Theoretical study of the NO β system

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Abstract
A b i n i t i o calculations including high levels of correlation treatment have been performed for the B 2Π–X 2Π β system of NO. The calculations are complicated by the fact that the B 2Π state gains considerable Rydberg character in the Franck–Condon region of this transition, as it approaches an avoided crossing with the C 2Π Rydberg state at shorter r values. The calculated lifetimes vary from 2.12 to 1.17 μs for v’=0 to 6, as compared with the recent measurements using laser induced fluorescence that vary from 2.00 to 0.85 μs. Nearly exact agreement with the experimental lifetimes can be achieved by shifting the transition moment function to larger r values to simulate a more rapid onset of the Rydbergization of the B 2Π state. The calculated Einstein coefficients for v’=6 to v‘=0–16 are in overall good agreement with experiment, but systematic differences remain that may be partially attributable to limitations in the calibration of the spectrometer.