A classical trajectory study of intramolecular vibrational relaxation and unimolecular decomposition in methyl hydroperoxide

Journal Article · Thu Jun 15 04:00:00 EDT 1989 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.456233· OSTI ID:6189439

Gai, H; Thompson, D L; Fisk, G A

This paper presents a quasiclassical trajectory study of the energy flow that occurs consequent to high-overtone excitations of either a CH or an OH local mode in methyl hydroperoxide, CH/sub 3/ OOH. The potential energy surface employed is an empirical one based on available spectroscopic, thermodynamic, and theoretical data. Energy initially localized in a CH stretch transfers irreversibly on the time scale of the calculations into the methyl bending modes within 0.2 ps. Transfer of energy out of the methyl group to the rest of the molecule occurs more slowly. An initially excited OH bond retains energy longer than does a CH bond and, unlike the energy transfer for an excited CH stretch, partial recurrences in the energy content of the OH mode occur for some excitations. Vibrational resonances are important in determining the rates and pathways of energy flow in the molecule. At total energies near 104 kcal/mol the rate of the O--O bond scission is twice as fast for OH excitation as it is for CH excitation.

• Research Organization: Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078(US); Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551
• OSTI ID: 6189439
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 90:12; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
DISSOCIATION
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
HYDROPEROXY RADICALS
HYDROXYL RADICALS
KINETICS
ORGANIC COMPOUNDS
RADICALS
REACTION KINETICS
RELAXATION
VIBRATIONAL STATES