Ab initio calculations of the structure, vibrational spectra, and thermodynamic properties of silver trifluoroacetates

The structure and properties of monomeric and dimeric silver trifluoroacetates were calculated at different levels of approximation, from RHF with the 3-21G basis set for all atoms to MP2 with the SBKJC and Stuttgart RSC relativistic effective core potentials for silver and the 6-311G (df) basis set for the other atoms. The monomer was found to exist as two conformers in the gas phase, in a more stable conformer, the Ag atom formed coordination bonds with two carboxyl oxygens, and a less stable conformer contained O-Ag-F bridges and the C=O double bond. The CF3 group freely rotated in the monomer without Ag-F bonds and experienced hindered rotations in the dimer. The theoretically predicted vibrational spectrum of the dimer and the thermodynamic functions of the dimerization reaction were consistent with the available experimental data. (C) 2002 Elsevier Science B.V. All rights reserved.