Eur. Phys. J. D (2013) 67: 267
https://doi.org/10.1140/epjd/e2013-40306-0

Regular Article

Minimal size of endohedral singly vanadium-doped aluminum cluster: a density-functional study

¹ Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, P.R. China
² College of electrical and information engineering, Southwest University for Nationalities, Chengdu 610041, P.R. China
³ Science and Technology on Surface Physics and Chemistry Laboratory, Mianyang 621907, P.R. China

^a e-mail: gjiang@scu.edu.cn

Received: 15 May 2013
Received in final form: 9 August 2013
Published online: 17 December 2013

Abstract

Energetically low-lying equilibrium geometric structures and electronic structures of Al_nV (n = 2–24) clusters were investigated using density-functional theory within generalized gradient approximation. From the most stable geometric structures, a structural transition with the doped vanadium atom residing from the surface to the interior of the cluster was found from n = 16 to 19. This geometric transition fits well with the early experimental result based on the argon physisorption [S.M. Lang, P. Claes, S. Neukermans, E. Janssens, J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. Due to the geometric transition, average Al-V bond lengths and coordination numbers of V atoms for the most stable structures of Al_nV clusters undergo an increases from n = 16 to 19. The relative stabilities, electronic structures, and other relevant properties were also discussed. It was found that doping of a V atom in the Al_n cluster strengthen the stability of the framework and the Al_{4,6,8,10,13,16,19,21}V clusters were more stable than their neighbors. Moreover, the Mulliken populations showed that the intra-atomic hybridization exists in both V and Al atoms and charge transfer from Al atoms to V atom were also found in these complexes, which could reflect the Al-V hybridizations. Electronic structure analysis based on the partial density of states reveals stronger Al-V hybridization for the endohedrally doped structures.