title: Proton affinity of methyl nitrite and methyl peroxynitrite: implications for measuring branching ratios of alkyl nitrates and nitrites.
abstract: Geometry optimizations for methyl nitrite and methyl peroxynitrite, along with various protonated isomers for each, have been investigated using ab initio and density functional methods. The lowest energy structure for protonated methyl nitrite is a complex between CH3OH and NO(+). For methyl peroxynitrite, the lowest energy protonated structure is a complex between CH3OOH and NO(+). Their respective proton affinities are estimated to be 195.2 and 195.8 kcal/mol at the QCISD(T)/6-311++G(3df,3pd) level of theory. The results, compared with past studies, suggest an alternative method for directly measuring branching ratios for production of alkyl nitrates and nitrites.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, USA.
authors.forename: Rose M
authors.initials: RM
authors.lastname: Ravelo
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Francisco
mesh_terms: D003198:Computer Simulation; D008956:Models, Chemical; D009566:Nitrates / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D030421:Peroxynitrous Acid / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory
chemical_list: D009566:Nitrates; D009573:Nitrites; D010545:Peroxides; D011522:Protons; C532428:methyl peroxynitrite; D030421:Peroxynitrous Acid; C037538:methyl nitrite