The chiral-induced spin selectivity (CISS) effect, which describes the spin-filtering ability of diamagnetic structures like DNA or peptides having chiral symmetry, has emerged in the past years as the central mechanism behind a number of important phenomena, like long-range biological electron transfer, enantiospecific electrocatalysis, and molecular recognition. Also, CISS-induced spin polarization has a considerable promise for new spintronic devices and the design of quantum materials. The CISS effect is attributed to spin–orbit coupling, but a sound theoretical understanding of the surprising magnitude of this effect in molecules without heavy atoms is currently lacking. We are taking an essential step into this direction by analyzing the importance of imaginary terms in the Hamiltonian as a necessary condition for nonvanishing spin polarization in helical structures. On the basis of first-principles calculations and analytical considerations, we perform a symmetry analysis of the key quantities determining transport probabilities of electrons of different spin orientations. These imaginary terms originate from the spin–orbit coupling, and they preserve the Hermitian nature of the Hamiltonian. Hence, they are not related to the breaking of time-reversal symmetry resulting from the fact that molecules are open systems in a junction. Our symmetry analysis helps to identify essential constraints in the theoretical description of the CISS effect. We further draw an analogy with the appearance of imaginary terms in simple models of barrier scattering, which may help understanding the unusually effective long-range electron transfer in biological systems.

Organic radicals are promising building blocks for molecular spintronics. Little is known about the role of unpaired electrons for electron transport at the single-molecule level. Here, we examine the impact of magnetic fields on electron transport in single oligo(p-phenyleneethynylene) (OPE)-based radical molecular junctions, which are formed with a mechanically controllable break-junction technique at a low temperature of 4.2 K. Surprisingly huge positive magnetoresistances (MRs) of 16 to 287% are visible for a magnetic field of 4 T, and the values are at least 1 order of magnitude larger than those of the analogous pristine OPE (2-4%). Rigorous analysis of the MR and of current-voltage and inelastic electron-tunneling spectroscopy measurements reveal an effective reduction of the electronic coupling between the current-carrying molecular orbital and the electrodes with increasing magnetic field. We suggest that the large MR for the single-radical molecular junctions might be ascribed to a loss of phase coherence of the charge carriers induced by the magnetic field. Although further investigations are required to reveal the mechanism underlying the strong MR, our findings provide a potential approach for tuning charge transport in metal-molecule junctions with organic radicals.

We have carried out a comprehensive study of the influence of electronic structure modeling and junction structure description on the first-principles calculation of the spin polarization in molecular junctions caused by the chiral induced spin selectivity (CISS) effect. We explore the limits and the sensitivity to modeling decisions of a Landauer/Green's function/two-component density functional theory approach to CISS. We find that although the CISS effect is entirely attributed in the literature to molecular spin filtering, spin−orbit coupling being partially inherited from the metal electrodes plays an important role in our calculations on ideal carbon helices, even though this effect cannot explain the experimental conductance results. Its magnitude depends considerably on the shape, size, and material of the metal clusters modeling the electrodes. Also, a pronounced dependence on the specific description of exchange interaction and spin−orbit coupling is manifest in our approach. This is important because the interplay between exchange effects and spin−orbit coupling may play an important role in the description of the junction magnetic response. Our calculations are relevant for the whole field of spinpolarized electron transport and electron transfer, because there is still an open discussion in the literature about the detailed underlying mechanism and the magnitude of physical parameters that need to be included to achieve a consistent description of the CISS effect: seemingly good quantitative agreement between simulation and the experiment can be caused by error compensation, because spin polarization as contained in a Landauer/Green's function/two-component density functional theory approach depends strongly on computational and structural parameters.

Employing the spin degree of freedom of charge carriers offers the possibility to extend the functionality of conventional electronic devices, while colloidal chemistry can be used to synthesize inexpensive and tunable nanomaterials. Here, in order to benefit from both concepts, we investigate Rashba spin–orbit interaction in colloidal lead sulphide nanosheets by electrical measurements on the circular photo-galvanic effect. Lead sulphide nanosheets possess rock salt crystal structure, which is centrosymmetric. The symmetry can be broken by quantum confinement, asymmetric vertical interfaces and a gate electric field leading to Rashba-type band splitting in momentum space at the M points, which results in an unconventional selection mechanism for the excitation of the carriers. The effect, which is supported by simulations of the band structure using density functional theory, can be tuned by the gate electric field and by the thickness of the sheets. Spin-related electrical transport phenomena in colloidal materials open a promising pathway towards future inexpensive spintronic devices.

Spin polarization in the electron transmission of radicals is important for understanding single-molecule conductance experiments focusing on shot noise, Kondo properties, or magnetoresistance. We study how stable radical substituents can affect such spin polarization when attached to oligo(p-phenyleneethynylene) (OPE) backbones. We find that it is not straightforward to translate the spin density on a stable radical substituent into spin-dependent transmission for the para-connected wires under study here, owing to increased steric interactions compared with meta-connected wires, and a resulting twisting of the radical substituent and OPE π systems. The most promising example is a t-butyl nitroxide substituent, which, despite little pronounced spin delocalization onto the backbone, yields a spindependent transmission feature, which one might be able to shift toward the Fermi energy by additional substituents. We also find that for bulkier substituents, dispersion interactions with the substituent can lead to twisting of one of the outer OPE rings, reducing the overall conductance. As a further potential design consideration, attaching radicals via linkers might increase the possibilities for spin-dependent intermolecular and molecule− electrode interactions.