Bend-stretch Fermi resonance in NO2+ observed by delayed pulsed-field ionization zero-electron kinetic energy photoelectron spectroscopy
✍ Scribed by Hiroshi Matsui; Jane M. Behm; Edward R. Grant
- Book ID
- 104307545
- Publisher
- Elsevier Science
- Year
- 1996
- Tongue
- English
- Weight
- 844 KB
- Volume
- 159
- Category
- Article
- ISSN
- 0168-1176
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✦ Synopsis
By means of zero-electron kinetic energy (ZEKE) threshold photoelectron spectroscopy, we examine bend-stretch Fermi resonance in NO;. Accurate fundamental frequencies are obtained by using the (000) 3~0 Rydberg state as a reference state for all ionic vibrational ZEKE spectra. The degree of ( 100)-(02°0) Fermi resonance observed in NO; is comparable to that found in the NO* 3pu Rydberg state, and results for both systems agree well with recent CCSD(T) and MRD-CI a6 ink calculations. Comparison of the vibrational frequencies of the 3pa Rydberg state and the cation suggests that the presence of the Rydberg electron slightly perturbs the harmonic potential and its second-order anharmonicities, but has little effect on the cubic coupling term associated with core Fermi resonance.