Disorder effect on heat capacity, self-diffusion coefficient, and choosing best potential model for melting temperature, in gold–copper bimetallic nanocluster with 55 atoms

  • Farid Taherkhani
  • Hamed Akbarzadeh
  • Mostafa Feyzi
  • Hamid Reza Rafiee
Research Paper


Molecular dynamics simulation has been implemented for doping effect on melting temperature, heat capacity, self-diffusion coefficient of gold–copper bimetallic nanostructure with 55 total gold and copper atom numbers and its bulk alloy. Trend of melting temperature for gold–copper bimetallic nanocluster is not same as melting temperature copper–gold bulk alloy. Molecular dynamics simulation of our result regarding bulk melting temperature is consistence with available experimental data. Molecular dynamics simulation shows that melting temperature of gold–copper bimetallic nanocluster increases with copper atom fraction. Semi-empirical potential model and quantum Sutton–Chen potential models do not change melting temperature trend with copper doping of gold–copper bimetallic nanocluster. Self-diffusion coefficient of copper atom is greater than gold atom in gold–copper bimetallic nanocluster. Semi-empirical potential within the tight-binding second moment approximation as new application potential model for melting temperature of gold–copper bulk structure shows better result in comparison with EAM, Sutton–Chen potential, and quantum Sutton–Chen potential models.


Molecular dynamics Quantum Sutton–Chen potential Self-diffusion coefficient Gold–copper bimetallic nanostructure Modeling and simulation 


  1. Akbarzadeh H, Parsafar GA (2009) A molecular-dynamics study of thermal and physical properties of platinum nanoclusters. Fluid Phase Equilib 280:16CrossRefGoogle Scholar
  2. Akbarzadeh H, Taherkhani F (2013) Cluster size dependence of surface energy of Ni nanocluster: a molecular dynamics study. Chem Phys Lett 558:57CrossRefGoogle Scholar
  3. Akbarzadeh H, Yaghoubi H, Shamkhali AN, Taherkhani F (2013) Effects of gas adsorption on the graphite-supported Ag nanoclusters: a molecular dynamics study. J Phys Chem C 117:26287–26294CrossRefGoogle Scholar
  4. Akbarzadeh H, Yaghoubi H, Shamkhali AN, Taherkhani F (2014) CO adsorption on Ag nanoclusters supported on carbon nanotube: a molecular dynamics study. J Phys Chem C 118:9187–9195CrossRefGoogle Scholar
  5. Ala-Nissila T, Ferrando R, Ying S (2002) Collective and single particle diffusion on surfaces. Adv Phys 51:949–1078CrossRefGoogle Scholar
  6. Baletto F, Ferrando R (2005) Structural properties of nanoclusters: Energetic, thermodynamic, and kinetic effects. Rev Mod Phys 77:1CrossRefGoogle Scholar
  7. Berry RS, Wales DJ (1989) Freezing, melting, spinodals, and clusters. Phys Rev Lett 63:156CrossRefGoogle Scholar
  8. Bracey CL, Ellis PR, Hutchings GJ (2009) Application of copper–gold alloys in catalysis: current status and future perspectives. Chem Soc Rev 38:2231–2243CrossRefGoogle Scholar
  9. Bulgac A, Kusnezov D (1992) Phase transitions in Na7–Na9 microclusters. Phys Rev B 45:988CrossRefGoogle Scholar
  10. Butrymowicz DB, Manning JR, Read E (1974) Diffusion in copper and copper alloys part V. Diffusion in systems involving elements of group VA. Phys Chem Ref Data 3:572Google Scholar
  11. Cai J, Ye YY (1996) Simple analytical embedded-atom-potential model including a long-range force for fcc metals and their alloys. Phys Rev B 54:8398Google Scholar
  12. Cheng D, Huang S, Wang W (2006) Thermal behavior of core–shell and three-shell layered clusters: melting of Cu1Au54 and Cu12Au43. Phys Rev B 74:064117CrossRefGoogle Scholar
  13. Cleri F, Rosato V (1993) Tight-binding potentials for transition metals and alloys. Phys Rev B 48:22CrossRefGoogle Scholar
  14. Couchman PR, Jesser WA (1977) Thermodynamic theory of size dependence of melting temperature in metals. Nature (London) 269:81CrossRefGoogle Scholar
  15. Darby S, Mortimer-Jones TV, Johnston RL, Roberts C (2002) Theoretical study of Cu–Au nanoalloy clusters using a genetic algorithm. J Chem Phys 116:1536CrossRefGoogle Scholar
  16. Della Pina C, Falletta E, Prati L, Rossi M (2008) Selective oxidation using gold. Chem Soc Rev 37:2077–2095CrossRefGoogle Scholar
  17. Doye JPK, Wales DJ (1998) Thermodynamics of global optimization. Phys Rev Lett 80:357CrossRefGoogle Scholar
  18. Ferrando R, Jellinek J, Johnston RL (2008) Nanoalloys: from theory to applications of alloy clusters and nanoparticles. Chem Rev 108:845–910CrossRefGoogle Scholar
  19. Gao Y, Shao N, Pei Y, Zeng XC (2010) Icosahedral crown gold nanocluster Au43Cu12 with high catalytic activity. Nano Lett 10:1055–1062CrossRefGoogle Scholar
  20. Garzón IL, Michaelian K, Beltrán MR, Posada-Amarillas A, Ordejón E, Artacho P, Sánchez-Portal D, Soler JM (1998) Lowest energy structures of gold nanoclusters. Phys Rev Lett 81:1600Google Scholar
  21. Häkkinen H, Moseler M, Kostko O, Morgner N, Hoffmann MA, Issendorff Bv (2004) Symmetry and electronic structure of noble-metal nanoparticles and the role of relativity. Phys Rev Lett 93:093401CrossRefGoogle Scholar
  22. Holmberg N, Chen JC, Foster AS, Laasonen K (2014) Dissolution of NaCl nanocrystals: an ab initio molecular dynamics study. Phys Chem Chem Phys 16:17437Google Scholar
  23. Holzapfel C, Chakraborty S, Rubie D, Frost D (2009) Fe–Mg interdiffusion in wadsleyite: the role of pressure, temperature and composition and the magnitude of jump in diffusion rates at the 410 km discontinuity. Phys Earth Planet Inter 172:28–33CrossRefGoogle Scholar
  24. Huang S-P, Balbuena PB (2002) Melting of bimetallic Cu–Ni nanoclusters. J Phys Chem B 106:7225–7236CrossRefGoogle Scholar
  25. Huang S-P, Mainardi DS, Balbuena PB (2003) Structure and dynamics of graphite-supported bimetallic nanoclusters. Surf Sci 545:163–179CrossRefGoogle Scholar
  26. Huang W, Ji M, Dong C-D, Gu X, Wang L-M, Gong XG, Wang L-S (2008) Relativistic effects and the unique low-symmetry structures of gold nanoclusters. ACS Nano 2:897–904CrossRefGoogle Scholar
  27. Huijben J, van Houselt A, Zandvliet HJW, Poelsema B (2006a) Semiconductors II: surfaces, interfaces, microstructures, and related topics-influence of dimer buckling on dimer diffusion: a scanning tunneling microscopy study. Phys Rev B 73:73311CrossRefGoogle Scholar
  28. Huijben J, van Houselt A, Zandvliet HJW, Poelsema B (2006b) Influence of dimer buckling on dimer diffusion: a scanning tunneling microscopy study. Phys Rev B 73:073311CrossRefGoogle Scholar
  29. Jellinek J, Krissinel EB (1999) In: Jellinek J (ed) Theory of atomic and molecular clusters. Springer, Berlin, p 277CrossRefGoogle Scholar
  30. Jesser WA, Shneck RZ, Gile WW (2004) Solid–liquid equilibria in nanoparticles of Pb–Bi alloys. Phys Rev B 69:44121CrossRefGoogle Scholar
  31. Kart H, Tomak M, Çağin T (2005) Thermal and mechanical properties of Cu–Au intermetallic alloys. Modell Simul Mater Sci Eng 13:657CrossRefGoogle Scholar
  32. Kim SG, Tomanek D (1994) Melting the fullerenes: a molecular dynamics study. Phys Rev Lett 72:418Google Scholar
  33. Kim DH, Kim HY, Kim HG, Ryu JH, Lee HM (2008) The solid-to-liquid transition region of an Ag–Pd bimetallic nanocluster. J Phys 20:035208Google Scholar
  34. Kuntova Z, Rossi G, Ferrando R (2008) Melting of core–shell Ag–Ni and Ag–Co nanoclusters studied via molecular dynamics simulations. Phys Rev B 77:205431CrossRefGoogle Scholar
  35. Kunz RE, Berry RS (1993) Coexistence of multiple phases in finite systems. Phys Rev Lett 71:987CrossRefGoogle Scholar
  36. Laasonen K, Panizon E, Bochicchio D, Ferrando R (2013) Competition between icosahedral motifs in AgCu, AgNi, and AgCo nanoalloys: a combined atomistic–DFT Study. J Phys Chem C 117:26405CrossRefGoogle Scholar
  37. Liang LH, Liu D, Jiang Q (2003) Size-dependent continuous binary solution phase diagram. Nanotechnology 14:38Google Scholar
  38. Liu X, Wang A, Wang X, Mou C-Y, Zhang T (2008) Au–Cu alloy nanoparticles confined in SBA-15 as a highly efficient catalyst for CO oxidation. Chem Commun 27:3187–3189CrossRefGoogle Scholar
  39. Lott K, Nirk T, Volobujeva O (2002) Chemical self-diffusion in undoped ZnS and in undoped CdSe. Cryst Eng 5:147–153CrossRefGoogle Scholar
  40. Luo J, Landmann U, Jortner J (1987) In: Jena P, Rao BK, Khanna S (eds) Physics and chemistry of small cluster, vol 158., NATO ASI series BPlenum, New York, p 155Google Scholar
  41. Lv YJ, Chen M (2011) Thermophysical properties of undercooled alloys: an overview of the molecular simulation approaches. Int J Mol Sci 12:278–316CrossRefGoogle Scholar
  42. Maillet JB, Boutin A, Fuchs AH (1996) Numerical evidence of an embryonic orientational phase transition in small nitrogen clusters. Phys Rev Lett 76:336CrossRefGoogle Scholar
  43. Mehrer H, Eggersmann M, Gude A, Salamon M, Sepiol B (1997) Diffusion in intermetallic phases of the Fe–Al and Fe–Si systems. Mater Sci Eng A 239:889–898CrossRefGoogle Scholar
  44. Mejía-Rosales SJ, Fernández-Navarro C, Pérez-Tijerina E, Montejano-Carrizales JM, José-Yacamán M (2006) Two-stage melting of Au–Pd nanoparticles. J Phys Chem B 110(26):12884–12889CrossRefGoogle Scholar
  45. Mottet C, Rossi G, Baletto F, Ferrando R (2005) Single impurity effect on the melting of nanoclusters. Phys Rev Lett 95:035501Google Scholar
  46. Negreiros F, Taherkhani F, Parsafar G, Fortunelli A (2012) Kinetics of chemical ordering in Ag–Pt nanoalloy via first-principal simulation. J. Chem. Phys. 137:194302CrossRefGoogle Scholar
  47. Özdemir S, Tomak M, Uludoğan M, Çağın T (2004) Liquid properties of Pd–Ni alloys. J Non-Cryst Solids 337:101–108CrossRefGoogle Scholar
  48. Panizon E, Bochicchio D, Rossi G, Ferrando R (2014) Tuning the structure of nanoparticles by small concentrations of impurities. Chem Mater 26:3354CrossRefGoogle Scholar
  49. Qi Y, Çağın T, Kimura Y, Goddard WA III (1999) Molecular-dynamics simulations of glass formation and crystallization in binary liquid metals: Cu–Ag and Cu–Ni. Phys Rev B 59:3527CrossRefGoogle Scholar
  50. Qi Y, Çağin T, Kimura Y, Goddard W III (2001) A. scosities of liquid metal alloys from nonequilibrium molecular dynamics. J Comput Aided Mater Des 8:233–243CrossRefGoogle Scholar
  51. Rodrıguez-López J, Montejano-Carrizales J, José-Yacamán M (2003) Molecular dynamics study of bimetallic nanoparticles: the case of AuxCuy alloy clusters. Appl Surf Sci 219:56–63CrossRefGoogle Scholar
  52. Ross J, Andres RP (1981) Melting temperature of small cluster. Surf Sci 106:1CrossRefGoogle Scholar
  53. Sankaranarayanan SK, Bhethanabotla VR, Joseph B (2005) Molecular dynamics simulation study of the melting of Pd–Pt nanoclusters. Phys Rev B 71:195415CrossRefGoogle Scholar
  54. Shirinyan AS, Gusak AM (2004) Phase diagrams of decomposing nanoalloys. Philos Magn 84:79CrossRefGoogle Scholar
  55. Shirinyan AS, Pasichnyy MO (2005) Size-induced hysteresis in the process of nucleation and phase separation in a nanopowder. Nanotechnology 16:724CrossRefGoogle Scholar
  56. Shirinyan A, Wautelet M, Belogorodsky YJ (2006) Solubility diagram of the Cu–Ni nanosystem. J Phys 18:537Google Scholar
  57. Smith W, Todorov ITA (2006) Short description of DL_POLY. Mol Simul 32:935–943CrossRefGoogle Scholar
  58. Taherkhani F, Rezania H (2012) Temperature and size dependency of thermal conductivity of aluminum nanocluster. J Nanopart Res 14:1–8Google Scholar
  59. Taherkhani F, Negreiros FR, Parsafar G, Fortunelli A (2010) Simulation of vacancy diffusion in a silver nanocluster. Chem Phys Lett 498:312–316CrossRefGoogle Scholar
  60. Taherkhani F, Akbarzadeh H, Abroshan H, Fortunelli A (2012) Dependence of self-diffusion coefficient, surface energy, on size, temperature, and Debye temperature on size for aluminum nanoclusters. Fluid Phase Equilib 335:26CrossRefGoogle Scholar
  61. Taherkhani F, Akbarzadeh H, Rezania H (2014) Chemical ordering effect on melting temperature, surface energy of copper–gold bimetallic nanocluster. J Alloy Compd 617:746CrossRefGoogle Scholar
  62. Toai TJ, Rossi G, Ferrando R (2008) Global optimisation and growth simulation of AuCu clusters. Faraday Discuss 138:49–58CrossRefGoogle Scholar
  63. Valle´e R, Wautelet M, Dauchot JP, Hecq M (2001) Size and segregation effects on the phase diagrams of nanoparticles of binary systems. Nanotechnology 12:8CrossRefGoogle Scholar
  64. Van Hoof T, Hou M (2005) Structural and thermodynamic properties of Ag–Co nanoclusters. Phys Rev B 72:15434Google Scholar
  65. Wales DJ, Berry RS (1994) Coexistence in finite systems. Phys Rev Lett 73:875CrossRefGoogle Scholar
  66. Xing X, Danell RM, Garzón IL, Michaelian K, Blom MN, Burns MM, Parks JH (2005) Size-dependent fivefold and icosahedral symmetry in silver clusters. Phys Rev B 72:081405CrossRefGoogle Scholar
  67. Yin J, Shan S, Yang L, Mott D, Malis O, Petkov V, Cai F, Shan Ng M, Luo J, Chen BH (2012) Gold–copper nanoparticles: nanostructural evolution and bifunctional catalytic sites. Chem Mater 24:4662–4674CrossRefGoogle Scholar
  68. Yoo W-J, Li C-J (2007) Copper-catalyzed oxidative esterification of alcohols with aldehydes activated by Lewis acids. Tetrahedron Lett 48:1033–1035CrossRefGoogle Scholar
  69. Zhang L (2012) A molecular dynamics study of thermal behavior of melting an Au54Cu1 cluster. Proc Eng 36:207–211CrossRefGoogle Scholar
  70. Zhang L, Zhang C-B, Qi Y (2008) Local structure changes of 54-, 55-, 56-atom copper clusters on heating. Phys Lett A 372:2874–2880CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Farid Taherkhani
    • 1
  • Hamed Akbarzadeh
    • 2
  • Mostafa Feyzi
    • 1
  • Hamid Reza Rafiee
    • 1
  1. 1.Department of Physical ChemistryRazi UniversityKermanshahIran
  2. 2.Department of ChemistryHakim Sabzevari UniversitySabzevarIran

Personalised recommendations