Liu Lina, Wei Zhihong, Chen Qiang, Shen Chaoren, Shen Tonghao, Tian Xinxin, Li Si-Dian
Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan, China.
Key Laboratory of Chemical Biology and Molecular Engineering of Ministry of Education, Shanxi University, Taiyuan, China.
J Comput Chem. 2024 Jan 30;45(3):159-169. doi: 10.1002/jcc.27226. Epub 2023 Sep 12.
Using full configuration interaction (FCI) and multi-reference configuration interaction methods (MRCI), reliable geometrical and energetic references for B (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 B B with a MAE of 12.8 kJ mol . Besides, B1B95, B971, TPSS, B3LYP, and BLYP functionals exhibited reasonable performance with MAE values of less than 15.0 kJ mol . T diagnostic values between 0.035 and 0.109 at the CCSD(T) level revealed strong correlations in B B 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.
使用全组态相互作用（FCI）和多参考组态相互作用方法（MRCI），建立了B（n = 1 - 4）团簇可靠的几何和能量参考。通过与现有实验数据比较，证实了计算结果的准确性。基准计算表明，B97D3、B97D、VSXC、HCTH407、BP86和CCSD(T)方法给出了合理的结构参数结果，平均绝对误差（MAE）在0.020 Å以内。在所测试的密度泛函理论（DFT）方法中，VSXC泛函在预测B—B的相对能量方面表现最佳，MAE为12.8 kJ mol⁻¹。此外，B1B95、B971、TPSS、B3LYP和BLYP泛函表现出合理的性能，MAE值小于15.0 kJ mol⁻¹。在CCSD(T)水平下0.035至0.109之间的T诊断值揭示了B—B团簇中的强相关性，突出了在将CCSD(T)用作小硼团簇能量参考时需要谨慎。包含三电子和四电子激发的CCSDT、CCSDT(Q)和CCSDT[Q]方法有效地提高了能量计算的准确性。
