A monomers-in-dimers model for carboxylic acid dimers

The OH stretching fundamental band system of carboxylic acid dimers is studied using acetic acid and its isotopomers as a model system. Comparing experimental jet spectra with multidimensional quantum mechanical calculations the origin of the extremely broad vibrational band structure (Delta(nu) over tilde approximate to800 cm(-1)) is found in strong anharmonic resonances involving the OH stretching vibration. Within an adiabatic picture of hydrogen bonding a new monomers-in-dimers model allows to analyze the observed vibrational band structure in terms of the anharmonic quantum dynamics of the CO2H functional group. The results are discussed in terms of the time-dependent population dynamics and its implications for the mode-specificity of the vibrational predissociation of the hydrogen bonds. On a subpicosecond time scale the intramolecular vibrational energy redistribution of the dimer remains effectively localized within the six-dimensional manifold of the internal vibrations of the carboxyl group, conserving its local C-S symmetry. (C) 2003 American Institute of Physics.