Terahertz spectroscopy of dicyanobenzenes: Anomalous absorption intensities and spectral calculations

Abstract

Terahertz absorption spectra of three isomeric structures of dicyanobenzene in chloroform solution and solid phase at 298 K are reported. These spectra exhibit enhanced absorption in low THz range compared to most organic systems because of strong coupling to phonon modes. Molecular vibrational spectral calculations show strong correlation with the experiment especially for solution spectra. All intramolecular modes were assigned and intermolecular modes identified. Out-of-plane intramolecular modes at low frequency exhibit ∼75 cm −1 blue shifts as the secondary CN group moves from the para to ortho position on the benzene ring, whereas almost no frequency shift occurs for low-frequency in-plane modes.