P-TYPE DOUBLING IN THE INFRARED SPECTRUM OF NO-HF
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Date
1990
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Publisher
Ohio State University
Abstract
The HF stretching band of the NO-HF open-shell complex has been recorded using a molecular-beam optothermal spectrometer. The spectrum exhibits P-type doubling indicative of an unpaired electron spin coupled to the rotational angular momentum of a bent complex with substantially quenched electron orbital angular momentum. From $\bar{B}^{\prime\prime}=0.111320(17) cm^{-1}$, and an off-axis angle for the NO of $30^{\circ}$, the zero-point center-of-mass separation is estimated to be $3.4396(3) {\AA}$. The HF frequency shift of $-84 cm^{-1}$ indicates that the complex is hydrogen bonded, and the spectral intensities imply that the HF axis is aligned closely to the center-of-mass axis and the NO is off axis by $30 \pm 15^{\circ}$. The Renner-Teller-like orbital quenching parameter is somewhat larger than the spin-orbit constant in the free NO molecule and increases substantially upon vibrational excitation. The transitions in this band exhibit vibrational predissociation broadening of $200 \pm 40$ MHz (FWHM), similar to that observed for a number of closed-shell hydrogen-bonded HF complexes
Description
Author Institution: Department of Chemistry, Brookhaven National Laboratory; Molecular Physics Division, National Institute of Standards and Technology