TY - JOUR
T1 - Chiroptical anisotropy of crystals and molecules
AU - Martin, Alexander T.
AU - Nichols, Shane M.
AU - Murphy, Veronica L.
AU - Kahr, Bart
N1 - Funding Information:
This work was primarily supported by the US National Science Foundation ((DGE-12342536, DMR-1105000) and the US National Institutes of Health (5R21GM107774-02) as well as the New York University Department of Chemistry Kramer and Sokol fellowship programs. Figures of tensors centered on molecules were drawn with a program courtesy of Professor J. Autschbach (University of Buffalo). BK thanks Professors W. Kaminsky (University of Washington), O. Arteaga (University of Barcelona), and A. G. Shtukenberg (New York University) for many important lessons. Thanks are additionally extended to Drs. K. Claborn, J. F. Freudenthal, X. Cui, for their PhD theses of 2007, 2012, and 2015, respectively.
Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2021/8/25
Y1 - 2021/8/25
N2 - Optical activity, a foundational part of chemistry, is not restricted to chiral molecules although generations have been instructed otherwise. A more inclusive view of optical activity is valuable because it clarifies structure-property relationships however, this view only comes into focus in measurements of oriented molecules, commonly found in crystals. Unfortunately, measurements of optical rotatory dispersion or circular dichroism in anisotropic single crystals have challenged scientists for more than two centuries. New polarimetric methods for unpacking the optical activity of crystals in general directions are still needed. Such methods are reviewed as well as some of the 'nourishment' they provide, thereby inviting to new researchers. Methods for fitting intensity measurements in terms of the constitutive tensor that manifests as the differential refraction and absorption of circularly polarized light, are described, and examples are illustrated. Single oriented molecules, as opposed to single oriented crystals, can be treated computationally. Structure-property correlations for such achiral molecules with comparatively simple electronic structures are considered as a heuristic foundation for the response of crystals that may be subject to measurement.
AB - Optical activity, a foundational part of chemistry, is not restricted to chiral molecules although generations have been instructed otherwise. A more inclusive view of optical activity is valuable because it clarifies structure-property relationships however, this view only comes into focus in measurements of oriented molecules, commonly found in crystals. Unfortunately, measurements of optical rotatory dispersion or circular dichroism in anisotropic single crystals have challenged scientists for more than two centuries. New polarimetric methods for unpacking the optical activity of crystals in general directions are still needed. Such methods are reviewed as well as some of the 'nourishment' they provide, thereby inviting to new researchers. Methods for fitting intensity measurements in terms of the constitutive tensor that manifests as the differential refraction and absorption of circularly polarized light, are described, and examples are illustrated. Single oriented molecules, as opposed to single oriented crystals, can be treated computationally. Structure-property correlations for such achiral molecules with comparatively simple electronic structures are considered as a heuristic foundation for the response of crystals that may be subject to measurement.
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U2 - 10.1039/d1cc00991e
DO - 10.1039/d1cc00991e
M3 - Review article
C2 - 34322691
AN - SCOPUS:85113531372
SN - 1359-7345
VL - 57
SP - 8107
EP - 8120
JO - Chemical Communications
JF - Chemical Communications
IS - 66
ER -