title: Ozonolysis of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal: kinetics and mechanisms.
abstract: A combined density functional theory and transition-state theory study of the mechanisms and reaction coefficients of gas-phase ozonolysis of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal is presented. The geometries, energies, and harmonic vibrational frequencies of each stationary point were determined by B3LYP/6-31(d,p), MPW1K/cc-pVDZ, and BH&HLYP/cc-pVDZ methods. According to the calculations, the ozone 6-methyl-5-hepten-2-one reaction is faster than the ozone 6-hydroxy-4-methyl-4-hexenal reaction, but both are slower than the ozone geraniol-trans reaction. By using the BH&HLYP/cc-pVDZ data, a global rate coefficient of 5.9 x 10(-16) cm(3) molecule(-1) s(-1) was calculated, corresponding to the sum of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal reactions with the ozone. These results are in good agreement with the experimental studies.
authors.affiliation: Departamento de Físico-Química, Universidade Federal do Rio de Janeiro, Instituto de Química, Ilha do Fundão, Rio de Janeiro, Brasil.
authors.forename: Tadeu
authors.initials: T
authors.lastname: Leonardo
authors.forename: Edilson Clemente
authors.initials: EC
authors.lastname: da Silva
authors.forename: Graciela
authors.initials: G
authors.lastname: Arbilla
mesh_terms: D006591:Hexobarbital / Q000031:analogs & derivatives* / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D010087:Oxides / Q000737:chemistry; D010126:Ozone / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: C531162:6-hydroxy-4-methyl-4-hexenal; D006838:Hydrocarbons; D007659:Ketones; D010087:Oxides; C029750:methylheptenone; D010126:Ozone; D006591:Hexobarbital