Chirality ('handedness') is a property that underlies a broad variety of phenomena in nature. Chiral molecules appear in two forms, and each is a mirror image of the other, the two enantiomers. The chirality of molecules is associated with their optical activity, and circular dichroism is commonly applied to identify the handedness of chiral molecules. Recently, the chiral induced spin selectivity (CISS) effect was established, according to which transfer of electrons within chiral molecules depends on the electron's spin. Which spin is preferred depends on the handedness of the chiral molecule and the direction of motion of the electron. Several experiments in the past indicated that there may be a relation between the optical activity of the molecules and their spin selectivity. Here, we show that for a molecule containing several stereogenic axes, when adsorbed on a metal substrate, the peaks in the CD spectra have the same signs for the two enantiomers. This is not the case when the molecules are adsorbed on a nonmetallic substrate or dissolved in solution. Quantum chemical simulations are able to explain the change in the CD spectra upon adsorption of the molecules on conductive and nonconductive surfaces. Surprisingly, the CISS properties are similar for the two enantiomers when adsorbed on the metal substrate, while when the molecules are adsorbed on nonmetallic surface, the preferred spin depends on the molecule handedness. This correlation between the optical activity and the CISS effect indicates that the CISS effect relates to the global polarizability of the molecule.
Bibliographical noteFunding Information:
R.N. acknowledges the support by a research grant from Jay and Sharon Levy, the Sassoon and Marjorie Peress Philanthropic Fund, and the Estate of Hermine Miller and from the US Department of Energy Grant ER46430. Y.P. and N.G. acknowledge the Ministry of Science, MOS. O.G. acknowledges the European Union’s Horizon 2020 research and innovation program (grant agreement no. 850836, ERC Starting Grant “PolyHelix”). We would like to acknowledge Yigal Lahav and Aditya G. Rao for their helpful discussion of the quantum chemical simulations.
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