title: A confidence level algorithm for the determination of absolute configuration using vibrational circular dichroism or Raman optical activity.
abstract: Spectral comparison is an important part of the assignment of the absolute configuration (AC) by vibrational circular dichroism (VCD), or equally by Raman optical activity (ROA). In order to avoid bias caused by personal interpretation, numerical methods have been developed to compare measured and calculated spectra. Using a neighbourhood similarity measure, the agreement between a computed and measured VCD or ROA spectrum is expressed numerically to introduce a novel confidence level measure. This allows users of vibrational optical activity (VOA) techniques (VCD and ROA) to assess the reliability of their assignment of the AC of a compound. To that end, a database of successful AC determinations is compiled along with neighbourhood similarity values between the experimental spectrum and computed spectra for both enantiomers. For any new AC determination, the neighbourhood similarities between the experimental spectrum and the computed spectra for both enantiomers are projected on the database allowing an interpretation of the reliability of their assignment.
authors.affiliation: Department of Chemistry, Syracuse University, 1-014 Center for Science and Technology, Syracuse, New York 13244-4100, USA.
authors.forename: Elke
authors.initials: E
authors.lastname: Debie
authors.forename: Ewoud
authors.initials: E
authors.lastname: De Gussem
authors.forename: Rina K
authors.initials: RK
authors.lastname: Dukor
authors.forename: Wouter
authors.initials: W
authors.lastname: Herrebout
authors.forename: Laurence A
authors.initials: LA
authors.lastname: Nafie
authors.forename: Patrick
authors.initials: P
authors.lastname: Bultinck
mesh_terms: D000465:Algorithms; D002942:Circular Dichroism; D008968:Molecular Conformation; D013059:Spectrum Analysis, Raman; D013237:Stereoisomerism