Computational study on the mechanism and kinetics for the reaction between HO₂ and n-propyl peroxy radical

Abstract

The negative temperature dependence for the HO2 + n-C3H7O2 reaction in lower temperature regime.

Computational Study on the Reaction of β-Hydroxyethylperoxy Radical with HO2 and Effects of Water Vapor

“…The calculated rate coefficient at 298 K and 1 atm, 2.34 × 10 –12 cm 3 molecule –1 s –1 , is slightly lower than the recommended value of 1.30 –0.48 +0.76 × 10 –11 cm 3 molecule –1 s –1 by Atkinson et al The rate coefficient is also close to that of the reaction between CH 3 CH 2 CH 2 O 2 and HO 2 (6.27 × 10 –12 cm 3 molecule –1 s –1 ), indicating that substituting −CH 3 by −OH does not greatly alter the kinetics of the reaction …”

“…However, with the large enough basis set used here, the CCSD­(T) calculations should grasp the dominant determinants even though T1 diagnostics for some transition states are higher than 0.03. Therefore, the CCSD­(T) method should be reliable . All geometrical optimizations were carried out using Gaussian 16 suite of programs and the F12 calculations were performed using the MOLPRO 2015.1 package. − …”

“…Therefore, the CCSD(T) method should be reliable. 11 All geometrical optimizations were carried out using Gaussian 16 suite of programs and the F12 calculations were performed using the MOLPRO 2015.1 package. 57−59 Kinetics.…”

“…There have been a number of experimental and computational studies on reactions between RO 2 and HO 2 . − Branching ratios of product channels change with the functional groups in −R. For the alkyl peroxy radicals, the reactions go through almost exclusively the R1a channel; while for the acyl and acetonyl peroxy radicals, the R1c channel becomes more significant.…”

Unknown Knowns: Case Studies in Uncertainties in the Computation of Thermochemical Parameters

“…Case study IV: CH 3 CH 2 CH 2 OO • n-Propyldioxy or the n-propyl peroxy radical is a key intermediate in the oxidation of propane and has thus been subject of many studies [59][60][61][62][63][64]. Cavity ringdown experiments backed up by electronic structure calculation pinpoint the G1G2 conformer (naming the ∠ OOCC first and the ∠ OCCC second; the third dihedral ∠ HCCC is almost always ignored or is less relevant) as the ground state [65][66][67].…”