Aggregation of acetic and propionic acid in argon matrices - A matrix isolation and computational study

Monomeric acetic acid M-A and propionic acid M-P were isolated in argon matrices at 10 K by using a pulse deposition technique. The dimerization of the monomers was induced by warming the matrices from 10 to 40 K. Under these conditions the diffusion of small trapped molecules is rapid and the dimerization could be monitored directly by IR spectroscopy. Both carboxylic acids form the symmetrical dimers B with two strong C=O... HO hydrogen bridges as the thermodynamically most stable dimers. With acetic acid a less stable dimer A(A) could be obtained if high concentrations of acetic acid in argon were used during the deposition of the matrix. On annealing this dimer rearranges to the more stable B-A. In contrast, propionic acid does not form a corresponding less stable dimer under any experimental condition. These observations are rationalized on the basis of DFT and ab initio calculations. (c) 2005 Elsevier B.V. All rights reserved.