Benchmarking boron cluster calculations: Establishing reliable geometrical and energetic references for Bn (n = 1–4)

• Published in: Journal of Computational Chemistry Vol. 45; no. 3; pp. 159 - 169
• Main Authors: Liu, Lina, Wei, Zhihong, Chen, Qiang, Shen, Chaoren, Shen, Tonghao, Tian, Xinxin, Li, Si‐Dian
• Format: Journal Article
• Language: English; Japanese
• Published: Hoboken, USA Wiley 30.01.2024; John Wiley & Sons, Inc; Wiley Subscription Services, Inc
• Subjects: Boron; Clusters; Configuration interaction; Density functional theory; Mathematical analysis; Performance prediction
• ISSN: 0192-8651; 1096-987X; 1096-987X
• DOI: 10.1002/jcc.27226

Using full configuration interaction (FCI) and multi‐reference configuration interaction methods (MRCI), reliable geometrical and energetic references for Bn (n = 1–4) clusters were established. The accuracy of the computed results was confirmed by comparison with available experimental data. Benchmark calculations indicated that B97D3, B97D, VSXC, HCTH407, BP86 and CCSD(T) methods provided reasonable results for structural parameters, with mean absolute error (MAEs) within 0.020 Å. Among the tested density functional theory (DFT) methods, the VSXC functional showed the best performance in predicting the relative energies of B1B4 with a MAE of 12.8 kJ mol−1. Besides, B1B95, B971, TPSS, B3LYP, and BLYP functionals exhibited reasonable performance with MAE values of less than 15.0 kJ mol−1. T1 diagnostic values between 0.035 and 0.109 at the CCSD(T) level revealed strong correlations in B2B4 clusters, highlighting the need for caution in using CCSD(T) as an energy reference for small boron clusters. The methods of CCSDT, CCSDT(Q) and CCSDT[Q], which incorporate three‐electron and four‐electron excitations, effectively improved the accuracy of the energy calculations.