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Theoretica chimica acta

, Volume 24, Issue 4, pp 346–370 | Cite as

Porphyrins XXIV. Energy, oscillator strength, and Zeeman splitting calculations (SCMO-CI) for phthalocyanine, porphyrins, and related ring systems

  • A. J. McHugh
  • Martin Gouterman
  • Charles WeissJr.
Commentationes

Abstract

Extensive CI calculations have been done on free base porphin and the metallo derivative of porphin, tetrazaporphin, phthalocyanine, various benzporphins, chlorin, and bacteriochlorin. The transition gradient operator gives good agreement with experimental intensities. Free base porphin may have a weakπ-π* transition around 480nm. Tetrabenzporphin and phthalocyanine are predicted to have much more intensity around 50000 cm−1 than porphin and tetrazaporphin due to benzenoid transitions, a prediction borne out by the available data. Magnetic effects are calculated for the low energy excited states. Q state angular momentum is calculated to be 4.35ħ for porphin and 3.13h for phthalocyanine. Although these numbers agree with some experimental results, the calculations show that the experimental analysis needs further refinement.

Keywords

Chlorin Porphyrin Phthalocyanine Oscillator Strength Magnetic Effect 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Zusammenfassung

Es wurden ausführliche CI-Rechnungen für die freie Porphinbase und die Metallderivate von Porphin, Tetrazaporphin, Phthalocyanin, verschiedene Benzporphine, Chlorin und Bacteriochlorin durchgeführt. Der Operator des Übergangsgradienten zeigt gute Übereinstimmung mit experimentellen Intensitäten. Die freie Base Porphin hat höchstwahrscheinlich bei 480nm einen schwachenπ-π*-Übergang. Mit Hilfe der vorhandenen Daten ist die Voraussage möglich, daß die benzoloiden Banden im Bereich um 50000 cm−1 im Falle von Tetrabenzporphin und Phthalocyanin intensiver als bei Porphin und Tetrazaporphin sind. Ferner werden die magnetischen Eigenschaften für angeregte Zustände niedriger Energie berechnet. Man erhält den Drehimpuls des Q-Zustandes zu 4,35ħ für Porphin und 3,13ħ für Phthalocyanin. Obwohl diese Werte mit einigen experimentellen Resultaten übereinstimmen, zeigen die Rechnungen, daß die experimentelle Analyse weiterer Verfeinerung bedarf.

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References

  1. 1.
    Gouterman,M., Wagnière,G.H.: J. molecular Spectroscopy11, 108 (1963), (Paper II).Google Scholar
  2. 2.
    Weiss,C., Kobayashi,H., Gouterman,M.: J. molecular Spectroscopy16, 415 (1965), (Paper III).Google Scholar
  3. 3.
    McHugh,A.J., Gouterman,M.: Theoret. chim. Acta (Berl.)13, 249 (1969).Google Scholar
  4. 4.
    Stephens,P.J., Suëtaka,W., Schatz,P.N.: J. chem. Physics44, 4592 (1966).Google Scholar
  5. 5.
    Mataga,N., Nishimoto,K.: Z. physik. Chem. (Frankfurt)13, 140 (1957).Google Scholar
  6. 6.
    Hoard,J.L., Hamor,M.J., Hamor,T.A.: J. Amer. chem. Soc.85, 2334 (1963).Google Scholar
  7. 7.
    Robertson,J.M., Woodward,I.: J. chem. Soc. (London)1837, 219.Google Scholar
  8. 8.
    Rimington,C., Mason,S.F., Kennard,O.: Spectrochim. Acta12, 65 (1958).Google Scholar
  9. 9.a
    Roos,B., Skancke,P.N.: Acta chem. scand.21, 607, (1967).Google Scholar
  10. 9.b
    Fischer-Hjalmars,I., Sundbom,M.: Acta chem. scand.22, 607 (1967).Google Scholar
  11. 9.c
    Sundbom,M.: Acta chem. scand.22, 1317 (1967).Google Scholar
  12. 9.d
    Knop,J.V., Knop,A.: Z. Naturforsch.25a, 1720 (1970).Google Scholar
  13. 10.a
    Gouterman,M.: J. chem. Physics30, 1139 (1959).Google Scholar
  14. 10.b
    Gouterman,M.: J. molecular Spectroscopy6, 138 (1961), (Paper I).Google Scholar
  15. 11.a
    Sevchenko,A.N., Solov'ev,K.N., Mashenkov,V.A., Shkirman,S.F.: Soviet Phys.-Dokl.10, 778 (1966).Google Scholar
  16. 11.b
    Gurinovich,G.P., Sevchenko,A.N., Solov'ev,K.N.: Spectroscopy of chlorophyll and related compounds. (Izdatel'stvo Nauka i Tekhnika, Minsk, 1968; Eng. trans.: National Technical Information Service, U.S. Dept. of Commerce, Springfield, Virginia 22151).Google Scholar
  17. 12.a
    Edwards,L.: Ph. D. Thesis, Committee on Chemical Physics, Harvard University (1969).Google Scholar
  18. 12.b
    Paper XVII: — Dolphin,D.H., Gouterman,M., Adler,A.D.: J. molecular Spectroscopy38, 16 (1971).Google Scholar
  19. 13.
    Kim, J.B., Leonard, J.J., Longo, F.R.: J. Amer. chem. Soc. [in press 1972].Google Scholar
  20. 14.a
    Eisner,U., Linstead,R.P.: J. chem. Soc. (London)1955, 3749.Google Scholar
  21. 14.b
    Linstead, R.P.: J. chem. Soc. (London)1952, 4839.Google Scholar
  22. 14.c
    - unpublished spectra some of which are reproduced in Ref. [10b].Google Scholar
  23. 15.a
    Schechtman,B.H.: Technical Report No. 5207-2, Solid State Laboratory, Stanford University (1968).Google Scholar
  24. 15.b
    —, Spicer,W.E.: J. molecular Spectroscopy33, 28 (1969).Google Scholar
  25. 16.
    Hochstrasser,R.M., Marzzacco,C.: J. chem. Physics49, 971 (1968).Google Scholar
  26. 17.
    Schaffer,A.M.: Ph. D. thesis, Department of Chemistry, University of Washington, Seattle (1972).Google Scholar
  27. 18.a
    Eastwood,D., Edwards,L., Gouterman,M., Steinfeld,J.: J. molecular Spectroscopy20, 381 (1966), Paper VII.Google Scholar
  28. 18.b
    Edwards,L., Gouterman,M.: J. molecular Spectroscopy33, 292 (1969), Paper XV.Google Scholar
  29. 19.
    Bajema,L., Gouterman,M., Rose,C.B.: J. molecular Spectroscopy39, 421 (1971), Paper XXIII.Google Scholar
  30. 20.
    Shashoua,V.E.: J. Amer. chem. Soc.86, 2109 (1964);87, 4044 (1965).Google Scholar
  31. 21.
    Dratz,E.A.: Ph.D. Thesis, University of California, Berkeley [Radiation Lab. Report UCRL-17200], (1966).Google Scholar
  32. 22.a
    Malley,M., Feher,G., Mauzerall,D.:J. molecular Spectroscopy26, 320 (1968).Google Scholar
  33. 22.b
    -: Private communication.Google Scholar
  34. 23.
    Pershan,P.S., Gouterman,M., Fulton,R.L.: Molecular Physics10, 397 (1966).Google Scholar
  35. 24.
    Chong,D.P.: Molecular Physics14, 275 (1968).Google Scholar
  36. 25.a
    Ditchburn,R.W.: Light, p. 469. New York: Interscience (1963).Google Scholar
  37. 25.b
    Bernheim,R.: Optical Pumping, p. 6. New York: W. A. Benjamin (1965).Google Scholar
  38. 26.
    Kobayashi,H., Shimizu,M., Fujita,I.: Bull. chem. Soc. Japan43, 2335 (1970).Google Scholar
  39. 27.a
    Briat,B., Schooley,D.A., Records,R., Bunnenberg,E., Djerassi,C.: J. Amer. chem. Soc.89, 6170 (1967).Google Scholar
  40. 27.b
    Djerassi,C.: Private communication.Google Scholar
  41. 28.
    Stephens,P.J., Schatz,P.N., Ritchie,A.B., McCaffery,A.J.: J. chem. Physics48, 132 (1968).Google Scholar
  42. 29.
    Sutherland,J.C., Axelrod,D., Klein,M.P.: J. chem. Physics54, 2888 (1971).Google Scholar
  43. 30.
    Clementi,E.: J. chem. Physics40, 1944 (1964), and IBM Tech. Rept. RJ-256, August, (1963).Google Scholar
  44. 31.
    Silverstone,H.J., Joy,H.W., Orloff,M.K.: J. Amer. chem. Soc.88, 1325 (1966).Google Scholar
  45. 32.
    Perrin,M.H., Gouterman,M., Perrin,C.L.: J. chem. Physics50, 4137 (1969).Google Scholar
  46. 33.
    Stern,A., Pruckner,F.: Z. Physik. Chem.178A, 420 (1937).Google Scholar
  47. 34.
    Longuet-Higgens,H.C., Rector,C.W., Platt,J.R.: J. chem. Physics18, 1174 (1950).Google Scholar
  48. 35.
    Zerner,M., Gouterman,M.: Theoret. chim. Acta (Berl.)4, 44 (1966), Paper IV.Google Scholar

Copyright information

© Springer-Verlag 1972

Authors and Affiliations

  • A. J. McHugh
    • 1
    • 3
  • Martin Gouterman
    • 1
  • Charles WeissJr.
    • 2
    • 4
  1. 1.Department of ChemistryUniversity of WashingtonSeattle
  2. 2.Lawrence Radiation LaboratoryUniversity of CaliforniaBerkeley
  3. 3.KillaraAustralia
  4. 4.International Bank for Reconstruction and DevelopmentWashington DCUSA

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