Abstract
The structures and properties of 13-atom silver and copper bimetallic clusters are systematically investigated by density functional theory (DFT) in the theoretical frame of the generalised gradient approximation (GGA) exchange-collection function. Optical absorption, Raman spectra, vibrational spectra, as well as electronic and magnetic properties are calculated by DFT/GGA and semi-core pseudopotentials. The following lowest-energy structures in the 13-atom Ag–Cu clusters are obtained: cuboctahedron for pure Ag13, icosahedrons for pure Cu13, Ag1Cu12, Ag6Cu7 and Ag12Cu1; and amorphous motifs for Ag m Cu13−m when m = 2–5 and 7–11. Ag2Cu11, Ag7Cu6 and Ag11Cu2 are magic clusters. The Ag2Cu11 cluster exhibits high energetic stability, strong electronic stability, multipole surface plasmon resonance (SPR) mode and small dipole moment. The Ag6Cu7 cluster is a Janus-separated cluster that possesses the strongest electronic stability with a band gap of 0.424 eV and a vertical ionisation potential of 5.8417 eV. The amorphous Ag7Cu6 cluster shows an Ag–Cu alloyed motif. The blue shift of the maximum SPR peak becomes increasingly evident as silver atoms are added. All Raman and vibrational spectra exhibit many significant vibration modes within the wavenumber ranges of 0–270 and 0–306.55 cm−1, respectively. Ferroelectric and ferromagnetic behaviours are observed in the 13-atom Ag–Cu nanoalloys, indicating their new potential applications in nonlinear optical devices.
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Bae GT, Aikens CM (2012) Time-dependent density functional theory studies of optical properties of Ag nanoparticles: octahedra, truncated octahedra, and icosahedra. J Phys Chem C 116:10356–10367. doi:10.1021/Jp300789x
Baishya K, Idrobo JC, Ogut S, Yang ML, Jackson KA, Jellinek J (2011) First-principles absorption spectra of Cu-n (n = 2–20) clusters. Phys Rev B 83:245402. doi:10.1103/Physrevb.83.245402
Baletto F, Mottet C, Ferrando R (2002) Growth simulations of silver shells on copper and palladium nanoclusters. Phys Rev B 66:155420. doi:10.1103/Physrevb.66.155420
Barcaro G, Fortunelli A, Rossi G, Nita F, Ferrando R (2006) Electronic and structural shell closure in AgCu and AuCu nanoclusters. J Phys Chem B 110:23197–23203. doi:10.1021/Jp064593x
Bechthold PS, Kettler U, Krasser W (1985) Trapping-site effects in resonance Raman-spectra of Ag2 molecules isolated in rare-gas matrices. Surf Sci 156:875–882. doi:10.1016/0039-6028(85)90261-4
Binns C (2001) Nanoclusters deposited on surfaces. Surf Sci Rep 44:1–49. doi:10.1016/S0167-5729(01)00015-2
Bochicchio D, Ferrando R (2010) Size-dependent transition to high-symmetry chiral structures in AgCu, AgCo, AgNi, and AuNi nanoalloys. Nano Lett 10:4211–4216. doi:10.1021/Nl102588p
Bochicchio D, Ferrando R (2012) Structure and thermal stability of AgCu chiral nanoparticles. Eur Phys J D 66:115. doi:10.1140/Epjd/E2012-30054-0
Brongersma ML, Hartman JW, Atwater HA (2000) Electromagnetic energy transfer and switching in nanoparticle chain arrays below the diffraction limit. Phys Rev B 62:16356–16359
Chang CM, Chou MY (2004) Alternative low-symmetry structure for 13-atom metal clusters. Phys Rev Lett 93:133401. doi:10.1103/Physrevlett.93.133401
Chen FY, Johnston RL (2007) Structure and spectral characteristics of the nanoalloy Ag3Au10. Appl Phys Lett 90:153123. doi:10.1063/1.2722702
Chen F, Johnston RL (2008) Charge transfer driven surface segregation of gold atoms in 13-atom Au–Ag nanoalloys and its relevance to their structural, optical and electronic properties. Acta Mater 56:2374–2380. doi:10.1016/j.actamat.2008.01.048
Cleri F, Rosato V (1993) Tight-binding potentials for transition-metals and alloys. Phys Rev B 48:22–33. doi:10.1103/Physrevb.48.22
Darbha GK, Ray A, Ray PC (2007) Gold nanoparticle-based miniaturized nanomaterial surface energy transfer probe for rapid and ultrasensitive detection of mercury in soil, water, and fish. ACS Nano 1:208–214. doi:10.1021/Nn7001954
Darby S, Mortimer-Jones TV, Johnston RL, Roberts C (2002) Theoretical study of Cu–Au nanoalloy clusters using a genetic algorithm. J Chem Phys 116:1536–1550. doi:10.1063/1.1429658
Delley B (1990) An all-electron numerical-method for solving the local density functional for polyatomic-molecules. J Chem Phys 92:508–517. doi:10.1063/1.458452
Delley B (2000) From molecules to solids with the DMol(3) approach. J Chem Phys 113:7756–7764. doi:10.1063/1.1316015
Delley B (2002) Hardness conserving semilocal pseudopotentials. Phys Rev B 66:155125. doi:10.1103/Physrevb.66.155125
Delley B (2010) Time dependent density functional theory with DMol(3). J Phys Condens Matter 22:384208. doi:10.1088/0953-8984/22/38/384208
Dreaden EC, Mackey MA, Huang XH, Kang B, El-Sayed MA (2011) Beating cancer in multiple ways using nanogold. Chem Soc Rev 40:3391–3404. doi:10.1039/C0cs00180e
Fedrigo S, Harbich W, Buttet J (1993) Collective dipole oscillations in small silver clusters embedded in rare-gas matrices. Phys Rev B 47:10706–10715. doi:10.1103/PhysRevB.47.10706
Ferrando R, Fortunelli A, Rossi G (2005) Quantum effects on the structure of pure and binary metallic nanoclusters. Phys Rev B 72:085449. doi:10.1103/Physrevb.72.085449
Ferrando R, Jellinek J, Johnston RL (2008a) Nanoalloys: from theory to applications of alloy clusters and nanoparticles. Chem Rev 108:845–910. doi:10.1021/Cr040090g
Ferrando R, Fortunelli A, Johnston RL (2008b) Searching for the optimum structures of alloy nanoclusters. Phys Chem Chem Phys 10:640–649. doi:10.1039/B709000e
Gupta RP (1981) Lattice-relaxation at a metal-surface. Phys Rev B 23:6265–6270. doi:10.1103/PhysRevB.23.6265
Horiuchi N (2012) View from… frontiers of plasmonics the new facets of plasmonics. Nat Photon 6:353–354. doi:10.1038/nphoton.2012.125
Idrobo JC, Ogut S, Jellinek J (2005) Size dependence of the static polarizabilities and absorption spectra of Ag-n (n = 2–8) clusters. Phys Rev B 72:085445. doi:10.1103/Physrev.72.085445
Jellinek J (2008) Nanoalloys: tuning properties and characteristics through size and composition. Faraday Discuss 138:11–35. doi:10.1039/B800086g
Jiang ZY, Lee KH, Li ST, Chu SY (2006) Structures and charge distributions of cationic and neutral Cun − 1Ag clusters (n = 2–8). Phys Rev B 73:235423. doi:10.1103/Physrevb.73.235423
Johnston RL (2003) Evolving better nanoparticles: genetic algorithms for optimising cluster geometries. Dalton Trans 4193–4207. doi:10.1039/B305686d
Kilimis DA, Papageorgiou DG (2010) Structural and electronic properties of small bimetallic Ag–Cu clusters. Eur Phys J D 56:189–197. doi:10.1140/epjd/e2009-00295-1
Knickelbein MB (1999) Reactions of transition metal clusters with small molecules. Annu Rev Phys Chem 50:79–115. doi:10.1146/annurev.physchem.50.1.79
Lewis LN (1993) Chemical catalysis by colloids and clusters. Chem Rev 93:2693–2730. doi:10.1021/Cr00024a006
Longo RC, Gallego LJ (2006) Structures of 13-atom clusters of FCC transition metals by ab initio and semiempirical calculations. Phys Rev B 74:193409. doi:10.1103/Physrevb.74.193409
Ma WQ, Chen FY (2012) Optical and electronic properties of Cu doped Ag clusters. J Alloy Compd 541:79–83. doi:10.1016/j.jallcom.2012.06.105
Michaelian K, Rendon N, Garzon IL (1999) Structure and energetics of Ni, Ag, and Au nanoclusters. Phys Rev B 60:2000–2010. doi:10.1103/PhysRevB.60.2000
Mirkin CA, Letsinger RL, Mucic RC, Storhoff JJ (1996) A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 382:607–609. doi:10.1038/382607a0
Molayem M, Grigoryan VG, Springborg M (2011) Global minimum structures and magic clusters of CumAgn nanoalloys. J Phys Chem C 115:22148–22162. doi:10.1021/Jp2050417
Nicewarner-Pena SR, Freeman RG, Reiss BD, He L, Pena DJ, Walton ID, Cromer R, Keating CD, Natan MJ (2001) Submicrometer metallic barcodes. Science 294:137–141. doi:10.1126/science.294.5540.137
Nunez S, Johnston RL (2010) Structures and chemical ordering of small Cu–Ag clusters. J Phys Chem C 114:13255–13266. doi:10.1021/Jp1048088
Ogut S, Idrobo JC, Jellinek J, Wang JL (2006) Structural, electronic, and optical properties of noble metal clusters from first principles. J Clust Sci 17:609–626. doi:10.1007/s10876-006-0075-8
Oviedo J, Palmer RE (2002) Amorphous structures of Cu, Ag, and Au nanoclusters from first principles calculations. J Chem Phys 117:9548–9551. doi:10.1063/1.1524154
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868. doi:10.1103/PhysRevLett.77.3865
Pereiro M, Baldomir D, Arias JE (2007) Unexpected magnetism of small silver clusters. Phys Rev A 75:063204. doi:10.1103/Physreva.75.063204
Quinten M, Leitner A, Krenn JR, Aussenegg FR (1998) Electromagnetic energy transport via linear chains of silver nanoparticles. Opt Lett 23:1331–1333. doi:10.1364/Ol.23.001331
Rao Y, Lei YM, Cui XY, Liu ZW, Chen FY (2013) Optical and magnetic properties of Cu-doped 13-atom Ag nanoclusters. J Alloy Compd 55:50–55. doi: 10.1016/j.jallcom.2013.02.185
Rapallo A, Rossi G, Ferrando R, Fortunelli A, Curley BC, Lloyd LD, Tarbuck GM, Johnston RL (2005) Global optimization of bimetallic cluster structures. I. Size-mismatched Ag–Cu, Ag–Ni, and Au–Cu systems. J Chem Phys 122:194308. doi:10.1063/1.898223
Rosato V, Guillope M, Legrand B (1989) Thermodynamical and structural-properties of Fcc transition-metals using a simple tight-binding model. Philos Mag A 59:321–336
Rossi G, Rapallo A, Mottet C, Fortunelli A, Baletto F, Ferrando R (2004) Magic polyicosahedral core–shell clusters. Phys Rev Lett 93:105503. doi:10.1103/Physrevlett.93.105503
Shin K, Kim DH, Yeo SC, Lee HM (2012) Structural stability of AgCu bimetallic nanoparticles and their application as a catalyst: a DFT study. Catal Today 185:94–98. doi:10.1016/j.cattod.2011.09.022
Tiago ML, Idrobo JC, Ogut S, Jellinek J, Chelikowsky JR (2009) Electronic and optical excitations in Ag-n clusters (n = 1–8): comparison of density-functional and many-body theories. Phys Rev B 79:155419. doi:10.1103/Physrevb.79.155419
Weissker HC, Mottet C (2011) Optical properties of pure and core–shell noble-metal nanoclusters from TDDFT: the influence of the atomic structure. Phys Rev B 84:165443. doi:10.1103/Physrevb.84.165443
Yabana K, Bertsch GF (1999) Optical response of small silver clusters. Phys Rev A 60:3809–3814. doi:10.1103/PhysRevA.60.3809
Yan J, Gao SW (2008) Plasmon resonances in linear atomic chains: free-electron behavior and anisotropic screening of d electrons. Phys Rev B 78:235413. doi:10.1103/Physrevb.78.235413
Yan SY, Zhang W, Zhao ZX, Lu WC, Zhang HX (2012) Geometries and stabilities of Ag-n(nu) (nu = ±1, 0; n = 21–29) clusters. Theor Chem Acc 131:1200. doi:10.1007/S00214-012-1200-4
Yang M, Jackson KA, Jellinek J (2006a) First-principles study of intermediate size silver clusters: shape evolution and its impact on cluster properties. J Chem Phys 125:144308. doi:10.1063/1.2351818
Yang ML, Jackson KA, Koehler C, Frauenheim T, Jellinek J (2006b) Structure and shape variations in intermediate-size copper clusters. J Chem Phys 124:024308. doi:10.1063/1.2150439
Yang XL, Cai WS, Shao XG (2007) Structural variation of silver clusters from Ag-13 to Ag-160. J Phys Chem A 111:5048–5056. doi:10.1021/Jp0711895
Yildirim H, Kara A, Rahman TS (2012) Tailoring electronic structure through alloying: the AgnCu34 − n (n = 0–34) nanoparticle family. J Phys Chem C 116:281–291. doi:10.1021/Jp208564h
Zeng Q, Wang X, Yang ML, Fu HB (2010) Interplay between geometrical and electronic stability of neutral and anionic Cu-13 clusters: a first-principles study. Eur Phys J D 58:125–129. doi:10.1140/epjd/e2010-00057-0
Acknowledgments
This study was supported by the National Natural Science Foundation of China (Grant Nos. 51271148 and 50971100), the Research Fund of State Key Laboratory of Solidification Processing in China (Grant No. 30-TP-2009), and the Aeronautic Science Foundation Program of China (Grant No. 2012ZF53073).
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Li, W., Chen, F. A density functional theory study of structural, electronic, optical and magnetic properties of small Ag–Cu nanoalloys. J Nanopart Res 15, 1809 (2013). https://doi.org/10.1007/s11051-013-1809-9
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DOI: https://doi.org/10.1007/s11051-013-1809-9