Altitude profile of the OH radical complex with water in Earth’s atmosphere: a quantum mechanical approach

Abstract

The hydroxyl radical (OH) is important in both tropospheric and stratospheric chemical processes that occur in Earth’s atmosphere. The OH radical can also strongly hydrogen-bond to form complexes with other atmospheric constituents, like water molecules. Consequently, there is potential for altered reaction dynamics/kinetics as a result of this complexation. Without direct measurements of the abundances of such complexes in Earth’s atmosphere, we have adopted a theoretical approach to determine such abundances. Electronic structures, enthalpies and free Gibbs energies of formation of OH, H₂O and H₂O-HO were calculated at CCSD(T) and QCISD(T) levels of theory with either 6–311++G(2d,2p) or aug-cc-pVTZ basis. Statistical thermodynamic concepts were then used to assess the abundance of the complex as function of altitude.