On the calculation and interpretation of centrifugal distortion constants: A statistical basis for model testing: The calculation of the force field

Abstract Watson's treatment of the theory of centrifugal distortion effects is reviewed in detail and special attention is drawn to the relationship between Watson's treatment and the Kivelson-Wilson treatment. The relationship between the distortion parameters and the force field for XYZ-type molecules is also reviewed in order to remove ambiguities and inconsistencies presently found in the literature. Finally, procedures for exploiting the statistics associated with a least-squares analysis of the data are presented as a guide for model testing and for detecting misassignments and mismeasurements. A series of examples illustrating the results of these procedures are presented using the published spectra of SO 2 , OF 2 , SiF 2 and NSF. In the cases of OF 2 , SiF 2 and NSF, improved values for the rotational constants are obtained.

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