The Radial Hamiltonians for the X(1)Sigma(+) and B(1)Sigma(+) States of HCl.
All literature vibration-rotational and pure rotational transition energies for the ground X(1)Sigma(+) electronic state of H(35)Cl, H(37)Cl, D(35)Cl, and D(37)Cl, along with the entire collection of electronic B(1)Sigma(+) --> X(1)Sigma(+) emission data for the four isotopomers, have been used in a least-squares fit of compact analytic Born-Oppenheimer potential functions for the B(1)Sigma(+) and X(1)Sigma(+) electronic states. Additional functions related to the adiabatic and nonadiabatic corrections have also been determined. Separate least-squares fits were made according to the hamiltonian operators of J. K. G. Watson (J. Mol. Spectrosc. 80, 411 (1980)) and R. M. Herman and J. F. Ogilvie (Adv. Chem. Phys. 103, 187 (1998)). The results from the separate analyses demonstrate clearly that the two hamiltonian operators are essentially equivalent, both achieving equally satisfactory representations of the spectral data, and furnishing virtually identical Born-Oppenheimer potential functions. Fully quantum-mechanical vibrational eigenvalues and rotational perturbation series parameters B(v)-O(v) are presented for the lower levels of the X(1)Sigma(+) ground state for which infrared and/or microwave data are available (v" </= 7 for H(35)Cl and H(37)Cl, v" </= 10 for D(35)Cl and D(37)Cl). These parameters collectively reproduce the corresponding spectroscopic line positions included in our fit to within the uncertainties of the measurements. Copyright 2000 Academic Press.
Coxon
JA
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3, Canada
Hajigeorgiou
PG