The attached extensive computational chemistry dataset involves detailed electronic structure (density functional theory - DFT) and kinetic calculation (master equation formalism) outputs for the reactions of isoprene and first generation oxidants with the hydroxyl radical. There are a total of 9 tabs in the Excel spreadsheet. The first two tabs provide the potential energy surfaces (PESs) of the isoprene+OH and isopOOH+OH (1st generation oxidant) reactions. The PESs are zero-point energy corrected and obtained at the M062x/maug-cc-pVTZ level of DFT. The third tab provides the reaction barriers for first and second generation 1,5-hydrogen atom shifts for two different isoprene peroxy radical isomers with several different DFT methods. The fourth and fifth tabs provide microcanonical rate constants for the reactions of isoprene and isopOOH with OH respectively. The remaining tabs give the rate constants for the 1,5-H shifts for four different isoprene peroxy radicals. The rate constants are computed using the M062x density functional and an average of 4 different DFT methods given in tab 3 for comparison. The average values are reported as the final rate constants determined by computational methods.

This dataset is associated with the following publication: Piletic, I., R. Howell, L. Bartolotti, T. Kleindienst, S. Kaushik, and E. Edney. Multigenerational Theoretical Study of Isoprene Peroxy Radical 1–5-Hydrogen Shift Reactions that Regenerate HOx Radicals and Produce Highly Oxidized Molecules. JOURNAL OF PHYSICAL CHEMISTRY A. American Chemical Society, Washington, DC, USA, 123(4): 906-919, (2019).