Vibrational studies of benzene, pyridine, pyridine-N-oxide and their cations

IR and Raman spectra of pyridine and pyridine-N-oxide have been recorded and analyzed. The optimized molecular geometries, APT charges and vibrational characteristics for benzene, pyridine, pyridine-N-oxide and their cations have been computed using DFT method. Due to attachment of O atom at N site or removal of electron all the modes are affected in magnitudes. However, significant changes are noticed in their IR intensities, Raman activities and depolarization ratios of the Raman bands in going from pyridine to its N-oxide or in going from neutrals to their cations. It is interesting to note that in going from benzene to benzene cation charge redistribution takes place to reduce the symmetry from D-6h to D-2h. The calculated frequencies have been correlated with the experimental frequencies for the pyridine and pyridine-N-oxide molecules. (C) 2013 Elsevier B.V. All rights reserved.