Abstract

<p>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<sup>++</sup>, Pb<sup>++</sup>, Zn<sup>++</sup>, and Sb<sup>3+</sup>.</p><p>The emission spectra due to Mn<sup>++</sup> are interpreted on the basis of crystal field theory for transition metalions. It is shown that the orange thermoluminescence in Mn-activated calcite, dolomite, and magnesite is due to the <sup>4</sup><i>G</i>(<i>T</i><sub>1<i>g</i></sub>) → <sup>6</sup><i>S</i> transition in the Mn<sup>++</sup> ion. The green thermoluminescent emission of Mn-activated anhydrite is attributed to the <sup>4</sup><i>G</i>(<i>T</i><sub>2<i>g</i></sub>) → <sup>6</sup><i>S</i> transition in Mn<sup>++</sup>. In all cases the same transitions account for the luminescent emission also. The yellow thermoluminescence in Mn-activated aragonite is tentatively assigned to the <sup>4</sup><i>G</i>(<i>T</i><sub>1<i>g</i></sub>) → <sup>6</sup><i>S</i> transition but there are no absorption data to verify this. The emission due to Pb<sup>++</sup> in calcite is attributed to the <sup>1</sup><i>P</i><sub>1</sub> → <sup>1</sup><i>S</i><sub>0</sub> and <sup>3</sup><i>P</i><sub>0</sub> → <sup>1</sup><i>S</i><sub>0</sub> transitions. In Zn-activated anhydrite the emission bands are identified with transitions between the <i>T</i><sub>2<i>g</i></sub> and <i>E<sub>g</sub></i>, levels of the ground states of ions in substitutional and interstitial positions.</p><p>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.</p>

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  2. L. E. Orgel, J. Chem. Phys. 23, 1958 (1955).
  3. W. L. Medlin, J. Phys. Chem. Solids 18, 238 (1961).
  4. W. L. Medlin, J. Chem. Phys. 30, 451 (1959).
  5. J. Handin, D. V. Higgs, D. R. Lewis, and P. K. Weyl, Bull. Geol. Soc. Am. 68, 1203 (1957).
  6. C. C. Klick, British J. Appl. Phys. 6, Suppl. 4, S74 (1955).
  7. W. L. Medlin, J. Chem. Phys. 34, 672 (1961).
  8. W. L. Medlin, J. Phys. Chem. 65, 1172 (1961).
  9. K. Watanabe, Phys. Rev. 83, 785 (1951).
  10. K. V. Rao, J. Phys. Chem. Solids 20, 193 (1961); W. F. Kolbe and A. Smakula, Phys. Rev. 124, 1754 (1961).
  11. J. H. Schulman, L. W. Evans, R. J. Ginther, and K. J. Murata, J. Appl. Phys. 18, 732 (1947).
  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, Te Structure of Crystals (Chemical Catalog Company, Inc., New York, 1931), 2nd ed.,). 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).
  18. L. E. Orgel, J. Chem. Phys. 23, 1004, 1824 (1955).
  19. J. W. Stout, J. Chem. Phys. 31, 709 (1959).
  20. R. Pappalardo, J. Chem. Phys. 31, 1050 (1959).
  21. C. Kikuchi and L. M. Mattarresse, J. Chem. Phys. 33, 601 (1960).
  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).
  24. C. K. Jorgensen, Acta Chem. Scand. 8, 1502 (1954).
  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).
  27. C. C. Klick and J. H. Schulman, J. Opt. Soc. Am. 42, 910 (1952).
  28. R. J. Ginther, J. Electrochem. Soc. 98, 74 (1951).
  29. O. G. Holmes and D. S. McClure, J. Chem. Phys. 26, 1686 (1957).
  30. R. Bowers and N. T. Melamed, Phys. Rev. 99, 1781 (1955).
  31. J. L. Birman, Phys. Rev. 121, 144 (1961).
  32. I. Broser and H. J. Schulz, J. Electrochem. Soc. 108, 545 (1961).
  33. E. F. Apple and J. S. Prener, J. Phys. Chem. Solids 13, 81 (1960).
  34. Y. Kaifu, J. Phys. Soc. Japan 16, 1605 (1961).
  35. F. E. Williams, Report on International Conference on Luminescence of Organic and Inorganic Materials, edited by H. P. Kallman & G. M. Spruch (John Wiley & Sons, Inc., New York, 1962), p. 305.

Apple, E. F.

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

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).

Bowers, R.

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

Broser, I.

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

Evans, L. W.

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

Ginther, R. J.

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

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

Handin, J.

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

Higgs, D. V.

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

Holmes, O. G.

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

Hughes, F. L.

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

Johnson, P. D.

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

Jorgensen, C. K.

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

Kaifu, Y.

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

Kikuchi, C.

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

Klick, C. C.

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

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

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).

Mattarresse, L. M.

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

McClure, D. S.

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

Medlin, W. L.

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

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

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

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

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

Melamed, N. T.

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

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).

Orgel, L. E.

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

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

Pappalardo, R.

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

Prener, J. S.

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

Rao, K. V.

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

Razumova, T. K.

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

Schulman, J. H.

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

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

Schulz, H. J.

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

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. 31, 709 (1959).

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

Sugano, S.

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

Tanabe, Y.

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

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).

Weyl, P. K.

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

Williams, F. E.

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

Wyckoff, R. W. G.

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

Other (35)

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

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

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

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

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

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

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

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

K. Watanabe, Phys. Rev. 83, 785 (1951).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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.

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

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

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

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

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

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

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

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

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

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

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