Understanding Solvent Effects in Vibrational Circular Dichroism Spectra: [1,1′-Binaphthalene]-2,2′-diol in Dichloromethane, Acetonitrile, and Dimethyl Sulfoxide Solvents

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 116; no. 32; pp. 8366 - 8373
• Main Authors: Nicu, Valentin Paul, Baerends, Evert Jan, Polavarapu, Prasad L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16-08-2012
• Subjects: Circularity; Dichroism; Dimethyl sulfoxide; Mathematical analysis; Perturbation methods; Solvent effect; Solvents; Spectra
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp303891x

We present a combined experimental and computational investigation of the vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of [1,1′-binaphthalene]-2,2′-diol. First, the sensitive dependence of the experimental VA and VCD spectra on the solvent is demonstrated by comparing the experimental spectra measured in CH2Cl2, CD3CN, and DMSO-d 6 solvents. Then, by comparing calculations performed for the isolated solute molecule to calculations performed for molecular complexes formed between solute and solvent molecules, we identify three main types of perturbations that affect the shape of the VA and VCD spectra when going from one solvent to another. These sources of perturbations are (1) perturbation of the Boltzmann populations, (2) perturbation of the electronic structure, and (3) perturbation of the normal modes.