Ground and excited states of the monomer and dimer of certain carboxylic acids

Abstract

The ground-state properties of the monomer and the dimer of formic acid, acetic acid, and benzoic acid have been investigated using Hartree-Fock (HF) and density functional theory (DFT) methods using the 6-311++G(d,p) basis set. Some of the low-lying excited states have been studied using the time-dependent density functional theory (TDDFT) with LDA and B3LYP functionals and also employing complete-active-space-self-consistent-field (CASSCF) and multireference configuration interaction (MRCI) methodologies. DFT calculations predict the ground-state geometries in quantitative agreement with the available experimental results. The computed binding energies for the three carboxylic acid dimers are also in accord with the known thermodynamic data. The TDDFT predicted wavelengths corresponding to the lowest energy n-π^∗ transition in formic acid (214 nm) and acetic acid (214 nm) and the π-π^∗ transition in benzoic acid (255 nm) are comparable to the experimentally observed absorption maxima. In addition, TDDFT calculations predict qualitatively correctly the blue shift (4-5 nm) in the excitation energy for the π-π^∗ transition in going from the monomer to the dimer of formic acid and acetic acid and the red shift (~19 nm) in π-π^∗ transition in going from benzoic acid monomer to dimer. This also indicates that the electronic interaction arising from the hydrogen bonds between the monomers is marginal in all three carboxylic acids investigated.