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Issue 23, 2009
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On the vibronic level structure in the NO3 radical
Part III. Observation of intensity borrowing via ground state mixing

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Abstract

The Ã2E″← [X with combining tilde]2A′2 absorption spectrum exhibits vibronically allowed transitions from the ground state of NO3 to upper state levels having a″1 and e′ vibronic symmetries. This paper explores the coupling mechanisms that lend intensities to these features. While transitions to e′ vibronic levels borrow intensity from the very strong [B with combining tilde]2E′← [X with combining tilde]2A′2 electronic transition, those to a″1 levels involve only negligible upper-state borrowing effects. Rather, it is the vibronic mixing of the ground vibronic level of NO3 with vibrational levels in the [B with combining tilde]2E′ electronic state that permit the a″1 levels to be seen in the spectrum. These ideas are supported by vibronic coupling calculations. The fact that the intensities of features corresponding to the two different vibronic symmetries are comparable is thus accidental.

Graphical abstract: On the vibronic level structure in the NO3 radical Part III. Observation of intensity borrowing via ground state mixing

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Publication details

The article was received on 02 Feb 2009, accepted on 27 Apr 2009 and first published on 18 May 2009


Article type: Paper
DOI: 10.1039/B902252J
Citation: Phys. Chem. Chem. Phys., 2009,11, 4742-4744
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    On the vibronic level structure in the NO3 radical

    J. F. Stanton and M. Okumura, Phys. Chem. Chem. Phys., 2009, 11, 4742
    DOI: 10.1039/B902252J

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