title: New insight into the gas-phase bimolecular self-reaction of the HOO radical.
abstract: The singlet and triplet potential energy surfaces (PESs) for the gas-phase bimolecular self-reaction of HOO*, a key reaction in atmospheric environments, have been investigated by means of quantum-mechanical electronic structure methods (CASSCF and CASPT2). All the reaction pathways on both PESs consist of a first step involving the barrierless formation of a prereactive doubly hydrogen-bonded complex, which is a diradical species lying about 8 kcal/mol below the energy of the reactants at 0 K. The lowest energy reaction pathway on both PESs is the degenerate double hydrogen exchange between the HOO* moieties of the prereactive complex via a double proton transfer mechanism involving an energy barrier of only 1.1 kcal/mol for the singlet and 3.3 kcal/mol for the triplet at 0 K. The single H-atom transfer between the two HOO* moieties of the prereactive complex (yielding HOOH + O2) through a pathway keeping a planar arrangement of the six atoms involves a conical intersection between either two singlet or two triplet states of A' and A" symmetries. Thus, the lowest energy reaction pathway occurs via a nonplanar cisoid transition structure with an energy barrier of 5.8 kcal/mol for the triplet and 17.5 kcal/mol for the singlet at 0 K. The simple addition between the terminal oxygen atoms of the two HOO* moieties of the prereactive complex, leading to the straight chain H2O4 intermediate on the singlet PES, involves an energy barrier of 7.3 kcal/mol at 0 K. Because the decomposition of such an intermediate into HOOH + O2 entails an energy barrier of 45.2 kcal/mol at 0 K, it is concluded that the single H-atom transfer on the triplet PES is the dominant pathway leading to HOOH + O2. Finally, the strong negative temperature dependence of the rate constant observed for this reaction is attributed to the reversible formation of the prereactive complex in the entrance channel rather than to a short-lived tetraoxide intermediate.
authors.affiliation: Institut d'Investigacions Químiques i Ambientals de Barcelona, CSIC, Jordi Girona 18-26, 08034-Barcelona, Catalonia, Spain. anglada@iiqab.csic.es
authors.forename: Josep M
authors.initials: JM
authors.lastname: Anglada
authors.forename: Santiago
authors.initials: S
authors.lastname: Olivella
authors.forename: Albert
authors.initials: A
authors.lastname: Solé
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D044367:Phase Transition
chemical_list: D005609:Free Radicals; D006859:Hydrogen; D010100:Oxygen