Document Type
Honors Project On-Campus Access Only
Abstract
The acetonyl peroxy (CH 3 C(O)OO) + HO 2 reaction has many impacts on the chemical composition of the troposphere, with both a triplet and singlet surface pathway. The radical termination triplet pathway (R1) leads to the production of a hydroperoxide species and O 2 . This pathway competes with two singlet surface pathways. The first produces OH radical, O 2 , and acetoxy (R2), the second results in the formation of ozone and acetonol (R3). We utilized MultiWell2021 to solve the master equation for this reaction and RRKM theory to find microcanonical rate constants ( k (E)). We used both the 𝜔B97X-D and DLPNO-CCSD(T1) levels of theory to find the energies of all species. By including extensive conformational analysis of the system in our RRKM/ME simulations, we were able to find strong agreement between the predicted rate constant of the singlet surface using DLPNO-CCSD(T1) level of theory (1.31 x 10 -12 cm 3 molecule -1 s -1 ) and experimentally found values (1.65 ± 0.50 x 10 -12 cm 3 molecule -1 s -1 ). Our predicted rate constants for DLPNO-CCSD(T1) for the triplet surface, however, were in poor agreement with experimental results. As were the simulations conducted with the 𝜔B97X-D level of theory.
Recommended Citation
Madell, Joe, " Improved Computational Modeling of the Kinetics of the Acetonyl Peroxy + HO2 Reaction " (2025). Chemistry Honors Projects. 45.
https://digitalcommons.macalester.edu/chem_honors/45
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