Vibrational circular dichroism

Vibrational circular dichroism (VCD) is a spectroscopic technique which detects differences in attenuation of left and right circularly polarized light passing through a sample. It is the extension of circular dichroism spectroscopy into the infrared and near infrared ranges.

Because VCD is sensitive to the mutual orientation of distinct groups in a molecule, it provides three-dimensional structural information. Thus, it is a powerful technique as VCD spectra of enantiomers can be simulated using ab initio calculations, thereby allowing the identification of absolute configurations of small molecules in solution from VCD spectra. Among such quantum computations of VCD spectra resulting from the chiral properties of small organic molecules are those based on density functional theory (DFT) and gauge-invariant atomic orbitals (GIAO). As a simple example of the experimental results that were obtained by VCD are the spectral data obtained within the carbon-hydrogen (C-H) stretching region of 21 amino acids in heavy water solutions. Measurements of vibrational optical activity (VOA) have thus numerous applications, not only for small molecules, but also for large and complex biopolymers such as muscle proteins (myosin, for example) and DNA.

While the fundamental quantity associated with the infrared absorption is the dipole strength, the differential absorption is also proportional to the rotational strength, a quantity which depends on both the electric and magnetic dipole transition moments. Sensitivity of the handedness of a molecule toward circularly polarized light results from the form of the rotational strength. A rigorous theoretical development of VCD was developed concurrently by the late Professor P.J. Stephens, FRS, at the University of Southern California, and the group of Professor A.D. Buckingham, FRS, at Cambridge University in the UK, and first implemented analytically in the Cambridge Analytical Derivative Package (CADPAC) by R.D. Amos. Previous developments by D.P. Craig and T. Thirmachandiman at the Australian National University and Larry A. Nafie and Teresa B. Freedman at Syracuse University though theoretically correct, were not able to be straightfowardly implemented, which prevented their use. Only with the development of the Stephens formalism as implemented in CADPAC did a fast efficient and theoretically rigorous theoretical calculation of the VCD spectra of chiral molecules become feasible. This also stimulated the commercialization of VCD instruments by Biotools, Bruker, Jasco and Thermo-Nicolet (now Thermo-Fisher).

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