Advertisement

Theoretica chimica acta

, Volume 53, Issue 3, pp 221–251 | Cite as

Two-photon spectroscopy of dipole-forbidden transitions

I. Dipole-forbidden transitions and double excited configurations in the CNDO-CI methods
  • Bernhard Dick
  • Georg Hohlneicher
Original Investigations

Abstract

We have investigated the applicability of CNDO/S-type methods for the calculation of optical spectra of molecules with the special implication that the calculations should not only describe the intense, dipole-allowed transitions which dominate the one-photon absorption spectrum but also those transitions which are one-photon forbidden in first-order approximation. We show that such a method is well suited to predict dipole allowed and dipole forbidden transitions at a similar level of accuracy if double excited configurations are taken into account. In spite of the lack of perfect pairing in NDO methods there are still two types of states which exhibit a different sensitivity towards correlation effects. Therefore, the approximation by which we describe the R-dependence of the Coulomb repulsion gains much more importance than in cases where mainly dipole allowed transitions are of interest. These findings confirm results obtained earlier from theories for which the pairing theorem is valid. The calculated data show an excellent stability with respect to further increase of the number of configurations if at least about 200 energy selected configurations are taken into account.

Key words

Dipole-forbidden transitions Two-photon spectroscopy 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Birks, J. B.: Organic molecular photophysics II, p. 99. London-New York-Toronto-Sydney: John WileyGoogle Scholar
  2. 2.
    Trajmar, S., Rice, J. K., Kuppermann, A.: Advan. Chem. Phys. 18, 15 (1970)Google Scholar
  3. 3.
    McClain, W. M.: Accounts Chem. Res. 7, 129 (1974); Drucker, R. P., McClain, W. M.: J. Chem. Phys. 61, 2609 (1974); Drucker, R. P., McClain, W. M.: J. Chem. Phys. 61, 2616 (1974)Google Scholar
  4. 4.
    Hohlneicher, G., Dick, B.: J. Chem. Phys., 70, 5427 (1979)Google Scholar
  5. 5.
    Pople, J. A.: Trans. Faraday Soc. 44, 1375 (1953)Google Scholar
  6. 6.
    Pariser, R.: J. Chem. Phys. 24, 250 (1956); Kohn, W.: Phys. Rev. A133, 171 (1964); McLachlan, A. D.: Mol. Phys. 2, 271 (1959); 4, 49 (1961)Google Scholar
  7. 7.
    Koutecky, J.: J. Chem. Phys. 44, 3702 (1966); 45, 3668 (1966)Google Scholar
  8. 8.
    Bulevskii, L. N.: Sov. Phys. JETP 24, 154 (1967); Visscher P. B., Falicov, L. M.: J. Chem. Phys. 52, 4217 (1970)Google Scholar
  9. 9.
    Bolton, J. R., Fraenkel, G. K.: J. Chem. Phys. 40, 3307 (1964)Google Scholar
  10. 10.
    Aalbersberg, W. I. J., Hoytink, G. J., Mackor, E. L., Weijland, W. P.: J. Chem. Soc. 3049 (1959)Google Scholar
  11. 11.
    Distler, D., Hohlneicher, G.: Chem. Phys. Letters 7, 345 (1970)Google Scholar
  12. 12.
    Ellis, R. L., Jaffé, H. H.: J. Mol. Spectry. 50, 474 (1974)Google Scholar
  13. 13.
    Parr, R. G., Pariser, R.: J. Chem. Phys. 21, 466 (1953)Google Scholar
  14. 14.
    Parr, R. G., Pariser, R.: J. Chem. Phys. 21, 767 (1953)Google Scholar
  15. 15.
    Clark, P. A., Ragle, J. L.: J. Chem. Phys. 46, 4235 (1967)Google Scholar
  16. 16.
    Del Bene, J., Jaffé, H. H.: J. Chem. Phys. 49, 1221 (1968); 48, 1807 (1968); 48, 4050 (1968); 50, 1126 (1969)Google Scholar
  17. 17.
    Lipari, N. O., Duke, C. B.: J. Chem. Phys. 63, 1748 (1975)Google Scholar
  18. 18.
    Zerner, M., Ridley, J.: Theoret. Chim. Acta (Berl.) 32, 111 (1973)Google Scholar
  19. 19.
    Krogh-Jespersen, K., Ratner, M.: Theoret. Chim. Acta (Berl.) 47, 283 (1978)Google Scholar
  20. 20.
    Pariser, R.: J. Chem. Phys. 21, 568 (1953)Google Scholar
  21. 21.
    Nishimoto, K., Mataga, N.: Z. Physik. Chem. 12, 335 (1957); 13, 140 (1957)Google Scholar
  22. 22.
    Ohno, K.: Theoret. Chim. Acta (Brb.) 2, 219 (1964)Google Scholar
  23. 23.
    Klopman, G.: J. Am. Chem. Soc. 86, 4550 (1964)Google Scholar
  24. 24.
    Lorquet, A. J.: Theoret. Chim. Acta (Berl.) 5, 192 (1966)Google Scholar
  25. 25.
    Dörr, F., Hohlneicher, G., Schneider, S.: Ber. Bunsenges. Physik. Chem. 70, 803 (1966)Google Scholar
  26. 26.
    Lo, D. H., Whitehead, M. A.: Can. J. Chem. 46, 2027 (1968)Google Scholar
  27. 27.
    Lo, D. H., Whitehead, M. A.: Can. J. Chem. 46, 2041 (1968)Google Scholar
  28. 28.
    Marschner, F., Goetz, H.: Tetrahedron 29, 3105 (1973)Google Scholar
  29. 29.
    Marschner, F., Goetz, H.: Tetrahedron 30, 3159 (1974)Google Scholar
  30. 30.
    Lipari, N. O., Duke, C. B.: J. Chem. Phys. 63, 1768 (1975)Google Scholar
  31. 31.
    Pohle, H.: Diss. Berlin 1976Google Scholar
  32. 32.
    Michl, J.: Intern. J. Quantum Chem. Symp. 10, 107 (1976)Google Scholar
  33. 33.
    Thulstrup, E. W., Downing, J. W., Michl, J.: Chem. Phys. 23, 307 (1977)Google Scholar
  34. 34.
    Loux, J. P.: Diss. Köln 1978Google Scholar
  35. 35.
    Roothaan, C. C. J.: J. Chem. Phys. 19, 1445 (1951)Google Scholar
  36. 36.
    Hohlneicher, G.: Habilitationsschrift, TU München 1967Google Scholar
  37. 37.
    Ellis, R. L., Jaffé, H. H., in: Modern theoretical chemistry, 8. Semiempirical methods of electronic structure calculations, A. Segal ed., p. 66ff. New York and London: Plenum Press 1977Google Scholar
  38. 38.
    Schneider, S.: Diplomarbeit, TU München 1965Google Scholar
  39. 39.
    Craig, D. P.: Proc. Roy. Soc. A200, 474 (1950)Google Scholar
  40. 40.
    Craig, D. P.: J. Chem. Phys. 17, 1358 (1949)Google Scholar
  41. 41.
    Parr, R. G., Craig, D. P., Ross, I. G.: J. Chem. Phys. 18, 1561 (1950)Google Scholar
  42. 42.
    Moser, C. M.: J. Chem. Soc. 3455 (1954)Google Scholar
  43. 43.
    Murrel, J. N., McEwen, K. L.: J. Chem. Phys. 25, 1143 (1956)Google Scholar
  44. 44.
    Bloor, J. E., Lee, J., Gartside, S.: Proc. Chem. Soc. 413 (1960)Google Scholar
  45. 45.
    Koutecký, J., Čižek, J., Dubsky, J., Hlavaty, H.: Theoret. Chim. Acta (Berl.) 2, 462 (1964)Google Scholar
  46. 46.
    Koutecký, J., Hlavaty, K., Hochmann, P.: Theoret. Chim. Acta (Berl.) 3, 341 (1965)Google Scholar
  47. 47.
    Koutecký, J.: J. Chem. Phys. 47, 1501 (1967)Google Scholar
  48. 48.
    Hudson, B. S., Kohler, B. E.: Chem. Phys. Letters 14, 299 (1972); J. Chem. Phys. 59, 4984 (1973)Google Scholar
  49. 49.
    Christensen, R. L., Kohler, B. E.: Photochern. Photobiol. 18, 293 (1973)Google Scholar
  50. 50.
    Schulten, K., Karplus, M.: Chem. Phys. Letters 14, 305 (1972)Google Scholar
  51. 51.
    Buenker, R. J., Whitten, J. L.: J. Chem. Phys. 49, 5381 (1968)Google Scholar
  52. 52.
    Dunning, T. H., Jr., Hosteny, R. P., Shavitt, I.: J. Am. Chem. Soc. 95, 5067 (1973)Google Scholar
  53. 53.
    Čižek, J., Paldus, J., Hubač, I.: Intern. J. Quantum Chem. 8, 951 (1974)Google Scholar
  54. 54.
    Paudus, J.: Intern. J. Quantum Chem. Symp. 8, 293 (1974)Google Scholar
  55. 55.
    Schulten, K., Ohmine, I., Karplus, M.: J. Chem. Phys. 64, 4422 (1976)Google Scholar
  56. 56.
    Paquette, L.: Z. Ang. Chemie 90, 114 (1978)Google Scholar
  57. 57.
    Giessner-Prettre, C., Pullman, A.: Theoret. Chim. Acta (Berl.) 17, 120 (1970); 13, 265 (1969); 18, 14 (1970); 20, 378 (1971)Google Scholar
  58. 58.
    Leclercq, J., Leclercq, J. M.: Chem. Phys. Letters 57, 54 (1978)Google Scholar
  59. 59.
    Spanget-Larsen, J., Gleiter, R.: Helv. Chim. Acta 61, 2999 (1978)Google Scholar
  60. 60.
    Dick, B.: Diplomarbeit, Univ. Köln 1977Google Scholar
  61. 61.
    McDiarmid, R.: J. Chem. Phys. 64, 514 (1976)Google Scholar
  62. 62.
    Mosher, O. A., Flicker, W. M., Kuppermann, A.: J. Chem. Phys. 59, 6502 (1973)Google Scholar
  63. 63.
    Buenker, R. J., Shih, S., Peyerimhoff, S. D.: Chem. Phys. Letters 44, 385 (1976)Google Scholar
  64. 64.
    Bender, C. F., Dunning, T. H., Jr., Schaefer, F. H., III, Goddard, W. A.III: Hunt, W. J.: Chem. Phys. Letters 15, 171 (1972); Ryan, J. A., Whitten, J. L.: Chem. Phys. Letters 15, 119 (1972); Basch, H.: Chem. Phys. Letters 19, 323 (1973)Google Scholar
  65. 65.
    Gavin, R. M., Rice, S. A.: J. Chem. Phys. 60, 3231 (1974)Google Scholar
  66. 66.
    Twarowski, A. J., Kliger, D. S.: Chem. Phys. Letters 50, 36 (1977)Google Scholar
  67. 67.
    Gavin, R. M., Riesemberg, S., Rice, S. A.: J. Chem. Phys. 58, 3160 (1973)Google Scholar
  68. 68.
    Karplus, M., Gavin, R. M., Rice, S. A.: J. Chem. Phys. 63, 5507 (1975)Google Scholar
  69. 69.
    Gavin, R. M., Jr., Weisman, Ch., McVey, J. K., Rice, S. A.: J. Chem. Phys. 68, 522 (1978)Google Scholar
  70. 70.
    Andrews, J. R., Hudson, B. S.: Chem. Phys. Letters 57, 600 (1978)Google Scholar
  71. 71.
    Platt, J. R.: J. Chem. Phys. 17, 481 (1949)Google Scholar
  72. 72.
    J. Chem. Phys. 23, 1997 (1955)Google Scholar
  73. 73.
    George, G. A., Morris, G. C.: J. Mol. Spectry. 26, 67 (1968)Google Scholar
  74. 74.
    Koch, E. E., Otto, A.: Chem. Phys. Letters 12, 476 (1972)Google Scholar
  75. 75.
    Mikami, N., Ito, I.: Chem. Phys. Letters 31, 472 (1977)Google Scholar
  76. 76.
    Ferguson, J., Reeves, L. W., Schneider, W. G.: Can. J. Chem. 35, 1117 (1957)Google Scholar
  77. 77.
    Koch, E. E., Otto, A., Radler, K.: Chem. Phys. Letters 21, 501 (1973)Google Scholar
  78. 78.
    Bergman, A., Jortner, J.: Chem. Phys. Letters 15, 309 (1972)Google Scholar
  79. 79.
    Kanda, Y., Shimada, R.: Spectrochim. Acta 15, 211 (1959)Google Scholar
  80. 80.
    Callomon, J. H., Dunn, T. M., Mills, I. M.: Phil. Trans. Roy. Soc. (London) A259, 499 (1966)Google Scholar
  81. 81.
    Koch, E. E., Otto, A.: Chem. Phys. Letters 12, 476 (1972)Google Scholar
  82. 82.
    Birks, J. B.: Chem. Phys. Letters 3, 567 (1969)Google Scholar
  83. 83.
    Twarowski, A. J., Kliger, D. S.: Chem. Phys. 20, 259 (1977)Google Scholar
  84. 84.
    Vaida, V., Robin, M. B., Kuebler, N. A.: Chem. Phys. Letters 58, 557 (1978)Google Scholar
  85. 85.
    DMS-UV Atlas of organic compounds. London: Butterworths 1971Google Scholar
  86. 86.
    Stachelek, T. M., Pazoha, T. A., McClain, W. M., Drucker, R. P.: J. Chem. Phys. 66, 4540 (1977)Google Scholar

Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Bernhard Dick
    • 1
  • Georg Hohlneicher
    • 1
  1. 1.Lehrstuhl für Theoretische Chemie der Universität zu KölnKölnFederal Republic of Germany

Personalised recommendations