Rotation-libration and rotor-rotor coupling in 4-methylpyridine.
The low temperature rotational dynamics of methyl groups in 4-methylpyridine is analyzed in terms of a model potential including rotation-libration and rotor-rotor coupling. The parameters of the model potential are adjusted by comparison of calculated with published and newly recorded inelastic neutron scattering spectra. Initial evaluations of the potential parameters of the model are obtained from molecular mechanics calculations. Experimental spectra are calculated from these potentials by numerical solution of Schrödinger's equation for clusters of coupled rotors embedded in a bigger ensemble of rotors treated in the mean field approximation. Adjustment of the potential parameters leads to excellent agreement with the experimental spectra of protonated 4-methylpyridine, measured at well-defined spin temperatures. At higher levels of deuteration, agreement with experiment is qualitative, only. The observed deviations are attributed to the increasing frustration of the system of coupled methyl groups and mutual localization, effects leading to a phase transition around 5.5 K in isotopic mixtures, as shown in diffraction experiments.
Institut Laue-Langevin, BP156, 38042 Grenoble 9, France.
M A
MA
Neumann
M
M
Plazanet
M R
MR
Johnson
H P
HP
Trommsdorff