Journal of Chemical Physics, Vol.121, No.7, 2992-3008, 2004
Direct potential fit analysis of the X-1 Sigma(+) ground state of CO
A collection of 21 559 highly precise spectroscopic line positions from pure rotational and vibration-rotational spectra for seven isotopomers of carbon monoxide in the X (1)Sigma(+) ground electronic state has been employed in direct least-squares fits of the rovibrational Hamiltonian operator obtained from Watson's work [J. Mol. Spectrosc. 80, 411 (1980)] and that obtained by Herman and Ogilvie [Adv. Chem. Phys 103, 187 (1998)]. Fully analytical models are used for the various functions, including the Born-Oppenheimer internuclear potential function, and an account is taken of breakdown of the Born-Oppenheimer approximation. The resulting representations are more compact than currently available traditional U-kl/Delta(kl) extended Dunham descriptions, and they generate quantum-mechanical eigenvalues that reproduce reliably the spectroscopic line positions to within the associated measurement uncertainties. Rayleigh-Schrodinger perturbation theory has been used to calculate highly accurate rotational and centrifugal distortion constants B-upsilon-O-upsilon for nine isotopomers of carbon monoxide. These constants are just as successful at reconstructing the observed spectroscopic information as the quantum-mechanical eigenvalues of the fitted Hamiltonian operators. (C) 2004 American Institute of Physics.