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. 2021 Apr 21;7(17):eabg2859.
doi: 10.1126/sciadv.abg2859. Print 2021 Apr.

Validation of microscopic magnetochiral dichroism theory

M Atzori  1 , H D Ludowieg  2 , Á Valentín-Pérez  3   4 , M Cortijo  3   4 , I Breslavetz  1 , K Paillot  1 , P Rosa  3 , C Train  1 , J Autschbach  5 , E A Hillard  3   4 , G L J A Rikken  6
Affiliations

Validation of microscopic magnetochiral dichroism theory

M Atzori et al. Sci Adv. .

Abstract

Magnetochiral dichroism (MChD), a fascinating manifestation of the light-matter interaction characteristic for chiral systems under magnetic fields, has become a well-established optical phenomenon reported for many different materials. However, its interpretation remains essentially phenomenological and qualitative, because the existing microscopic theory has not been quantitatively confirmed by confronting calculations based on this theory with experimental data. Here, we report the experimental low-temperature MChD spectra of two archetypal chiral paramagnetic crystals taken as model systems, tris(1,2-diaminoethane)nickel(II) and cobalt(II) nitrate, for light propagating parallel or perpendicular to the c axis of the crystals, and the calculation of the MChD spectra for the Ni(II) derivative by state-of-the-art quantum chemical calculations. By incorporating vibronic coupling, we find good agreement between experiment and theory, which opens the way for MChD to develop into a powerful chiral spectroscopic tool and provide fundamental insights for the chemical design of new magnetochiral materials for technological applications.

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Figures

Fig. 1
Fig. 1. Molecular structure of the investigated systems.
View of the molecular structure of Λ-[MII(dae)3]2+ (left) and Δ-[MII(dae)3]2+ (right) (MII = Ni, Co) complex cations. Color codes: red, MII; blue, N; gray, C; white, H. Nitrate anions are omitted for clarity.
Fig. 2
Fig. 2. Experimental MChD, NCD, and absorption spectra.
Orthoaxial ΔAMChD spectra for Λ and Δ single crystals of 1 (A) and 2 (B) for several temperatures. The inset in (A) shows the MChD strength as a function of the magnetic field strength; the straight line is a fit. The inset in (B) shows the MChD strength as a function of the inverse temperature; the straight line is a fit. Absorption spectra (points) versus irradiation wavelength for single crystals of 1 (C) and 2 (D) in orthoaxial configuration. The spectral deconvolution analysis (solid lines) and NCD spectra T = 80 K (dashed lines) are also shown.
Fig. 3
Fig. 3. Comparison between experimental and calculated MChD spectra.
Experimental ΔAMChD spectra for a single crystal of 1-Δ in axial and orthoaxial configuration (A), corresponding calculated ΔAMChD spectra (B) and calculated ΔAMChD spectra with only C2 terms (note change in scale) (C).
See this image and copyright information in PMC

References

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