Odd-hydrogen: An account on electronic structure, kinetics, and role of water in mediating reactions with atmospheric ozone. Just a catalyst or far beyond?

Abstract

Odd-hydrogen (any hydrogen-oxygen radical containing but a single hydrogen atom) plays a key role in atmospheric chemistry, particularly in the chemistry of ozone. Notable is also the role played by water in atmospheric and environmental chemistry. Without attempting a broad coverage, the present survey focuses on the electronic structure and dynamics of odd-hydrogen and related water-mediated complexes with impact in atmospheric chemistry, with emphasis on systems studied at the author's laboratory. Review oriented, it contains some ab initio results for HO3 and insights on hydrogen bonding and the role of water in mediating HOx reactions with ozone that have not appeared elsewhere. While providing an account on the status of the title topical issues, it is hoped that it may encourage new research directions. © 2013 Wiley Periodicals, Inc. Odd-hydrogen, the family of hydrogen-oxygen radicals with a single H-atom, plays a crucial role in the atmosphere but this may be affected by the presence of water, another key atmospheric constituent. Despite their small sizes, an accurate description of their electronic, thermochemical and kinetic properties is challenging. While introducing a new accurate ab initio scheme for the study of odd-hydrogen with up to three O atoms, a systematic cost-effective approach is undertaken for larger species, naked or water-dressed. © 2013 Wiley Periodicals, Inc.