Computational Study of Oxidation Products Derived from 4-hydroxy Isoprene (4-ISOPO) Radicals

Authors

Manik R. Reddy, Macalester CollegeFollow

Document Type

Honors Project On-Campus Access Only

Abstract

Isoprene, an abundant biogenic hydrocarbon, is readily oxidized by the hydroxyl radical, significantly impacting atmospheric chemistry and the global radiation budget. In high isoprene emission regions, intramolecular hydrogen shifts within a subset of isoprene 4-hydroxy peroxy (4-ISOPOO) intermediates dictate subsequent oxidation chemistry. However, the corresponding rate coefficients and functionalized product yields remain uncertain. This study attempts to address these limitations by conducting reaction simulations using computed ωB97X-D/def2-TZVP energies for pathways that oxidize isoprene into carbonyl species downstream of 4-ISOPOO. RRKM master equation simulations at low temperatures (200-310 K) yielded a pressure-independent pseudo steady-state cis: trans ratio of 0.81:0.19 for the allyl precursor of 4-ISOPOO. Additionally, Transition State Theory calculations generated rate coefficients of 4.6 s^-1 for the 1,6 H-shift and 6.3 × 10^-4 s^-1 for the 1,5 H-shift in 4-ISOPOO at 298.15 K.

Recommended Citation

Reddy, Manik R., "Computational Study of Oxidation Products Derived from 4-hydroxy Isoprene (4-ISOPO) Radicals" (2021). Chemistry Honors Projects. 33.
https://digitalcommons.macalester.edu/chem_honors/33