Density functional theory (DFT) at the B3LYP/6-31++G(d,p) level was employed to obtain the optimized (Py)-water(W) complexes with stoichiometric ratios geometries and vibrational spectra of several pyridine(Py) ranging from 2:1 (Py2W) to 1:3 (PyW3). The harmonic vibrational wavenumbers of pyridine ring modes and the fundamental modes of water were calculated in order to examine the influence of hydrogen bonding on the normal modes of both pyridine and water upon complexation. The Raman spectra in the wavenumber region 960-1060 cm(-1) covering the ring modes v(1) and v(12) of pyridine (in Wilson's notation) as a function of pyridine. mole fraction were recorded. The integrated Raman intensities in the isotropic components of the spectra were used to determine the relative concentration of "free" pyridine molecules in close neighborhood with other Py-W complexes. The combination of both experimental wavenumbers yielding the overall shift induced by the entirety of hydrogen-bonded complexes in the mixture and the DFT-derived vibrational wavenumbers of the isolated species provides the possibility to probe concentration profiles as a function of pyridine mole fraction. The examination of the concentration dependence of line widths reveals that the counter competing influences of different dynamic processes are simultaneously present in this binary mixture.