Molecular structure and large-amplitude motion of p-diethynylbenzene from gas-phase electron diffraction and theoretical calculations

Aldo Domenicano, Antonio Arcadi, Fabio Ramondo, Anna Rita Campanelli, Gustavo Portalone, György Schultz, István Hargittai

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Abstract

The molecular structure of p-diethynylbenzene has been determined by gas-phase electron diffraction and ab initio MO calculations at the HF/6-31G* and MP2/6-31G*(fc) levels. The two ethynyl groups undergo large-amplitude bending motions, making the equilibrium D2h model inadequate to describe the average structure from electron diffraction. Based on spectroscopic information on low-frequency modes, the electron diffraction data were approximated by a model consisting of a mixture of rigid conformers, differing only in the extent of the symmetric out-of-plane bending of the substituents. This gave the following geometrical parameters: 〈Cortho-Cipso-Cortho = 119.2 ± 0.2°, 〈rg(C-C)〉 = 1.402 ± 0.003 Å, rg(Cring-Csp) = 1.431 ± 0.003 Å, and rg(C≡C) = 1.211 ± 0.003 Å. The computed re values (MP2) are 119.2°, 1.401 Å, 1.430 Å, and 1.223 Å, respectively, with the Cipso-Cortho bond 0.016 Å longer than the central C-C bond. The HF/6-31G* geometries of ethynylbenzene and p-diethynylbenzene indicate that the interaction of the ethynyl group with the ring is not affected by the presence of another ethynyl group in the para position. Comparison with solid-state results shows no appreciable effect of crystal environment on the ring deformation in these molecules.

Original languageEnglish
Pages (from-to)14625-14629
Number of pages5
JournalJournal of physical chemistry
Volume100
Issue number35
Publication statusPublished - Aug 29 1996

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ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Domenicano, A., Arcadi, A., Ramondo, F., Campanelli, A. R., Portalone, G., Schultz, G., & Hargittai, I. (1996). Molecular structure and large-amplitude motion of p-diethynylbenzene from gas-phase electron diffraction and theoretical calculations. Journal of physical chemistry, 100(35), 14625-14629.