Theoretical quantum chemical study of benzoic acid: Geometrical parameters and vibrational wavenumbers

The structure of benzoic acid as monomer was studied by semiempirical, ab initio, and density functional methods using several basis sets. The performance of these methods in calculating and describing the vibrational frequencies of benzoic acid and several derivatives was determined. The cyclic dimer form of benzoic acid was also reproduced. Two new procedures of scaling the frequencies were presented. For the ring modes, specific scale equations and scale factors were used from benzene molecule. For the carboxylic group, scaling equations and specific scale factors at different levels were also determined to be used in benzoic acid derivatives. A reassignment of several bands was done. A comparison of the cost/effective method and procedure of scaling was carried out. A significant reduction of the error in the predicted frequencies was obtained over the one-factor standard scaling procedure. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002