Skip to main content
SpringerLink
Log in

State-Specific Theory of Electron Correlation in Excited States

  • Chapter
Advanced Theories and Computational Approaches to the Electronic Structure of Molecules

Part of the book series: NATO ASI Series ((ASIC,volume 133))

Abstract

An approach to the many-electron problem is reviewed which, apart from being practical and general, essentially addresses the “basis set problem”. It puts emphasis on the separate and appropriate choice and optimization of the function spaces describing the zeroth order and the remaining part of the N-electron wavefunction, especially in excited states. The calculated wavefunctions are compact and physically transparent while the results for properties which are obtained from them are reliable. The characteristic numerical examples which are given cover a wide spectrum: the importance of higher than pair subshell correlation clusters in certain excited states, (triple excitations in Cl KL3s3p6 2S), positions of resonances and autoionizing states in He- and He, the “sudden polarization effect” in ethylene, the transition probabilities to the valence-Rydberg 2S series of boron, the second-order perturbation theory calculation of electron correlation in CH4, the ls binding energies in atomic as well as in metallic Be, and the Hartree-Fock calculation of transition probabilities to multiply excited states and of the binding of the first excited state of the noble gas dihydrides, HeH2, NeH2 and ArH2.

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

Access this chapter

Log in via an institution
eBook
USD 16.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 16.99
Price excludes VAT (USA)
  • Compact, lightweight 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.

Similar content being viewed by others

References

  1. Beck, D. R. and Nicolaides, C. A., in “Excited States in Quantum Chemistry”, eds. Nicolaides, C. A. and Beck, D. R., Reidel (1978), p. 105 and p. 329.

    Google Scholar 

  2. Nicolaides, C. A. and Beck, D. R., in “Excited States in Quantum Chemistry”, eds. Nicolaides, C. A., Beck, D. R., Reidel (1978), p. 143.

    Google Scholar 

  3. Komninos, Y., Aspromallis, G. and Nicolaides, C. A., Phys. Rev. A27, 1865 (1983).

    Google Scholar 

  4. Nicolaides, C. A., Komninos, Y. and Beck, D. R., Phys. Rev. A27, 3044 (1983).

    Google Scholar 

  5. Nicolaides, C. A. and Beck, D. R., Int. J. Quant. Chem. 14, 457 (1978)

    Article  CAS  Google Scholar 

  6. Nicolaides, C. A., Komninos, Y. and Merkouris, Th., J. Quant. Chem. S15, 355 (1981).

    Google Scholar 

  7. Nicolaides, C. A. and Theodorakopoulos, G., Int. J. Quant. Chem. S14, 315 (1980).

    Google Scholar 

  8. Petsalakis, J., Theodorakopoulos, G., Nicolaides, C. A., Buenker, R. J. and Peyerimhoff, S. D., “Non-orthonormal CI in Excited States. I: The Sudden Polarization Effect in Ethylene”, to be published.

    Google Scholar 

  9. Nicolaides, C. A., Chem. Phys. Letts. 101, 435 (1983).

    Article  CAS  Google Scholar 

  10. Weiss, A. W., Phys. Rev. 188, 119 (1969).

    Article  CAS  Google Scholar 

  11. Buenker, R. J. and Peyerimhoff, S. D., in “Excited States in Quantum Chemistry” eds. Nicolaides, C. A., Beck, D. R., Reidel (1978) pp. 45–103.

    Google Scholar 

  12. Kelly, H. P. and Carter, S. L., Phys. Scripta 21, 448 (1980).

    Article  CAS  Google Scholar 

  13. Robb, M. A., Hegarty, D. and Prime, S., in “Excited States in Quantum Chemistry” eds. Nicolaides, C. A., Beck, D. R., Reidel (1978) p. 297.

    Google Scholar 

  14. Von Niessen, W., Cederbaum, L. S. and Domcke, W., in “Excited States in Quantum Chemistry” eds. Nicolaides, C. A., Beck, D. R., Reidel (1978) p. 183.

    Google Scholar 

  15. Linderberg, J. and Ohrn, Y., in “Excited States in Quantum Chemistry”, eds. Nicolaides, C. A., Beck, D. R., Reidel (1978) p. 35 and p. 317.

    Google Scholar 

  16. W. Meyer, J. Chem. Phys. 64, 2901 (1976)

    Article  CAS  Google Scholar 

  17. W. Meyer, J. Chem. Phys. 58, 1017 (1973).

    Article  CAS  Google Scholar 

  18. Burke, P. G. and Robb, W. D., Adv. At. Mol. Phys. 11, 143 (1975).

    Article  CAS  Google Scholar 

  19. Berrington, K., Burke, P. G. and Kingston, A. E., J. Phys. B8, 1459 (1975).

    Google Scholar 

  20. Nitzsche, L. E. and Davidson, E. R., J. Chem. Phys. 68, 3103 (1978).

    Article  CAS  Google Scholar 

  21. Brooks, B. R. and Schaefer, H. F., J. Am. Chem. Soc. 101, 307 (1979).

    Article  CAS  Google Scholar 

  22. Bonacic-Koutecky, V., Buenker, R. J. and Peyerimhoff, S. D., J. Am. Chem. Soc. 101, 5917 (1979).

    Article  CAS  Google Scholar 

  23. Nicolaides, C. A., Phys. Rev. A6, 2078 (1972).

    Google Scholar 

  24. Nicolaides, C. A. and Beck, D. R., J. Phys. B6, 535 (1973).

    Google Scholar 

  25. Nicolaides, C. A. and Beck, D. R., Phys. Rev. A18, 1307 (1978).

    Google Scholar 

  26. Silverstone, H. J. and Sinanoglu, O., J. Chem. Phys. 44, 1898 (1966)

    Google Scholar 

  27. Sinanoglu, O., J. Chem. Phys. 36, 706 (1962).

    Article  CAS  Google Scholar 

  28. Sinanoglu, O. and Brueckner, K. A., “Three Approaches to Electron Correlation in Atoms”, Yale Press (1970).

    Google Scholar 

  29. Froese-Fischer, C., Comp. Phys. Comm. 4, 107 (1972).

    Article  Google Scholar 

  30. Beck, D. R. and Nicolaides, C. A., Int. J. Quant. Chem. S8, 17 (1974).

    Google Scholar 

  31. Nicolaides, C. A. and Beck, D. R., Chem. Phys. Lett. 36, 79 (1975).

    Article  CAS  Google Scholar 

  32. Aspromallis, G., Nicolaides, C. A. and Beck, D. R., Phys. Rev. A28, 1879 (1983).

    Google Scholar 

  33. Beck, D. R., Int. J. Quant. Chem. S15, 521 (1981)

    Google Scholar 

  34. Beck, D. R. and Kunz, A. B., unpublished.

    Google Scholar 

  35. Nicolaides, C. A., Komninos, Y. and Beck, D. R. Phys. Rev. A24, 1103 (1981).

    Google Scholar 

  36. Beck, D. R., Nicolaides, C. A., and Aspromallis, G., Phys. Rev. A24, 3252 (1981).

    Google Scholar 

  37. King, H. F., Stanton, R. E., Kim, H., Wyatt, R. E. and Parr, R. G., J. Chem. Phys. 47, 1936 (1967).

    Article  CAS  Google Scholar 

  38. Schneider, B. I. and Collins, L. A., J. Phys. B15, L335 (1982).

    Google Scholar 

  39. Schneider, B. I., LeDourneuf, M. and Lan, V. K., Phys. Rev. Lett. 43, 1926 (1979).

    Article  CAS  Google Scholar 

  40. Nicolaides, C. A. and Adamides, E., Phys. Rev. A27, 1691 (1983).

    Google Scholar 

  41. Beck, D. R. and Nicolaides, C. A., Phys. Lett. 61A, 227 (1977).

    CAS  Google Scholar 

  42. Nesbet, R. K. Phys. Rev. A14, 1065 (1976).

    Google Scholar 

  43. Kernahan, J. A., Pinnington, E. H., Livingston, A. E. and Irwin, D. J. G. Phys. Scripta 12, 319 (1975).

    Article  CAS  Google Scholar 

  44. Martinson, I., Bickel, W. S. and Olme, A., J. Opt. Soc. Am. 60, 1213 (1970).

    Article  CAS  Google Scholar 

  45. Mulliken, R. S., Phys. Rev. 43, 279 (1933).

    Article  CAS  Google Scholar 

  46. Nicolaides, C. A., Zdetsis, A. and Andriotis, A., unpublished.

    Google Scholar 

  47. Butscher, W., Buenker, R. J. and Peyerimhoff, S. D., Chem. Phys.. Letts. 52, 449 (1977).

    Article  CAS  Google Scholar 

  48. Cederbaum, L. S. and Domcke, W., J. Chem. Phys. 66, 5084 (1977).

    Article  Google Scholar 

  49. Beck, D. R. and Nicolaides, C. A., Phys. Rev. A26, 857 (1982).

    Google Scholar 

  50. Shirley, D. A., Martin, R. L., Kowalczyk, S. P., McFeely, F. R. and Ley, L., Phys. Rev. 15, 544 (1977).

    Article  CAS  Google Scholar 

  51. Hochst, H., Steiner, P. and Hufner, S., Phys. Lett. 60A, 69 (1977).

    Google Scholar 

  52. Nicolaides, C. A. and Zdetsis, A., “Theory of Chemical Reactions of Vibronically Excited H2(B1∑ +u ): Bound Excited States of Noble Gas Dihydrides”, J. Chem. Phys., in press.

    Google Scholar 

  53. Nicolaides, C. A., Theodorakopoulos, G., and Petsalakis, I., “Prediction of a Strongly Bound Excited State of H4”, J. Chem. Phys., in press.

    Google Scholar 

  54. Farantos, S., Theodorakopoulos, G. and Nicolaides, C. A., Chem. Phys. Lett. 100, 263 (1983).

    Article  CAS  Google Scholar 

  55. Hunt, W. J., Dunning, T. H. and Goddard, W. A., Chem. Phys. Lett. 3, 606 (1969).

    Article  CAS  Google Scholar 

  56. Madden, R. P. and Codling, K., Astr. J. 141, 364 (1965).

    Article  CAS  Google Scholar 

  57. Schulman, J. M. and Kaufman, D. N., J. Chem. Phys. 53, 477 (1970).

    Article  CAS  Google Scholar 

  58. Pople, J. A., Binkley, J. S. and Seeger, R., Int. J. Quant. Chem. S10, 1 (1976).

    Google Scholar 

  59. Krishnan, R. and Pople, J. A., Int. J. Quant. Chem. 14, 91 (1978).

    Article  CAS  Google Scholar 

  60. Eggarter, E. and Eggarter, T. P., J. Phys. B11, 1157 (1978).

    Google Scholar 

  61. Bartlett, R. J. and Purvis, G. D., Phys. Scripta, 21, 255 (1980).

    Article  CAS  Google Scholar 

  62. Frisch, M. J., Drishnan, R. and Pople, J. A., Chem. Phys. Lett. 75, 66 (1980).

    Article  CAS  Google Scholar 

  63. Morrison, R. C., Chem. Phys. Lett. 62, 131 (1979).

    Article  CAS  Google Scholar 

  64. Walter, O. and Schirmer, J., J. Phys. B14, 3805 (1981).

    Google Scholar 

  65. Bisgaard, P., Bruch, R., Dahl, P., Fastrup, B. and Robro, M., Phys. Scripta 17, 49 (1978).

    Article  CAS  Google Scholar 

  66. Bunge, C. F., Phys. Rev. A14, 1965 (1976).

    Google Scholar 

  67. Brunt, J. N. H., King, G. C., Read, F. H., J. Phys. B10, 433 (1977).

    Google Scholar 

  68. Wakid, S., Bhatia, A. K. and Temkin, A., Phys. Rev. A21, 496 (1980).

    Google Scholar 

  69. Chung, K. T., Phys. Rev. A23, 1079 (1981).

    Google Scholar 

  70. Bhatia, A. K. and Temkin, A., Phys. Rev. A23, 3361 (1981).

    Google Scholar 

  71. Aspromallis, G., Komninos, Y. and Nicolaides, C. A., J. Phys. B, in press.

    Google Scholar 

  72. Beck, D. R. and Nicolaides, C. A., Int. J. Quant. Chem. S10, 119 (1976).

    Google Scholar 

  73. Beck, D. R. and Nicolaides, C. A., Chem. Phys. Lett. 59, 525 (1978).

    Article  CAS  Google Scholar 

  74. Bhatia, A. K., Phys. Rev. A6, 120 (1972).

    Google Scholar 

  75. Komninos, Y. and Nicolaides, C. A., Phys. Scripta 28, 472 (1983).

    Article  CAS  Google Scholar 

  76. Cederquist, H., Kisielinski, M. and Mannervik, S., J. Phys. B16, L479 (1983).

    Google Scholar 

  77. Aspromallis, G. and Nicolaides, C. A., J. Phys. B16, L251 (1983).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Vas. Constantinou Avenue 48, Athens, 501/1, Greece

    Cleanthes A. Nicolaides

Authors
  1. Cleanthes A. Nicolaides
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. School of Chemical Sciences, University of Illinois, 505 South Mathews Avenue, 61801, Urbana, Illinois, USA

    Clifford E. Dykstra

Rights and permissions

Reprints and permissions

Copyright information

© 1984 D. Reidel Publishing Company

About this chapter

Cite this chapter

Nicolaides, C.A. (1984). State-Specific Theory of Electron Correlation in Excited States. In: Dykstra, C.E. (eds) Advanced Theories and Computational Approaches to the Electronic Structure of Molecules. NATO ASI Series, vol 133. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-6451-8_9

Download citation

  • DOI: https://doi.org/10.1007/978-94-009-6451-8_9

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-009-6453-2

  • Online ISBN: 978-94-009-6451-8

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation