title: 4d and 5d bimetal doped tubular silicon clusters Si12M2with M = Nb, Ta, Mo and W: a bimetallic configuration model.
abstract: Geometries and electronic properties related to the ground state stabilities of several Si12M2clusters (M: second-row (Nb and Mo) and third-row (Ta and W) transition metals, and their mixed bimetallic clusters M2: NbMo and TaW) were explored using density functional theory (DFT) computations. The computed results show that two different structural motifs emerge as the global energy minima of such clusters. They are basically singlet tubular structures in either a C2vprism (1A1) or a C6vantiprism (1A1) form. Other structural shapes are also possible for higher-energy isomers and in higher spin states. 58-valence electron systems including Nb2Si12, Ta2Si12, Mo2Si122+, W2Si122+, NbMoSi12+and TaWSi12+are thermodynamically stable as C2vprism global minima on the corresponding potential energy surfaces. Clusters containing 60 valence electrons include Mo2Si12, W2Si12, Nb2Si122-, Ta2Si122-, NbMoSi12-and TaWSi12-and they prefer a C6vanti-prism form. In the mixed MoNbSi12and TaWSi12open-shell systems, both resulting C2(2A) and C2v(2A1) forms are nearly degenerate. The formation of Si12M2clusters in such specific ground state symmetry is explained using the Jellium model and orbital interaction analyses. The investigations lead further to a proposal for a simple model of a bimetallic configuration using the nature of interactions of the transition metal d-d dimeric bond with the Si12host, to interpret the formation of such M2Si12clusters.
authors.affiliation: Computational Chemistry Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam. phamtanhung@tdt.edu.vn and Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam.
authors.forename: Hung Tan
authors.initials: HT
authors.lastname: Pham
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi 39217, USA. devashis@icnanotox.org jerzy@icnanotox.org.
authors.forename: Devashis
authors.initials: D
authors.lastname: Majumdar
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi 39217, USA. devashis@icnanotox.org jerzy@icnanotox.org.
authors.forename: Jerzy
authors.initials: J
authors.lastname: Leszczynski
authors.affiliation: Computational Chemistry Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam. phamtanhung@tdt.edu.vn and Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam and Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium. minh.nguyen@kuleuven.be.
authors.forename: Minh Tho
authors.identifier: http://orcid.org/0000-0002-3803-0569
authors.initials: MT
authors.lastname: Nguyen