Local mode excitation and direct unimolecular reaction rate measurements in tetramethyldioxetane

Journal Article · Sat Aug 15 04:00:00 EDT 1981 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.442253· OSTI ID:6467407

Cannon, B D; Crim, F F

Direct excitation of overtone vibrations combined with time-resolved detection of product chemiluminescence produces both overtone vibration excitation spectra and directly measured unimolecular decay rates of tetramethyldioxetane. The spectra show increasingly pure local mode character in higher vibrational levels and exhibit splittings which arise from nonequivalent sites occupied by methyl hydrogens. The temporal evolution of the signal reflects the unimolecular decomposition rate of the highly vibrationally excited molecule, and comparing the observed behavior to Rice--Ramsperger--Kassel--Marcus theory calculations shows that they adequately describe the decomposition if properly averaged over the thermal vibrational energy content of the molecule.

• Research Organization: Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706
• OSTI ID: 6467407
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 75:4; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMILUMINESCENCE
DECOMPOSITION
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
KINETICS
LUMINESCENCE
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
REACTION KINETICS
VIBRATIONAL STATES