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Fluorescence excitation spectroscopy of the Ar-HCO(X∼ <SUP>2</SUP>A',B∼ <SUP>2</SUP>A') van der Waals complex

Abstract

The fluorescence excitation spectrum of the Ar-HCO van der Waals complex in the vicinity of the B∼ 2A'-X∼2A' 000 band of free HCO is reported. At least eight bands associated with the complex have been detected. From the spectral shift of the lowest energy Ar-HCO band from the origin of the free HCO transition, we estimate the Ar-HCO binding energy in the excited electronic state to be at least 13 cm-1 greater than that in the ground state. Rotational analysis of some of the bands has been carried out, and average Ar-HCO separations (∼3.7 Å) in both electronic states determined. Several of the bands were assigned as hot bands from the first excited bend-stretch level (K=1) in the ground electronic state. From the derived A rotational constants, we conclude that the ArCO framework has an approximately T-shaped geometry in both electronic states. The decay lifetime of the upper state of the strongest Ar-HCO band was measured and was found to be somewhat smaller than those previously measured for low rotational levels of free HCO. With the high signal-to-noise ratio in this study, it was also possible to observe transitions in the free H13CO isotopomer. A rotational analysis of the B∼ 2A'-X∼2A' 000 band of the H13CO isotopomer was carried out. The isotopic shifts of the origins of the 301 and 201 bands were also measured, and a normal mode analysis of HCO(B∼) was carried out.


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