Fine Structure, Dipole Moment, and Perturbation Analysis of a 3Π CO

Theedio‐frequency spectrum of the a 3Π state of carbon monoxide from 5 to 1000 MHz has been measured in a molecular beam electric resonance spectrometer. Lambda doubling transitions in Ω=2, J=2–8, v=0–5 and several in Ω=1 have been measured to an accuracy of 1 kHz as a function of electric field. A simultaneous least squares fit to optical and radio‐frequency data on a 3Π determines a set of fine structure constants which reproduce the optical and radio‐frequency measurements within their respective experimental errors. The vibrational dependence of the constants which determine the lambda doubling in the a 3Π state is accounted for. v=4 and 5 of a 3Π are perturbed by v=0 and 1 of a′ 3Σ+, respectively. Analysis of the radio‐frequency lambda doublings and perturbed optical spectra determines two vibration‐independent matrix elements of the Hamiltonian off diagonal in electronic state which describe the a 3Π‐a′ 3Σ+ interaction, 〈 a 3Π, v|AL+/2|a′ 3Σ+, v′〉/〈 v|v′〉=0.74± 0.15 cm−1 and 〈 a 3Π, v|BL+|a′ 3Σ+, v′...

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