Bend–Stretch Fermi Resonance in[formula]as Observed in the Two-Photon Absorption Spectroscopy of the 3p[formula]Rydberg State of NO2
✍ Scribed by Hiroshi Matsui; Eric E. Mayer; Edward R. Grant
- Publisher
- Elsevier Science
- Year
- 1996
- Tongue
- English
- Weight
- 342 KB
- Volume
- 175
- Category
- Article
- ISSN
- 0022-2852
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✦ Synopsis
Ionization-detected two-photon absorption spectroscopy has been used to resolve highly excited vibrational levels of the 3ps Rydberg state of NO 2 . Rotational assignments establish the exact positions of selected vibrational states, enabling the calculation of harmonic frequencies, anharmonic constants, and the cubic force constant, k 122 . Experimental results agree well with new CCSD(T)/[4s3p2d1f] ab initio calculations including Fermi resonance effects. It is shown that this system yields new information on NO / 2 , relating both to the most elementary type of bend-stretch Fermi resonance between ( 100) and (02 0 0), and to that coupling sets of higher vibrational states such as ( 110)-(03 1 0), (04 2 0)-(12 2 0), and (04 0 0)-(12 0 0)-( 200). Experimental values for Fermi matrix elements are consistent with values obtained by theory. From this consistency it is concluded that three-vibrational state mixing in the (04 0 0)-(12 0 0)-( 200) case can be well approximated in terms of two-state interactions.