Modulation of the Double-Helical Cores: A New Strategy for Structural Predictions of Thiolate-Protected Gold Nanoclusters.,The Journal of Physical Chemistry Letters

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Modulation of the Double-Helical Cores: A New Strategy for Structural Predictions of Thiolate-Protected Gold Nanoclusters.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-01-07 , DOI: 10.1021/acs.jpclett.9b03515
Wen Wu Xu _{1,

2} , Xiangmei Duan _{1,

2} , Xiao Cheng Zeng ₃

Affiliation

A fundamental understanding of the structural growth of thiolate-protected gold nanoclusters not only benefits experimental synthesis but also will advance the methodology for structural predictions and for rational design of highly stable nanoclusters. Herein, we report numerous new structures (11 total) of thiolate-protected gold nanoclusters predicted from theoretical modulation of the double-helical cores of experimentally determined nanoclusters. Among these newly predicted structures, Au32(SR)22, Au40(SR)26, and Au48(SR)30 are obtained by adding a defective layer containing 4 gold atoms on a structural sequence of experimentally crystallized nanoclusters, namely, Au28(SR)20, Au36(SR)24, and Au44(SR)28. The generic growth pattern underlying this sequence of nanoclusters can be viewed as adding the highly stable tetrahedral Au4 unit on the double-helical cores. Likewise, the other eight newly predicted structures, including two groups of isomeric structures corresponding to the sequence of experimentally determined Au28(SR)20, Au36(SR)24, Au44(SR)28, and Au52(SR)32 nanoclusters, are successfully predicted. Density functional theory calculations show that these 11 newly predicted nanoclusters exhibit large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps and all-positive harmonic vibrational frequencies, suggesting their high chemical stabilities. Additional analyses on the structures and properties suggest that these newly predicted nanoclusters are very likely to be synthesized in the laboratory. Confirmation by experiments would validate the new strategy for structural prediction of thiolate-protected gold nanoclusters by taking advantage of a large structure database of crystallized ligand-protected gold nanoclusters with a variety of gold cores.

中文翻译：

双螺旋核的调制：硫氰酸盐保护的金纳米团簇结构预测的新策略。

对硫醇盐保护的金纳米团簇的结构生长的基本理解，不仅有利于实验合成，而且还将为结构预测和高度稳定的纳米团簇的合理设计提供先进的方法。在这里，我们报告了许多新的结构（共11个），由硫醇盐保护的金纳米团簇构成，这些结构是通过实验确定的纳米团簇的双螺旋核的理论调制来预测的。在这些新预测的结构中，Au32（SR）22，Au40（SR）26和Au48（SR）30是通过在实验结晶的纳米团簇的结构序列（即Au28（SR））上添加包含4个金原子的缺陷层而获得的20，Au36（SR）24和Au44（SR）28。这种纳米簇序列的基本生长模式可以看作是在双螺旋核上添加了高度稳定的四面体Au4单元。同样，其他八种新预测的结构（包括与实验确定的Au28（SR）20，Au36（SR）24，Au44（SR）28和Au52（SR）32纳米簇的序列相对应的两组同分异构结构）也成功地获得了成功。预料到的。密度泛函理论计算表明，这11个新预测的纳米团簇具有较大的最高占据分子轨道，最低的未占据分子轨道间隙和全正谐波振动频率，表明它们具有较高的化学稳定性。对结构和性质的其他分析表明，这些新预测的纳米簇很可能在实验室中合成。

更新日期：2020-01-08

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