Reanalysis of the Microwave Absorption Spectrum of Dimethyl Methylphosphonate and Its Internal Rotation Problem

Published

January 10, 2007

Author(s)

Nobukimi Ohashia, Jon T. Hougen

Abstract

The Fourier transform microwave spectrum of dimethyl methylphosphonate studied by us previously is reanalyzed here to obtain more physically reasonable parameters describing the various Coriolis-like couplings between overall rotation and internal rotation of the two methoxy methyl tops. In particular, we use exactly the same frequencies and spectral assignments as in our previous study, but the least squares fit is started from a rather different set of initial molecular parameters and is carried out with a slightly smaller set of adjustable parameters. The standard deviation of the fit is not significantly changed, but convergence to a rather different minimum in parameter space is obtained. This new minimum does not change the three rotational constants signficantly, but values for the twelve Coriolis coupling constants are dramatically rearranged, so that parameters arising from coupling between the two internal rotation motions are greatly reduced in magnitude. These new Coriolis constants bring the derived direction cosines for the methoxy methyl groups in the principal axis system into much better agreement with ab initio predictions. We have used our new parameters to derive internal rotation barrier heights for the two methyl groups of 281 cm-1 and 187 cm-1.

Citation

Journal of Molecular Spectroscopy

Volume

243

Pub Type

Journals

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Keywords

dimethymethylphosphonate, internal rotation, least-squares fit, methyl tops, microwave spectrum, tunneling Hamiltonian

Citation

Ohashia, N. and Hougen, J. (2007), Reanalysis of the Microwave Absorption Spectrum of Dimethyl Methylphosphonate and Its Internal Rotation Problem, Journal of Molecular Spectroscopy, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=841062 (Accessed October 6, 2024)