Quantum-chemical modeling of energy parameters and vibrational spectra of chain and cyclic clusters of monohydric alcohols

• Systematic investigation of cluster structures in monohydric alcohols was performed.
• Total energy of interaction, entropy, free Gibbs energies at 293 K for these clusters were calculated.
• Modeling of vibrational spectra of chosen clusters was made.
• Comparison of these spectra with experimental ones was made.

The specific peculiarities of alcohols such as heightened viscosity, boiling temperature and surface tension can be explained by the capability of their molecules to form relatively stable associates named clusters due to hydrogen bonding. In present work the stability of different chain-like and cyclic clusters of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol was investigated by means of quantum-chemical simulation and particular by recently developed DFT exchange–correlation functional M06-2X. The relative stability of the cluster structure was evaluated by the total energy per molecule at low temperatures (where all alcohols exist in solid state) and by the changing of the free Gibbs energy upon cluster formation at the room temperature. For the verification of revealed results the conformity of calculated IR spectra of the most stable cluster structures with the experimental IR spectra at different temperatures was analyzed.