title: Molecular dynamics simulation of the HOONO decomposition and the HO*/NO2* caged radical pair in water.
abstract: The decomposition of HOONO in water gives nitrate and a reactive oxidant whose identity has been debated. This oxidant has been argued to be a hydroxyl radical, but reported yields of hydroxyl-radical-trapped products range from only 0% to 40% in different experiments. Other oxidants, including the metastable HOONO*, have been proposed as intermediates. CPMD metadynamics simulations reported here show the mechanism of HOONO decomposition in water and the nature of the caged radical pair.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
authors.forename: Hakan
authors.initials: H
authors.lastname: Gunaydin
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D008956:Models, Chemical; D009566:Nitrates / Q000737:chemistry*; D009569:Nitric Oxide; D030421:Peroxynitrous Acid / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D009566:Nitrates; D014867:Water; D030421:Peroxynitrous Acid; D009569:Nitric Oxide