Accessibility navigation


Rotational spectra induced by vibrations

Mills, I., Watson, J. K. G. and Smith, W. L. (1969) Rotational spectra induced by vibrations. Journal of Molecular Physics, 16 (4). pp. 329-344. ISSN 0026-8976

Full text not archived in this repository.

To link to this article DOI: 10.1080/00268976900100391

Abstract/Summary

Mizushima and Venkateswarlu showed in 1953 that certain molecules have the property that excited vibrational states may possess rotational spectra even when the rotational spectrum of the ground vibrational state is forbidden by symmetry. We call such a spectrum a vibrationally induced rotational spectrum, and have made a systematic examination of the point groups which permit such behaviour. We also give formulae for the approximate line frequencies and intensities in these spectra, and discuss some of the problems involved in observing them. The spectra can only arise from degenerate vibrational states, and are of three possible types: i) symmetric top perpendicular spectra, shown by molecules belonging to the point groups Dnh, Dn and Cnh, where n is odd; (ii) symmetric top parallel spectra, shown by molecules belonging to Dnd and S2n, where n is even; and (iii) spherical top spectra, shown by molecules belonging to T or Td. Excited vibrational states of polar molecules of point groups Cnv or Cn, where n is odd, may also possess vibrationally induced perpendicular components of type (i), in addition to their ordinary parallel spectra. In addition to the above limitations on the point groups there are, in general, limitations on the symmetry species of the degenerate vibrational states.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:7342
Publisher:Taylor and Francis

University Staff: Request a correction | Centaur Editors: Update this record

Page navigation