Abstract

The difference between the lowest energy level of the fqd1s2 electron configuration and the lowest energy level of the fq+1s2 electron configuration for the metal vapors of nine members of the lanthanide series and four members of the actinide series are shown to be neatly and simply correlated by an adaptation of Jørgensen’s refined electron-spin-pairing energy theory. The theory is also used to extrapolate the corresponding energy differences for those lanthanide and actinide metal vapors for which this information was previously undetermined. The results will be helpful as a guide in making spectral assignments, and they are generally useful in correlating the thermodynamic properties of the chemical compounds of the lanthanide and actinide series. The theoretical basis of the treatment should also be applicable for correlating the relative energies of other electron configurations in these metal atoms and ions.

© 1971 Optical Society of America

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References

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  1. W. C. Martin, private communication.
  2. J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).
  3. J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).
  4. A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
    [CrossRef]
  5. G. Smith and M. Wilson, J. Opt. Soc. Am. 60, 1527 (1970).
    [CrossRef]
  6. Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).
  7. P. F. A. Klinkenberg and Th. A. M. van Kleef, Physica 50, 625 (1970).
    [CrossRef]
  8. J. G. Conway and E. F. Worden, private communication.
  9. L. C. Marquet and W. E. Behring, J. Opt. Soc. Am. 55, 576 (1965).
    [CrossRef]
  10. P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).
  11. J. Bauche, J. Blaise, and M. Fred, J. Opt. Soc. Am. 54, 565A (1964).
  12. M. Fred and F. S. Tomkins, J. Opt. Soc. Am. 47, 1076 (1957).
    [CrossRef]
  13. M. Fred, Lanthanide/Actinide Chemistry, Advances in Chemistry Series 71 (American Chemical Society, Washington, D. C., 1971), p. 180.
  14. C. K. Jørgensen, Mol. Phys. 5, 271 (1962).
    [CrossRef]
  15. E. Loh, Phys. Rev. 147, 332 (1966), and the references therein.
    [CrossRef]
  16. L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
    [CrossRef]
  17. L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
    [CrossRef]
  18. C. K. Jørgensen, J. Inorg. Nucl. Chem. 32, 3127 (1970).
    [CrossRef]
  19. L. J. Nugent, J. Inorg. Nucl. Chem. 32, 3485 (1970).
    [CrossRef]
  20. Note in Ref. 17 that the q values listed there do not relate to the same elements as in the present problem where q= 0 → La, q= 1 → Ce, etc. Note also in Ref. 19 that the q values listed there do relate to the same elements as in the present problem.
  21. It may appear to be more consistent to use the An(iii) aquo-ion values rather than the crystal-ion values, but we cannot do this because the former have not been reported. Nevertheless, the differences involved here are not expected to be large enough to make any significant differences in our results.
  22. C. K. Jørgensen, Chem. Phys. Letters 2, 549 (1968); C. K. Jørgensen, Oxidation Numbers and Oxidation States(Springer, New York, 1969); C. K. Jørgensen, Orbitals in Atoms and Molecules (Academic, New York, 1962).
    [CrossRef]
  23. D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
    [CrossRef]
  24. Z. B. Goldschmidt, J. Opt. Soc. Am. 53, 594 (1963).
    [CrossRef]
  25. B. R. Judd, Phys. Rev. 125, 613 (1962).
    [CrossRef]
  26. A. Giacchetti and J. Blaise, private communication.
  27. J. Blaise, private communication.
  28. W. F. Meggers and N. Spector, private communication.

1971 (1)

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

1970 (7)

C. K. Jørgensen, J. Inorg. Nucl. Chem. 32, 3127 (1970).
[CrossRef]

L. J. Nugent, J. Inorg. Nucl. Chem. 32, 3485 (1970).
[CrossRef]

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

G. Smith and M. Wilson, J. Opt. Soc. Am. 60, 1527 (1970).
[CrossRef]

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

P. F. A. Klinkenberg and Th. A. M. van Kleef, Physica 50, 625 (1970).
[CrossRef]

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

1969 (3)

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).

L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
[CrossRef]

1968 (2)

A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
[CrossRef]

C. K. Jørgensen, Chem. Phys. Letters 2, 549 (1968); C. K. Jørgensen, Oxidation Numbers and Oxidation States(Springer, New York, 1969); C. K. Jørgensen, Orbitals in Atoms and Molecules (Academic, New York, 1962).
[CrossRef]

1966 (1)

E. Loh, Phys. Rev. 147, 332 (1966), and the references therein.
[CrossRef]

1965 (1)

1964 (1)

J. Bauche, J. Blaise, and M. Fred, J. Opt. Soc. Am. 54, 565A (1964).

1963 (1)

1962 (2)

B. R. Judd, Phys. Rev. 125, 613 (1962).
[CrossRef]

C. K. Jørgensen, Mol. Phys. 5, 271 (1962).
[CrossRef]

1957 (1)

Bauche, J.

J. Bauche, J. Blaise, and M. Fred, J. Opt. Soc. Am. 54, 565A (1964).

Baybarz, R. D.

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
[CrossRef]

Behring, W. E.

Blaise, J.

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
[CrossRef]

J. Bauche, J. Blaise, and M. Fred, J. Opt. Soc. Am. 54, 565A (1964).

A. Giacchetti and J. Blaise, private communication.

J. Blaise, private communication.

Bloomquist, C. A. A.

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

Burnett, J. L.

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
[CrossRef]

Camus, P.

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).

Carlier, A.

A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
[CrossRef]

Chevillard, J.

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

Conway, J. G.

J. G. Conway and E. F. Worden, private communication.

Fred, M.

J. Bauche, J. Blaise, and M. Fred, J. Opt. Soc. Am. 54, 565A (1964).

M. Fred and F. S. Tomkins, J. Opt. Soc. Am. 47, 1076 (1957).
[CrossRef]

M. Fred, Lanthanide/Actinide Chemistry, Advances in Chemistry Series 71 (American Chemical Society, Washington, D. C., 1971), p. 180.

Giacchetti, A.

A. Giacchetti and J. Blaise, private communication.

Goldschmidt, Z. B.

Guelachvili, G.

P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).

Horwitz, E. P.

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

Jørgensen, C. K.

C. K. Jørgensen, J. Inorg. Nucl. Chem. 32, 3127 (1970).
[CrossRef]

C. K. Jørgensen, Chem. Phys. Letters 2, 549 (1968); C. K. Jørgensen, Oxidation Numbers and Oxidation States(Springer, New York, 1969); C. K. Jørgensen, Orbitals in Atoms and Molecules (Academic, New York, 1962).
[CrossRef]

C. K. Jørgensen, Mol. Phys. 5, 271 (1962).
[CrossRef]

Judd, B. R.

B. R. Judd, Phys. Rev. 125, 613 (1962).
[CrossRef]

Klinkenberg, P. F. A.

P. F. A. Klinkenberg and Th. A. M. van Kleef, Physica 50, 625 (1970).
[CrossRef]

Lewey, S.

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

Loh, E.

E. Loh, Phys. Rev. 147, 332 (1966), and the references therein.
[CrossRef]

Marquet, L. C.

Martin, W. C.

W. C. Martin, private communication.

Mason, G. W.

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

Meggers, W. F.

W. F. Meggers and N. Spector, private communication.

Morillon, C.

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

Nugent, L. J.

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

L. J. Nugent, J. Inorg. Nucl. Chem. 32, 3485 (1970).
[CrossRef]

L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
[CrossRef]

Peppard, D. F.

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

Ryan, J. L.

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

Schweighofer, M.

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
[CrossRef]

Slooten, R.

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

Smith, G.

Spector, N.

W. F. Meggers and N. Spector, private communication.

Tomkins, F. S.

van Kleef, Th. A. M.

P. F. A. Klinkenberg and Th. A. M. van Kleef, Physica 50, 625 (1970).
[CrossRef]

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

Vergès, J.

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).

Wilson, M.

Worden, E. F.

J. G. Conway and E. F. Worden, private communication.

Wyart, J. F.

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

Chem. Phys. Letters (1)

C. K. Jørgensen, Chem. Phys. Letters 2, 549 (1968); C. K. Jørgensen, Oxidation Numbers and Oxidation States(Springer, New York, 1969); C. K. Jørgensen, Orbitals in Atoms and Molecules (Academic, New York, 1962).
[CrossRef]

Compt. Rend. (1)

Th. A. M. van Kleef, R. Slooten, J. Blaise, and P. Camus, Compt. Rend. 270B, 204 (1970).

J. Inorg. Nucl. Chem. (4)

L. J. Nugent, R. D. Baybarz, J. L. Burnett, and J. L. Ryan, J. Inorg. Nucl. Chem. 33, No. 8 (1971).
[CrossRef]

C. K. Jørgensen, J. Inorg. Nucl. Chem. 32, 3127 (1970).
[CrossRef]

L. J. Nugent, J. Inorg. Nucl. Chem. 32, 3485 (1970).
[CrossRef]

D. F. Peppard, C. A. A. Bloomquist, E. P. Horwitz, S. Lewey, and G. W. Mason, J. Inorg. Nucl. Chem. 32, 339 (1970).
[CrossRef]

J. Opt. Soc. Am. (5)

J. Phys. (France) (1)

A. Carlier, J. Blaise, and M. Schweighofer, J. Phys. (France) 29, 729 (1968).
[CrossRef]

J. Phys. Chem. (1)

L. J. Nugent, R. D. Baybarz, and J. L. Burnett, J. Phys. Chem. 73, 1177 (1969).
[CrossRef]

Mol. Phys. (1)

C. K. Jørgensen, Mol. Phys. 5, 271 (1962).
[CrossRef]

Phys. Rev. (2)

E. Loh, Phys. Rev. 147, 332 (1966), and the references therein.
[CrossRef]

B. R. Judd, Phys. Rev. 125, 613 (1962).
[CrossRef]

Physica (1)

P. F. A. Klinkenberg and Th. A. M. van Kleef, Physica 50, 625 (1970).
[CrossRef]

Spectrochim. Acta (3)

P. Camus, G. Guelachvili, and J. Vergès, Spectrochim. Acta 24B, 373 (1969).

J. Blaise, J. Chevillard, J. Vergès, and J. F. Wyart, Spectrochim. Acta 25B, 333 (1970).

J. Blaise, C. Morillon, M. Schweighofer, and J. Vergès, Spectrochim. Acta 24B, 405 (1969).

Other (8)

W. C. Martin, private communication.

J. G. Conway and E. F. Worden, private communication.

M. Fred, Lanthanide/Actinide Chemistry, Advances in Chemistry Series 71 (American Chemical Society, Washington, D. C., 1971), p. 180.

Note in Ref. 17 that the q values listed there do not relate to the same elements as in the present problem where q= 0 → La, q= 1 → Ce, etc. Note also in Ref. 19 that the q values listed there do relate to the same elements as in the present problem.

It may appear to be more consistent to use the An(iii) aquo-ion values rather than the crystal-ion values, but we cannot do this because the former have not been reported. Nevertheless, the differences involved here are not expected to be large enough to make any significant differences in our results.

A. Giacchetti and J. Blaise, private communication.

J. Blaise, private communication.

W. F. Meggers and N. Spector, private communication.

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Figures (2)

Fig. 1
Fig. 1

ΔE′ vs q for the lanthanide (solid line) and actinide (dotted line) gaseous atoms. The intercepts, W, are −15.2 and −32.5 kK, and the slopes, (EA), are 3.58 and 6.38 kK. These data were determined by linear least-squares fits to the experimental points (○) and (□) for the lanthanides and actinides, respectively.

Fig. 2
Fig. 2

Experimental (○, □) and calculated (——, – – –) differences, ΔE, between the lowest enrgey level of the fqd1s2 configuration and the lowest level of the fq+1s2 configuration for lanthanide and actinide gaseous atoms.

Tables (1)

Tables Icon

Table I Calculated and experimental differences, ΔE, between the lowest energy level of the fqd1s2 configuration and the lowest energy level of the fq+1s2 configuration, for the lanthanide and actinide gaseous atoms.

Equations (1)

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Δ E ( q ) = W + q ( E - A ) - ( 9 / 104 ) N ( S ) E 1 - M ( L ) E 3 - P ( S , L , J ) ζ ,