Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first-principles anharmonic couplings

Carboxylic acid dimers serve as prototypical systems for modeling the unusual spectral behavior of the hydride stretch fundamental. Large anharmonic effects associated with the pair of cooperatively strengthened OH ̄OvC hydrogen bonds produces complicated infrared spectra in which the OH stretch oscillator strength is spread over hundreds of wave numbers, resulting in a complicated band sub-structure. In this work cubic anharmonic constants are computed along internal coordinates associated with the intramolecular OH stretch, intermolecular stretch, and OH bend internal coordinates for the formic acid and benzoic acid dimers. These are then projected onto the normal coordinates to produce mixed states that are used in computing the OH stretch infrared spectrum. For the benzoic acid dimer the calculations accurately reproduce for three deuterated isotopomers the overall breadth and much of the vibrational sub-structure in the observed spectra. For the formic acid dimer, the spectrum is calculated using a model employing a subset of the cubic force constants as well as using the full cubic force field. The spectra calculated for the formic acid dimer are sparser and somewhat more sensitive to the exact positions of the anharmonically coupled states than that of the benzoic acid dimer. Again semiquantitative agreement with experiment is obtained. © 2003 American Institute of Physics. @DOI: 10.1063/1.1530573#