Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Rotamerism and intramolecular interactions of n-propyl halides and their partially and fully fluorinated derivatives. Electronic structure, topology and vibrational spectroscopy. / Benassi, Enrico; Fan, Haiyan.
в: Journal of Molecular Liquids, Том 342, 116943, 15.11.2021.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Rotamerism and intramolecular interactions of n-propyl halides and their partially and fully fluorinated derivatives. Electronic structure, topology and vibrational spectroscopy
AU - Benassi, Enrico
AU - Fan, Haiyan
N1 - Funding Information: HF thanks Nazarbayev University small grant 110119FD4542 and the computational resources offered by Nazarbayev University. The Authors are grateful to the Siberian Supercomputer Centre of Institute of Computational Mathematics and Mathematical Geophysics (Russian Academy of Sciences, Novosibirsk, Russian Federation) for kindly providing the computational resources; the technical staff of the Institute is also thanked for the assistance. Funding Information: HF thanks Nazarbayev University small grant 110119FD4542 and the computational resources offered by Nazarbayev University. Publisher Copyright: © 2021 Elsevier B.V.
PY - 2021/11/15
Y1 - 2021/11/15
N2 - n-Propyl halides (C3H7X; X = Cl, Br, I) and their partially and fully fluorinated analogues were investigated through quantum mechanical calculations and vibrational spectroscopy. Two energetic minima, corresponding to the rotational isomers (s-trans and s-gauche) were identified for all the species. The Bader quantum theory of Atoms-In-Molecules (AIM) analysis identified some bond and ring critical points for CF3-type gauche compounds involving F atoms on the CF3 group and X and F atoms on the CXF2 group. Such non-covalent intramolecular interactions are found not only responsible for the physical properties of n-propyl halides, but also the features of 19F NMR of n-perfluoropropyl iodide. The comparison between experimental vibrational spectra of some compounds and the calculated ones in both harmonic and anharmonic approximation indicated the frozen phase of these compounds is dominated with s-trans isomers, whereas the liquid phase is a mixture of both isomers. Rovibrational coupling was hypothesized to be responsible for the anharmonicity reflected in the vibrational spectra of C3H7X (X = Br and I). Based on the maps of Molecular Electrostatic Potential (MEP) surfaces, a σ-hole was featured for all 24 compounds in both isomers. The thermodynamics of isomerisation and fluorination was thoroughly analysed and well supported by the Highest Occupied Molecular Orbitals (HOMOs) and MEP.
AB - n-Propyl halides (C3H7X; X = Cl, Br, I) and their partially and fully fluorinated analogues were investigated through quantum mechanical calculations and vibrational spectroscopy. Two energetic minima, corresponding to the rotational isomers (s-trans and s-gauche) were identified for all the species. The Bader quantum theory of Atoms-In-Molecules (AIM) analysis identified some bond and ring critical points for CF3-type gauche compounds involving F atoms on the CF3 group and X and F atoms on the CXF2 group. Such non-covalent intramolecular interactions are found not only responsible for the physical properties of n-propyl halides, but also the features of 19F NMR of n-perfluoropropyl iodide. The comparison between experimental vibrational spectra of some compounds and the calculated ones in both harmonic and anharmonic approximation indicated the frozen phase of these compounds is dominated with s-trans isomers, whereas the liquid phase is a mixture of both isomers. Rovibrational coupling was hypothesized to be responsible for the anharmonicity reflected in the vibrational spectra of C3H7X (X = Br and I). Based on the maps of Molecular Electrostatic Potential (MEP) surfaces, a σ-hole was featured for all 24 compounds in both isomers. The thermodynamics of isomerisation and fluorination was thoroughly analysed and well supported by the Highest Occupied Molecular Orbitals (HOMOs) and MEP.
KW - Anharmonic calculations
KW - Bader's theory
KW - Fluorination effects
KW - FT-IR and Raman spectroscopies
KW - Natural bond orbitals analysis
KW - Non-covalent interactions
KW - Quantum chemical calculations
KW - Rotational isomers in liquid and frozen phases
UR - http://www.scopus.com/inward/record.url?scp=85112655980&partnerID=8YFLogxK
U2 - 10.1016/j.molliq.2021.116943
DO - 10.1016/j.molliq.2021.116943
M3 - Article
AN - SCOPUS:85112655980
VL - 342
JO - Journal of Molecular Liquids
JF - Journal of Molecular Liquids
SN - 0167-7322
M1 - 116943
ER -
ID: 34208974