ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The microwave spectrum of PO+ has been detected in discharges in mixtures of PF3, O2, and Ar. Precise frequencies were obtained for 48 rotational transitions in the range 140–470 GHz, including all vibrational states v=0–11. Eight of the lines measured were transitions of P18O+, obtained using 18O2. To fit all of these to a mass independent Dunham expansion, a Watson ΔO01 parameter was required to describe the oxygen isotope shift. From the combined analysis a set of eight mass independent Dunham parameters Ukl and the Dunham potential constants a1–a5 were extracted. Harmonic and anharmonic vibrational constants are obtained from the microwave analysis and compare very well to published results from low resolution emission spectroscopy; the final microwave values of re and ωe are 1.424 992 7(4) A(ring) and 1411.5(3) cm−1. These and the a1–a5 coefficients are in very good agreement with the results of several ab initio calculations we have done on PO+ (and other 22 electron diatomics), including those that were used to define the limits of our initial search for the microwave spectrum of PO+. The vibrational temperature of PO+ in our magnetically enhanced negative glow discharge was found to be very high, near 5500 (500) K. Some additional observations of the microwave spectrum of SiF+, used as a probe of the dynamical and chemical behavior of SiF+ in discharges, are also reported.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.459771
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