New Insights on the Vibrational Dynamics of 2-Methoxy-, 4-Methoxy- and 4-Ethoxy-Benzaldehyde from INS Spectra and Periodic DFT Calculations

• Autor(a) principal: Ribeiro-Claro, Paulo J. A.
• Data de Publicação: 2021
• Outros Autores: Vaz, Pedro D., Nolasco, Mariela M., Gil, Francisco P. S. C., Carvalho, Luís A. E. Batista de, Catarro, Maria Paula M. Marques, Amado, Ana M.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10316/95671; https://doi.org/10.3390/ma14164561
• topic: C–H…O hydrogen bonds; Density functional theory; Inelastic neutron scattering; Molecular crystal; Torsional potential; Vibrational assignment

The dynamics of 2-methoxybenzaldehyde, 4-methoxybenzaldehyde, and 4-ethoxybenzaldehyde in the solid state are assessed through INS spectroscopy combined with periodic DFT calculations. In the absence of experimental data for 4-ethoxybenzaldehyde, a tentative crystal structure, based on its similarity with 4-methoxybenzaldehyde, is considered and evaluated. The excellent agreement between calculated and experimental spectra allows a confident assignment of the vibrational modes. Several spectral features in the INS spectra are unambiguously assigned and torsional potential barriers for the methyl groups are derived from experimental frequencies. The intramolecular nature of the potential energy barrier for methyl rotation about O– CH3 bonds compares with the one reported for torsion about saturated C–CH3 bonds. On the other hand, the intermolecular contribution to the potential energy barrier may represent 1/3 of the barrier height in these systems. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.