, we have observed that H-shift reactions in a pentane acyl peroxy radical (C5-AOO) is fast (>1 s–1); this can have a significant influence on the possible formation of large acyl peroxy nitrate molecules
AB - We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H-shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1 with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H-shift reactions are much faster than the reactions with NO and HO2 under most atmospheric conditions and must be included in the atmospheric models when hydroperoxy acyl peroxy radicals are oxidized. Finally, we have observed that H-shift reactions in a pentane acyl peroxy radical (C5-AOO) is fast (>1 s–1); this can have a significant influence on the possible formation of large acyl peroxy nitrate molecules
U2 - 10.1021/acs.jpca.6b12787
DO - 10.1021/acs.jpca.6b12787
M3 - Journal article
C2 - 28145705
VL - 121
SP - 1470
EP - 1479
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 7
ER -
ID: 176370696