Advertisement

Bonding and structure of water molecules in solid hydrates. Correlation of spectroscopic and structural data

  • Heinz Dieter Lutz
Conference paper
Part of the Structure and Bonding book series (STRUCTURE, volume 69)

Abstract

Solid hydrate research of the last fifteen years is critically evaluated with regard to bonding and structure of water molecules. This review focusses on new results of structure determination and infrared and Raman studies in terms of hydrogen bonding and other intermolecular bonding interactions, distortion and disorder of water molecules, intermolecular and intramolecular coupling and anharmonicity of water bands, isotopic effects, and phase transitions. The techniques used for structure determination and spectroscopic measurements of solid hydrates are discussed.

Keywords

Water Molecule Isotopic Shift Water Band Single Crystal Study Hydrogen Position 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Falk, M., Knop, O.: Water, A Comprehensive Treatise (F. Frank Ed.), Plenum Press, New York, Vol. 2, 1973, p. 106ff.Google Scholar
  2. 2.
    Buchmeier, W., Lutz, H. D.: Z. anorg. allg. Chem. 538, 131 (1986)Google Scholar
  3. 3.
    Lutz, H. D., Buchmeier, W., Engelen, B.: Acta Cryst. B43, 71 (1987)Google Scholar
  4. 4.
    Engelen, B.: Habilitationsschrift, Univ. Siegen 1983Google Scholar
  5. 5.
    McGrath, J. W., Silvidi, A. A.: J. Chem. Phys. 34, 322 (1961)Google Scholar
  6. 6.
    ElSaffar, Z. M.: ibid. 45, 4643 (1966)Google Scholar
  7. 7.
    Sasidhar, Y. U., Rao, K. V. S. R.: J. Mol. Struct. 147, 113 (l986); J. Phys. C.: Solid State Phys. 19, 6241 (1986)Google Scholar
  8. 8.
    Chihara, H., Kawakami, T., Soda, G.: J. Magn. Reson. 1, 75 (1969)Google Scholar
  9. 9.
    Seryshev, S. A., Vakhrameev, A. M., Afanas'ev, M. L., Kruglik, A. I., Bondarenko, V. S.: Yad. Magn. Rezon. Vnutr. Dvizheniya Krist. 1981, 105 (1981)Google Scholar
  10. 10.
    Svare, I., Fimland, B. O., Otnes, K., Janik, J. A., Janik, J. M., Mikuli, E., Migdal-Mikuli, A.: Physica B + C 106, 195 (1981)Google Scholar
  11. 11.
    Amm, D. T., Segel, S. L.: Z. Naturforsch. 41a, 279 (1986)Google Scholar
  12. 12.
    McGrath, J. W.: J. Chem. Phys. 42, 4111 (1965)Google Scholar
  13. 13.
    Afanas'ev, M. L., Kubarev, Yu. G., Zeer, E. P.: Yad. Magn. Rezon. Strukt. Krist. 1984, 87 (1984)Google Scholar
  14. 14.
    Tanaka, H., Henning, J., Lutz, H. D., Kliche, G.: Spectrochim. Acta 43A, 395 (1987)Google Scholar
  15. 15.
    Lutz, H. D., Christian, H., Eckers, W.: ibid. 41A, 637 (1985)Google Scholar
  16. 16.
    Amalvy, J. I., Varetti, E. L., Aymonino, P. J., Castellano, E. E., Piro, O. E., Punte, G.: J. Crystallogr. Spectrosc. Res. 13, 107 (1983)Google Scholar
  17. 17.
    Vergara, M. M., Varetti, E. L.: J. Phys. Chem. Solids 48, 13 (1987)Google Scholar
  18. 18.
    Takahashi, H., Maehara, I., Kaneko, N.: Spectrochim. Acta 39A, 449 (1983)Google Scholar
  19. 19.
    Waschenbach, G., Lutz, H. D.: ibid, 42A, 983 (1986)Google Scholar
  20. 20.
    Hayward, H. P., Schiffer, J.: J. Chem. Phys. 62, 1473 (1975)Google Scholar
  21. 21.
    Wood, D. L.: ibid. 75, 4809 (1981)Google Scholar
  22. 21a.
    Henning, J.: Thesis, Univ. Siegen 1988Google Scholar
  23. 22.
    Torres, A., Rull, F., DeSaja, J. A.: Spectrochim. Acta 36A, 425 (1980)Google Scholar
  24. 23.
    Savatinova, I., Chisler, E. V., Rohleder, J., Jakubovski, B.: phys. stat. sol. (b) 101, 233 (1980)Google Scholar
  25. 24.
    Choudhury, P., Ghosh, B., Raghuvanshi, G. S., Bist, H. D.: J. Raman Spectrosc. 14, 99 (1983)Google Scholar
  26. 25.
    Lang, W., Claus, R.: J. Phys. Chem. Solids 44, 789 (1983)Google Scholar
  27. 26.
    Lutz, H. D., Eckers, W., Christian, H., Engelen, B.: Thermochim. Acta 44, 337 (1981)Google Scholar
  28. 27.
    Taylor, T. J., Dollimore, D., Gamlen, G. A., Barnes, A. J., Stuckey, M. A.: ibid. 101, 291 (1986)Google Scholar
  29. 28.
    Lutz, H. D., Eckers, W., Schneider, G., Haeuseler H.: Spectrochim. Acta 37A, 561 (1981)Google Scholar
  30. 29.
    Thaper, C. L., Dasannacharya, B. A., Sequeira, A., Iyengar, P. K.: Solid State Commun. 8, 497 (l970)Google Scholar
  31. 30.
    Kim, H.-J., Yoon, B.-G.: J. Korean Nucl. Soc. 11, 1 (1979)Google Scholar
  32. 31.
    Boutin, H., Safford, G. J., Danner, H. R.: J. Chem. Phys. 40, 2670 (1964)Google Scholar
  33. 32.
    Stahn, M., Lechner, R. E., Dachs, H., Jacobs, H. E.: J. Phys. C 16, 5073 (1983)Google Scholar
  34. 33.
    Andersen, N. H., Kjems, J. K., Poulsen, F. W.: Phys. Scr. 25, 780 (1982)Google Scholar
  35. 34.
    Hornig, D. F., White, H. F., Reding, F. P.: Spectrochim. Acta 12, 338 (1958)Google Scholar
  36. 35.
    Kling, R., Schiffer, J.: Chem. Phys. Lett. 3, 64 (1969)Google Scholar
  37. 36.
    Seidl, V., Knop, O., Falk, M.: Can. J. Chem. 47, 1361 (1969)Google Scholar
  38. 37.
    Wells, A. F.: Structural Inorganic Chemistry, Clarendon Press, Oxford 1986, p. 659ff.Google Scholar
  39. 38.
    Bernal, J. D.: J. Chim. Phys. Physicochim. Biol. 50, C1 (1953)Google Scholar
  40. 39.
    Chidambaram, R., Sequeira, A., Sikka, S. K.: J. Chem. Phys. 41, 3616 (1964)Google Scholar
  41. 40.
    Hamilton, W. C., Ibers, J. A.: Hydrogen Bonding in Solids, Benjamin Inc., New York 1968, p. 204ff.Google Scholar
  42. 41.
    Ferraris, G., Franchini-Angela, M.: Acta Cryst. B28, 3572 (1972)Google Scholar
  43. 42.
    Chiari, G., Ferraris, G.: ibid. B38, 2331 (1982)Google Scholar
  44. 43.
    LeClaire, A., Monier, J. C.: ibid. B38, 724 (1982)Google Scholar
  45. 44.
    Mikenda, W.: J. Mol. Struct. 147, 1 (1986)Google Scholar
  46. 45.
    Schiwy, W., Pohl, S., Krebs, B.: Z. anorg. allg. Chem. 402, 77 (1973)Google Scholar
  47. 46.
    Bottomley, F., White, P. S.: Acta Cryst. B35, 2193 (1979)Google Scholar
  48. 47.
    Pedersen, B.: ibid. B30, 289 (1974)Google Scholar
  49. 48.
    Savage, H. F. J., Finney, J. L.: Nature (London) 322, 717 (1986)Google Scholar
  50. 49.
    Ichikawa, M.: Acta Cryst. B34, 2074 (1978)Google Scholar
  51. 50.
    Cook, R. L., DeLucia, F. C., Helminger, P.: J. Mol. Spectrosc. 53, 62 (1974)Google Scholar
  52. 51.
    Petrusevski, V., Soptrajanov, B.: J. Mol. Struct. 115, 343 (l984)Google Scholar
  53. 52.
    Kristiansson, O., Eriksson, A., Lindgren, J.: VIIth International Workshop “Horizons in H-Bond Research”, Marburg (FRG) 1985Google Scholar
  54. 53.
    Lutz, H. D., Henning, J.: J. Mol. Struct. 142, 575 (1986)Google Scholar
  55. 53a.
    Lutz, H. D., Alici, E., Buchmeier, W.: Z. anorg. allg. Chem. 535, 31 (1985)Google Scholar
  56. 53b.
    Ferraris, G., Fuess, H., Joswig, W.: Acta Cryst. B42, 253 (1986)Google Scholar
  57. 54.
    Kuske, P., Engelen, B., Henning, J., Gregson, D., Lutz, H. D., Fuess, H.: Z. Kristallogr. (communicated)Google Scholar
  58. 55.
    Pedersen, B.: Acta Cryst. B31, 869 (1975)Google Scholar
  59. 56.
    Eriksson, A., Berglund, B., Tegenfeldt, J., Lindgreen, J.: J. Mol. Struct. 52, 107 (1979)Google Scholar
  60. 57.
    Hermansson, K.: Acta Cryst. B41, 161 (1985)Google Scholar
  61. 58.
    Satija, S. K., Wang, C. H.: J. Chem. Phys. 68, 4612 (1978)Google Scholar
  62. 59.
    Lutz, H. D., Henning, J., Buchmeier, W., Engelen, B.: J. Raman Spectrosc. 15, 336 (1984)Google Scholar
  63. 60.
    Schaak, G.: J. Mol. Struct. 79, 361 (1982)Google Scholar
  64. 61.
    Benedict, W. S., Yailar, N., Plyler, E. K.: J. Chem. Phys. 24, 1139 (1956)Google Scholar
  65. 62.
    Nibler, J. W., Pimentel, G. C.: J. Mol. Spectrosc. 26, 294 (1968)Google Scholar
  66. 63.
    Lutz, H. D., Pobitschka, W., Frischemeier, B., Becker, R. A.: J. Raman Spectrosc. 7, 130 (1978)Google Scholar
  67. 64.
    Lutz, H. D., Pobitschka, W., Christian, H., Becker, R.-A.: ibid. 8, 189 (1979)Google Scholar
  68. 65.
    Lutz, H. D., Christian, H.: J. Mol. Struct. 96, 61 (1982)Google Scholar
  69. 66.
    Lutz, H. D.: Spectrochim. Acta 38A, 921 (1982)Google Scholar
  70. 66a.
    Engdahl, A., Nelander, B.: J. Phys. Chem. 90, 4982 (1986)Google Scholar
  71. 66b.
    Nelander, B.: XVIIIth European Congress on Molecular Spectroscopy, Amsterdam (Netherlands) 1987; J. Mol. Struct. (in press)Google Scholar
  72. 67.
    Lutz, H. D., Pobitschka, W., Frischemeier, B., Becker, R. A.: Appl. Spectrosc. 32, 541 (1978)Google Scholar
  73. 68.
    Eriksson, A., Hussein, M. A., Berglund, B., Tegenfeldt, J., Lindgren, J.: J. Mol. Struct. 52, 95 (1979)Google Scholar
  74. 69.
    Lutz, H. D., Kuske, P., Henning, J.: ibid. (in press)Google Scholar
  75. 70.
    Schiffer, J., Intenzo, M., Hayward, P., Calabrese, C.: J. Chem. Phys. 64, 3014 (1976)Google Scholar
  76. 71.
    Novak, A.: Struct. Bonding 18, 177 (1974)Google Scholar
  77. 72.
    Berglund, B., Lindgren, J., Tegenfeldt, J.: J. Mol. Struct. 43, 179 (1978)Google Scholar
  78. 73.
    Minceva-Sukarova, B., Sherman, W. F., Wilkinson, G. R.: Spectrochim. Acta 41A, 315 (1985)Google Scholar
  79. 74.
    Prieto, A. C., Rull, F., DeSaja, J. A.: J. Mol. Struct. 143, 117 (1986)Google Scholar
  80. 74a.
    Lutz, H. D., Henning, J.: Z. Kristallogr.Z 178, I48 (1987)Google Scholar
  81. 75.
    Savatinova, I., Anachkova, E.: Int. J. Quantum Chem. 29, 1383 (1986)Google Scholar
  82. 76.
    Scherer, J. R., Snyder, R. G.: J. Chem. Phys. 67, 4794 (1977)Google Scholar
  83. 77.
    John, I. G., Bacskay, G. B., Hush, N. S.: Chem. Phys. 51, 49 (1980) 78. Keresztury, G.: J. Mol. Struct. 143, 47 (1986)Google Scholar
  84. 79.
    Fifer, R. A., Schiffer, J.: J. Chem. Phys. 54, 5097 (1971)Google Scholar
  85. 80.
    Schiffer, J., Hornig, D. F.: ibid. 49, 4150 (1968)Google Scholar
  86. 81.
    Giguere, P. A.: Rev. Chim. Miner. 20, 588 (1983)Google Scholar
  87. 82.
    Brink, G., Falk, M.: Can. J. Chem. 48, 2096 (1970)Google Scholar
  88. 83.
    Kristiansson, O., Eriksson, A., Lindgren, J.: Acta Chem. Scand. A38, 613 (1984)Google Scholar
  89. 84.
    Buchmeier, W., Engelen, B., Lutz, H. D.: Z. Naturforsch. 416, 852 (1986)Google Scholar
  90. 85.
    Mikenda, W., Steidl, H.: Spectrochim. Acta 38A, 1059 (1982)Google Scholar
  91. 85a.
    Kleeberg, H.: The Proceedings of the Interaction of Water in Ionic and Nonionic Hydrates (H. Kleeberg Ed.), Springer Verlag, Berlin, Heidelberg p.89 (1987)Google Scholar
  92. 85b.
    Brakaspathy, R., Singh, S.: Chem. Phys. Lett. 131, 394 (1986)Google Scholar
  93. 86.
    Falk, M., Huang, C.-H., Knop, O.: Can. J. Chem. 52, 2380 and 2928 (1974)Google Scholar
  94. 87.
    Sartori, G., Furlani, F., Damiani, A.: J. Inorg. Nucl. Chem. 8, 119 (1958)Google Scholar
  95. 87a.
    Zundel, G.: Angew. Chem. 81, 507 (1969)Google Scholar
  96. 88.
    Lutz, H. D., Klöppel, H.-J., Feher, M., Bursian, S.: Ber. Bunsenges. Phys. Chem. 75, 583 (1971)Google Scholar
  97. 89.
    Hermansson, K., Olovsson, I., Lunell, S.: Theor. Chim. Acta 64, 265 (1984)Google Scholar
  98. 90.
    Falk, M., Flakus, H. T., Boyd, R. J.: Spectrochim. Acta 42A, 175 (1986)Google Scholar
  99. 91.
    Kleeberg, H., Heinje, G., Luck, W. A. P.: J. Phys. Chem. 90, 4427 (1986)Google Scholar
  100. 92.
    Varetti, E. L., Aymonino, P. J.: J. Mol. Struct. 79, 281 (1982)Google Scholar
  101. 93.
    Amalvy, J. I., Aymonino, P. J.: Z. Phys. Chem. (Leipzig) 268, 15 (1987)Google Scholar
  102. 93a.
    Lutz, H. D., Henning, J.: The Proceedings of the Interaction of Water in Ionic and Nonionic Hydrates (H. Kleeberg Ed.), Springer Verlag, Berlin, Heidelberg p.63 and 69 (1987)Google Scholar
  103. 94.
    Lutz, H. D., Eckers, W., Haeuseler, H.: J. Mot. Struct. 80, 221 (1982)Google Scholar
  104. 95.
    Werner, H. J., Rosmus, P., Reinsch, E. A.: J. Chem. Phys. 79, 905 (1983)Google Scholar
  105. 96.
    Owrutsky, J. C., Rosenbaum, N. H., Tack, L. M., Saykally, R. J.: ibid. 83, 5338 (1985)Google Scholar
  106. 97.
    Stanek, T., Pytasz, G.: Acta Phys. Pol. A52, 119 (1977)Google Scholar
  107. 98.
    Lutz, H. D., Henning, J., Haeuseler, H.: J. Mot. Struct. 156, 143 (1987)Google Scholar
  108. 99.
    Poulsen, F. W.: J. Raman Spectrosc. 17, 189 (1986)Google Scholar
  109. 100.
    Jenkins, T. E., Lewis, J.: Phys. Scr. 18, 351 (1978); J. Raman Spectrosc. 11, 1 (1981)Google Scholar
  110. 101.
    Savatinova, L, Anachkova, E., Ratajczak, H.: Raman Spectrosc., Proc. Int. Conf., 8th, 475 (1982); phys. stat. sot. (b) 91, 413 (1979)Google Scholar
  111. 102.
    White, M. A., Falk, M.: J. Chem. Phys. 83, 2467 (1985) and 84, 3484 (1986)Google Scholar
  112. 103.
    Brink, G.: Spectrochim. Acta 28A, 1151 (1972)Google Scholar
  113. 104.
    McCarthy, P. J., Walker, I. M.: ibid. 39A, 827 (1983)Google Scholar
  114. 105.
    Walker, J. M., McCarthy, P. J.: Can. J. Chem. 64, 1012 (1986)Google Scholar
  115. 106.
    Berglund, B., Lindgren, J., Tegenfeldt, J.: J. Mot. Struct. 43, 169 (1978)Google Scholar
  116. 107.
    Wojcik, M. J., Lindgren, J., Tegenfeldt, J.: Chem. Phys. Letters 99, 112 (1983)Google Scholar
  117. 108.
    Sceats, M. G., Rice, S. A.: J. Chem. Phys. 71, 973 (1979)Google Scholar
  118. 109.
    Sandorfy, C.: The Hydrogen Bond (P. Schuster, G. Zundel, S. Sandorfy Eds.), North Holland, Amsterdam, Vol. II, Chap. 13 (1976)Google Scholar
  119. 110.
    Fifer, R. A., Schiffer, J.: J. Chem. Phys. 52, 2664 (1970)Google Scholar
  120. 111.
    Eriksson, A., Lindgren, J.: J. Mot. Struct. 53, 97 (1979)Google Scholar
  121. 112.
    Mills, I. M., Robiette, A. G.: Molecular Physics 56, 743 (1985)Google Scholar
  122. 113.
    Falk, M.: Spectrochim. Acta 40A, 43 (1984)Google Scholar
  123. 114.
    Lutz, H. D., Christian, H., Haeuseler, H.: C.R.-Conf. Int. Spectrosc. Raman, 7th, Ottawa (W. F. Murphy Ed.), p. 120 (1980)Google Scholar
  124. 115.
    Othen, D. A., Knop, O., Falk, M.: Can. J. Chem. 53, 3837 (1975)Google Scholar
  125. 116.
    Eriksson, A., DeVillepin, J., Romain, F.: J. Mot. Struct. 140, 19 (1986)Google Scholar
  126. 117.
    Tayal, V. P., Srivastava, B. K., Khandelwal, D. P., Bist, H. D.: Appl. Spectrosc. Rev. 16, 43 (1980)Google Scholar
  127. 118.
    Lutz, H. D., Henning, J., Jacobs, H., Mach, B.: to be publishedGoogle Scholar
  128. 119.
    Lutz, H. D., Christian, H.: J. Mot. Struct. 101, 199 (1983)Google Scholar
  129. 120.
    Thomas, G. H., Falk, M., Knop, O.: Can. J. Chem. 52, 1029 (1974)Google Scholar
  130. 121.
    Eriksson, A., Lindgren, J.: J. Mot. Struct. 48, 417 (1978); Acta Chem. Scand. A32, 737 (1978)Google Scholar
  131. 122.
    Singh, B., Khanna, B. N.: Spectrochim. Acta 42A, 181 (1986)Google Scholar
  132. 123.
    Eckers, W., Lutz, H. D.: ibid. 41A, 1321 (1985)Google Scholar
  133. 124.
    Falk, M., Huang, C.-H., Knop, O.: Can. J. Chem. 53, 51 (1975)Google Scholar
  134. 125.
    Berenblut, B. J., Dawson, P., Wilkinson, G. R.: Spectrochim. Acta 29A, 29 (1973)Google Scholar
  135. 126.
    Soptrajanov, B., Ristova, M.: J. Mot. Struct. 115, 359 (1984)Google Scholar
  136. 127.
    Miyazawa, T.: Bull. Chem. Soc. Jpn. 34, 202 (1961)Google Scholar
  137. 128.
    Ichida, K., Kuroda, Y., Nakamura, D., Kubo, M.: Spectrochim. Acta 28A, 2433 (1972)Google Scholar
  138. 129.
    Lutz, H. D., Klöppel, H.-J., Pobitschka, W., Baasner, B.: Z. Naturforsch. 29B, 723 (1974)Google Scholar
  139. 130.
    Meshitsuka, S., Takahashi, H., Higasi, K.: Bull. Chem. Soc. Jpn. 44, 3255 (1971)Google Scholar
  140. 131.
    Tayal, V. P., Khandelwal, D. P., Bist, H. D.: Chem. Phys. Lett. 55, 136 (1978)Google Scholar
  141. 132.
    Sato, I.: J. Phys. Soc. Jpn. 20, 275 (1965)Google Scholar
  142. 133.
    Anachkova, E., Ratajczak, H., Savatinova, I.: phys. stat. sol. (b) 108, 65 (1981)Google Scholar
  143. 134.
    Canterford, R. P., Ninio, F.: Solid State Commun. 15, 1451 (1974)Google Scholar
  144. 135.
    Frindi, M., 8Peyrard, M., Remoissenet, M.: J. Phys. C13, 3493 (1980)Google Scholar
  145. 135a.
    Jain, Y. S., Singh, B., Khanna, B. N.: Pramana 18, 511 (1982)Google Scholar
  146. 136.
    Savatinova, I., Anachkova, E.: phys. stat. sot. (b) 82, 677 (1977) and (b) 84, 401 (1977)Google Scholar
  147. 137.
    Heyns, A. M.: Spectrochim. Acta 33A, 315 (1977)Google Scholar
  148. 138.
    Jain, Y. S.: Solid State Commun. 17, 605 (1975)Google Scholar
  149. 139.
    Corn, R. M., Strauss, H. L.: J. Chem. Phys. 76, 4834 (1982)Google Scholar
  150. 140.
    Pigenet, C.: J. Raman Spectrosc. 13, 66 (1982)Google Scholar
  151. 141.
    Donnelly, T. C., Nash, C. P.: Appl. Spectrosc. 36, 698 (1982)Google Scholar
  152. 142.
    Bertie, J. E., Heyns, A. M., Oehler, O.: Can. J. Chem. 51, 2275 (1973)Google Scholar
  153. 143.
    Fredin, L., Nelander, B., Ribbegard, G.: J. Chem. Phys. 66, 4065 (1977)Google Scholar
  154. 144.
    Eriksson, A., Hermansson, K.: Acta Cryst. B39, 703 (1983)Google Scholar
  155. 145.
    Hayward, H. P., Schiffer, J.: J. Chem. Phys. 64, 3961 (1976)Google Scholar
  156. 146.
    Wojcik, M. J., Lindgren, J.: Chem. Phys. Lett. 99, 116 (1983)Google Scholar
  157. 147.
    Tanaka, H., Negita, H.: Kagaku (Kyoto) 36, 482 (1981)Google Scholar
  158. 148.
    Price, G. H., Stuart, W. I.: J. Chem. Soc. Faraday Trans. 169, 1498 (1973)Google Scholar
  159. 149.
    Tanaka, H., Negita, H.: Thermochim. Acta 41, 305 (1980)Google Scholar
  160. 150.
    Bastow, T. J., Elcombe, M. M., Howard, C. J.: Solid State Commun. 57, 339 (1986)Google Scholar
  161. 151.
    Jacobs, H., Mach, B., Lutz, H. D., Henning, J.: Z. anorg. allg. Chem. 544, 28 (1987)Google Scholar
  162. 152.
    Swanton, D. J., Bacskay, G. B., Hush, N. S.: J. Chem. Phys. 84, 5715 (1986)Google Scholar
  163. 153.
    Patel, M. B.: Solid State Commun. 53, 431 (1983)Google Scholar

Copyright information

© Springer-Verlag 1988

Authors and Affiliations

  • Heinz Dieter Lutz
    • 1
  1. 1.Universität SiegenSiegenGermany

Personalised recommendations