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Theoretical investigations of molecules composed only of fluorine, oxygen and nitrogen: determination of the equilibrium structures of FOOF, (NO)2 and FNNF and the transition state structure for FNNF cis-trans isomerization

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Abstract

The deficiencies of common ab initio methods for the reliable prediction of the equilibrium structures of compounds composed of only the fluorine, oxygen and nitrogen atoms are investigated. Specifically, the importance of using large one-particle basis sets with multiple sets of polarization functions has been studied. Additionally, the need for a set of f basis functions was investigated. Several different single reference electron correlation methods have been tested in order to determine whether it is possible for a single reference based method to be routinely used on such chemical systems. These electron correlation methods include second order Møller-Plesset perturbation theory (MP2), singles and doubles configuration interaction (CISD), the coupled pair functional (CPF) approach and singles and doubles coupled cluster (CCSD) theory. The molecular systems studied include difluoroperoxide (FOOF), the cis form of the NO dimer, cis and trans difluorodiazene (FNNF) and the transition state to interconversion of the cis and trans isomers of FNNF. To the best of our knowledge, this is the first time that the cis-trans isomerization transition state has been reported. At the highest level of theory employed, the equilibrium structures of cis and trans FNNF agree very well with the experimental structures. However, the barrier to interconversion is predicted to be 65 kcal/mole, which is substantially higher than the experimental activation energy of 32 kcal/mole. Potential sources of error are discussed. A new diagnostic method for determining a priori the reliability of single reference based electron correlation methods is suggested and discussed.

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Author notes

  1. Timothy J. Lee (NATO/NSF Postdoctoral Fellow)

    Present address: NASA Ames Research Center, Mail Stop 230-3, 94035, Muffett Field, CA, USA

Authors and Affiliations

  1. University Chemical Laboratory, Lensfield Road, CB2 1EW, Cambridge, UK

    Timothy J. Lee (NATO/NSF Postdoctoral Fellow) & Julia E. Rice (Research Fellow)

  2. Center for Computational Quantum Chemistry, School of Chemical Sciences, University of Georgia, 30602, Athens, GA, USA

    Gustavo E. Scuseria & Henry F. Schaefer III

  3. Newnham College, Cambridge

    Julia E. Rice (Research Fellow)

Authors
  1. Timothy J. Lee
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  2. Julia E. Rice
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  3. Gustavo E. Scuseria
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  4. Henry F. Schaefer III
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Contribution CCQC No. 36

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Lee, T.J., Rice, J.E., Scuseria, G.E. et al. Theoretical investigations of molecules composed only of fluorine, oxygen and nitrogen: determination of the equilibrium structures of FOOF, (NO)2 and FNNF and the transition state structure for FNNF cis-trans isomerization. Theoret. Chim. Acta 75, 81–98 (1989). https://doi.org/10.1007/BF00527711

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  • DOI: https://doi.org/10.1007/BF00527711

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