Another look at energetically quasi-degenerate structures of the gold cluster Au27q with q = 1, 0, −1,Journal of Computational Chemistry

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Another look at energetically quasi-degenerate structures of the gold cluster Au27q with q = 1, 0, −1
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2021-08-26 , DOI: 10.1002/jcc.26744
Pham Vu Nhat ₁ , Nguyen Thanh Si ₁ , Vitaly G Kiselev _{2,

3} , Minh Tho Nguyen ₄

Affiliation

Quantum chemical computations were used to reinvestigate the geometries, spectroscopic, and energetic properties of the gold clusters Au₂₇^q in three charge states (q = 1, 0, −1). Density functional theory (DFT) and the domain-based local pair natural orbital modification of the coupled-cluster theory DLPNO-CCSD(T) calculations revealed that, at variance with earlier reports in the literature, while the anion Au₂₇⁻ tends to exist in a tube-like form, both the lowest-energy Au₂₇ and Au₂₇⁺ isomers exhibit a pyramidal shape. However, several isomers were found to lie very close in energy, thus rendering a structural transition and their coexistence easy to occur. More specifically, the equilibrium geometry of the neutral Au₂₇ is a core-shell pyramid-like structure with one gold atom located inside. We also identified a novel ground state for the anion Au₂₇⁻ and located for the first time the global minimum of the cation Au₂₇⁺. The vertical detachment energies of the neutral and anionic states were also computed and used to assign the available experimental photoelectron spectra. Although many Au₂₇ isomers were predicted to be energetically quasi-degenerate, the corresponding distinctive vibrational signatures can be used as fingerprints for the identification of cluster geometrical features.

中文翻译：

另一个观察金簇 Au27q 的能量准简并结构，q = 1, 0, -1

量子化学计算被用来重新研究金簇 Au ₂₇^q在三种电荷态 (q = 1, 0, -1)的几何结构、光谱和能量特性。密度泛函理论 (DFT) 和耦合簇理论 DLPNO-CCSD(T) 计算的基于域的局部对自然轨道修改表明，与文献中早期的报道不同，而阴离子 Au ₂₇^-往往存在以管状形式，最低能量的 Au ₂₇和 Au ₂₇⁺异构体呈金字塔形。然而，发现几种异构体的能量非常接近，因此容易发生结构转变和它们的共存。更具体地说，中性 Au ₂₇的平衡几何形状是核壳金字塔状结构，内部有一个金原子。我们还确定了阴离子 Au ₂₇^-的新基态，并首次定位了阳离子 Au ₂₇⁺的全局最小值。还计算了中性和阴离子状态的垂直脱离能量，并用于分配可用的实验光电子光谱。虽然很多 Au ₂₇ 异构体被预测为能量准简并，相应的独特振动特征可用作识别簇几何特征的指纹。

更新日期：2021-10-09

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