THE MICROWAVE-SPECTRUM, STRUCTURE, AND TUNNELING MOTION OF THE SULFUR-DIOXIDE DIMER

The microwave spectrum of (SO2)2 has been reinvestigated using a pulsed beam Fourier-transform microwave spectrometer. Several new a-type transitions for the normal species and the a-type spectra of eight isotopically substituted species were measured. The spectra indicate that the SO2 dimer undergoes a high-barrier tunneling motion. Based on the analysis used for (H2O)2 by Coudert and Hougen [J. Mol. Spectrosc. 130, 86 (1988)], the internal motion is identified as a geared interconversion motion similar to that displayed by (H2O)2. From the analysis of the moments of inertia of the various isotopic species, an ac plane of symmetry is established for the dimer and the tilt angles of the C2 axes of each subunit relative to the line joining their centers of mass were determined. From Stark effect measurements, mu-a was redetermined and mu-c was shown to be nearly zero. Electrostatic calculations using distributed multipoles were carried out to explore the structure of this dimer.