A group-theoretic approach to chirality-induced spin selectivity in molecular junctions*

Spin-orbit coupling gives rise to a range of spin-charge interconversion phenomena in non-magnetic systems where certain spatial symmetries are absent. Chirality-induced spin selectivity (CISS), a term that generically refers to a spin-dependent electron transfer in non-magnetic chiral systems, is one such case, appearing in a variety of seemingly unrelated situations ranging from inorganic materials to molecular devices. In particular, the origin of CISS in molecular junctions is a matter of an intense current debate. Here we contend that CISS can be generally and fully understood on the basis of a complete symmetry analysis of the molecular junction, and not only of the molecule. Our approach, which draws on the use of point-group symmetries within the scattering formalism for transport, shows that electrode symmetries are as important as those of the molecule when it comes to the appearance of CISS. It turns out that standalone metallic nanocontacts can exhibit spin-polarization when relative rotations which reduce the symmetry are introduced. As a corollary, molecular junctions with achiral molecules can also exhibit spin polarization along the direction of transport, provided that the whole junction is chiral in some way. This formalism also allows to predict the qualitative changes on the spin-polarization upon substitution of a chiral molecule in the junction with its enantiomeric partner. Quantum transport calculations based on DFT corroborate all of our predictions and provide further quantitative insight.