Manifestation of intermolecular interactions in FTIR spectra of methylene blue molecules

Abstract Fourier-transform infrared (FTIR) spectra of cationic dye methylene blue (MB) were analyzed in its free form (gas-phase), hydrated crystalline state, and dried MB solution. A good agreement of experimental FTIR spectra with the results of theoretical calculations of MB vibration modes was observed. The calculations were performed by means of the density functional theory (DFT/B3LYP/6–31 + G(d)), using Gaussian-03 software package. Vibrational bands of the N + (CH 3 ) 2 (1640–1650 cm −1 ) and C-S-C (625-615, 1095 cm −1 ) functional groups are characteristic of the presence of MB monomers in the studied samples. The participation of the N + (CH 3 ) 2 functional group in the formation of one bridging H-bond with OH groups of the solvent has been confirmed. The decrease in intensity of these bands with the increase of the fraction of dimers and H-aggregates of MB was observed. It was concluded that the configuration and primary localization of the charge in the heterocycle of ionic form MB + are changed in the case of formation of dimers and H-aggregates. For samples with a dominant fraction of dimers and H-aggregates, the occurrence of intermolecular H-bonds of the type N het …Н-O⋯S + het was found. The occurrence of peaks at 1339–1356, 1481–1491, and 885 cm −1 was observed. It was concluded that there is formation of dimers and H-aggregates due to interaction of sulfur and nitrogen atoms with OH groups of water molecules. Moreover, the manifestation of π-π stacking interactions of aromatic rings of the heterocycle of ionic form MB + during self-association was determined on the basis of data on the behavior of the peaks of heterocyclic of СН (3050–3015 cm −1 ), С С, С N (1600–1595 cm −1 ), С С, and С N (1564–1546 cm −1 ) vibrations.