Journal of Physical Chemistry A, Vol.118, No.26, 4766-4777, 2014
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.