Structural evolution and relative stability of vanadium-doped boron clusters

Abstract

Cluster is the intermediate of individual atom and larger agglomeration. The structural evolutions of clusters are critically important to explore the physical properties of bulk solids. Here, we carry out systematic structure predictions of medium-sized vanadium-doped boron clusters by using CALYPSO method combined with DFT calculations. A great deal of low-lying isomers with attractive geometries are discovered, such as the crown-like VB18 − cluster and the drum-like VB20 − cluster. Interestingly, the VB12 − cluster possesses excellently relative stability due to its higher second-order difference and larger HOMO-LUMO energy gap. The molecular orbitals and AdNDP analysis indicate that the 3d orbitals of V atom and the 2p and 2s orbitals of B atoms are the primary constituents of the molecular orbitals, and the interactions between V and B atoms are the main factor for the robust stabilization of the anionic VB12 − cluster. The present findings advance the understanding of the structural evolution of transition metal doped boron clusters and offer crucial insights for future experiments.

Intelligent Structure Searching and Designs for Nanoclusters: Effective Units in Atomic Manufacturing

“…[ 98 ] By CALYPSO, stable structures of transition metal (including Mo, W, Ta, Rh, Co, Ru, Zr, Sc, Ir, Nb, Cr, V, Mn, Fe, Ni, Pd, Ti, Hf) doped B clusters were widely studied. [ 99–120 ] Interestingly, transition metal doping can convert the ground‐state structure of small‐sized boron cluster, B 24 , from a quasi‐planar structure to a cage structure (Figure 18b). [ 99 ] Alkaline metal doping of boron clusters has also been extensively studied by CALYPSO code, which suggests that alkaline metal doping can greatly improve the stability of boron clusters (Figure 18c).…”

Structural evolution, charge transfer and bonding properties of medium-sized atomic rubidium-doped boron clusters

“…36,37 In the CALYPSO based cluster structure prediction study of Tian's group, we found that they mentioned a number of interesting phenomena for metal-doped boron clusters with Li 2 B 24 tubular structures, MgB 18 drum-like tubular clusters, BeB 38,39 The properties and geometry of atomic clusters are sizedependent and highly sensitive to the nature of the dopant. [40][41][42] Yang's group searched for the structure of the Cs 2 B n (n = 1-12) clusters using unbiased crystal structure analysis and determined the global minimum. It was found that the ground state structures of the clusters have four geometries: arch-bridge, planar, shielded shape, and bipyramidal.…”

“…The properties and geometry of atomic clusters are size-dependent and highly sensitive to the nature of the dopant. 40–42 Yang's group searched for the structure of the Cs 2 B n ( n = 1–12) clusters using unbiased crystal structure analysis and determined the global minimum. It was found that the ground state structures of the clusters have four geometries: arch-bridge, planar, shielded shape, and bipyramidal.…”

Bismuth Infrared Star: Being at a Glance

“…This method is capable of providing not only Lewis's bonding elements (1c-2e lone pairs and 2c-2e "classical" bonds) but also a non-classic multi-center representation of delocalized bonds (nc-2e bonds, where n � 3), which allows to introduce the concepts of aromaticity naturally. AdNDP is effectively used to decipher the chemical bonding pattern of molecules, [24,25] solid materials, [28,29] and clusters, which is the most essential for the current work; more specifically, it was applied for describing and interpreting structure properties of Boron clusters, [30][31][32][33] Aluminum clusters, [34][35] Tin clusters, [36][37] Germanium [38][39][40] and many others. [41][42][43][44][45][46][47] This makes the approach adequate for bonding analysis of bismuth polycation clusters.…”