Effects of molecular symmetry on the directions of nuclear flux densities during tunnelling in double well potentials

Abstract

Coherent tunnelling in molecular systems with cyclic and non-cyclic symmetric double well potentials may proceed with similar nuclear densities, but with entirely different flux densities. For sufficiently high potential barriers, the nuclear densities may even become indistinguishable, whereas the patterns of the flux densities at a given time remain pincer-motion type for the cyclic systems, but unidirectional for the non-cyclic one. This effect is traced back to symmetry breaking of the cyclic to the non-cyclic model. Accordingly, nuclear flux densities are much more sensitive to symmetry breaking than nuclear densities. For a proof of principle, the phenomenon is demonstrated by means of three one-dimensional models. The cyclic model I represents torsion in oriented B2Cl2F2, the non-cyclic model II is constructed from I by symmetry breaking and the non-cyclic model III represents tunnelling by inversion of oriented NH3.