Studies of the Jahn - Teller effect III. The rotational and vibrational spectra of symmetric-top molecules in electronically degenerate states

The Royal Society - Tập 254 Số 1041 - Trang 259-294 - 1961
M. S. Child1, Hugh Christopher Longuet-Higgins1
1Department of Theoretical Chemistry, University of Cambridge

Tóm tắt

We have developed the physical theory required for interpreting the infra-red, Raman and microwave spectra of molecules in orbitally degenerate electronic states in which spin-orbit coupling is unimportant. Formulae are obtained which relate the oscillator strengths and scattering cross-sections to the electrical and mechanical properties of the molecule, and group theoretical selection rules are derived and applied to the common point groups. Among other results we find: ( a )that in an electronically degenerate state a molecule may exhibit a dipole moment which would be symmetry-forbidden if the electronic state were non-degenerate, ( b ) that certain lines in the Raman spectrum may have depolarization ratio greater than f, because of the possibility of pseudo-vector scattering, and ( c ) that in both the infra-red and Raman spectra a Jahn-Teller active vibration may give rise to overtones of extremely high intensity but irregular spacing.

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