Structures and Electronic Properties of V3Sin– (n = 3–14) Clusters: A Combined Ab Initio and Experimental Study

Huang, Xiaoming; Lu, Sheng-Jie; Liang, Xiaoqing; Su, Yan; Sai, Linwei; Zhang, Zeng-Guang; Zhao, Jijun; Xu, Hong‐Guang; Zheng, Wei‐Jun

doi:10.1021/jp5112845

Cited by 63 publications

(40 citation statements)

References 65 publications

(110 reference statements)

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“…The most stable isomer of Al 7 V – (7a – ) is of C 1 symmetry, in which all of the atoms form a 1-4-3 layered structure . The calculated VDE (2.35 eV) of isomer 7a – is slightly lower than the experimental value (2.60 eV), but the spectrum features for simulated and experimental PES match very well.…”

Section: Resultsmentioning

confidence: 81%

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Xia

Zhang

et al. 2018

J. Phys. Chem. C

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Aluminum and aluminum-doped clusters have gained much attention in cluster science due to their potential applications in nanotechnology. Here, we report a combined photoelectron spectroscopy and density functional theory study of V-doped aluminum clusters. The lowest-energy geometric structures of neutral and anionic Al n V0/– (n = 5–14) clusters are identified by comparing the theoretical photoelectron spectra with the experimental results. Our results reveal that ground-state structural evolution of neutral and anionic clusters follows different patterns. The V atom in neutral Al n V clusters moves from convex capped to surface-substituted, to encapsulated site at n = 12, and then returns to surface-substituted sites again. However, as for the anionic Al n V–, the metal V atom always occupies the convex capped sites with the cluster size increasing to n = 14. The most stable structure of Al14V– cluster possesses a C 3v symmetric cagelike structure with the highest occupied molecular orbital–lowest unoccupied molecular orbital gap of 1.52 eV. Molecular orbital and adaptive natural density partitioning analysis of Al14V– suggests that the peripheral Al–Al interactions and delocalized Al–V interactions play important roles in its structural stability.

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Section: Resultsmentioning

confidence: 81%

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Xia

Zhang

et al. 2018

J. Phys. Chem. C

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“…[6][7][8][9][10][11][12] Different from carbon clusters that usually show sp 2 hybridization, bonding in pure silicon clusters occurs through sp 3 hybridization and thus they are more chemically reactive due to the existence of unsaturated dangling bonds on the clusters' surface, making them less suitable as nanoscale building blocks. 13 However, it has been found that silicon clusters can be stabilized by doping with transition metal (TM) atoms, [14][15][16] and by now a great number of studies, both experimentally [17][18][19][20][21][22][23][24][25][26][27][28][29] and theoretically, [30][31][32][33][34][35][36] have explored the structures and electronic properties of TM-doped silicon clusters for their potential use in silicon-based nanomaterials. In fact, doping silicon clusters with appropriate transition metal atoms [37][38][39][40][41] can reduce the number of dangling bonds on the cluster surface or even fully saturate them via pd hybridization, and thereby change the geometrical structures and chemical reactivities compared to pure silicon clusters.…”

Section: Introductionmentioning

confidence: 99%

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

Claes

Haertelt

et al. 2016

Phys. Chem. Chem. Phys.

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In this work, the structures of cationic Si n Nb + (n = 4-12) clusters are determined using the combination of infrared multiple photon dissociation (IR-MPD) and density functional theory (DFT) calculations. The experimental IR-MPD spectra of the argon complexes of Si n Nb + are assigned by comparison to the calculated IR spectra of low-energy structures of Si n Nb + that are identified using the stochastic 'random kick' algorithm in conjunction with the BP86 GGA functional. It is found that the Nb dopant tends to bind in an apex position of the Si n framework for n = 4-9 and in surface positions with high coordination numbers for n = 10-12. For the larger doped clusters, it is suggested that multiple isomers coexist and contribute to the experimental spectra. The structural evolution of Si n Nb + clusters is similar to V-doped silicon clusters (J. Am. Chem. Soc., 2010, 132, 15589-15602), except for the largest size investigated (n = 12), since V takes an endohedral position in Si 12 V + . The interaction with a Nb atom, with its partially unfilled 4d orbitals leads to a significant stability enhancement of the Si n framework as reflected, e.g. by high binding energies and large HOMO-LUMO gaps.

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“…So far, little is known about doping of multiple TM atoms inside Si clusters. Huang et al [76] systematically studied V 3 Si n − (n = 3-14) clusters using CGA-DFT method and simulated the anion photoelectron spectra, VDEs and ADEs. The lowest energy structures and ADEs of V 3 Si 3-14 − from theoretical calculations are displayed in Figure 8, showing excellent agreement with experiment.…”

Section: Alloy Clustersmentioning

confidence: 99%

Comprehensive genetic algorithm forab initioglobal optimisation of clusters

Zhao

Shi

Sai

et al. 2016

Molecular Simulation

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Cluster, as the aggregate of a few to thousands of atoms or molecules, bridges the microscopic world of atoms and molecules and the macroscopic world of condensed matters. The physical and chemical properties of a cluster are determined by its ground state structure, which is significantly different from its bulk structure and sensitively relies on the cluster size. As a well-known nondeterministic polynomial-time hard problem, determining the ground state structure of a cluster is a challenging task due to the extreme complexity of high-dimensional potential energy surface (PES). Genetic algorithm (GA) is an efficient global optimisation method to explore the PES of clusters. Recently, we have developed a GA-based programme, namely comprehensive genetic algorithm (CGA), and incorporated it with ab initio calculations. Using this programme, the lowest energy structures of a variety of elemental and compound clusters with different types of chemical bonding have been determined, and their physical properties have been investigated and compared with experimental data. In this article, we will describe the technique details of CGA programme and present an overview of its successful applications.

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Structures and Electronic Properties of V₃Si_n^– (n = 3–14) Clusters: A Combined Ab Initio and Experimental Study

Cited by 63 publications

References 65 publications

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

Comprehensive genetic algorithm forab initioglobal optimisation of clusters

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Structures and Electronic Properties of V3Sin– (n = 3–14) Clusters: A Combined Ab Initio and Experimental Study

Cited by 63 publications

References 65 publications

Geometric Structures and Electronic Properties of AlnV0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Geometric Structures and Electronic Properties of AlnV0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

Comprehensive genetic algorithm forab initioglobal optimisation of clusters

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Product

Resources

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Structures and Electronic Properties of V₃Si_n^– (n = 3–14) Clusters: A Combined Ab Initio and Experimental Study

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations

Geometric Structures and Electronic Properties of Al_nV^0/– (n = 5–14) Clusters: Photoelectron Spectroscopy and Theoretical Calculations