Renewed spectroscopic and theoretical research of hydrogen bonding in ascorbic acid

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 320; p. 124585
• Main Authors: Jóźwiak, Kinga, Jezierska, Aneta, Panek, Jarosław J., Łydżba-Kopczyńska, Barbara, Filarowski, Aleksander
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 05.11.2024
• Subjects: Ascorbic acid; CPMD simulations; Hydrogen bond; Isotopic effect; Vitamin C; CPMD simulations; Ascorbic acid; Vitamin C; Isotopic effect; Hydrogen bond
• ISSN: 1386-1425; 1873-3557
• DOI: 10.1016/j.saa.2024.124585

[Display omitted] •The renewed and corrected interpretations of experimental vibrational spectra and hydrogen bonds in the L- and D-iso ascorbic acids.•The d(OO) = f(γ(OH)) correlation is a tool for verification of the dissimilarity between the resonance-assisted hydrogen bond (RAHB) and the charge assisted hydrogen bond (CAHB).•The difference between the bridged proton dynamics of the intramolecular and intermolecular hydrogen bonds in ascorbic acids shown by CPMD and DFT calculations. The studies of two isomers of ascorbic acid and their deuteroanalogues, presented in the paper, have been accomplished by vibrational spectroscopy methods and quantum-chemical simulations. The spectroscopic research of L-ascorbic and D-isoascorbic acids have been carried out by the infrared (IR) and Raman (R) techniques. On the basis of the obtained results the spectral interpretation of the hydrogen bonded groups of ascorbic acids has been performed. Car-Parrinello Molecular Dynamics (CPMD) and Density Functional Theory (DFT) have been employed to support spectroscopic experimental findings and shed light onto the bridged proton dynamics in the L- and D- isomers of ascorbic acids. The accurate assignments of the hydrogen bond modes have been accomplished with the application of deuterosubstitution, CPMD-solid state simulations and Potential Energy Distribution (PED) analysis. The spectral and structural results have shown that dependency ν(OH) = f(γ(OH)) is the most common for the OHO hydrogen bond, whereas dependency d(OO) = f(γ(OH)) differs as for the ionic and resonance assisted hydrogen bonds.