Quantum Mechanical Investigation of the Atmospheric Reaction CH3O2 + NO

 
This item is provided by the institution :
University of Ioannina
Repository :
Repository of UOI Olympias
see the original item page
in the repository's web site and access all digital files if the item*
share



2006 (EN)
Quantum Mechanical Investigation of the Atmospheric Reaction CH3O2 + NO (EN)

A. Lesar, (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
A. Lesar, (EN)

The important stationary points on the potential energy surface of the reaction CH3O2 + NO have been investigated using ab initio and density functional theory techniques. The optimizations were carried out at the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels of theory while the energetics have been refined using the G2MP2, G3//B3LYP, and CCSD(T) methodologies. The calculations allow the proper characterization of the transition state barriers that determine the fate of the nascent association conformeric minima of methyl peroxynitrite. The main products, CH3O + NO2, are formed through either rearrangement of the trans-conformer to methyl nitrate and its subsequent dissociation or via the breaking of the peroxy bond of the cis-conformer to CH3O + NO2 radical pair. The important consequences of the proposed mechanism are (a) the allowance on energetic grounds for nitrate formation parallel to radical propagation under favorable external conditions and (b) the confirmation of the conformational preference of the homolytic cleavage of the peroxy bond, discussed in previous literature. (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

J. Phys. Chem. A (EN)

English

2006


American Chemical Society (EN)



*Institutions are responsible for keeping their URLs functional (digital file, item page in repository site)