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Comprehensive study of sodium, copper, and silver clusters over a wide range of sizes 2<=N<=75

J. Chem. Phys. 131, 174510 (2009); doi:10.1063/1.3187934

Published 6 November 2009

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Masahiro Itoh,1,2 Vijay Kumar,1,3 Tadafumi Adschiri,2 and Yoshiyuki Kawazoe1
1Institute for Materials Research, Tohoku University, Aoba-ku, Sendai 980-8577, Japan
2Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Aoba-ku, Sendai 980-8577, Japan
3Dr. Vijay Kumar Foundation, 45 Bazaar Street, K. K. Nagar (West), Chennai 600 078, India
The geometric and electronic structures of NaN, CuN, and AgN metal clusters are systematically studied based on the density functional theory over a wide range of cluster sizes 2<=N<=75. A remarkable similarity is observed between the optimized geometric structures of alkali and noble metal clusters over all of the calculated cluster sizes N. The most stable structures are the same for the three different metal clusters for approximately half the cluster sizes N considered in this study. Even if the most stable structures are different, the same types of structures are obtained when the metastable structures are also considered. For all of the three different metal clusters, the cluster shapes change in the order of linear, planar, opened, and closed structures with increasing N. This structural-type transition leads to a deviation from the monotonic increase in the specific volume with N. A remarkable similarity is also observed for the N dependence of the cluster energy E(N) for the most stable geometric structures. The amplitude of this energy difference is larger in the two noble metal clusters than in the alkali metal cluster. This is attributed to the contribution of d electrons to the bonds. The magic number is explicitly defined with a new criterion in the framework of total energy calculations. In the case of NaN, a semiquantitative comparison between the experimental abundance spectra [Knight et al., Phys. Rev. Lett. 52, 2141 (1984)] and the total energy calculations is carried out. The changing aspect of the Kohn–Sham eigenvalues from N=2 to N=75 is presented for the three different metal clusters. The feature of the bulk density of states already appears at N=75 for all of three clusters. With increasing N, the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap clearly exhibits an odd-even alternation and converges to 0. Although there is a similarity in the N dependence of the HOMO-LUMO gap between the three metal clusters, it is much stronger between the two noble metal clusters. The growth aspect of the d band below the Fermi level of the noble metal clusters with increasing N is presented. A good correspondence is observed in the d characteristic of the electronic states between the cluster composed of 75 atoms and the bulk metal. The similarities observed in the N dependence of the geometric structures and E(N)s originate from the similarity in that of the electronic structures. ©2009 American Institute of Physics
History: Received 3 February 2009; accepted 29 June 2009; published 6 November 2009; publisher error corrected 10 November 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/174510/1
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KEYWORDS and PACS

Keywords
PACS
  • 71.15.Mb
    Density functional theory, local density approximation, gradient and other corrections (condensed matter electronic structure)
  • 61.46.Bc
    Structure of clusters (nanoscale materials)
  • 71.15.Nc
    Total energy and cohesive energy calculations (condensed matter)
  • 71.20.Dg
    Electronic structure of crystalline alkali and alkaline earth metals and alloys
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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