3-hydroperoxypropanal is a small γ-ketohydroperoxide with importance in autoxidation and low-temperature combustion chemistry. It has been a model molecule in recent theoretical studies to compare automated reaction path exploration methods due to the richness of its chemistry.<sup>1</sup> The two main decomposition pathways from 3-hydroperoxypropanal are the homolytic O-O scission and the formation of a cyclic peroxide, which is the first step of the Korcek decomposition, but there are several other competing pathways as well. Here we present our calculated pressure- and temperature-dependent rate coefficients for the unimolecular decomposition of 3-hydroperoxypropanal at the CCSD(T)-F12/cc-pVTZ-F12//M06-2X/6-311++G** level using the KinBot<sup>2,3</sup> workflow code. KinBot allows the automated exploration and characterization of gas-phase reactions via barriers to yield rate coefficients and their uncertainty estimates. The barrierless homolytic scission reaction was modeled using variable reaction-coordinate transiton state theory using the CASPT2 multireference method. Finally, we also investigate the possibility of dynamical effects modifying the decomposition chemistry through Born-Oppenheimer molecular dynamics simulations.

Decomposition of 3-hydroperoxypropanal

ACS Spring Meeting 2021

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