Predicted Chemical Activation Rate Constants for HO2 + CH2NH: The Dominant Role of a Hydrogen-Bonded Pre-reactive Complex.

Abstract

The reaction of methanimine (CH2NH) with the hydroperoxy (HO2) radical has been investigated by using a combination of ab initio and density functional theory (CCSD(T)/CBSB7//B3LYP+Dispersion/CBSB7) and master equation calculations based on transition state theory (TST). Variational TST was used to compute both canonical (CVTST) and microcanonical (μVTST) rate constants for barrierless reactions. The title reaction starts with the reversible formation of a cyclic prereactive complex (PRC) that is bound by ∼11 kcal/mol and contains hydrogen bonds to both nitrogen and oxygen. The reaction path for the entrance channel was investigated by a series of constrained optimizations, which showed that the reaction is barrierless (i.e., no intrinsic energy barrier along the path). However, the variations in the potential energy, vibrational frequencies, and rotational constants reveal that the two hydrogen bonds are formed sequentially, producing two reaction flux bottlenecks (i.e., two transition states) along the reaction path, which were modeled using W. H. Miller's unified TST approach. The rate constant computed for the formation of the PRC is pressure-dependent and increases at lower temperatures. Under atmospheric conditions, the PRC dissociates rapidly and its lifetime is too short for it to undergo significant bimolecular reaction with other species. A small fraction isomerizes via a cyclic transition state and subsequent reactions lead to products normally expected from hydrogen abstraction reactions. The kinetics of the HO2 + CH2NH reaction system differs substantially from the analogous isoelectronic reaction systems involving C2H4 and CH2O, which have been the subjects of previous experimental and theoretical studies.