The importance of large amplitude motions for the interpretation of mid-infrared vibrational absorption and circular dichroism spectra: 6,6'-dibromo-[1,1'-binaphthalene]-2,2'-diol in dimethyl sulfoxide

Using the 6,6-dibromo-[1,1-binaphthalene]-2,2-diol molecule and its vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra measured in deuterated dimethyl sulfoxide as example, we present a first detailed study of the effects induced in VCD spectra by the large-amplitude motions of solvent molecules loosely bound to a solute molecule. We show that this type of perturbation can induce significant effects in the VA and VCD spectra. We also outline a computational procedure that can effectively model the effects induced in the spectra and at the same time provide detailed structural information regarding the relative orientations of moieties involved in a solute-solvent molecular complex. © 2014 American Chemical Society.