“Long-distance” H/D isotopic self-organization phenomena in scope of the infrared spectra of hydrogen-bonded terephthalic and phthalic acid crystals

Abstract

This paper deals with the experimental and theoretical studies of abnormal properties of terephthalic acid (TAC) and phthalic acid (PAC) crystals manifested in the H/D isotopic exchange. The widely utilized deuteration routine appeared to be insufficiently effective in the case of the h6-TAC isotopomer. In the case of the d4-TAC derivative the isotopic exchange process occurred noticeably more effectively. In contrast, both isotopomers of PAC, h6 and d4, appeared much more susceptible for deuteration. A theoretical model was elaborated describing “long-distance” dynamical co-operative interactions involving hydrogen bonds in TAC and PAC crystals. The model assumes extremely strong dynamical co-operative interactions of hydrogen bonds from the adjacent (COOH)2 cycles. This leads to an additional stabilization of h6–TAC molecular chains. The interaction energies affect the chemical equilibrium of the H/D isotopic exchange. The model predicts a differentiated influence of the H and D atoms linked to the aromatic rings on to the process. In this approach the totally-symmetric CH bond stretching vibrations and the proton stretching totally symmetric vibrations couple with the π-electronic motions. It was also shown that identical hydrogen isotope atoms, H or D, in whole TAC molecules, noticeably enlarge the energy of the dynamical co-operative interactions in the crystals, in contrast to the case of different hydrogen isotopes present in the carboxyl groups and linked to the aromatic rings. The “long-distance” dynamical co-operative interactions in PAC crystals were found of a minor importance due to the electronic properties of PAC molecules.