Contact Transformations and Determinable Parameters in Spectroscopic Fitting Hamiltonians.
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 </= 20 unitless 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 kappa of the least-squares matrix, which is a measure of its invertibility in the presence of round-off and other errors. When kappa is very large, parameters must be removed from the fit until kappa becomes acceptably small, corresponding to procedures which lead to reduced Hamiltonians in molecular spectroscopy. We find that under certain circumstances kappa 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. Transferring this numerical and algebraic understanding to the more complicated four-dimensional methyl-top internal rotor problem supports the empirical observation that presently existing data sets for methanol and acetaldehyde are most efficiently fit using partially reduced Hamiltonians and further suggests that expanding the methanol data set to transitions involving levels of higher J, K, and v(t) would favor even more strongly the use of partially reduced fourth-order Hamiltonians.