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Ab initio studies of tetrafluoroethylene and tetratrifluoromethylethylene molecules in the ground and “twisted” states

  • Physical Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

Ab initio calculations with full optimization of geometry have been carried out with the 6–31 G* basis set on tetrafluoroethylene (with the unrestricted Hartree-Fock method—UHF and the second-order Moller-Plesset perturbation theory—MP2) and tetratrifluoromethylethylene (with UHF) molecules in the singlet ground and triplet biradical states. The symmetry of the tetrafluoroethylene molecule in the triplet biradical state was demonstrated to differ from that of ethylene (D 2d ) due to the deviation of fluorine atoms from CCFF plane. The MP2 optimized geometries of ethylene and tetrafluoroethylene were used for higher level calculations (MP3, MP4, CCSD). The energy of the ground state singlet-biradical triplet splitting decreases in the series: ethylene>tetrafluoroethylene> tetratrifluoromethylethylene. These data on energy splitting explain the increase in reactivity toward the [2+2]-cycloaddition on going from ethylene to tetrafluoroethylene.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    Yu. A. Borisov

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  1. Yu. A. Borisov
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 605–607, April, 1998.

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Borisov, Y.A. Ab initio studies of tetrafluoroethylene and tetratrifluoromethylethylene molecules in the ground and “twisted” states. Russ Chem Bull 47, 584–586 (1998). https://doi.org/10.1007/BF02495957

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  • DOI: https://doi.org/10.1007/BF02495957

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