Rotational tunnelling splitting of a chain of four coupled methyl groups

Abstract

It is our goal to obtain a reliable prediction of the rotational tunnelling spectrum to be expected for a long chain of coupled one-dimensional quantum rotors. The problem is intractable by the simple methods used so far for up to three coupled methyl groups. Therefore, an efficient, nevertheless sufficiently precise method for solving the stationary Schrodinger equation of interacting methyl groups is developed first; it proves to be valid for a broad range of not too weak potential strengths. Then, three scenarios are investigated: they differ with respect to the relative strength of the single-rotor potential and the interaction potential. For each scenario, we illustrate the dependence of the energy level scheme on the number of coupled groups. For strong coupling and weak single-particle potential, the characteristic features of the energy level scheme of interacting methyls are most clearly observable: For as few as four coupled methyl groups we predict tunnelling spectra which are hardly distinguishable from single-methyl spectra. However, the collective behaviour is still important for the value of the tunnelling splitting. Therefore, the interpretation of such a spectrum in terms of single-methyl tunnelling is obvious but misleading with respect to the potential seen by a methyl group in the crystal.