Comparison of overtone-induced and electronic photochemistry of liquid tert-butyl hydroperoxide: supporting evidence for vibrational mode selectivity
Journal Article
·
· J. Phys. Chem.; (United States)
The spectroscopy and unimolecular decomposition kinetics of tert-butyl hydroperoxide have been studied both in neat liquid and diluted in carbon tetrachloride. The data show that the tail of a transition to a repulsive electronic state extends to 540 nm but it is insignificant at longer wavelengths. The peak cross section of the 6-0 O-H overtone of tert-butyl hydroperoxide at 535 nm is estimated to be 5-24 times more intense than the electronic tail. tert-Butyl alcohol can be observed when photolyzing on the electronic tail, but no vibration-induced effect can be observed when photolyzing on the 5-0 O-H overtone. This study supports the contention that a small mode-selective effect is present in the gas-phase unimolecular decomposition of tert-butyl hydroperoxide when the 5-0 O-H overtone is excited by excluding the possibility of the electronic tail contributing to the nonstatistical component. Furthermore, the lifetime of this nonstatistical component is estimated to be longer than 0.1 ps.
- Research Organization:
- Stanford Univ., CA
- OSTI ID:
- 5476945
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:1; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKANES
BUTANE
CHEMICAL REACTIONS
CHEMISTRY
CROSS SECTIONS
DATA
DECOMPOSITION
DIMERS
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HARMONICS
HYDROCARBONS
HYDROPEROXY RADICALS
INFORMATION
INFRARED SPECTRA
LASERS
MONOMERS
NEODYMIUM LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
OSCILLATIONS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADICALS
RYDBERG STATES
SOLID STATE LASERS
SPECTRA
VIBRATIONAL STATES
400500* -- Photochemistry
ALKANES
BUTANE
CHEMICAL REACTIONS
CHEMISTRY
CROSS SECTIONS
DATA
DECOMPOSITION
DIMERS
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HARMONICS
HYDROCARBONS
HYDROPEROXY RADICALS
INFORMATION
INFRARED SPECTRA
LASERS
MONOMERS
NEODYMIUM LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
OSCILLATIONS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADICALS
RYDBERG STATES
SOLID STATE LASERS
SPECTRA
VIBRATIONAL STATES