New Insights on the Vibrational Dynamics of 2-Methoxy-, 4-Methoxy- and 4-Ethoxy-Benzaldehyde from INS Spectra and Periodic DFT Calculations
authors Ribeiro-Claro, PJA; Vaz, PD; Nolasco, MM; Gil, FPSC; de Carvalho, LAEB; Marques, MPM; Amado, AM
nationality International
journal MATERIALS
author keywords density functional theory; inelastic neutron scattering; vibrational assignment; molecular crystal; torsional potential; C-H horizontal ellipsis O hydrogen bonds
keywords INELASTIC NEUTRON-SCATTERING; DENSITY-FUNCTIONAL THEORY; AB-INITIO; INTERNAL-ROTATION; FT-RS; X-RAY; SPECTROSCOPY; RAMAN; IR; NMR
abstract 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.
publisher MDPI
isbn 1996-1944
year published 2021
volume 14
issue 16
digital object identifier (doi) 10.3390/ma14164561
web of science category 16
subject category Chemistry, Physical; Materials Science, Multidisciplinary; Metallurgy & Metallurgical Engineering; Physics, Applied; Physics, Condensed Matter
unique article identifier WOS:000689431800001
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journal impact factor 3.057
5 year journal impact factor 3.424
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