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The hydroperoxyalkyl radicals (.QOOH) are known to play a significant role incombustion and tropospheric processes, yet their direct spectroscopic detectionremains challenging. In this study, we investigate molecular stereo-electroniceffects influencing the kinetic and thermodynamic stability of a .QOOH alongits formation path from the precursor, alkylperoxyl radical (ROO.), and thedepletion path resulting in the formation of cyclic ether + .OH. We focus onreactive intermediates encountered in the oxidation of acyclic hydrocarbonradicals: ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, and theiralicyclic counterparts: cyclohexyl, cyclohexenyl, and cyclohexadienyl. Wereport reaction energies and barriers calculated with the highly accuratemethod Weizmann-1 (W1) for the channels: ROO. <=> .QOOH, ROO. <=> alkene +.OOH, .QOOH <=> alkene + .OOH, and .QOOH <=> cyclic ether + .OH. Using W1results as a reference, we have systematically benchmarked the accuracy ofpopular density functional theory (DFT), composite thermochemistry methods, andan explicitly correlated coupled-cluster method. We ascertain inductive,resonance, and steric effects on the overall stability of .QOOH andcomputationally investigate the possibility of forming more stable species.With new reactions as test cases, we probe the capacity of various ab initiomethods to yield quantitative insights on the elementary steps of combustion.

physical chemistry chemical physics/pccp. physical chemistry chemical physics

Stereo-Electronic Factors Influencing the Stability of Hydroperoxyalkyl  Radicals: Transferability of Chemical Trends across Hydrocarbons and ab  initio Methods