title: Atomic contributions to the optical rotation angle as a quantitative probe of molecular chirality.
abstract: Chiral molecules are characterized by a specific rotation angle, the angle through which plane-polarized light is rotated on passing through an enantiomerically enriched solution. Recent developments in methodology allow computation of both the sign and the magnitude of these rotation angles. However, a general strategy for assigning the individual contributions that atoms and functional groups make to the optical rotation angle and, more generally, to the molecular chirality has remained elusive. Here, a method to determine the atomic contributions to the optical rotation angle is reported. This approach links chemical structure with optical rotation angle and provides a quantitative measure of molecular asymmetry propagation from a center, axis, or plane of chirality.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.
authors.forename: R K
authors.initials: RK
authors.lastname: Kondru
authors.forename: P
authors.initials: P
authors.lastname: Wipf
authors.forename: D N
authors.initials: DN
authors.lastname: Beratan
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D005027:Ethylene Oxide / Q000031:analogs & derivatives / Q000737:chemistry*; D006586:Hexanes / Q000737:chemistry*; D008433:Mathematics; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D009904:Optical Rotation; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: C116364:2-fluorohexane; D019086:Bridged Bicyclo Compounds, Heterocyclic; D006586:Hexanes; D005027:Ethylene Oxide