FT‐Raman, FTIR and density functional theory studies of a hydrogen‐bonded formamide:pyridine complex

Abstract

AbstractRaman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm−1 (ν1 region of Py), whose intensity depends on the FA concentration, is assigned to an FA:Py adduct and this result is in excellent agreement with those of other authors who employed noisy light‐based coherent Raman scattering spectroscopy (I(2) CARS). Another band at 1587 cm−1 (ν8 region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA:Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the ν1 region of Py has been chosen for the quantitative analysis and a stoichiometry of 1:1 FA:Py is reported. The experimental data are very well supported by the density functional theory (DFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that the solvent dielectric constant determines the stoichiometry of a given Lewis acid–base adduct in the infinite dilution limit. Copyright © 2009 John Wiley & Sons, Ltd.