Infrared spectra of neutral dimethylamine clusters: An infrared-vacuum ultraviolet spectroscopic and anharmonic vibrational calculation study

Abstract

Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral dimethylamine clusters, (DMA)_n (n = 2-5), were measured in the spectral range of 2600-3700 cm^-1. The experimental IR-VUV spectra show NH stretch modes gradually redshift to 3200-3250 cm^-1 with the increase in the cluster size and complex Fermi Resonance (FR) pattern of the CH₃ group in the 2800-3000 cm^-1 region. Ab initio anharmonic vibrational calculations were performed on low-energy conformers of (DMA)₂ and (DMA)₃ to examine vibrational coupling among CH/NH and to understand the Fermi resonance pattern in the observed spectra features. We found that the redshift of NH stretching mode with the size of DMA cluster is moderate, and the overtone of NH bending modes is expected to overlap in frequency with the CH stretching fundamental modes. The FR in CH₃ groups is originated from the strong coupling between CH stretching fundamental and bending overtone within a CH₃ group. Well-resolved experimental spectra also enable us to compare the performance of ab initio anharmonic algorithms at different levels.