DIRECT DETERMINATION OF THE RADIAL HAMILTONIAN FOR THE $X^{2}\Pi$ STATE OF OH, OD AND OT
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Date
1992
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Ohio State University
Abstract
The wide range of spectroscopic data for the $X^{2}\Pi$ ground state of the hydroxyl radical, including new results for high vibrational levels, are considered simultaneously in a novel procedure that provides an accurate estimate of the radial Hamiltonian. The isotopically self-consistent Hamiltonian contains the ``Born-Oppenheimer potential” in analytical form, together with functions describing spin-orbit coupling and firsth and second-order Born-Oppenheimer breakdown effects (including A-type doubling). Numerical solution of the radial Schr\""{o}dinger equation using the derived Hamiltonian yields eigenvalues that represent the entire body of spectroscopic line positions for all three isotopomers to within the accuracies of the measurements. The method offers significant advantages over traditional fitting methods, including a full and self-consistent account of centrifugal distortion.
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Author Institution: Department of Chemistry, Dalhousie University