Testing the vibrational exciton and the local mode models on the instructive cases of dicarvone, dipinocarvone, and dimenthol vibrational circular dichroism spectra

Abstract

The vibrational circular dichroism (VCD) spectra of dicarvone (1), dipinocarvone (2), and dimenthol (3) have been recorded in the range 900-3200 cm^-1 , encompassing the mid-infrared (mid-IR), the CO stretching, and the CH-stretching regions. For compound 3 also, the fundamental and the first overtone OH stretching regions have been investigated by IR/NIR absorption and VCD. Density functional theory (DFT) calculations allow one to interpret the IR and VCD spectra and to confirm the configuration/conformational studies previously conducted by X-ray diffraction. The most intense VCD signals are associated with the vibrational normal modes involving symmetry-related groups close to the CC bond connecting covalently the two molecular units. The vibrational exciton (VCDEC) model is fruitfully tested on the VCD data of compounds 1 and 2 for the spectroscopic regions at ~1700 cm^-1 , and the local mode model is tested on compound 3 at ~3500 and ~6500 cm^-1 . For compounds 1 and 2 also, ECD spectra are reported, and the exciton mechanism is tested also there, and connections to the VCDEC model are examined.

Keywords: ECD; NIR-VCD; VCD; dicarvone; dimenthol; dipinocarvone; local modes; vibrational excitons.