Elucidating the Infrared Spectral Properties of Succinic Molecular Acid Crystals: Illustration of the Structure and the Hydrogen Bond Energies of the Crystal and Its Deuterated Analogs

Abstract

Herein, the infrared spectroscopic properties of molecular succinic acid crystals (SA) and their four isotopic analogs [C 2 H 4 (COOH) 2 , h 6 -SA; C 2 H 4 (COOD) 2 , d 2 -SA; C 2 D 4 (COOH) 2 , d 4 -SA; C 2 D 4 (COOD) 2 , d 6 -SA] are reported. The correlation between the structure of succinic acid molecules and their corresponding hydrogen bond energies is elucidated. The effects related to the isotopic dilution as well as the changes in the spectrum recording temperature on the fine structures of the v O−H and v O−D bands are interpreted. The infrared spectral anomalies detected in the spectra of isotopically neat succinic nanocrystal acids are confirmed by theoretical calculations using density functional theory (DFT). According to previous spectroscopic studies of succinic acid and those carried out for α,ω-dicarboxylic acids, a decent agreement between the experimental results and the theoretical DFT simulations is obtained. Moreover, the spectra of single crystals of the h 6 and d 4 succinic acid variants prove that the vibrational coupling mechanism between the (COOH) 2 cycles is rigorously convergent to that detected in the spectra of aromatic carboxylic acids, suggesting thereby that the promotion of symmetryforbidden high stretching IR transitions plays a crucial role. Furthermore, the obtained experimental results reveal that the succinic acid shows a spectral behavior significantly different from that characteristic of hydrogen associations of other acids of homologous series, such as the glutaric, adipic, malonic, and pimelic acid crystals. The results obtained herein shed light on the way to explore the revealed structure of isotopic derivatives of succinic acid crystals and may prove to be useful results for understanding the nature of unconventional interactions as well as the macroscopic energy effects directing the development of hydrogen associations.

The Analytical Possibilities of FT-IR Spectroscopy Powered by Vibrating Molecules

“…The family of unconventional infrared spectral effects for molecular crystals includes H/D isotopic substitution within hydrogen bonds and areas of molecules that are not formally involved in their formation [ 27 , 28 ].…”

“…This fact is confirmed by the significant invariance of the ν X–H and ν X–D bands. The discovery of H/D isotopic “self-organisation”, which is a consequence of the dynamic cooperativeness of hydrogen bridges, is a very significant contribution to the development of modern chemical physics [ 6 , 27 , 28 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ].…”