Global Analysis of a-, b-, and c-Type Transitions Involving Tunneling Components of K = 0 and 1 States of the Methanol Dimer.

Spectral data on K = 0 and 1 levels of the methanol dimer available from previous and present Fourier transform microwave measurements have been interpreted globally, using a group-theoretically derived effective Hamiltonian and corresponding tunneling matrix elements to describe the splittings arising from a large number of tunneling motions. In the present work, 302 new measurements (40 K = 1-1 and 262 K = 1-0 transitions) were added to the previous data set to give a total of 584 assigned transitions with J </= 6. As a result of the rather complete K = 0, 1 data set for J </= 4, the lone-pair exchange tunneling splittings were obtained experimentally. Matrix element expansions in J(J + 1) used in the previous K = 0 formalism were modified to apply to K > 0, essentially by making a number of real coefficients complex, as required by the generalized internal-axis-method tunneling formalism. To reduce the number of adjustable parameters to an acceptable level in both the K = 0 and K = 1 effective Hamiltonians (used in separate K = 0 and K = 1 least-squares fits), a rather large number of assumptions concerning probably negligible parameters had to be made. The present fitting results should thus be considered as providing assurance of the group-theoretical line assignments as well as a nearly quantitative global interpretation of the tunneling splittings, even though they do not yet unambiguously determine the relative contributions from all 25 group-theoretically inequivalent tunneling motions in this complex, nor do they permit quantitative extrapolation to higher K levels. Copyright 1999 Academic Press.