Transfer of Clusters Between the Vibrational Components of CF4

Abstract

The pattern of the rotation-vibrational energy levels in isolated vibrational components of CF4 has recently been described (B. I. Zhilinskii et al., J. Mol. Spectrosc.160, 192-216, 1993) in terms of the semiclassical model for the rotation of molecules. The present paper discusses the interaction between neighboring vibrational components due to a transfer from one component to the other of either one 6-fold cluster, one 8-fold cluster, one 12-fold cluster, or two 6-fold clusters. The rules for which transfers are possible are derived from a consideration of the formation of common points between the two corresponding classical rotational energy surfaces. These rules are conveniently stated in terms of the local symmetry indices (B. I. Zhilinskii and S. Brodersen, J. Mol. Spectrosc.163, 326-338, 1994) characterizing the symmetries of the two vibrational components. Three examples of such interactions are discussed in detail: first a crossing of one vibrational component from the ν3 vibrational state with one of the components from the 2ν4 state; second, a crossing of one vibrational component from the ν3 vibrational state with the two components of the E substate of 3ν2; and finally, the rearrangement of the vibrational components of the E and F2 substates of the 2ν4 vibrational state into five components of the combined E + F2 substate.