Optical Activity Anisotropy of Benzil

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

Research output: Contribution to journalArticle

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 (US)
Pages (from-to)25494-25502
Number of pages9
JournalJournal of Physical Chemistry C
Volume121
Issue number45
DOIs
StatePublished - Nov 16 2017

Fingerprint

optical activity
Optical rotation
Anisotropy
Polarimeters
Crystalline materials
Crystals
anisotropy
Optics
Crystal symmetry
Birefringence
Electronic structure
optics
crystals
D lines
Sodium
Boundary conditions
polarimetry
polarimeters
division
birefringence

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

Optical Activity Anisotropy of Benzil. / Nakagawa, Kenta; Martin, Alexander T.; Nichols, Shane M.; Murphy, Veronica L.; Kahr, Bart; Asahi, Toru.

In: Journal of Physical Chemistry C, Vol. 121, No. 45, 16.11.2017, p. 25494-25502.

Research output: Contribution to journalArticle

Nakagawa, K, Martin, AT, Nichols, SM, Murphy, VL, Kahr, B & Asahi, T 2017, 'Optical Activity Anisotropy of Benzil', Journal of Physical Chemistry C, vol. 121, no. 45, pp. 25494-25502. https://doi.org/10.1021/acs.jpcc.7b08831
Nakagawa K, Martin AT, Nichols SM, Murphy VL, Kahr B, Asahi T. Optical Activity Anisotropy of Benzil. Journal of Physical Chemistry C. 2017 Nov 16;121(45):25494-25502. https://doi.org/10.1021/acs.jpcc.7b08831
Nakagawa, Kenta ; Martin, Alexander T. ; Nichols, Shane M. ; Murphy, Veronica L. ; Kahr, Bart ; Asahi, Toru. / Optical Activity Anisotropy of Benzil. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 45. pp. 25494-25502.
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