Application of terahertz spectroscopy combined with density functional theory to analysis of intermolecular weak interactions for coumarin and 6-methylcoumarin

Abstract

The terahertz (THz) absorption spectra of coumarin and 6-methylcoumarin have been investigated by terahertz time-domain spectroscopy (THz-TDS) system in the frequency range from 0.4 to 2.8 THz. Density functional theory (DFT) calculations, both with and without London force dispersion corrections, have been used for the assignment of the experimental THz spectra. To thoroughly interpret the spectrum information, we used potential energy distribution (PED) method to assign the vibrational modes of the absorption peaks, and identify the origin of the absorption peaks by electrostatic potential (ESP) and van der Waals (vdW) potential distribution analysis method. The results show that absorption peaks both for coumarin and 6-methylcoumarin are caused by electrostatic interaction in the lower frequency range, while vdW interaction in the higher frequency. Moreover, the potential energy distribution of electrostatic and vdW between them is basically the same, and it led to the similarity of THz spectra between coumarin and 6-MC. This work has demonstrated that using THz spectroscopy combined with DFT calculations is an effective way to analysis of intermolecular weak interactions and biomolecules with similar structures.