| Autor: |
Morozov AN; Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States., Medvedkov IA; Samara National Research University, Samara 443086, Russian Federation.; Lebedev Physical Institute, Samara 443011, Russian Federation., Azyazov VN; Samara National Research University, Samara 443086, Russian Federation.; Lebedev Physical Institute, Samara 443011, Russian Federation., Mebel AM; Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2021 May 13; Vol. 125 (18), pp. 3965-3977. Date of Electronic Publication: 2021 Apr 30. |
| DOI: |
10.1021/acs.jpca.1c01545 |
| Abstrakt: |
Quantum chemical calculations of the C 6 H 5 O 2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O( 3 P) and phenyl + O 2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multireference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O( 3 P) reaction. Stationary points on the C 6 H 5 O 2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multireference character of the wave function. Conventional, variational, and variable reaction coordinate transition-state theories were employed in Rice-Ramsperger-Kassel-Marcus master equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. The main bimolecular product channels of the phenoxy + O( 3 P) reaction are concluded to be para/ortho -benzoquinone + H, 2,4-cyclopentadienone + HCO and, at high temperatures, also phenyl + O 2 . The main bimolecular product channels of the phenyl + O 2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures and phenoxy + O( 3 P) at higher temperatures. For both the phenoxy + O( 3 P) and phenyl + O 2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
