Optical Activity Anisotropy of Benzil

Kenta Nakagawa, Alexander T. Martin, Shane M. Nichols, Veronica L. Murphy, Bart Kahr, Toru Asahi

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    Abstract

    Optical activity (OA) along the optic axis of crystalline benzil has been measured by many over the past 150 years. However, the OA anisotropy remains uncharacterized due to difficulties in sample preparation as well as competition with linear birefringence (LB). The challenges associated with measuring OA along low-symmetry directions in crystals have too often left scientists with only average values of nonresonant OA in solution, i.e., specific rotations, which continue to resist interpretation in terms of structure. Measuring OA anisotropy has been facilitated by recent advances in polarimetry and optical modeling and here we compare results from two distinct division-of-time polarimeters. The absolute structure of crystalline benzil was established for the first time. The optical rotation (OR) of (+)-crystalline benzil (space group P3121) perpendicular to the optic axis at the sodium D-line is -24.6 ± 1.1°/mm. A spectroscopic optical model in the transparent region of the crystal is provided. Electronic structure calculations of OR inform the polarimetric measurements and point to the necessity of developing linear response theory with periodic boundary conditions in order to interpret the results of chiroptical measurements in crystals.

    Original languageEnglish
    Pages (from-to)25494-25502
    Number of pages9
    JournalJournal of Physical Chemistry C
    Volume121
    Issue number45
    DOIs
    Publication statusPublished - 2017 Nov 16

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    ASJC Scopus subject areas

    • Electronic, Optical and Magnetic Materials
    • Energy(all)
    • Physical and Theoretical Chemistry
    • Surfaces, Coatings and Films

    Cite this

    Nakagawa, K., Martin, A. T., Nichols, S. M., Murphy, V. L., Kahr, B., & Asahi, T. (2017). Optical Activity Anisotropy of Benzil. Journal of Physical Chemistry C, 121(45), 25494-25502. https://doi.org/10.1021/acs.jpcc.7b08831