Application of direct potential fitting to line position data for the X (1)Sigma(+) and A (1)Sigma(+) states of LiH.
A collection of 9089 spectroscopic LiH line positions, of widely varying precision, which sample 84.9% and 98.6% of the A and X state well depths, respectively, have been employed in a direct least-squares fit of the effective potential energy and Born-Oppenheimer breakdown functions for the two states. For the four isotopomers (6)LiH, (7)LiH, (6)LiD, and (7)LiD, the data comprise both pure rotational and vibration-rotational transitions within the ground state, as well as rotationally resolved transitions in the A-X system. Despite the unusual shape and associated anomalous properties of the A state potential, no special features or considerations were required in the direct potential fitting approach. The reduced standard deviation of the fit was close to unity, indicating that the quantum mechanical eigenvalues calculated from the fully analytical functions of the Hamiltonians of the two states, which are characterized by a total of only 53 fitted parameters, represent the line positions, on average, to within the estimated uncertainties. A quantum mechanical calculation of the molecular constants G(nu), B(nu), D(nu), H(nu), L(nu), M(nu), N(nu), and O(nu) from the fitted potential for the A state of (7)LiH confirms that the usual polynomial expansion in J(J+1) is an unsatisfactory representation for the rotational terms of the lowest vibrational levels.
Coxon
John A
JA
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H4J3, Canada. John.Coxon@Dal.Ca
Dickinson
Cameron S
CS