Tho Nguyen Huu, Tran Ngo Huyen, Cam Pham Hong, Tam Nguyen Minh
Faculty of Natural Sciences Education, Saigon University, Ho Chi Minh City, Vietnam.
Faculty of Basic Sciences, University of Phan Thiet, 225 Nguyen Thong, Phan Thiet City, Binh Thuan, Vietnam.
J Mol Model. 2025 May 30;31(6):179. doi: 10.1007/s00894-025-06381-0.
Besides small pure boron clusters which have been well studied, doped boron clusters, in particular with transition metal dopants, are also increasingly investigated due to their unique geometrical structures accompanied by novel physical and chemical properties. However, studies on copper-doped boron clusters are still scarce despite copper being a transition metal with important properties. In this context, the geometry, stability, and electronic properties of copper-doped boron clusters BCu (n = 1-13) were systematically studied. The obtained results show that the geometries of neutral and anionic clusters are very similar only at sizes n = 2, 5, 6, 8, and 10. In the ground state, both neutral and anionic clusters tend to be in the low-spin state, except for BCu and BCu. The relative stability of these structures was evaluated using various energetic parameters. Moreover, the aromaticity of the BCu anion along with its enhanced stability are also discussed and rationalized in detail.
In this work, the geometry optimization and the following molecular orbital analyses of BCu (n = 1-13) structures are performed using density functional theory (DFT), specifically the hybrid functional TPSSh combined with the 6-311+ G(d) basis set for boron atoms and the aug-cc-pVTZ-PP basis set for a copper atom. To obtain more reliable results, the single point energies of some lowest lying isomers whose relative energy values are close corresponding to geometries optimized at the TPSSh/6-311+ G(d) (B) / aug-cc-pVTZ-PP (Cu) level were determined with higher precision at the CCSD(T) level with the same basis sets. Based on the obtained results at the DFT level, the energetic parameters are determined to elucidate thermodynamic stability of BCu clusters. NICS and ELF indices, the density of states, and AdNDP bond analysis are then examined to rationalize the aromaticity of the anion BCu. All calculations were performed using the Gaussian 09 and Multiwfn programs.
除了已得到充分研究的小尺寸纯硼团簇外，掺杂硼团簇，特别是含有过渡金属掺杂剂的硼团簇，由于其独特的几何结构以及新颖的物理和化学性质，也受到越来越多的研究。然而，尽管铜是一种具有重要性质的过渡金属，但关于铜掺杂硼团簇的研究仍然很少。在此背景下，对铜掺杂硼团簇BCu（n = 1 - 13）的几何结构、稳定性和电子性质进行了系统研究。所得结果表明，中性和阴离子团簇的几何结构仅在n = 2、5、6、8和10时非常相似。在基态下，除了BCu⁺和BCu⁻外，中性和阴离子团簇都倾向于处于低自旋状态。使用各种能量参数评估了这些结构的相对稳定性。此外，还详细讨论并合理解释了BCu⁻阴离子的芳香性及其增强的稳定性。
在本工作中，使用密度泛函理论（DFT）对BCu（n = 1 - 13）结构进行几何优化以及后续的分子轨道分析，具体而言，采用杂化泛函TPSSh并结合用于硼原子的6 - 311 + G(d)基组和用于铜原子的aug - cc - pVTZ - PP基组。为了获得更可靠的结果，对于一些相对能量值接近且对应于在TPSSh/6 - 311 + G(d)(B)/aug - cc - pVTZ - PP(Cu)水平优化的几何结构的最低能量异构体，在相同基组下于CCSD(T)水平以更高精度确定其单点能量。基于在DFT水平获得的结果，确定能量参数以阐明BCu团簇的热力学稳定性。然后检查NICS和ELF指数、态密度以及AdNDP键分析，以合理解释BCu⁻阴离子的芳香性。所有计算均使用Gaussian 09和Multiwfn程序进行。
