Physical achirality in geometrically chiral rotamers of hydrazine and boranylborane molecules

Abstract

The diagonal components and the trace of tensors which account for chiroptical response of the hydrazine molecule N2H4, that is, static anapole magnetizability and frequency-dependent electric dipole-magnetic dipole polarisability, are a function of the (Formula presented.) H─N─N─H dihedral angle. They vanish for symmetry reasons at ϕ = 0° and ϕ = 180°, corresponding respectively to C2v and C2h point group symmetries, that is, cis and trans conformers characterized by the presence of molecular symmetry planes. Nonetheless, vanishing diagonal components have been observed also in the proximity of (Formula presented.) H─N─N─H = 90°, in which the point group symmetry is C2 and hydrazine is unquestionably chiral. In the boranylborane molecule B2H4, assuming the B─B bond in the y direction, the ayy component of the anapole magnetizability tensor approximately vanishes for dihedral angles (Formula presented.) H─B─B─H corresponding to chiral rotamers which belong to D2 symmetry. Such anomalous effects have been ascribed to physical achirality of these conformers, that is, to their inability to sustain electronic current densities inducing either anapole moments, or electric and magnetic dipole moments, about the chiral axis connecting heavier atoms, as well as perpendicular directions. In other terms, the structure of certain geometrically chiral rotamers may be such that neither toroidal nor helical flow, which determine chiroptical phenomenology, can take place in the presence of perturbing fields parallel or orthogonal to the chiral axis.