Identification of Di(oxymethylene)glycol in the Raman Spectrum of Formaldehyde Aqueous Solutions by ab Initio Molecular Dynamics Simulations and Quantum Chemistry Calculations

Pauline Delcroix (1) , Marco Pagliai (2) , Didier Bégué (3) , Benjamin Hanoune (1)

1 PC2A - Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522
2 UniFI - Università degli Studi di Firenze = University of Florence = Université de Florence
3 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

Di(oxymethylene)glycol forms in formaldehyde aqueous solutions by polymerization of methanediol. The structure and hydrogen bond interactions of di(oxymethylene)glycol with water were characterized by performing Car–Parrinello molecular dynamics simulations. The anharmonic vibrational frequencies of di(oxymethylene)glycol in solution were determined with ab initio calculations considering explicitly the hydrogen-bonded water molecules, while other interactions with solvent were described within a polarizable continuum model approach. The calculations allow for a detailed interpretation of the experimental Raman spectrum of formaldehyde aqueous solutions, leading to the assignment of the band at 920 cm–1 to the symmetric CO stretching mode of di(oxymethylene)glycol.

Keywords: Solvents; Quantum mechanics; Solution chemistry; Aldehydes; Molecules

Domains: Theoretical and/or physical chemistry; Chemical Physics [physics.chem-ph]

Pauline Delcroix, Marco Pagliai, Didier Bégué, Benjamin Hanoune. Identification of Di(oxymethylene)glycol in the Raman Spectrum of Formaldehyde Aqueous Solutions by ab Initio Molecular Dynamics Simulations and Quantum Chemistry Calculations. Journal of Physical Chemistry A, 2015, J. Phys. Chem. A, 119 (38), pp.9785-9793. ⟨10.1021/acs.jpca.5b06293⟩. ⟨hal-02957791⟩