Local mode excitation and direct unimolecular reaction rate measurements in tetramethyldioxetane
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), Vol. 75:4
- Country of Publication:
- United States
- Language:
- English
Similar Records
Unimolecular dynamics of internal energy selected molecules. Technical progress report. [Tetramethyldioxetane; t-butylhydroperoxide]
Unimolecular decay dynamics of internal energy selected molecules. Technical progress report. [Tetramethyldioxetane]
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC OXYGEN COMPOUNDS
DECOMPOSITION
CHEMICAL REACTION KINETICS
CHEMILUMINESCENCE
EXCITATION
EXCITED STATES
PEROXIDES
VIBRATIONAL STATES
CHEMICAL REACTIONS
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
KINETICS
LUMINESCENCE
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
REACTION KINETICS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)