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Ingolfsson, O.
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article
A-band methyl halide dissociation via electronic curve crossing as studied by electron energy loss spectroscopy
Abstract
<p>Excitation of the A -band low-lying electronic states in the methyl halides, CH<sub>3</sub>I, CH<sub>3</sub>Br, CH<sub>3</sub>Cl, and CH<sub>3</sub>F, has been investigated for the (n→ σ<sup>*</sup>) transitions, using electron energy loss spectroscopy (EELS) in the range of 3.5-7.5 eV. For the methyl halides, CH<sub>3</sub>I, CH<sub>3</sub>Br, and CH<sub>3</sub>Cl, three components of the Q complex (<sup>3</sup>Q<sub>1</sub>,<sup>3</sup>Q<sub>0</sub>, and<sup>1</sup>Q<sub>1</sub>) 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<sup>3</sup>Q<sub>0</sub>and<sup>1</sup>Q<sub>1</sub>states, with spin-orbit splitting observed and quantified against results from recent ab initio studies.</p>