Article

A-band methyl halide dissociation via electronic curve crossing as studied by electron energy loss spectroscopy.

Department of Physics, Sophia University, Tokyo 102-8554, Japan.
The Journal of chemical physics (impact factor: 3.09). 08/2010; 133(5):054304. DOI:10.1063/1.3464483 pp.054304
Source: PubMed

ABSTRACT Excitation of the A-band low-lying electronic states in the methyl halides, CH(3)I, CH(3)Br, CH(3)Cl, and CH(3)F, has been investigated for the (n-->sigma*) transitions, using electron energy loss spectroscopy (EELS) in the range of 3.5-7.5 eV. For the methyl halides, CH(3)I, CH(3)Br, and CH(3)Cl, three components of the Q complex ((3)Q(1), (3)Q(0), and (1)Q(1)) were directly observed, with the exception of methyl fluoride, in the optically forbidden EELS experimental conditions of this investigation. The effect of electronic-state curve crossing emerged in the transition probabilities for the (3)Q(0) and (1)Q(1) states, with spin-orbit splitting observed and quantified against results from recent ab initio studies.

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Keywords

A-band low-lying electronic states
 
components
 
EELS
 
electron energy loss spectroscopy
 
electronic-state curve
 
methyl fluoride
 
methyl halides
 
optically forbidden EELS experimental conditions
 
recent ab initio studies