Contact Transformations and Determinable Parameters in Spectroscopic Fitting Hamiltonians

Published

February 1, 2000

Author(s)

M A. Mekhtiev, Jon T. Hougen

Abstract

In recent least-squares fits of torsion-rotation spectra of acetaldehyde and methanol it was found possible to adjust more fourth-order parameters than would be expected from traditional contact-transformation considerations. To investigate this discrepancy between theory and practice we have carried out numerical fitting experiments on the simpler three-dimensional (three-Eulerian-angle) asymmetric rotor problem, using J less than or equal} 20 energy levels generated artificially from a full orthorhombic Hamiltonian with quadratic through octic operators in the angular momentum components. Results are analyzed using the condition number κ of the least-squares matrix, which is a measure of its invertibility in the presence of round-off and other errors. When κ is very large, parameters must be removed from the fit until κ becomes acceptably small, corresponding to procedures which lead to reduced Hamiltonians in molecular spectroscopy. We find that under certain circumstances κ can be decreased to an acceptable level for Hamiltonians which are only partially reduced when compared to Watson A and S reductions. Some insight into this behavior is obtained from classical mechanics and from the concept of delayed contact transformations. Our attempts to transfer this understanding to the four-dimensional methyl-top internal rotor problem are complicated by the fact that both order of magnitude considerations and commutation relations are somewhat different.

Citation

Journal of Molecular Spectroscopy

Volume

199

Issue

No. 2

Pub Type

Journals

Keywords

asymmetric rotor, contact transformation, determinable parameters, methanol, reduced Hamiltonian, torsion-rotation

Citation

Mekhtiev, M. and Hougen, J. (2000), Contact Transformations and Determinable Parameters in Spectroscopic Fitting Hamiltonians, Journal of Molecular Spectroscopy (Accessed May 18, 2024)