The Fermi doublet V2−V3 + V4 of CH3CN as a probe of molecular interactions

Bertrán, José Fernández; Serna, Boris La; Doerffel, Klaus; Dathe, Klaus; Kabish, Gunther

doi:10.1016/0022-2860(82)90129-6

Cited by 27 publications

(1 citation statement)

References 13 publications

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“…Instead, liquid acetonitrile would have a cluster structure with molecules located in two different environments (in the clusters' periphery and inside the clusters) giving rise to two separated vibrational signals. On the other hand, several authors have justified the complex band structure of this acetonitrile fundamental as because of Fermi resonance with the combination band ν 3 + ν 4 (CH 3 deformation and C−C stretching bands) , or by the presence of hot band transitions from the first excited state of the degenerate C−C⋮N bending ν 8 mode. − These problems, inherent in the complex vibrational behavior of acetonitrile, could be avoided by using acrylonitrile, which is simpler from a spectroscopic point of view. Furthermore, because of its low symmetry, it has no degenerate vibrations.…”

Section: Introductionmentioning

confidence: 99%

An Experimental Raman and Theoretical DFT Study on the Self-Association of Acrylonitrile

et al. 2007

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The liquid structure of acrylonitrile (propenenitrile) has been investigated using Raman spectroscopy and density functional theory (DFT) ab initio calculations with the 6-311++G** basis set. Two different and complementary experimental approaches were undertaken: FT-Raman spectra of 13 acrylonitrile solutions in carbon tetrachloride (concentration range=0.25-12.0 mol.L-1) were studied in detail including principal component analysis (PCA) of the CN stretching band. Furthermore, dispersive Raman spectra of neat acrylonitrile were obtained at eight different temperatures from 238 up to 343 K. The complex and asymmetric acrylonitrile Raman CN stretching band can be decomposed into two components attributed to monomeric and self-associated forms. Ab initio results fully support this assignment and suggest that the self-associated complex is a nonplanar trimer held together by dipole-dipole interactions. At ambient temperature, the composition of acrylonitrile can be expressed as a mixture of 25% monomers and 75% trimers. Close to the boiling point, trimers still represent 65% of the liquid composition. The corresponding enthalpy of association was estimated to be -22+/-2 kJ.mol-1.

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Section: Introductionmentioning

confidence: 99%

An Experimental Raman and Theoretical DFT Study on the Self-Association of Acrylonitrile

et al. 2007

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ChemInform Abstract: THE FERMI DOUBLET V2‐V3 + V4 OF ACETONITRILE AS A PROBE OF MOLECULAR INTERACTIONS

Bertrán¹,

Serna²,

Doerffel³

et al. 1983

Chemischer Informationsdienst

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Ab initio study of the influence of aggregation on the infrared spectrum of acetonitrile

Mathieu¹,

Defranceschi²,

Delhalle

1993

Int J of Quantum Chemistry

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With the aim of investigating the influence of direct intermolecular interactions between nitrile groups on the infrared features of nitrile polymers, vibrational frequencies and infrared intensities of acetonitrile and of its antiparallel dimer are compared. It is found that whereas frequencies are unchanged upon association infrared intensities are dramatically affected. In particular, the striking difference between the intensities of the CN stretching band measured in gas phase, on the one hand, and in the liquid, on the other, is already accounted for at the dimer level. Despite the poor reliability of absolute values of calculated intensities, it is interesting to note that consistent trends are obtained at various levels of theory. These results suggest that ab initio calculations of infrared intensities can be useful to interpret infrared measurements, thus contributing to the elucidation of molecular structure of materials. 0 1993 John Wiley & Sons, Inc.

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The Fermi doublet V2−V3 + V4 of CH3CN as a probe of molecular interactions

Cited by 27 publications

References 13 publications

An Experimental Raman and Theoretical DFT Study on the Self-Association of Acrylonitrile

An Experimental Raman and Theoretical DFT Study on the Self-Association of Acrylonitrile

ChemInform Abstract: THE FERMI DOUBLET V2‐V3 + V4 OF ACETONITRILE AS A PROBE OF MOLECULAR INTERACTIONS

Ab initio study of the influence of aggregation on the infrared spectrum of acetonitrile

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