Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
96 (1992), S. 2740-2744
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We have measured vibrational branching ratios for 2σ−1u photoionization of N2 in an effort to elucidate fundamental aspects of continuum channel coupling. Calculations have shown that photoejection of a 2σu electron from N2 should be influenced by a shape resonance in the 3σg →εσu photoionization channel and that this continuum channel coupling can result in deviations from Franck–Condon behavior for the resulting N+2(B 2Σ+u) ion. In the present study, the N2 molecules are ionized by monochromatic synchrotron radiation (25〈hν〈55 eV) and dispersed fluorescence is measured to determine the vibrational branching ratios v'=1/v'=0 and v'=2/v'=0 for the N+2(B 2Σ+u) state. The observed branching ratios are enhanced at hν≈30 eV and we attribute this Franck–Condon breakdown to continuum coupling between the 2σ−1u and 3σ−1g ionization channels. However, our results exhibit significant discrepancies with theory. The areas of agreement and disagreement suggest useful avenues of further study to clarify the nature of continuum channel coupling in molecular photoionization.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.462022
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