Abstract
The B97D/aug-cc-pvtz optimized molecular geometry of the monomeric acetic acid with a syn COOH group and the degree of dimerization agree well with the experimental data. The anti COOH conformation was estimated at a relative free energy of 4.22 and 4.85kcal/mol at the B97D/CBS and CCSD(T)/CBS (complete basis set limit) levels, respectively. The relative free energy for the anti conformer decreases by about 2 and 3kcal/mol in infinitely dilute chloroform and water solutions, respectively, as calculated by means of the IEF-PCM continuum dielectric solvent approximation. Modeling very dilute and 0.1M aqueous solutions in Monte Carlo simulations, the syn conformer has been predicted to be present at populations of 83% and 98%, respectively. Possible syn–anti transformation paths have been proposed by considering a neutral and a protonated acetic acid tetrahydrate complex.The syn conformer forms a stably maintained, doubly-hydrogen-bonded dimer in chloroform. In-water calculations for an about 0.2M model are sensitive to the applied atomic charges. Ultimately, an association degree of 96% has been obtained for a dimer with one hydrogen bond.
Published Version
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