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Keywords:

  • vibrational optical activity;
  • ab initio calculations;
  • Raman optical activity;
  • solution conformation;
  • absolute configuration

Abstract

The samples used for the first observations of vibrational Raman optical activity (ROA) in 1972, namely both enantiomers of 1-phenylethanol and 1-phenylethylamine, have been revisited using a modern commercial ROA instrument together with state-of-the-art ab initio calculations. The simulated ROA spectra reveal for the first time the vibrational origins of the first reported ROA signals, which comprised similar couplets in the alcohol and amine in the spectral range ∼280–400 cm−1. The results demonstrate how easy and routine ROA measurements have become, and how current ab initio quantum–chemical calculations are capable of simulating experimental ROA spectra quite closely provided sufficient averaging over accessible conformations is included. Assignment of absolute configuration is, inter alia, completely secure from results of this quality. Anharmonic corrections provided small improvements in the simulated Raman and ROA spectra. The importance of conformational averaging emphasized by this and previous related work provides the underlying theoretical background to ROA studies of dynamic aspects of chiral molecular and biomolecular structure and behavior. Chirality 21:E4–E12, 2009. © 2009 Wiley-Liss, Inc.