Nonlinear dynamics of a model hydrogen bond

The dynamics of a model triatomic hydrogen bond are analyzed through classical mechanics. The approximate separability of the equations of motion induces the existence of an adiabatic invariant for the intramolecular mode motion. This mode is governed by a Mathieu equation, a feature already present for the antisymmetric mode in symmetric triatomics. The corresponding spectrum readily obtained as the Fourier transform of a classical trajectory shows that the fundamental frequency is shifted to lower values owing to the anharmonicity of the potential. We observe also a substructure of combination lines generated by a nonlinear resonance with the intermolecular mode. These properties are consistent with experimental observation. In a four-atoms model, the lines are split when intramolecular Fermi resonance occurs. When the intermolecular mode becomes chaotic there is no vibrational heating of the intramolecular neighboring mode which tends to behave like a local isolated oscillator.