Skip to main content
SpringerLink
Log in

Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

After the separation of the donor, the acceptor, and the σ-type bridge from the π-σ-π system, the geometries of biphenyl, biphenyl anion radical, naphthalene, and naphthalene anion radical are optimized, and then the reorganization energy for the intermolecular electron transfer (ET) at the levels of HF/4-31G and HF/DZP is calculated. The ET matrix elements of the self-exchange reactions of theπ-σ-π systems have been calculated by means of both the direct calculation based on the variational principle, and the transition energy between the molecular orbitals at the linear coordinateR = 0.5. For the cross reactions, the ET matrix element and the geometry of the transition state are determined by searching the minimum energy splitting Δmin along the reaction coordinate. In the evaluation of the solvent reorganization energy of the ET in solution, the Marcus’ two- sphere model has been invoked. A few of ET rate constants for the intramolecular ET reactions for the π-σ-π systems, which contain the biphenylyl as the donor and both biphenylyl and naphthyl as the acceptor, have been obtained.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Barbara, P. F., Meyer, T. J., Ratner, M. A., Contemporary issues in electron transfer research,J. Phys. Chem., 1996, 100: 13148.

    Article  CAS  Google Scholar 

  2. Miller, G. L., Calcaterra, L. T., Green, N. J. et al., Distance, stereoelectronic effects, and the Marcus inverted region in intramolecular electron transfer in organic radical anions,J. Phys. Chem., 1986, 90: 3673.

    Article  Google Scholar 

  3. Miller, J. R., Paulson, B. P., Bal, R. et al., Torsional low-frequency reorganization energy of biphenyl anion in electron transfer reactions,J. Phys. Chem., 1995, 99: 6923.

    Article  CAS  Google Scholar 

  4. Bobrowski, K., Holeman, J., Poznanski, J. et al., Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 5. Trp.→Tyr. radical transformation in H-Trp-(pro)n-Tyr-OH series of peptides,J. Phys. Chem., 1992, 96: 10036.

    Article  CAS  Google Scholar 

  5. Braga, M., Larson, S., Electronic factor for electron transfer through cyclohexane-type spacer,J. Phys. Chem., 1993, 97: 8929.

    Article  CAS  Google Scholar 

  6. Siddarth, P., Marcus, R. A., Electron transfer in proteins: an artificial intelligence approach to electronic coupling,J. Phys. Chem., 1993, 97: 2400.

    Article  CAS  Google Scholar 

  7. Yoshimura, A., Nozaki, K., Ikeda, N. et al., Photoinduced electron transfer and back electron transfer within binuclear complexes of Ru(II) andCo(III),J. Am. Chem. Soc., 1993, 115: 7521.

    Article  CAS  Google Scholar 

  8. Li Xiangyuan, He Fucheng, Electron transfer NO2 ++NO→ N02+NO+ in aromatic nitration,Science in China, Ser. B, 1997, 40 (5): 523.

    Article  CAS  Google Scholar 

  9. Li Shunlai, Li Zonghe, Xu Huijun, The theoretical study of the intramolecular electron transfer reactions for a series of organic systems,Science in China (in Chinese), Ser. B, 1997, 27(4): 325.

    Google Scholar 

  10. Takei, Y., Yamaguchi, T., Osamura, Y. et al., Electronic spectra and molecular structure of biphenyl and para-substituted biphenyls in a supersonic jet,J. Phys. Chem., 1988, 92: 577.

    Article  CAS  Google Scholar 

  11. Rubio, M., Merchan, M., Orti, E., The internal rotational barrier of biphenyl studied with multiconfigurational second-order perturbation theory (CASPT2),Theor. Chim. Acta, 1995, 91: 17.

    CAS  Google Scholar 

  12. Eberson, L., Radner, F., Electron transfer reaction in organic chemistry, VI. Possible role of electron transfer in aromatic nitration by nitrosonium and nitronium ion,Acta Chem. Scand., 1984, B38: 861.

    Article  CAS  Google Scholar 

  13. Farazdel, A., Dupuis, M., Clementi, E. et al., Electric field induced intramolecular electron transfer in spiro π-electron systems and their suitability as molecular electronic devices, A theoretical study,J. Am. Chem. Soc., 1990, 112: 4206.

    Article  CAS  Google Scholar 

  14. Li, X. Y., Tian, A. M., He, F. C. et al., Electron transfer integral between two zero-overlap states,J. Comput. Chem., 1996, 17: 1108.

    Article  CAS  Google Scholar 

  15. Rodriguez-Monge, L., Larson, S., Conductivity in polyacetylene. 3.Ab initio calculations for a two-site model for electron transfer,J. Phys. Chem., 1996, 100: 6298.

    Article  CAS  Google Scholar 

  16. Dupuis, M., Marquez, A., Davidson, E. R.,“HOND095.6”, New York: IBM Corporation, 1995, 12401.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Sichuan Union University, 610065, Chengdu, China

    Xiangyuan Li, Shunqing Xiao & Fucheng He

Authors
  1. Xiangyuan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shunqing Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Fucheng He
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Project supported by the National Natural Science Foundation of China (Grant Nos. 29706104 and 29573112), the State Key Laboratory of Theoretical and Computational Chemistry of Jilin University.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Li, X., Xiao, S. & He, F. Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene. Sc. China Ser. B-Chem. 42, 441–448 (1999). https://doi.org/10.1007/BF02873974

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02873974

Keywords

Search

Navigation