High vibrational overtone photochemistry of 1-cyclopropylcyclobutene
Laser excitation of high CH stretching overtones has been used to induce the isomerization of 1-cyclo-propylcyclobutene (CYCB) to 2-cyclopropyl-1,3-butadiene. Values of the unimolecular isomerization rate constant, k(E), have been measured for excitation of the fifth cyclobutenyl and cyclopropyl methylenic CH stretching overtones. The values of k(E) depend only on total energy and do not show any identifiable dependence on which type of CH overtone is excited. In particular, excitation of the cyclobutenyl methylenic CH overtone transition does not lead to any observable enhancement in k(E) relative to excitation of the cyclopropyl methylenic CH overtone transition. The value of k(E) for excitation of the cyclobutenyl methylenic CH overtone transition does not increase even when 99.8% of the excited molecules are collisionally deactivated prior to reaction. This leads to the conclusion that any vibrational energy which is introduced into the cyclobutenyl ring by overtone excitation is randomized over both the cyclobutenyl and cyclopropyl rings prior to reaction. 4 figures.
- Research Organization:
- Lawrence Berkeley Lab., CA
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5580992
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:20; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ALKANES
ALKENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHROMATOGRAPHY
CYCLOALKANES
CYCLOALKENES
DATA
DATA ACQUISITION
DIENES
DYE LASERS
ELECTROMAGNETIC RADIATION
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
IONIZATION
ISOMERIZATION
KINETICS
LASER RADIATION
LASERS
LIQUID LASERS
LOW PRESSURE
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOACOUSTIC EFFECT
PHOTOIONIZATION
POLYENES
PRESSURE DEPENDENCE
RADIATIONS
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TIME DEPENDENCE
YIELDS