The structures, electronic properties, and chemical bonding of binary alloy boron–aluminum clusters series B4Aln 0/−/+ (n = 1–5)

Limei Wen, Guoliang Li, Li Ming Yang, Hui Pan, Eric Ganz

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Abstract

The geometry structures, electronic properties, and chemical bonding of neutral, anionic and cationic alloy B4Aln (n = 1–5) clusters series were systematically studied by using density functional theory at the B3LYP/6-311+G(d) level of theory for geometry optimization and using coupled cluster single point energy calculations at the CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) level of theory. Comprehensive structure search and calculations demonstrate that the Al atoms tend to occupy the periphery sites of all alloy clusters, and the lowest–energy structures prefer low spin states (singlet or doublet). For small alloy cluster with total number of atoms ≤6, the clusters display the rare Anti-Van't Hoff/Le Bel motifs planar tetracoordinate boron (ptB) and planar pentacoordinate boron (ppB), whereas, for total number of atoms ≥7, it shows 3D configuration. To evaluate the stabilities and electronic properties of the global minimum isomers of each stoichiometry at different charge states, the binding energy, fragmentation energy, second–order difference of the total energy, HOMO–LUMO gap, ionization potential, and electron affinity have been evaluated. We find that for anionic and cationic alloy B4Aln −/+ (n = 1–5) clusters, the odd–n systems are more stable than the even–n ones. AdNDP analyses of the chemical bonding of the global minimum structures indicate that the classical 2c–2e bonds and multicenter nc–2e (n = 3–9) delocalized bonds are responsible for the stability of boron–aluminum mixed alloy clusters.

Original languageEnglish (US)
Article number100914
JournalMaterials Today Communications
Volume24
DOIs
StatePublished - Sep 2020

Bibliographical note

Funding Information:
L. M. W and L.–M. Y. gratefully acknowledge support from the National Natural Science Foundation of China ( 21673087 , 21873032 , 21903032 ), startup fund ( 2006013118 and 3004013105 ) from Huazhong University of Science and Technology , and the Fundamental Research Funds for the Central Universities ( 2019kfyRCPY116 ). H. P. gratefully acknowledge support by Science and Technology Development Fund from Macau SAR ( FDCT-0102/2019/A2 ) and Multi-Year Research Grants ( MYRG2018-00003-IAPME and MYRG2017-00027-FST ) from the Research & Development Office at the University of Macau . The authors thank the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for supercomputing resources. The work was carried out at LvLiang Cloud Computing Center of China, and the calculations were performed on TianHe-2. We thank Professor Longjiu Cheng for stimulating discussion on AdNDP analysis.

Funding Information:
L. M. W and L.?M. Y. gratefully acknowledge support from the National Natural Science Foundation of China (21673087, 21873032, 21903032), startup fund (2006013118 and 3004013105) from Huazhong University of Science and Technology, and the Fundamental Research Funds for the Central Universities (2019kfyRCPY116). H. P. gratefully acknowledge support by Science and Technology Development Fund from Macau SAR (FDCT-0102/2019/A2) and Multi-Year Research Grants (MYRG2018-00003-IAPME and MYRG2017-00027-FST) from the Research & Development Office at the University of Macau. The authors thank the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for supercomputing resources. The work was carried out at LvLiang Cloud Computing Center of China, and the calculations were performed on TianHe-2. We thank Professor Longjiu Cheng for stimulating discussion on AdNDP analysis.

Publisher Copyright:
© 2020 Elsevier Ltd

Keywords

  • AdNDP analysis
  • Boron–aluminum binary alloy clusters
  • CCSD(T)
  • Chemical bonding
  • Density functional theory (DFT)

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