Abstract

The glow peak emission due to impurities in calcite, dolomite, magnesite, aragonite, and anhydrite have been investigated by measuring and interpreting the associated spectra. The impurities considered are Mn++, Pb++, Zn++, and Sb3+.

The emission spectra due to Mn++ are interpreted on the basis of crystal field theory for transition metal ions. It is shown that the orange thermoluminescence in Mn-activated calcite, dolomite, and magnesite is due to the 4G(T1g)→6S transition in the Mn++ ion. The green thermoluminescent emission of Mn-activated anhydrite is attributed to the 4G(T2g)→6S transition in Mn++. In all cases the same transitions account for the luminescent emission also. The yellow thermoluminescence in Mn-activated aragonite is tentatively assigned to the 4G(T1g)→6S transition but there are no absorption data to verify this. The emission due to Pb++ in calcite is attributed to the 1P11S0 and 3P11S0 transitions. In Zn-activated anhydrite the emission bands are identified with transitions between the T2g and Eg levels of the ground states of ions in substitutional and interstitial positions.

Fine structure is observed in the emission bands of the Mn-activated carbonates and there is no evidence of temperature broadening. In Mn-activated anhydrite, the fine structure is missing, temperature broadening is evident, and a characteristic long-wavelength tail is observed. These effects are discussed and interpreted. An approximate configurational coordinate diagram is constructed for Mn-activated calcite and dolomite and some conclusions are drawn from the results.

© 1963 Optical Society of America

Full Article  |  PDF Article

References

  • View by:
  • |
  • |
  • |

  1. W. L. Medlin, J. Chem. Phys. 38, 1132 (1963).
    [CrossRef]
  2. L. E. Orgel, J. Chem. Phys. 23, 1958 (1955).
    [CrossRef]
  3. W. L. Medlin, J. Phys. Chem. Solids 18, 238 (1961).
    [CrossRef]
  4. W. L. Medlin, J. Chem. Phys. 30, 451 (1959).
    [CrossRef]
  5. J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
    [CrossRef]
  6. C. C. Klick, British J. Appl. Phys. 6, Suppl. 4, S74 (1955).
    [CrossRef]
  7. W. L. Medlin, J. Chem. Phys. 34, 672 (1961).
    [CrossRef]
  8. W. L. Medlin, J. Phys. Chem. 65, 1172 (1961).
    [CrossRef]
  9. K. Watanabe, Phys. Rev. 83, 785 (1951).
    [CrossRef]
  10. K. V. Rao, J. Phys. Chem. Solids 20, 193 (1961); W. F. Kolbe and A. Smakula, Phys. Rev. 124, 1754 (1961).
    [CrossRef]
  11. J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
    [CrossRef]
  12. V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).
  13. C. J. Ballhausen, Introduction to Ligand Field Theory (McGraw-Hill Book Company, Inc., New York, 1962).
  14. R. W. G. Wyckoff, The Structure of Crystals (Chemical Catalog Company, Inc., New York, 1931), 2nd ed., p. 275.
  15. “X-Ray Powder Data File,” edited by J. V. Smith, American Society for Testing Materials, Philadelphia (1960).
  16. C. E. Moore, Natl. Bur. Std. U. S. Circ. 467, 11 (1952).
  17. Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753 (1954).
    [CrossRef]
  18. L. E. Orgel, J. Chem. Phys. 23, 1004, 1824 (1955).
    [CrossRef]
  19. J. W. Stout, J. Chem. Phys. 31, 709 (1959).
    [CrossRef]
  20. R. Pappalardo, J. Chem. Phys. 31, 1050 (1959).
    [CrossRef]
  21. C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
    [CrossRef]
  22. C. W. Stillwell, Crystal Chemistry (McGraw-Hill Book Company, Inc., New York, 1958), p. 269.
  23. P. D. Johnson and F. L. Hughes, J. Chem. Phys. 26, 612 (1957).
    [CrossRef]
  24. C. K. Jorgensen, Acta Chem. Scand. 8, 1502 (1954).
    [CrossRef]
  25. H. W. Leverenz, An Introduction to the Luminescence of Solids (John Wiley Sons, Inc., New York, 1950), p. 175; P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949), p. 627.
  26. J. W. Stout, J. Chem. Phys. 33, 303 (1960).
    [CrossRef]
  27. C. C. Klick and J. H. Schulman, J. Opt. Soc. Am. 42, 910 (1952).
    [CrossRef]
  28. R. J. Ginther, J. Electrochem. Soc. 98, 74 (1951).
    [CrossRef]
  29. O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
    [CrossRef]
  30. R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
    [CrossRef]
  31. J. L. Birman, Phys. Rev. 121, 144 (1961).
    [CrossRef]
  32. I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
    [CrossRef]
  33. E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
    [CrossRef]
  34. Y. Kaifu, J. Phys. Soc. Japan 16, 1605 (1961).
    [CrossRef]
  35. F. E. Williams, Report on International Conference on Luminescence of Organic and Inorganic Materials, edited by H. P. Kallman and G. M. Spruch (John Wiley Sons, Inc., New York, 1962), p. 305.

1963 (1)

W. L. Medlin, J. Chem. Phys. 38, 1132 (1963).
[CrossRef]

1961 (7)

W. L. Medlin, J. Chem. Phys. 34, 672 (1961).
[CrossRef]

W. L. Medlin, J. Phys. Chem. 65, 1172 (1961).
[CrossRef]

W. L. Medlin, J. Phys. Chem. Solids 18, 238 (1961).
[CrossRef]

K. V. Rao, J. Phys. Chem. Solids 20, 193 (1961); W. F. Kolbe and A. Smakula, Phys. Rev. 124, 1754 (1961).
[CrossRef]

J. L. Birman, Phys. Rev. 121, 144 (1961).
[CrossRef]

I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
[CrossRef]

Y. Kaifu, J. Phys. Soc. Japan 16, 1605 (1961).
[CrossRef]

1960 (3)

E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
[CrossRef]

C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
[CrossRef]

J. W. Stout, J. Chem. Phys. 33, 303 (1960).
[CrossRef]

1959 (3)

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

R. Pappalardo, J. Chem. Phys. 31, 1050 (1959).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 30, 451 (1959).
[CrossRef]

1958 (1)

V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).

1957 (3)

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

P. D. Johnson and F. L. Hughes, J. Chem. Phys. 26, 612 (1957).
[CrossRef]

O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
[CrossRef]

1955 (4)

R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
[CrossRef]

C. C. Klick, British J. Appl. Phys. 6, Suppl. 4, S74 (1955).
[CrossRef]

L. E. Orgel, J. Chem. Phys. 23, 1958 (1955).
[CrossRef]

L. E. Orgel, J. Chem. Phys. 23, 1004, 1824 (1955).
[CrossRef]

1954 (2)

Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753 (1954).
[CrossRef]

C. K. Jorgensen, Acta Chem. Scand. 8, 1502 (1954).
[CrossRef]

1952 (2)

C. C. Klick and J. H. Schulman, J. Opt. Soc. Am. 42, 910 (1952).
[CrossRef]

C. E. Moore, Natl. Bur. Std. U. S. Circ. 467, 11 (1952).

1951 (2)

K. Watanabe, Phys. Rev. 83, 785 (1951).
[CrossRef]

R. J. Ginther, J. Electrochem. Soc. 98, 74 (1951).
[CrossRef]

1947 (1)

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

Apple, E. F.

E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
[CrossRef]

Arkhangelskaya, V. A.

V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).

Ballhausen, C. J.

C. J. Ballhausen, Introduction to Ligand Field Theory (McGraw-Hill Book Company, Inc., New York, 1962).

Birman, J. L.

J. L. Birman, Phys. Rev. 121, 144 (1961).
[CrossRef]

Bowers, R.

R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
[CrossRef]

Broser, I.

I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
[CrossRef]

Evans, L. W.

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

Ginther, R. J.

R. J. Ginther, J. Electrochem. Soc. 98, 74 (1951).
[CrossRef]

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

Handin, J.

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

Higgs, D. V.

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

Holmes, O. G.

O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
[CrossRef]

Hughes, F. L.

P. D. Johnson and F. L. Hughes, J. Chem. Phys. 26, 612 (1957).
[CrossRef]

Johnson, P. D.

P. D. Johnson and F. L. Hughes, J. Chem. Phys. 26, 612 (1957).
[CrossRef]

Jorgensen, C. K.

C. K. Jorgensen, Acta Chem. Scand. 8, 1502 (1954).
[CrossRef]

Kaifu, Y.

Y. Kaifu, J. Phys. Soc. Japan 16, 1605 (1961).
[CrossRef]

Kikuchi, C.

C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
[CrossRef]

Klick, C. C.

C. C. Klick, British J. Appl. Phys. 6, Suppl. 4, S74 (1955).
[CrossRef]

C. C. Klick and J. H. Schulman, J. Opt. Soc. Am. 42, 910 (1952).
[CrossRef]

Leverenz, H. W.

H. W. Leverenz, An Introduction to the Luminescence of Solids (John Wiley Sons, Inc., New York, 1950), p. 175; P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949), p. 627.

Lewis, D. R.

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

Mattarresse, L. M.

C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
[CrossRef]

McClure, D. S.

O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
[CrossRef]

Medlin, W. L.

W. L. Medlin, J. Chem. Phys. 38, 1132 (1963).
[CrossRef]

W. L. Medlin, J. Phys. Chem. Solids 18, 238 (1961).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 34, 672 (1961).
[CrossRef]

W. L. Medlin, J. Phys. Chem. 65, 1172 (1961).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 30, 451 (1959).
[CrossRef]

Melamed, N. T.

R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
[CrossRef]

Moore, C. E.

C. E. Moore, Natl. Bur. Std. U. S. Circ. 467, 11 (1952).

Murata, K. J.

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

Orgel, L. E.

L. E. Orgel, J. Chem. Phys. 23, 1958 (1955).
[CrossRef]

L. E. Orgel, J. Chem. Phys. 23, 1004, 1824 (1955).
[CrossRef]

Pappalardo, R.

R. Pappalardo, J. Chem. Phys. 31, 1050 (1959).
[CrossRef]

Prener, J. S.

E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
[CrossRef]

Rao, K. V.

K. V. Rao, J. Phys. Chem. Solids 20, 193 (1961); W. F. Kolbe and A. Smakula, Phys. Rev. 124, 1754 (1961).
[CrossRef]

Razumova, T. K.

V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).

Schulman, J. H.

C. C. Klick and J. H. Schulman, J. Opt. Soc. Am. 42, 910 (1952).
[CrossRef]

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

Schulz, H. J.

I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
[CrossRef]

Stillwell, C. W.

C. W. Stillwell, Crystal Chemistry (McGraw-Hill Book Company, Inc., New York, 1958), p. 269.

Stout, J. W.

J. W. Stout, J. Chem. Phys. 33, 303 (1960).
[CrossRef]

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

Sugano, S.

Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753 (1954).
[CrossRef]

Tanabe, Y.

Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753 (1954).
[CrossRef]

Vaynberg, B. A.

V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).

Watanabe, K.

K. Watanabe, Phys. Rev. 83, 785 (1951).
[CrossRef]

Weyl, P. K.

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

Williams, F. E.

F. E. Williams, Report on International Conference on Luminescence of Organic and Inorganic Materials, edited by H. P. Kallman and G. M. Spruch (John Wiley Sons, Inc., New York, 1962), p. 305.

Wyckoff, R. W. G.

R. W. G. Wyckoff, The Structure of Crystals (Chemical Catalog Company, Inc., New York, 1931), 2nd ed., p. 275.

Acta Chem. Scand. (1)

C. K. Jorgensen, Acta Chem. Scand. 8, 1502 (1954).
[CrossRef]

British J. Appl. Phys. (1)

C. C. Klick, British J. Appl. Phys. 6, Suppl. 4, S74 (1955).
[CrossRef]

Bull. Geol. Soc. Am. (1)

J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
[CrossRef]

J. Appl. Phys. (1)

J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
[CrossRef]

J. Chem. Phys. (11)

L. E. Orgel, J. Chem. Phys. 23, 1004, 1824 (1955).
[CrossRef]

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

R. Pappalardo, J. Chem. Phys. 31, 1050 (1959).
[CrossRef]

C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 30, 451 (1959).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 38, 1132 (1963).
[CrossRef]

L. E. Orgel, J. Chem. Phys. 23, 1958 (1955).
[CrossRef]

W. L. Medlin, J. Chem. Phys. 34, 672 (1961).
[CrossRef]

J. W. Stout, J. Chem. Phys. 33, 303 (1960).
[CrossRef]

P. D. Johnson and F. L. Hughes, J. Chem. Phys. 26, 612 (1957).
[CrossRef]

O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
[CrossRef]

J. Electrochem. Soc. (2)

I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
[CrossRef]

R. J. Ginther, J. Electrochem. Soc. 98, 74 (1951).
[CrossRef]

J. Opt. Soc. Am. (1)

J. Phys. Chem. (1)

W. L. Medlin, J. Phys. Chem. 65, 1172 (1961).
[CrossRef]

J. Phys. Chem. Solids (3)

W. L. Medlin, J. Phys. Chem. Solids 18, 238 (1961).
[CrossRef]

E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
[CrossRef]

K. V. Rao, J. Phys. Chem. Solids 20, 193 (1961); W. F. Kolbe and A. Smakula, Phys. Rev. 124, 1754 (1961).
[CrossRef]

J. Phys. Soc. Japan (2)

Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753 (1954).
[CrossRef]

Y. Kaifu, J. Phys. Soc. Japan 16, 1605 (1961).
[CrossRef]

Natl. Bur. Std. U. S. Circ. (1)

C. E. Moore, Natl. Bur. Std. U. S. Circ. 467, 11 (1952).

Opt. i Spektroskopiya (1)

V. A. Arkhangelskaya, B. A. Vaynberg, and T. K. Razumova, Opt. i Spektroskopiya 4, 681 (1958).

Phys. Rev. (3)

K. Watanabe, Phys. Rev. 83, 785 (1951).
[CrossRef]

R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
[CrossRef]

J. L. Birman, Phys. Rev. 121, 144 (1961).
[CrossRef]

Other (6)

F. E. Williams, Report on International Conference on Luminescence of Organic and Inorganic Materials, edited by H. P. Kallman and G. M. Spruch (John Wiley Sons, Inc., New York, 1962), p. 305.

H. W. Leverenz, An Introduction to the Luminescence of Solids (John Wiley Sons, Inc., New York, 1950), p. 175; P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949), p. 627.

C. J. Ballhausen, Introduction to Ligand Field Theory (McGraw-Hill Book Company, Inc., New York, 1962).

R. W. G. Wyckoff, The Structure of Crystals (Chemical Catalog Company, Inc., New York, 1931), 2nd ed., p. 275.

“X-Ray Powder Data File,” edited by J. V. Smith, American Society for Testing Materials, Philadelphia (1960).

C. W. Stillwell, Crystal Chemistry (McGraw-Hill Book Company, Inc., New York, 1958), p. 269.

Cited By

OSA participates in CrossRef's Cited-By Linking service. Citing articles from OSA journals and other participating publishers are listed here.

Alert me when this article is cited.


Figures (8)

Fig. 1
Fig. 1

Emission spectra for principal glow peaks due to Mn++ and Pb++ and for luminescence due to Mn++ in calcite.

Fig. 2
Fig. 2

Emission spectra for principal glow peaks due to Mn++ in dolomite.

Fig. 3
Fig. 3

Emission spectra for principal glow peaks due to Mn++ in magnesite and aragonite.

Fig. 4
Fig. 4

Emission spectra for principal glow peaks due to Mn++, Zn++, and Sb3+ in anhydrite.

Fig. 5
Fig. 5

Emission spectra for luminescence due to Mn++ at various temperatures.

Fig. 6
Fig. 6

Optical absorption spectrum of rhodochrosite showing assignment of levels.

Fig. 7
Fig. 7

Reflectance curves for MnCO3 and MnSO4 powder samples.

Fig. 8
Fig. 8

Approximate configurational coordinate diagram for Mn++ levels in calcite.

Tables (1)

Tables Icon

Table I Comparison of MnCO3 absorption data with computed values.