Abstract
Chirality is a structural property of molecules lacking mirror symmetry that has strong implications in diverse fields, ranging from life sciences to materials science. Chirality-sensitive spectroscopic methods, such as circular dichroism, exhibit weak signal contributions on an achiral background. Helical dichroism, which is based on the orbital angular momentum (OAM) of light, offers a new approach to probe molecular chirality, but it has never been demonstrated on disordered samples. Furthermore, in the optical domain the challenge lies in the need to transfer the OAM of the photon to an electron that is localized on an ångström-size orbital. Here we overcome this challenge using hard X-rays with spiral Fresnel zone plates, which can induce an OAM. We present the helical dichroism spectra of a disordered powder sample of enantiopure salts of the molecular complex of [Fe(4,4′-diMebpy)3]2+ at the iron K edge (7.1 keV) with OAM-carrying beams. The asymmetry ratios for the helical dichroism spectra are within one to five percent for OAM beams with topological charges of one and three. These results open a new window into the studies of molecular chirality and its interaction with the OAM of light.
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Acknowledgements
This work was supported by the European Research Council Advanced Grants H2020 ERCEA 695197 DYNAMOX, the Swiss NSF via the NCCR:MUST and grants 200020_169914 and 200021_175649. D.K. acknowledges funding from SNSF under grant no. 200021_175905. J.R.R. was supported by the Fédération André Marie Ampère (FRAMA) and the LABEX MANUTECH-SISE (ANR-10-LABX-0075) of the Université de Lyon, within the program ‘Investissements d’Avenir’ (ANR-11-IDEX-0007) operated by the French National Research Agency (ANR). C.B. and G.F.M. were supported via the InterMUST Women Fellowship. G.F.M. acknowledges the support of the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 851154). F.Z. and J.L. thank the University of Geneva and the Swiss NSF for support via grant 200020-184843.
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J.R.R., B.R., D. Karpov and M.C. conceived and organized the experiments. J.R.R., B.R., D. Karpov, C.B., G.F.M., D. Kinschel, O.C., C.S. and A.D. carried out the experiments. B.R. and C.D. designed and fabricated the spiral Fresnel zone plates. F.Z. and J.L. synthesized the chiral salts. M.O. characterized the samples and provided critical feedback. J.R.R., B.R. and M.C. interpreted the results and wrote the manuscript with contributions from all authors.
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Nature Photonics thanks Jianhui Chen, Olga Smirnova and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Rouxel, J.R., Rösner, B., Karpov, D. et al. Hard X-ray helical dichroism of disordered molecular media. Nat. Photon. 16, 570–574 (2022). https://doi.org/10.1038/s41566-022-01022-x
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DOI: https://doi.org/10.1038/s41566-022-01022-x
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