Structural and electronic properties of boron-doped lithium clusters: Ab initio and DFT studies

✍ Scribed by Ying Li; Di Wu; Zhi-Ru Li; Chia-Chung Sun

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 347 KB
• Volume: 28
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20637

✦ Synopsis

Abstract

The lowest‐energy structures and electronic properties of the BLi__~n~__ (n = 1–7) clusters are reported using the B3LYP, MP2, and CCSD(T) methods with the aug‐cc‐pVDZ basis set. Though the results at the B3LYP level agree well with those at the CCSD(T) level, the MP2 method is rather unsatisfactory. The first three‐dimensional ground state in the BLi__~n~__ clusters occurs for BLi~4~, and the impurity B atom is seen to be trapped in a Li cage from the BLi~6~ cluster onwards. The evolution of the binding energies, vertical ionization potentials, and polarizability with size of cluster shows the BLi~5~ cluster to be most stable among the BLi__~n~__ clusters. Besides, the BLi~5~ cluster is also found to have the largest reaction enthalpy (49.8 kcal/mol) upon losing a Li atom, which is different from the previous prediction. The unique stability of the 8‐valence electron BLi~5~ can be understood from the cluster electronic shell model (CSM). However, in contradiction to the prediction of the CSM, the 2s level is filled prior to the 1d level in the BLi__~n~__ clusters. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007