NON-PLANAR STRUCTURES OF THE HIGH-ENERGY ROTATIONAL CONFORMERS OF \\ 2-METHYLBUTA-1,3-DIENE (ISOPRENE) AND 2,3-DIMETHYLBUTA-1,3-DIENE

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2009

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Ohio State University

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Optimization of the geometrical parameters and determination of the force fields for rotamers of the title molecules were performed at the MP2(FC)/aug-cc-pVDZ//MP2(FC)/aug-cc-pVDZ computational level. The vibrational analyses of these conformers were carried out using scaled quantum-mechanical force field methodology. Recent experimental wavenumbers for these conformers and their deuteroisomers were incorporated into these analyses. The theoretical non-planar structures of the high-energy conformers of 2-methylbuta-1,3-diene (isoprene) and 2,3-dimethylbuta-1,3-diene were corroborated by good agreement between the experimental and theoretical wavenumbers of the molecules under investigation. The dihedral angles of the non-planar high-energy conformers for rotation around the =C--C= bond are as follows: $41.6^{irc}$ for 2-methylbuta-1,3-diene (isoprene) \underline{19}, 421 (2008).} and $47.0^{irc}$ for 2,3-dimethylbuta-1,3-diene \underline{19}, 793 (2008).}. Previous studies performed at the HF/6-31G level gave $41.0^{irc}$ and $48.5^{irc}$ for the first and second compounds, respectively.

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% Yu.~N.~Panchenko, Ch.~W.~Bock, J.~D.~Larkin, A.~V.~Abramenkov, F.~Kuhnemann, \textit{Struct. Chem.% Yu.~N.~Panchenko, Ch.~W.~Bock, J.~D.~Larkin, A.~V.~Abramenkov, \textit{Struct. Chem.
Author Institution: Dept. of Chemistry, M. V. Lomo\-no\-sov Moscow State University; Moscow 119992, Russian Federation; Dept. of Chemistry and Biochemistry, Philadelphia University; Philadelphia, PA 19144; Dept. of Chemistry, Bloomsburg University of Pennsylvania; Bloomsburg, PA 17815; Dept. of Chemistry, M. V. Lomo\-no\-sov Moscow State University; Moscow 119992, Russian Federation; Institute of Applied Physics, Bonn University, 53115 Bonn, Germany

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