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On the vibronic level structure in the NO3 radical Part III.w Observation of...

Stanton, J. F., and M. Okumura (2009), On the vibronic level structure in the NO3 radical Part III.w Observation of intensity borrowing via ground state mixing, PCCP, 2009, 4742-4744, doi:10.1039/b902252j.

The A2E00 ’ X2A 0 2 absorption spectrum exhibits vibronically allowed transitions from the ground state of NO3 to upper state levels having a00 1 and e 0 vibronic symmetries. This paper explores the coupling mechanisms that lend intensities to these features. While transitions to e 0 vibronic levels borrow intensity from the very stroñg B2E 0 ’ X2A 0 2 electronic transition, those to

00 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 B2E 0 electroñic state that permit

00 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.

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Tropospheric Composition Program (TCP)
Upper Atmosphere Research Program (UARP)