authors |
Nolasco, MM; Araujo, CF; Vaz, PD; Amado, AM; Ribeiro-Claro, P |
nationality |
International |
journal |
MOLECULES |
author keywords |
inelastic neutron scattering; density functional theory; vibrational assignment; molecular crystal; torsional potential; C-H center dot center dot center dot O hydrogen bonds |
keywords |
INELASTIC NEUTRON-SCATTERING; DOT-O INTERACTIONS; HYDROGEN-BOND; FLUORESCENCE-SPECTRA; MOLECULAR-CRYSTALS; RAMAN; ROTATION; IR; SPECTROSCOPY; S-0 |
abstract |
The present work emphasizes the value of periodic density functional theory (DFT) calculations in the assessment of the vibrational spectra of molecular crystals. Periodic calculations provide a nearly one-to-one match between the calculated and observed bands in the inelastic neutron scattering (INS) spectrum of crystalline 4-phenylbenzaldehyde, thus validating their assignment and correcting previous reports based on single molecule calculations. The calculations allow the unambiguous assignment of the phenyl torsional mode at ca. 118-128 cm(-1), from which a phenyl torsional barrier of ca. 4000 cm(-1) is derived, and the identification of the collective mode involving the antitranslational motion of CH...O bonded pairs, a hallmark vibrational mode of systems where C-H...O contacts are an important feature. |
publisher |
MDPI |
isbn |
1420-3049 |
year published |
2020 |
volume |
25 |
issue |
6 |
digital object identifier (doi) |
10.3390/molecules25061374 |
web of science category |
Biochemistry & Molecular Biology; Chemistry, Multidisciplinary |
subject category |
Biochemistry & Molecular Biology; Chemistry |
unique article identifier |
WOS:000530248700117
|