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Relativistic quantum calculations on some mercury sulfide molecules

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Abstract

Relativistic quantum calculations at the CASSCF- and CCI-levels were performed on the Hg(SH)2, HgSH and HgS molecules. The relativistic effects were taken into account by a relativistic effective core potential method. Dissociation energies and optimal geometries were calculated for these three molecules, which are plausible atmospheric Hg compounds. The Hg(SH)2 and HgSH molecules (in the gaseous phase) have never been studied before, neither experimentally nor theoretically, i.e. the existence of these molecules are uncertain. The theoretical dissociation energies, De's, of Hg(SH)2 and HgSH (at the CCI-level) were 59 kcal·mol−1 and 3 kcal·mol−1, respectively, indicating that Hg(SH)2 could be stable in the atmosphere but probably not HgSH. The theoretical De of HgS differs very much from the experimental one, but the reason for this is not clear. The Hg-S distances for Hg(SH)2, HgSH and HgS were found to be 2.38, 2.63 and 2.30 Å, respectively. The Hg-S-H angle in Hg(SH)2 was optimized to 93°. The excitation energies of Hg(SH)2, Hg(SH)2(H2O)4 and (HSHg)2S were calculated in order to see whether these species can absorb photons with wavelengths longer than 290 nm (the sunlight limit) and subsequently be photolyzed. The Hg(SH)2(H2O)4 complex is intended as a model for Hg(SH)2(aq). Photoreduction of Hg-sulfide species in sea water, yielding Hg0, could be an important source of Hg in the atmosphere. Excitation energies lower than the sunlight limit (4.3 eV≈290 nm) were found for Hg(SH)2 and Hg(SH)2(H2O)4, although the lowest spin and dipole allowed excitations probably lie slightly (0.2 to 0.3 eV) above this limit. Therefore a photodecomposition of Hg(SH)2(g) and Hg(SH)2(aq) by sunlight seems likely to occur.

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References

  1. Lindqvist, O., Jernelöv, A., Johansson, K. and Rodhe, H. : 1984, Mercury in the Swedish Environment, Global and Local Sources, Report SNV pm 1816, National Swedish Environment Protection board,

  2. Lindqvist, O. and Rodhe, H.: 1985, Tellus 37B, 136

    Article  CAS  Google Scholar 

  3. Schwarzenbach, G. and Widmer, M.: 1963, Helv. Chim. Acta 46, 2613

    Article  CAS  Google Scholar 

  4. Grade, M. and Hirswald, W.: 1982, Buns. Phys. Chem. 86, 899

    CAS  Google Scholar 

  5. Wayne, P. P. : 1985, Chemistry of the Atmospheres, Oxford Univ. Press

  6. Strömberg, D., Gropen, O. and Wahlgren, U.: 1989, Chem. Phys. 133, 207.

    Article  Google Scholar 

  7. Bauschlicher Jr, C. W. and Langhoff, S. R.: 1986, Chem. Phys. Lett. 126, 163

    Article  CAS  Google Scholar 

  8. Bauschlicher Jr, C. W., Nelin, C. J. and Bagus, P. S.: 1985, J. Chem. Phys. 82, 3265

    Article  CAS  Google Scholar 

  9. Schwerdtfeger, P., Dolg, M., Schwarz, W. H. E., Bowmaker, G. A. and Boyd, P. D. W.: 1989, J. Chem. Phys. 91, 1762

    Article  CAS  Google Scholar 

  10. Hoffman, H. and Leone, S.: 1978, J. Chem. Phys. 69, 3819

    Article  Google Scholar 

  11. Zepp, R.G., Wolfe, N. L. and Gordon, J. A.: 1973, Chemosphere 3, 93

    Article  Google Scholar 

  12. Baughman, G. L, Gordon, J. A., Wolfe, N. L and Zepp, R. G. : 1973, Chemistry of Organomercurials in Aquatic Systems, U.S EPA Report, EPA-660/3-73-012, September

  13. Kiemeneij, A. M. and Kloosterboer, J. G.: 1976, Anal. Chem. 48, 575

    Article  CAS  Google Scholar 

  14. Leighton, P. A.: 1961, Photochemistry of air pollution, Academic press, New York, N.Y.

    Google Scholar 

  15. Cutter, G. A. and Oatts, T. J.: 1987, Anal. Chem. 59, 717

    Article  CAS  Google Scholar 

  16. Dyrssen, D. and Wedborg, M.: 1988, Mar. Chem. 24, 143

    Article  CAS  Google Scholar 

  17. Dyrssen, D.: 1988, Kemisk Tidskrift 7, 53 (In Swedish)

    Google Scholar 

  18. Strömberg, D.: 1990, Ph.D. Thesis, Univ.of Gothenburg, Sweden.

    Google Scholar 

  19. Fitzgerald, W. F. : 1986, ‘Cycling of Mercury between the Atmosphere and Oceans’, in The Role of Air-Sea Exchanhge in Geochemical Cycling, Reidel Publ.Company, 363–408

  20. Hägg, G.: 1979, General and Inorganic Chemistry, Almqvist&Wiksell, Uppsala, Sweden (In Swedish).

    Google Scholar 

  21. MOLECULE is a gaussian integral program written by Almlöf, J.. SWEDEN is a vectorized SCF-MC/SCF-CI program written by Siegbahn, P. E. M., Bauschlicher Jr, C. W., Roos, B. O., Taylor, P. R., Heiberg, A and Almlöf, J.

  22. Roos, B., Taylor, P. and Siegbahn, P. E. M.: 1980, Chem. Phys 48, 157

    Article  CAS  Google Scholar 

  23. Siegbahn, P. E. M., Almlöf, J., Heiberg, A. and Roos, B.: 1981, J. Chem. Phys 74, 2384

    Article  CAS  Google Scholar 

  24. Siegbahn, P. E. M.: 1983, Int. J. Quant. Chem. 23, 1869

    Article  CAS  Google Scholar 

  25. Davidson, E. R.: 1974, in The World of Quantum Chemistry, eds Daudel, R. and Pullman, D., (Reidel Dordrecht)

    Google Scholar 

  26. Moss, P. E.: 1973, Advanced Molecular Quantum Mechanics, Chapman and Hall, London.

    Google Scholar 

  27. Sucher, J.: 1980, Phys. Rev. A 22, 348

    Google Scholar 

  28. Almlöf, J., Faegri, K. and Grelland, H. H.: 1985, Chem. Phys. Lett. 114, 53

    Article  Google Scholar 

  29. Pettersson, L. G. M., Wahlgren, U. and Gropen, O.: 1983, Chem. Phys. 80, 7

    Article  CAS  Google Scholar 

  30. Pettersson, L. G. M., Wahlgren, U, and Gropen, O.: 1987, J. Chem. Phys. 86, 2176

    Article  CAS  Google Scholar 

  31. Pettersson, L. G. M. and Bauschlicher Jr., C. W., unpublished.

  32. Roos, B and Siegbahn, P.: 1970, Theor. Chim. Acta 17, 209

    Article  CAS  Google Scholar 

  33. Strömberg, A., Wahlgren, U, Pettersson, L. G. M. and Siegbahn, P. E. M.: 1984, Chem. Phys. 89, 323.

    Article  Google Scholar 

  34. Duijneveldt, F. B.: 1971, IBM J. Res. Develop. 20, 945

    Google Scholar 

  35. Kashiwabara, K., Konaka, S. and Kimura, M.: 1973, Bull Chem. Soc. Japan 46, 410

    Article  CAS  Google Scholar 

  36. Krasnov, K. S., Timoshinin, V. S., Danilova, T. G. and Khandozhko, S. : 1970, Handbook of Molecular Constants of Inorganic compounds (Iraeli Program for Scientific Translation, Jerusalem)

  37. Jackson, R. L.: 1989, Chem. Phys. Lett. 163, 315

    Article  CAS  Google Scholar 

  38. Desclaux, J. P.: 1973, At. Data Nucl. Tables 12, 311

    Article  CAS  Google Scholar 

  39. Wilcomb, R. E. and Bernstein, R. B.: 1976, J. Mol. Spectrosc. 62, 442

    Article  CAS  Google Scholar 

  40. Maya, J.: 1977, J. Chem. Phys. 67, 4976

    Article  CAS  Google Scholar 

  41. Wieland, K.: 1932, Z. Phys. 76, 801 :

    Article  CAS  Google Scholar 

  42. Wieland, K.: 1932, Z. Phys. 77, 157 :

    Article  CAS  Google Scholar 

  43. Wehrli, M.: 1938, Helv. Phys. Acta 11, 339

    CAS  Google Scholar 

  44. Johansson, G.: 1971, Acta Chem. Scand 25, 2787

    Article  CAS  Google Scholar 

  45. Griffiths, T. R. and Anderson, R. A.: 1984, J. Chem. Soc. Farad. Trans. 1 80, 2361

    Article  CAS  Google Scholar 

  46. Fromherz, H. and Lih, K. H.: 1933, Z. Phys. Chem. A 167, 103

    Google Scholar 

  47. Roxlo, C. and Mandl, A.: 1980, J. Appl. Phys. 51, 2969

    Article  CAS  Google Scholar 

  48. Templet, P., McDonald, J. R., McGlynn, S. P., Kendrow, C. H., Roebber, J. L and Weiss, K.: 1972, J. Chem. Phys. 56, 5746

    Article  CAS  Google Scholar 

  49. Ley, H. and Arends, B.: 1931, Z. Physical. Chem. B 15, 311

    Google Scholar 

  50. Ley, H. and Arends, B.: 1929, Z. Physical. Chem. B 6, 240

    Google Scholar 

  51. Brosset, C.: 1987, Water, Air and Soil Poll. 34, 145

    Article  CAS  Google Scholar 

  52. Wells, A. F. : 1984, Structural Inorganic Chemistry, Oxford Univ. Press.

  53. Soler, G. A., Aicardi, J. P. and Leyris, J. P.: 1981, Phys. Stat. Sol. B 105, 249

    Google Scholar 

  54. Doni, E., Resca, L., Rodriguez, S. and Becker, W. M.: 1979, Phys. Rev. B 20, 1663

    Google Scholar 

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Authors and Affiliations

  1. Dep of Inorganic chemistry, University of Gothenburg, S-412 96, Göteborg, Sweden

    Dan Strömberg & Ann Strömberg

  2. Dep of Physics, University of Stockholm, Vanadisvägen 9, S-113 46, Stockholm, Sweden

    Ulf Wahlgren

Authors
  1. Dan Strömberg
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  2. Ann Strömberg
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  3. Ulf Wahlgren
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Strömberg, D., Strömberg, A. & Wahlgren, U. Relativistic quantum calculations on some mercury sulfide molecules. Water, Air, and Soil Pollution 56, 681–695 (1991). https://doi.org/10.1007/BF00342309

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