Abstract
The evolution of atomic and electronic structure of small Au n (n = 1–16, and 55) clusters doped with a Gd atom has been investigated using density functional theory within generalized gradient approximation for the exchange–correlation energy. Pure gold neutral clusters with n up to 15 are planar. However, with the doping of a Gd atom, the atomic structure of gold clusters changes, and there is a transition from planar-like structures to three dimensional structures at n = 10. The electronic structure of Gd-doped gold clusters shows a sharp increase in the highest occupied–lowest unoccupied molecular orbital (HOMO–LUMO) gap for certain sizes giving rise to their magic behavior. All clusters are magnetic with large magnetic moments ranging from 6 to 8 μB primarily due to the localized 4f electrons on Gd. This makes such clusters with large HOMO–LUMO gaps magnetic superatoms. The main interaction between gold and gadolinium atoms in the clusters is due to hybridization between Au-6s and Gd-5d6s orbitals. Our results indicate the emergence of a wheel structure for Gd@Au7, a symmetric cage structure at n = 15 for Gd@Au15 and n = 16 for Gd@Au16 + and Eu@Au16 corresponding to an electronic shell closing at 18 valence electrons leaving aside the f electrons on Gd while for Gd-doped Au55 corresponding to 58 valence electrons, a Au9Gd@Au46 core–shell structure is obtained in which the Gd atom connects the core of Au9 with the Au46 shell. The binding energy shows odd–even oscillations with enhancement due to Gd doping compared with pure gold clusters. Such magnetic clusters of gold could have multifunctional biological applications in drug delivery, sensor, imaging, and cancer treatment.
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References
Han G, Ghosh P, Rotello VM (2007) Nanomedicine (Lond) 2:113
Wang Y, Huang L (2012) Mol Therapy 20:10
Giljohann DA, Seferos DS, Daniel WL, Massich MD, Patel PC, Mirkin CA (2010) Angew Chem Int Ed 49:3280
Pankhurst QA, Connolly J, Jones SK, Dobson J (2003) J Phys D Appl Phys 36:R167
Jiang DE, Whetten RL (2009) Phys Rev B 80:115402
Frimpong RA, Hilt JZ (2010) Nanomedicine (Lond) 5:1401
Banerjee R, Katsenovich Y, Lagos L, McIintosh M, Zhang X, Li CZ (2010) Curr Med Chem 17:3120
Hao R, Xing R, Xu Z, Hou Y, Gao S, Sun S (2010) Adv Mater 22:2729
Namdeo M, Saxena S, Tankhiwale R, Bajpai M, Mohan YM, Bajpai SK (2008) J Nanosci Nanotechnol 8:3247
Gupta AK, Naregalkar RR, Vaidya VD, Gupta M (2007) Nanomedicine (Lond) 2:23
Yadav BD, Kumar V (2010) Appl Phys Lett 97:133701
McCarthy JR, Kelly KA, Sun EY, Weissleder R (2007) Nanomedicine (Lond) 2:153
Sandhu A, Handa H, Abe M (2010) Nanotechnology 21:442001
Wang L-M, Bai J, Lechtken A, Huang W, Schooss D, Kappes MM, Zeng XC, Wang L-S (2009) Phys Rev B 79:033413
Sun C, Lee JS, Zhang M (2008) Adv Drug Deliv Rev 60:1252
Wang J, Bai J, Jellinek J, Zeng XC (2007) J Am Chem Soc 129:4110
Ishida T, Haruta M (2007) Angew Chem Int Ed 46:7154
Yoon B, Koskinen P, Huber B, Kostko O, von Issendorff B, Hakkinen H, Moseler M, Landman U (2007) ChemPhysChem 8:157
Zhu Y, Qian H, Jin R (2011) J Mater Chem 21:6793
Jin R (2010) Nanoscale 2:343
Tong X, Benz L, Kemper P, Metiu H, Bowers MT, Buratto SK (2005) J Am Chem Soc 127:13516
Veldeman N, Lievens P, Andersson M (2005) J Phys Chem A 109:11793
Zhu M, Aikens CM, Hendrich MP, Rupal (2009) J Am Chem Soc 131:2490
Jia C-J, Liu Y, Bongard H, Schüth F (2010) J Am Chem Soc 132:1520
Lopez N, Nørskov JK (2002) J Am Chem Soc 124:11262
Furche F, Ahlrichs R, Weis P, Jacob C, Gilb S, Bierweiler T, Kappes MM (2002) J Chem Phys 117:6982
Cabrera-Trujillo JM, Montejano-Carrizales JM, Rodríguez-López JL, Zhang W, Velázquez-Salazar JJ, José-Yacamán M (2010) J Phys Chem C 114:21051
Häkkinen H, Yoon B, Landman U, Li X, Zhai H-J, Wang L-S (2003) J Phys Chem A 107:6168
Häkkinen H, Moseler M, Landman U (2002) Phys Rev Lett 89:033401
Fernández EM, Balbás LC (2011) Phys Chem Chem Phys 13:20863
Huang W, Wang L-S (2009) Phys Rev Lett 102:153401
Bulusu S, Zeng XC (2006) J Chem Phys 125:154303
Li H, Pei Y, Zeng XC (2010) J Chem Phys 133:134707
Tsunoyama H, Sakurai H, Negishi Y, Tsukuda T (2005) J Am Chem Soc 127:9374
Uzun A, Ortalan V, Hao Y, Browning ND, Gates BC (2009) ACS Nano 3:3691
Herzing AA, Kiely CJ, Carley AF, Landon P, Hutchings GJ (2008) Science 321:1331
Li C-Y, Wu C-M, Karna SK, Wang C-W, Hsu D, Wang C-J, Li W-H (2011) Phys Rev B 83:174446
Li X, Kiran B, Cui L-F, Wang L-S (2005) Phys Rev Lett 95:253401
Pyykkö P, Runeberg N (2002) Angew Chem Int Ed 41:2174
Li X, Kiran B, Li J, Zhai H-J, Wang L-S (2002) Angew Chem Int Ed 41:4786
Zhang M, He L-M, Zhao L-X, Feng X-J, Luo Y-H (2009) J Phys Chem C 113:6491
Kumar V, Kawazoe Y (2003) Appl Phys Lett 83:2677
Neukermans S, Wang X, Veldeman N, Janssens E, Silverans RE, Lievens P (2006) Int J Mass Spectrom 252:145
Yim H, Seo S, Na K (2011) J Nanomater Article 747196
Kumar V (2009) Phys Rev B 79:085423
Itoh M, Kumar V, Adschiri T, Kawazoe Y (2009) J Chem Phys 131:174510
Fernández EM, Soler JM, Garz′on IL, Balbás LC (2006) Phys Rev B 73:235433
Kresse G, Joubert D (1999) Phys Rev B 59:1758
Blöchl PE (1994) Phys Rev 50:17953
Perdew JP (1991) In: Ziesche P, Eschrig H (eds) Electronic structure of solids 91. Akademie, Berlin
Kumar V (2011) In: Sattler K (ed) Handbook of nanophysics: principles and methods. Taylor and Francis, Boca Raton, p 4-1
Neukermans S, Janssens E, Tanaka H, Silverans RE, Lievens P (2003) Phys Rev Lett 90:033401
Janssens E, Tanaka H, Neukermans S, Silverans RE, Lievens P (2004) Phys Rev B 69:085402
Gao Y, Bulusu S, Zeng XC (2006) ChemPhysChem 7:2275
Reimann SM, Koskinen M, Häkkinen Lindelof PE, Manninen M (1997) Phys Rev B 56:12147
Dong CD, Gong XG (2010) J Chem Phys 132:104301
Acknowledgements
We are thankful to the staff of the Center for Development of Advanced Computing (CDAC) for allowing us to use the supercomputing facilities and for their excellent support. Partial support from Asian Office of Aerospace Research and Development is thankfully acknowledged.
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Shinde, P.P., Yadav, B.D. & Kumar, V. Evolution of atomic and electronic structure of magnetic Gd-doped gold clusters. J Mater Sci 47, 7642–7652 (2012). https://doi.org/10.1007/s10853-012-6632-7
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DOI: https://doi.org/10.1007/s10853-012-6632-7