Anomalous V/sub 1/reverse arrowN vibrational band intensities in the low energy electron impact spectra of trans-dienes
A detailed examination of the extremely broad and diffuse vibrational structure of the V/sub 1/reverse arrowN allowed valence transition in trans-1,3-butadiene, three related trans-dienes (cis-1,3-pentadiene, trans, trans-2,4-hexadiene, and 2,3-dimethyl-1,3-butadiene), and the cis-diene 1,3-cyclohexadiene has shown that the effect observed previously by Doering, in which the lower vibrational bands of the transition are enhanced in intensity relative to the higher bands at low incident electron energies, occurs in all the trans-dienes studied. This result shows that the effect cannot be due to an underlying, forbidden electronic transition. It appears that in these trans-dienes, the configurational composition of the V/sub 1/ ''state'' depends on the geometry of the molecule and that the configurational components of the excited state that are important in the vertical transition have different electron impact excitation cross sections than those that are important in the adiabatic transition. These results suggest that electron energy loss spectroscopy is a unique tool for probing the configurational composition of certain highly distorted excited states.
- Research Organization:
- Laboratory of Chemical Physics, National Institute of Arthritis, Metabolism and Digestive Diseases, National Institutes of Health, Bethesda, Maryland 20205
- OSTI ID:
- 7053785
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 73:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
BUTADIENE
ELECTRON-MOLECULE COLLISIONS
DIENES
EXCITATION
PENTADIENES
ENERGY-LEVEL TRANSITIONS
EXPERIMENTAL DATA
VIBRATIONAL STATES
COLLISIONS
DATA
ELECTRON COLLISIONS
ENERGY LEVELS
EXCITED STATES
HYDROCARBONS
INFORMATION
MOLECULE COLLISIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
640304* - Atomic
Molecular & Chemical Physics- Collision Phenomena