First-Principles Calculation of Terahertz Absorption with Dispersion Correction of 2,2 '-Bithiophene as Model Compound

Abstract

Terahertz absorption of organic materials is closely linked to molecular arrangements and their intermolecular interactions and is important for material identification as well as THz generation. Theoretical calculations of solid-state vibrations known as phonons help to understand intermolecular interactions responsible for THz absorption but frequently are of limited use without considering dispersion interaction. In this study, we have calculated the THz phonon modes of an organic model crystal 2,2'-bithiophene, considering dispersion intermolecular interactions assuming the fixed cell dimensions. Both energies and intensities of phonon modes at low frequencies were interpreted concentrating on the intermolecular level in conjunction with hydrogen bonds rand showed an excellent agreement with the experimental results. This approach to identify the phonon modes responsible for strong THz absorptions and to interpret those modes in terms of intermolecular vibrations is also expected to be applicable to the field of THz generation using nonlinear optical organic crystals.