Exploring Relative Thermodynamic Stabilities of Formic Acid and Formamide Dimers - Role of Low-Frequency Hydrogen-Bond Vibrations.

Abstract

The low-frequency fundamentals together with the high-frequency modes, responsible for hydrogen bonding (OH/NH stretching modes), were analyzed to correlate the intensities with the hydrogen-bond strengths/binding energies of the formic acid and formamide dimers using Møller-Plesset second-order perturbation (MP2) and coupled cluster computations with explicit anharmonicity corrections. Linear correlations were observed for both the formic acid and formamide dimers, and as consequence of such correlation an additive properties of binding energies with respect to the local hydrogen-bond energies of fragments involved (for these dimers) has been proposed. It has been further observed that (i) the nature of their six low-frequency fundamentals are very similar, and (ii) the in-plane bending and stretch-bend fundamentals of different dimers of these two species (depending on the dimer structure), in this low-frequency region, modulate their strength of hydrogen-bond/binding hence their relative stability order. These results were further verified against the results from Gaussian-G4-MP2 (G4MP2), Gaussian-G2-MP2 (G2MP2), and complete basis set (CBS-QB3) methods of high accuracy energy calculations.