Temperature and H/D Isotopic Effects in the IR Spectra of the Hydrogen Bond in Solid-State 2-Furanacetic Acid and 2-Furanacrylic Acid

Abstract

Polarized IR spectra of 2-furanacetic acid and of 2-furanacrylic acid crystals were measured at 293 K and 77 K in the 𝑣O−H and 𝑣O−H band frequency ranges. The corresponding spectra of the two individual systems strongly differ, one from the other, by the corresponding band shapes as well as by the temperature effect characterizing the bands. The crystal spectral properties remain in a close relation with the electronic structure of the two different molecular systems. We show that a vibronic coupling mechanism involving the hydrogen bond protons and the electrons on the π-electronic systems in the molecules determines the way in which the vibrational exciton coupling between the hydrogen bonds in the carboxylic acid dimers occurs. A strong coupling in 2-furanacrylic acid dimers prefers a “tail-to-head-” type Davydov coupling widespread by the π-electrons. A weak through-space coupling in 2-furanacetic acid dimers is responsible for a “side-to-side-” type coupling. The relative contribution of each exciton coupling mechanism in the dimer spectra generation is temperature and the molecular electronic structure dependent. This explains the observed difference in the temperature-induced evolution of the compared spectra.