All JournalsPhysics Magazine

Export citation

Export citation

Choose format for download:

Download Citation
  • Access by Xinjiang University

Hyperpolarizabilities of H, He, and Li+

M. N. Grasso and Kwong T. Chung

R. P. Hurst

  • Department of Physics, State University College at Fredonia, Fredonia, New York

  • State University of New York at Buffalo, Buffalo, New York

Phys. Rev. 167, 1 – Published 5 March, 1968

DOI: https://doi.org/10.1103/PhysRev.167.1

Abstract

The Ritz variational approximation is used to calculate the energy of the ground state of He, Li+, and H in the presence of a uniform external electric field. The interaction energies are expressed as power series in the electric-field intensity. From the coefficients of these expansions, the polarizabilities α and the hyperpolarizabilities γ are obtained. In this study the hyperpolarizabilities are computed with Hylleraas-type wave functions consisting of 78, 96, 102, and 150 terms. The convergence of α and γ are satisfactory for He and Li+, but not for H. For H it is suggested that in order to obtain proper convergence one would need to include more terms in the wave function than would be tractable for our computer. Thus, a different type of function should be used for this ion. The 150-term wave functions gave 169, 1.383, and 0.1925 atomic units (a.u.) for the polarizabilities of H, He, and Li+, respectively. This 150-term function also gave 1.74 × 107, 42.8, and 0.244 a.u. for the hyperpolarizabilities of these same atoms. It is suggested from a study of the convergence of α and γ as more terms are included in the wave function, of the accuracy of the computed α's, and of the free atom energies that the computed γ results are correct to within a few percent or better for He and Li+, but that the γ computed for H is unreliable. The only available measurement of γ, for these ions, gave 51.6±7.9 a.u. for the helium atom.

References (19)

  1. A. Dalgarno, Advan. Phys. 11, 281 (1962)
  2. K. S. Pitzer, in Advances in Chemical Physics, edited by I. Prigogine (Interscience Publishers, Inc., New York, 1959), Vol. 2, p. 59
  3. R. M. Sternheimer, Phys. Rev. 80, 102 (1950) ibid.84, 244 (1951) ibid.102, 731 (1956) ibid.107, 1565 (1957) ibid.115, 1198 (1959) ibid.127, 1220 (1962) ibid.130, 1423 (1963) ibid.132, 1637 (1963)
  4. P. W. Langhoff and R. P. Hurst, Phys. Rev. 139, A1415 (1965)
  5. A. D. Buckingham and B. J. Orr, Quart. Rev. (London) 21, 195 (1967)
  6. A. D. Buckingham and M. J. Stephen, Trans. Faraday Soc. 53, 884 (1957)
  7. H. Jeffreys, Cartesion Tensors (Cambridge University Press, London, 1952), p. 66
  8. H. Goldstein, Classical Mechanics (Addison-Wesley Publishing Co., Inc., Reading, Mass., 1950), p. 129
  9. P. W. Langhoff, J. D. Lyons, and R. P. Hurst, Phys. Rev. 148, 18 (1966)
  10. C. W. F. Drake and M. Cohen, Bull. Am. Phys. Soc. 12, 701 (1967)
  11. L. L. Boyle, A. D. Buckingham, R. L. Disch, and D. A. Dunmar, J. Chem. Phys. 45, 1318 (1966)
  12. A. Dalgarno and A. L. Stewart, Proc. Roy. Soc. (London) A238, 269 (1956)
  13. J. O. Hirschfelder, W. B. Brown, and S. T. Epstein, in Advances in Quantum Chemistry, edited by Per-Olov Löwdin (Academic Press Inc., New York, 1964), Vol. 1, p. 256
  14. Kwong T. Chung and R. P. Hurst, Phys. Rev. 152, 35 (1966)
  15. E. A. Hylleraas, Z. Physik, 54, 347 (1930)
  16. H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One-and Two-Electron Atoms (Academic Press Inc., New York, 1957), p. 149
  17. M. N. Grasso, M.A. thesis, State University of New York at Buffalo, 1968 (unpublished)
  18. E. A. Hylleraas, in Advances in Quantum Chemistry, edited by Per-Olov Löwdin (Academic Press Inc., New York, 1964), Vol. 1, p. 1
  19. C. Schwartz (private communication)

Outline

Information

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation