The Influence of Intramolecular Coupling between v(XH) and v(XH…Y) Modes on the IR Absorption Spectra of Hydrogen Bonded Species XH…Y

By modifying the simple Morse oscillator model usually used for describing the vibrational motion of a linear XH…Y complex a more realistic model is proposed, which is in better agreement with experimental results. The potential energy surface is derived by fitting the bond length, the dissociation energy of the H-bond, the bond length shortening, and the normal frequency of the v(XH) vibration to their observed values. From the resulting values of the transition matrix elements between low excited v(XH) and high excited v(XH…Y) quantum states it is shown, that for explaining the smoothness of the IR absorption bands the intramolecular coupling between v(XH) and v(XH…Y) stretching modes of vibration should be taken into account.