Skip to main content
SpringerLink
Log in

Electric Field Perturbation of Electronic (Vibronic) Absorption Envelopes: Application to Characterization of Mixed-Valence States

  • Chapter
Mixed Valency Systems: Applications in Chemistry, Physics and Biology

Part of the book series: NATO ASI Series ((ASIC,volume 343))

Abstract

Perturbation of electronic/vibronic absorption envelopes by application of an external electric field is a powerful potential source of valuable information about the nature of excited and ground states. We discuss here the theory of such effects for the ground and excited states of single and mixed-valence complexes; it is related to the recent experimental work of Oh and Boxer on electric field perturbation of Metal-to-Ligand and intervalence transitions for a number of Ruthenium complexes, including the Creutz-Taube ion. The electric field perturbation method, which has hitherto been very little used in transition metal studies, is capable of yielding unequivocal answers to questions of extent of electron delocalization, and may also reveal and permit characterisation of electronic states not easily seen in the unperturbed absorption spectra. Analysis of the perturbed vibronic wavefunctions for these systems shows that departures from ‘classical’ spectroelectric theories in some circumstances will be pronounced.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Cohen, H.D.; Roothan, C.C.J. J. Chem. Phys., 1965, 43, 534.

    Google Scholar 

  2. Hush, N.S.; Williams, M.L. Chem. Phys. Lett., 1970, 5, 507.

    Article  CAS  Google Scholar 

  3. Hush, N.S.; Williams, M.L. Chem. Phys. Lett., 1970, 6, 163.

    Article  CAS  Google Scholar 

  4. Hush, N.S.; Williams, M.L. Theor. Chim. Acta, 1972, 25, 346.

    Article  CAS  Google Scholar 

  5. Rendell, A.P.L.; Bacskay, G.B.; Hush, N.S.; Handy, N.C. J. Chem. Phys., 1987, 87, 5976.

    Article  CAS  Google Scholar 

  6. Gready, IE.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1977, 22, 141.

    Article  CAS  Google Scholar 

  7. Gready, J.E.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1978, 31, 375.

    Article  CAS  Google Scholar 

  8. Gready, J.E.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1978, 31, 467.

    Article  CAS  Google Scholar 

  9. John, I.G.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1979, 38, 319.

    Article  CAS  Google Scholar 

  10. John, I.G.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1980, 51, 49.

    Article  CAS  Google Scholar 

  11. Swanton, D.J.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1983, 82, 303.

    Article  CAS  Google Scholar 

  12. Swanton, D.J.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1984, 83, 69.

    Article  CAS  Google Scholar 

  13. Swanton, D.J.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1986, 107, 9.

    Article  CAS  Google Scholar 

  14. Swanton, D.J.; Bacskay, G.B.; Hush, N.S. Chem. Phys., 1986, 107, 25.

    Article  CAS  Google Scholar 

  15. Cummins, P.L.; Bacskay, G.B.; Hush, N.S. J. Phys. Chem., 1985, 89, 2151.

    Article  CAS  Google Scholar 

  16. Cummins, P.L.; Bacskay, G.B.; Hush, N.S.; Halle, B.; Engstrom, S. J. Chem. Phys., 1985, 82, 2002.

    Article  CAS  Google Scholar 

  17. Hush, N.S.; Williams, M.L. J. Mol. Spectrosc, 1974, 50, 349.

    Article  CAS  Google Scholar 

  18. Gready, J.E.; Bacskay, G.B.; Hush, N.S. J. Chem. Soc., Faraday Trans. 2, 1978, 74, 1430.

    Article  CAS  Google Scholar 

  19. Hush, N.S.; Wong, A.T.; Bacskay, G.B.; Reimers, J.R. J. Am. Chem. Soc., 1990, 112, 4192.

    Article  CAS  Google Scholar 

  20. Scheps, R.; Lombardi, J.R. Chem. Phys., 1975, 10, 445.

    Article  CAS  Google Scholar 

  21. Johnson, L.W. J. Chem. Phys., 1983, 79, 1096.

    Article  CAS  Google Scholar 

  22. Høg, J.H.; Ballhausen, C.J.; Solomon, E.I. Mol. Phys., 1976, 32, 807.

    Article  Google Scholar 

  23. Davidsson, Å. Chem. Phys., 1980, 45, 409.

    Article  CAS  Google Scholar 

  24. Davidsson, Å. Chem. Phys. Lett., 1983, 65, 101.

    Google Scholar 

  25. Liptay, W. In Modern Quantum Chemistry Vol. 3; Sinanoglu, O., Ed.; Academic Press: New York, 1965.

    Google Scholar 

  26. Liptay, W. Angew. Chem. Internat. Edit., 1969, 8, 177.

    Article  CAS  Google Scholar 

  27. Liptay, W. In Excited states; Lim, E.C. Ed.; Academic Press: New York, 1974; p 129.

    Google Scholar 

  28. Varma, C.A.G.O. Helv. Chim. Acta, 1978, 61, 773.

    Article  Google Scholar 

  29. Lin, S.H. J. Chem. Phys., 1975, 62, 4500.

    Article  CAS  Google Scholar 

  30. Lockhart, D.J.; Boxer, S.G. Chem. Phys. Lett., 1988, 144, 243.

    Article  CAS  Google Scholar 

  31. Lockhart, D.J.; Goldstein, R.F.; Boxer, S.G. J. Phys. Chem., 1988, 89, 1408.

    Article  CAS  Google Scholar 

  32. Boxer, S.G.; Goldstein, R.A.; Lockhart, D.J.; Middendorf, T.R.; Takiff, L. J. Phys. Chem., 1989, 93, 8280.

    Article  CAS  Google Scholar 

  33. Oh, D.H.; Boxer, S.G. J. Am. Chem. Soc., 1989, 111, 1130.

    Article  CAS  Google Scholar 

  34. Oh, D.H.; Boxer, S.G., Private communication.

    Google Scholar 

  35. Liptay, W.; Wortmann, R.; Schaffrin, H.; Burkhard, O.; Reitinger, W.; Detzer, N. Chem. Phys., 1988, 120, 429.

    Article  CAS  Google Scholar 

  36. Liptay, W.; Wortmann, R.; Bohm, R.; Detzer, N. Chem. Phys., 1988, 120, 439.

    Article  CAS  Google Scholar 

  37. Wortmann, R.; Elich, K.; Liptay, W. Chem. Phys., 1988, 124, 395.

    Article  CAS  Google Scholar 

  38. Woitellier, S.; Launay, J.P.; Spangler, C.W. Inorg. Chem., 1989, 28, 758.

    Article  CAS  Google Scholar 

  39. Reimers, J.R.; Hush, N.S. Inorg. Chem., 1990, in press.

    Google Scholar 

  40. Reimers, J.R.; Hush, N.S. Inorg. Chem., 1990, in press.

    Google Scholar 

  41. Hush, N.S.; Paddon-Row, M.N.; Cotsaris, E.; Oevering, H.; Verhoeven, J.W.; Heppener, M. Chem. Phys. Lett., 1985, 117, 8.

    Article  CAS  Google Scholar 

  42. Warman, J.M.; de Haas, M.P.; Paddon-Row, M.N.; Cotsaris, E.; Hush, N.S.; Oevering, H.; Verhoeven, J.W. Nature, 1986, 320, 615.

    Article  CAS  Google Scholar 

  43. Creutz, C.; Taube, H. J. Am. Chem. Soc., 1969, 91, 3988.

    Article  CAS  Google Scholar 

  44. Creutz, C.; Taube, H. J. Am. Chem. Soc., 1973, 95, 1086.

    Article  CAS  Google Scholar 

  45. Werner, H.-J.; Meyer, W. Mol. Phys., 1976, 31, 855.

    Article  CAS  Google Scholar 

  46. Gress, M.E.; Creutz, C.; Quicksall, C.O. J. Am. Chem. Soc., 1981, 20,1522.

    CAS  Google Scholar 

  47. Richardson, D.E.; Taube, H. J. Am. Chem. Soc., 1983, 105, 40.

    Article  CAS  Google Scholar 

  48. Sutton, C.A.; Taube, H. Inorg. Chem., 1981, 20, 3125.

    Article  CAS  Google Scholar 

  49. Ikeyama, I.; Azumi, T. J. Chem. Phys., 1982, 76, 5672.

    Article  CAS  Google Scholar 

  50. Henneker, W.H.; Siebrand, W.; Zgierski, M.Z. J. Chem. Phys., 1983, 79, 2495.

    Article  CAS  Google Scholar 

  51. Bogner, U.; Schatz, P.; Seel, R.; Maier, M. Chem. Phys. Lett., 1983, 102, 267.

    Article  CAS  Google Scholar 

  52. Gerblinger, j.; Bogner, U.; Maier, M. Chem. Phys. Lett., 1987, 141, 31.

    Article  CAS  Google Scholar 

  53. Agranovitch, V.M.; Ivanov, Y.K.; Personov, R.I.; Rasumova, N.Y. Phys. Lett. A, 1986, 118, 239.

    Article  Google Scholar 

  54. Ellis, V.M. Ph.D. Thesis; University of Sydney, 1979.

    Google Scholar 

  55. Zhang, L.T.; Ko, J.; Ondrechen, M.J. J. Am. Chem. Soc., 1987, 109, 1666.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Theoretical Chemistry, University of Sydney, Sydney, NSW, 2006, Australia

    J. R. Reimers & N. S. Hush

Authors
  1. J. R. Reimers
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. N. S. Hush
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. School of Chemistry and Molecular Sciences, University of Sussex, Falmer, Brighton, UK

    Kosmas Prassides

Rights and permissions

Reprints and permissions

Copyright information

© 1991 Springer Science+Business Media Dordrecht

About this chapter

Cite this chapter

Reimers, J.R., Hush, N.S. (1991). Electric Field Perturbation of Electronic (Vibronic) Absorption Envelopes: Application to Characterization of Mixed-Valence States. In: Prassides, K. (eds) Mixed Valency Systems: Applications in Chemistry, Physics and Biology. NATO ASI Series, vol 343. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-3606-8_3

Download citation

  • DOI: https://doi.org/10.1007/978-94-011-3606-8_3

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-5599-4

  • Online ISBN: 978-94-011-3606-8

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation