1. The role of dispersion and anharmonic corrections in conformational analysis of flexible molecules: the allyl group rotamerization of matrix isolated safrole
- Author
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Malgorzata Biczysko, Maria Wierzejewska, Justyna Krupa, and Hongli Zhang
- Subjects
Materials science ,Anharmonicity ,General Physics and Astronomy ,Infrared spectroscopy ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Matrix (mathematics) ,Coupled cluster ,Computational chemistry ,Molecule ,Density functional theory ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,0210 nano-technology ,Conformational isomerism ,Basis set - Abstract
Conformational changes of the monomeric safrole (5-(2-propenyl)-1,3-benzodioxole) isolated in low temperature xenon matrices were induced thermally or using narrow-band UV radiation. The rotation of the allyl group taking place in the studied matrices was followed by FTIR spectroscopy. Safrole represents a challenging example of a flexible molecule highlighting the importance of dispersion interactions and anharmonic effects in the structural, spectroscopic and energetic analysis. Structures of the safrole conformers, their energetics and infrared spectra have been calculated using various computational methods ranging from density functional theory (DFT) to coupled cluster (CC). The best theoretical results were obtained by integrating CCSD(T) energies including complete basis set extrapolation and core-valence corrections with B2PLYP-D3 equilibrium structures and hybrid B2PLYP-D3/B3LYP-D3 anharmonic computations for IR spectra and thermodynamics.
- Published
- 2019
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