Evolution of Co n Al clusters and chemisorption of hydrogen on Co n Al clusters

  • Ling Guo
Research Paper


The growth behavior of Co n Al (n = 1–15) and the chemisorptions of hydrogen on the ground state geometries have been studied using the density functional theory (DFT) within the generalized gradient approximation (GGA). The growth pattern for Co n Al is Al-substituted Co n+1 clusters, and it keeps the similar frameworks of the most stable Co n+1 clusters except for n = 2, 3, and 6. The Al atom substitutes the surface atom of the Co n+1 clusters for n ≤ 13. Starting from n = 14, the Al atom completely falls into the center of the Co-frame. The dissociation energy, the second-order energy differences, and the HOMO–LUMO gaps indicate that the magic numbers of the calculated Co n Al clusters are 7, 9, and 13, corresponding to the high symmetrical structures. To my knowledge, this is the first time that a systematic study of chemisorption of hydrogen on cobalt aluminum clusters. The twofold bridge site is identified to be the most favorable chemisorptions site for one hydrogen adsorption on Co n Al (n = 1–6, 8, 10), and two hydrogen adsorption on Co n Al (n = 1–7), while threefold hollow site is preferred for one hydrogen adsorption on Co n Al (n = 7, 9, 11–15) and two hydrogen adsorption on Co n Al (n = 8–10, 12–15) clusters. The ground state structure of two hydrogen adsorption on Co11Al is exceptional. In general, the binding energy of both H and 2H of Co n Al (n = 1–12) is found to increase with the cluster size. And the result shows that large binding energies of the hydrogen atoms and large fragmentation energies for Co11AlH and Co12AlH make these species behaving like magic clusters.


ConAl cluster Hydrogenated cobalt aluminum cluster Stability Electronic properties 



This work was financially supported by the National Natural Science Foundation of China (Grant No. 20603021), Youth Foundation of Shanxi (Grant No. 2007021009), and the Youth Academic Leader of Shanxi.


  1. Behm JM, Brugh DJ, Morse MD (1994) Spectroscopic analysis of the open 3d subshell transition metal aluminides: AlV, AlCr, and AlCo. J Chem Phys 101(8):6487–6499CrossRefGoogle Scholar
  2. Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys 92(1):508–517CrossRefGoogle Scholar
  3. Dhilip Kumar TJ, Tarakeshwar P, Balakrishnan N (2009) Geometric and electronic structures of hydrogenated transition metal (Sc, Ti, Zr) clusters. Phys Rev B 79(20): 205415-1-11Google Scholar
  4. Hales DA, Su CX, Lian L, Armentrout BP (1994) Collisioninduced dissociation of Con+ (n = 2–18) with Xe: bond energies of cationic and neutral cobalt clusters, dissociation pathways, and structures. J Chem Phys 100(2):1049–1057CrossRefGoogle Scholar
  5. Huda MN, Kleinman L (2006) Hydrogen adsorption and dissociation on small platinum clusters: an electronic structure density functional study. Phys Rev B 74(19):195407-1-7Google Scholar
  6. Kant A, Strauss B (1964) Dissociation energies of diatomic molecules of the transition elements. II. Titanium, chromium, manganese, and cobalt. J Chem Phys 41(12):3806–3808CrossRefGoogle Scholar
  7. Laguna A, Lasanta T, Lopez-de-Luzuriaga JM, Monge M, Naumov P, Olmos ME (2010) Combining aurophilic interactions and halogen bonding to control the luminescence from bimetallic gold silver clusters. J Am Chem Soc 132(2):456–457CrossRefGoogle Scholar
  8. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37(2):785–789CrossRefGoogle Scholar
  9. Lu C, Kuang XY, Lu ZW, Mao AJ, Ma YM (2011) Determination of structures, stabilities, and electronic properties for bimetallic cesium-doped gold clusters: a density functional theory study. J Phys Chem A 115(33):9273–9281CrossRefGoogle Scholar
  10. Ma QM, Xie Z, Wang J, Liu Y, Li YC (2006) Structures, stabilities and magnetic properties of small Co clusters. Phys Lett A 358(4):289–296CrossRefGoogle Scholar
  11. Menezes WJC, Knickelbein MB (1991) Bimetallic clusters of cobalt and aluminum: ionization potentials versus reactivity, and the importance of geometric structure. Chem Phys Lett 183(5–6):357–362CrossRefGoogle Scholar
  12. Menezes WJC, Knickelbein MB (1993) The evolution of electronic structure in AlnCom. Z Phys D 26:322–325CrossRefGoogle Scholar
  13. Nonose S, Sone Y, Onodera K, Sudo S, Kaya K (1989) Reactivity study of alloy clusters made of aluminum and some transition metals with hydrogen. Chem Phys Lett 164(4):427–432CrossRefGoogle Scholar
  14. Pramann A, Nakajima A, Kaya K (2001) Photoelectron spectroscopy of bimetallic aluminum cobalt cluster anions: comparison of electronic structure and hydrogen chemisorption rates. J Chem Phys 115(12):5404–5410CrossRefGoogle Scholar
  15. Rosen B (1970) Spectroscopic data relative to diatomic molecules. Pergamon, OxfordGoogle Scholar
  16. Varano A, Henry DJ, Yarovsky I (2010) DFT study of H adsorption on magnesium-doped aluminum clusters. J Phys Chem A 114(10):3602–3608CrossRefGoogle Scholar
  17. Wang SY, Yu JZ, Mizuseki H, Yan JA (2004) First-principles study of the electronic structures of icosahedral TiN(N = 13,19,43,55) clusters. J Chem Phys 120(18):8463–8468CrossRefGoogle Scholar
  18. Xie Z, Ma QM, Liu Y, Li YC (2005) First-principles study of the stability and Jahn-Teller distortion of nickel clusters. Phys Lett A 342(5):459–467CrossRefGoogle Scholar
  19. Zanti G, Peeters D (2010) DFT study of bimetallic palladium gold clusters PdnAum of low nuclearities (n + m <14). J Phys Chem A 114(38):10345–10356CrossRefGoogle Scholar
  20. Zhang DB, Shen J (2004) Ground state, growth, and electronic properties of small lanthanum clusters. J Chem Phys 120(11):5104–5109CrossRefGoogle Scholar
  21. Zhao YR, Kuang XY, Zheng BB, Li YF, Wang SJ (2011) Equilibrium geometries, stabilities, and electronic properties of the bimetallic M2-doped Aun (M = Ag, Cu; n = 1–10) clusters: comparison with Pure Gold clusters. J Phys Chem A 115(5):569–576CrossRefGoogle Scholar

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© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  1. 1.School of Chemistry and Material ScienceShanxi Normal UniversityLinfenChina

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