A Multi-Electronic-State Model to Interpret the Apparent Anomalous Arrhenius Curve of OH + HO$_2$ $\to$ O$_2$ + H$_2$O

TL;DR

This paper develops a multi-electronic-state model for the OH + HO2 reaction, explaining anomalous features in the Arrhenius curve and matching experimental data through detailed quantum calculations and a radiation model.

Contribution

It introduces a comprehensive multi-electronic-state model incorporating eight processes, explaining temperature-dependent rate constants and anomalous Arrhenius behavior in the reaction.

Findings

Reproduces the deep well in the Arrhenius curve near 1100K.

Shows rate constant independence below 500K due to exothermic pathways.

Predicts temperature dependence above 1242K due to activation of endothermic processes.

Abstract

A comprehensive multi-electronic-state model for OH + HO2 -> O2 + H2O has been developed through extensive multi-reference configuration interaction (MRCI) calculations, aiming to elucidate two key experimental observations: (1) an unusually deep and narrow ``well'' in the Arrhenius curve near 1100K and (2) a slightly negative temperature dependence in the range of 200K~500K. Moreover, the present model can serve as the basis for constructing multi-state Hamiltonian in multi-dimensional quantum dynamics calculations. The present model incorporates eight state-to-state processes involving OH (X) + HO2 (X/A), where three of four processes associated with HO2 (X) are exothermic, while those associated with HO2 (A) have three endothermic channels with the smallest barrier of 0.107 eV. At temperatures below 500K, the processes of HO2 (A) remain inaccessible, and the dominance of exothermic pathways results in a temperature-independent rate constant. To enable HO2 excitation at temperatures above 900K, a black-body radiation model that facilitates endothermic processes is introduced and reproduces the reduction factor of 0.3711 at 1100K. This value falls within the experimentally observed range of 0.30~0.76. Furthermore, a recombination process involving HO2 (A) is proposed to provide additional reduction of the rate constant. In conjunction with our previous works (J. Chem. Phys. 152 (2020), 134309 and J. Chem. Theory Comput. 20 (2024), 597), predicted values of the rate constants are well agree with experiments. At elevated temperatures exceeding 1242K (namely >0.107eV), the overall rate constant becomes temperature-dependent due to the activation of endothermic processes, leading to a distinct well in the Arrhenius curve between 900K and 1242K.