Methyl tunnelling in trihalogeno-trimethyl-benzenes

Abstract Results of inelastic neutron scattering (INS) from 1,3,5-trihalogeno-2,4,6-trimethyl-benzenes are reported for the chloro-, the bromo- and the iodo-case. For the whole family the spectra show numerous similarities, in the μeV as well as in the meV range. We observe three tunnelling lines of equal intensity corresponding to three crystallographically inequivalent methyl rotors. The observed librational peaks are at much lower energies than expected from a pure threefold potential. Within the halogen family a systematic reduction of the barrier height is found with larger halogen sizes. The temperature dependence of the tunnelling energies shows the most pronounced difference between TBM and TIM, where the corresponding tunnelling lines even shift in opposite directions.