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Photodissociation of the hydroxymethyl radical. I. The role of conical intersections in line broadening and decomposition pathways
When the 3 2A state of D2COH is excited broadened lines are observed and both D and H atoms are produced. When the 2 2A state is excited the spectrum is quite diffuse. These experimental observations ...
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Memory kernels and effective Hamiltonians from time-dependent methods. II. Vibrational predissociation
The overlapping resonance regime is studied from a temporal viewpoint for a model vibrational predissociation in the framework of the Feshbach partitioning method. The memory kernels that are related ...

Entropic effects on the structure of Lennard-Jones clusters

J. Chem. Phys. 116, 8307 (2002); doi:10.1063/1.1469616

Issue Date: 15 May 2002

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Jonathan P. K. Doye
University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW, United Kingdom

Florent Calvo
Laboratoire de Physique Quantique, IRSAMC, Université Paul Sabatier, 118 Route de Narbonne, F31062 Toulouse Cedex, France
We examine in detail the causes of the structural transitions that occur for those small Lennard-Jones clusters that have a nonicosahedral global minima. Based on the principles learned from these examples, we develop a method to construct structural phase diagrams that show in a coarse-grained manner how the equilibrium structure of large clusters depends on both size and temperature. The method can be augmented to account for anharmonicity and quantum effects. Our results illustrate that the vibrational entropy can play a crucial role in determining the equilibrium structure of a cluster. ©2002 American Institute of Physics.
History: Received 19 December 2001; accepted 22 February 2002
Permalink: http://link.aip.org/link/?JCPSA6/116/8307/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.Ei
    Exotic atoms and molecules; macromolecules; clusters Atomic and molecular clusters Phase transitions in clusters
  • 64.70.Kb
    Equations of state, phase equilibria, and phase transitions Specific phase transitions Solid–solid transitions
  • YEAR: 2002

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (121)
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For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. E. K. Parks, G. C. Niemann, K. P. Kerns, and S. J. Riley, J. Chem. Phys. 107, 1861 (1997).
  2. I. A. Harris, R. S. Kidwell, and J. A. Northby, Phys. Rev. Lett. 53, 2390 (1984).
  3. J. A. Northby, J. Chem. Phys. 87, 6166 (1987).
  4. T. P. Martin, Phys. Rep. 273, 199 (1996).
  5. C. J. Tsai and K. D. Jordan, J. Phys. Chem. 97, 11227 (1993).
  6. F. H. Stillinger, Phys. Rev. E 59, 48 (1999).
  7. J. P. K. Doye, M. A. Miller, and D. J. Wales, J. Chem. Phys. 111, 8417 (1999).
  8. R. H. Leary, J. Global Optim. 18, 367 (2000).
  9. J. P. K. Doye, in Global Optimization—Selected Case Studies, edited by J. D. Pinter (Kluwer Academic, Dordrecht, 2002).
  10. D. M. Deaven, N. Tit, J. R. Morris, and K. M. Ho, Chem. Phys. Lett. 256, 195 (1996).
  11. D. J. Wales and J. P. K. Doye, J. Phys. Chem. A 101, 5111 (1997).
  12. An up-to-date list of the Lennard-Jones global minima, along with points files of each global minimum, is maintained at the The Cambridge Cluster Database, http://www-wales.ch.cam.ac.uk/CCD.html
  13. R. H. Leary and J. P. K. Doye, Phys. Rev. E 60, R6320 (1999).
  14. D. Romero, C. Barrón, and S. Gómez, Comput. Phys. Commun. 123, 87 (1999).
  15. B. Hartke, in Ref. 9.
  16. Y. J. Twu, C. W. S. Conover, Y. A. Yang, and L. A. Bloomfield, Phys. Rev. B 42, 5306 (1990).
  17. T. P. Martin, T. Bergmann, H. Göhlich, and T. Lange, Chem. Phys. Lett. 172, 209 (1990).
  18. H. Hubert, B. Devouard, L. A. J. Garvie, M. O'Keeffe, P. R. Buseck, W. T. Petuskey, and P. F. McMillan, Nature (London) 391, 376 (1998).
  19. J. Xie, J. A. Northby, D. L. Freeman, and J. D. Doll, J. Chem. Phys. 91, 612 (1989).
  20. B. W. van de Waal, J. Chem. Phys. 90, 3407 (1989).
  21. B. Raoult, J. Farges, M.-F. de Feraudy, and G. Torchet, Philos. Mag. B 60, 881 (1989).
  22. L. Marville and L. Andreoni, J. Phys. Chem. 91, 2645 (1987).
  23. C. L. Cleveland and U. Landman, J. Chem. Phys. 94, 7376 (1991).
  24. Q. Wang, M. D. Glossman, M. P. Iniguez, and J. A. Alonso, Philos. Mag. B 69, 1045 (1994).
  25. H. S. Lim, C. K. Ong, and F. Ercolessi, Surf. Sci. 269/270, 1109 (1992).
  26. N. A. Besley, R. L. Johnston, A. J. Stace, and J. Uppenbrink, J. Mol. Struct.: THEOCHEM 341, 75 (1995).
  27. C. L. Cleveland, U. Landman, M. N. Shafgullin, P. W. Stephens, and R. L. Whetten, Phys. Rev. Lett. 79, 1873 (1997).
  28. J. E. Hearn and R. L. Johnston, J. Chem. Phys. 107, 4674 (1997).
  29. C. Barreteau, M. C. Desjonquères, and D. Spanjaard, Eur. Phys. J. D 11, 395 (2000).
  30. G. W. Turner, R. L. Johnston, and N. T. Wilson, J. Chem. Phys. 112, 4773 (2000).
  31. F. Calvo, G. Torchet, and M.-F. de Feraudy, J. Chem. Phys. 111, 4650 (1999).
  32. J.-B. Maillet, A. Boutin, and A. H. Fuchs, J. Chem. Phys. 111, 2095 (1999).
  33. A. Boutin, B. Rousseau, and A. H. Fuchs, Chem. Phys. Lett. 218, 122 (1994).
  34. L. D. Marks, Philos. Mag. A 49, 81 (1984).
  35. J. Farges, M.-F. de Feraudy, B. Raoult, and G. Torchet, Adv. Chem. Phys. 70, 45 (1988).
  36. S. Kakar, O. Björneholm, J. Weigelt, A. R. B. de Castro, L. Tröger, R. Frahm, T. Möller, A. Knop, and E. Rühl, Phys. Rev. Lett. 78, 1675 (1997).
  37. G. Torchet, M.-F. de Feraudy, A. Boutin, and A. H. Fuchs, J. Chem. Phys. 105, 3671 (1996).
  38. D. Reinhard, B. D. Hall, S. Valkealahti, and R. Monot, Phys. Rev. Lett. 79, 1459 (1997).
  39. J. P. K. Doye and D. J. Wales, Phys. Rev. Lett. 80, 1357 (1998).
  40. J. P. K. Doye, D. J. Wales, and M. A. Miller, J. Chem. Phys. 109, 8143 (1998).
  41. J. P. K. Doye, M. A. Miller, and D. J. Wales, J. Chem. Phys. 110, 6896 (1999).
  42. C. L. Cleveland, W. D. Luedtke, and U. Landman, Phys. Rev. Lett. 81, 2036 (1998).
  43. C. L. Cleveland, W. D. Luedtke, and U. Landman, Phys. Rev. B 60, 5065 (1999).
  44. J. P. K. Doye, D. J. Wales, and R. S. Berry, J. Chem. Phys. 103, 4234 (1995).
  45. R. S. Berry and B. M. Smirnov, J. Chem. Phys. 113, 728 (2000).
  46. F. Calvo, J. P. K. Doye, and D. J. Wales, Phys. Rev. Lett. 87, 119301 (2001).
  47. J. P. K. Doye, D. J. Wales, W. Branz, and F. Calvo, Phys. Rev. B 64, 235409 (2001).
  48. G. Torchet, M.-F. de Feraudy, and B. Raoult, J. Chem. Phys. 103, 3074 (1995).
  49. P. M. Ajayan and L. D. Marks, Phys. Rev. Lett. 60, 585 (1988).
  50. J. P. K. Doye and F. Calvo, Phys. Rev. Lett. 86, 3570 (2001).
  51. J. E. Jones and A. E. Ingham, Proc. R. Soc. London, Ser. A 107, 636 (1925).
  52. A. L. Mackay, Acta Crystallogr. 15, 916 (1962).
  53. S. Gomez and D. Romero, in Proceedings of the First European Congress of Mathematics (Birkhauser, Basel, 1994), Vol. III, pp. 503–509.
  54. J. Pillardy and L. Piela, J. Phys. Chem. 99, 11805 (1995).
  55. J. P. K. Doye and D. J. Wales, Chem. Phys. Lett. 247, 339 (1995).
  56. M. A. Miller, J. P. K. Doye, and D. J. Wales, Phys. Rev. E 60, 3701 (1999).
  57. E. Marinari and G. Parisi, Europhys. Lett. 19, 451 (1992).
  58. F. Calvo and J. P. K. Doye, Phys. Rev. E 63, 010902(R) (2001).
  59. J. P. Neirotti, F. Calvo, D. L. Freeman, and J. D. Doll, J. Chem. Phys. 112, 10340 (2000).
  60. F. Calvo, J. P. Neirotti, D. L. Freeman, and J. D. Doll, J. Chem. Phys. 112, 10350 (2000).
  61. D. J. Wales, Mol. Phys. 78, 151 (1993).
  62. G. Franke, E. R. Hilf, and P. Borrmann, J. Chem. Phys. 98, 3496 (1993).
  63. J. P. K. Doye and D. J. Wales, J. Chem. Phys. 102, 9659 (1995).
  64. D. J. Wales, J. P. K. Doye, M. A. Miller, P. N. Mortensen, and T. R. Walsh, Adv. Chem. Phys. 115, 1 (2000).
  65. M. A. Miller, J. P. K. Doye, and D. J. Wales, J. Chem. Phys. 110, 328 (1999).
  66. D. J. Wales, M. A. Miller, and T. R. Walsh, Nature (London) 394, 758 (1998).
  67. F. Calvo, J. P. K. Doye, and D. J. Wales, J. Chem. Phys. 114, 7312 (2001).
  68. F. Calvo, J. P. K. Doye, and D. J. Wales, J. Chem. Phys. 115, 9627 (2001).
  69. D. D. Frantz, J. Chem. Phys. 102, 3747 (1995).
  70. D. D. Frantz, J. Chem. Phys. 115, 6136 (2001).
  71. It is also apparent from Fig. 3 that jumps in nu-bar occur at those sizes where the structure of the incomplete surface layer of the icosahedra changes from anti-Mackay to Mackay at N = 31 and N = 82–86.
    72. The consequent large differences in vibrational entropy drive surface transitions (Refs. 58, 70) as will be explored elsewhere (J. P. K. Doye and F. Calvo, unpublished).
  72. R. E. Kunz and R. S. Berry, Phys. Rev. Lett. 71, 3987 (1993).
  73. R. E. Kunz and R. S. Berry, Phys. Rev. E 49, 1895 (1994).
  74. J. P. K. Doye and D. J. Wales, Z. Phys. D: At., Mol. Clusters 40, 466 (1997).
  75. F. H. Stillinger, J. Chem. Phys. 115, 5208 (2001).
  76. J. P. Wittmer, A. Tanguy, J. Barrat, and L. Lewis, Europhys. Lett. 57, 423 (2002).
  77. M. A. van der Hoef, J. Chem. Phys. 113, 8142 (2000).
  78. S. Hendy and B. D. Hall, Phys. Rev. B 64, 085425 (2001).
  79. P. Labastie and R. L. Whetten, Phys. Rev. Lett. 65, 1567 (1990).
  80. M. Schmidt, R. Kusche, T. Hippler, J. Donges, W. Kronmüller, B. von Issendorff, and H. Haberland, Phys. Rev. Lett. 86, 1191 (2001).
  81. R. S. Berry, T. L. Beck, H. L. Davis, and J. Jellinek, Adv. Chem. Phys. 70, 75 (1988).
  82. J. P. Neirotti, D. L. Freeman, and J. D. Doll, J. Chem. Phys. 112, 3990 (2000).
  83. W. Branz, N. Malinowski, H. Schaber, and T. P. Martin, Chem. Phys. Lett. 328, 245 (2000).
  84. G. M. Wang, E. Blaisten-Barojas, A. E. Roitberg, and T. P. Martin, J. Chem. Phys. 115, 3640 (2001).
  85. A. P. Sutton and J. Chen, Philos. Mag. Lett. 61, 139 (1990).
  86. J. Jortner, Z. Phys. D: At., Mol. Clusters 24, 247 (1992).
  87. L. D. Marks, Rep. Prog. Phys. 57, 603 (1994).
  88. D. Zanchet, B. D. Hall, and D. Ugarte, J. Phys. Chem. B 104, 11013 (2000).
  89. B. D. Hall, M. Flüeli, R. Monot, and J.-P. Borel, Phys. Rev. B 43, 3906 (1991).
  90. D. Reinhard, B. D. Hall, D. Ugarte, and R. Monot, Phys. Rev. B 55, 7868 (1997).
  91. R. P. Andres, J. D. Bielefeld, J. I. Henderson, D. B. Janes, V. R. Kolagunta, C. P. Kubiak, W. J. Mahoney, and R. G. Osifchin, Science 273, 1690 (1996).
  92. F. Baletto, J. P. K. Doye, and R. Ferrando, Phys. Rev. Lett. 88, 075503 (2002).
  93. J. P. K. Doye and D. J. Wales, J. Chem. Phys. 111, 11070 (1999).
  94. J. P. K. Doye, D. J. Wales, and S. I. Simdyankin, Faraday Discuss. 118, 159 (2001).
  95. F. Baletto, C. Mottet, and R. Ferrando, Phys. Rev. Lett. 84, 5544 (2000).
  96. F. Baletto, C. Mottet, and R. Ferrando, Phys. Rev. B 63, 155408 (2001).
  97. Y. Chusak and L. S. Bartell, Eur. Phys. J. D 16, 43 (2001).
  98. J. P. K. Doye, Phys. Rev. E 62, 8753 (2000).
  99. I. A. Harris, K. A. Norman, R. V. Mulkern, and J. A. Northby, Chem. Phys. Lett. 130, 316 (1986).
  100. O. Echt, K. Sattler, and E. Recknagel, Phys. Rev. Lett. 47, 1121 (1981).
  101. W. Miehle, O. Kandler, T. Leisner, and O. Echt, J. Chem. Phys. 91, 5940 (1989).
  102. T. D. Märk and P. Scheier, Chem. Phys. Lett. 137, 245 (1987).
  103. F. Y. Naumkin and D. J. Wales, Mol. Phys. 93, 633 (1998).
  104. J. Farges, M.-F. de Feraudy, B. Raoult, and G. Torchet, J. Chem. Phys. 78, 5067 (1983).
  105. J. Farges, M.-F. de Feraudy, B. Raoult, and G. Torchet, J. Chem. Phys. 84, 3491 (1986).
  106. M.-F. de Feraudy and G. Torchet, J. Cryst. Growth 217, 449 (2000).
  107. B. W. van de Waal, Phys. Rev. Lett. 67, 3263 (1991).
  108. B. W. van de Waal, J. Chem. Phys. 98, 4909 (1993).
  109. B. W. van de Waal, Phys. Rev. Lett. 76, 1083 (1996).
  110. B. W. van de Waal, J. Cryst. Growth 158, 153 (1996).
  111. B. W. van de Waal, G. Torchet, and M.-F. de Feraudy, Chem. Phys. Lett. 331, 57 (2000).
  112. T. Ikeshoji, G. Torchet, M.-F. de Feraudy, and K. Koga, Phys. Rev. E 63, 031101 (2001).
  113. M. Dove, Introduction to Lattice Dynamics (Cambridge University Press, Cambridge, 1993).
  114. G. C. Maitland, M. Rigby, E. B. Smith, and W. A. Wakeham, Intermolecular Forces (Clarendon, Oxford, 1981).
  115. V. Ozolins and M. Asta, Phys. Rev. Lett. 86, 448 (2001).
  116. M. Asta and V. Ozolins Phys. Rev. B 64, 094104 (2001).
  117. A. van de Walle and G. Ceder, Rev. Mod. Phys. 74, 11 (2002).
  118. S. Sastry, Nature (London) 409, 164 (2001).
  119. D. J. Wales and J. P. K. Doye, Phys. Rev. B 63, 214204 (2001).
  120. J. S. van Duijneveldt and D. Frenkel, J. Chem. Phys. 96, 4655 (1992).
  121. R. M. Lynden-Bell, Mol. Phys. 86, 1353 (1995).

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