Transition from exohedral to endohedral structures of AuGen− (n = 2–12) clusters: photoelectron spectroscopy and ab initio calculations

Literature Information

Publication Date 2016-03-24
DOI 10.1039/C6CP00373G
Impact Factor 3.676
Authors

Sheng-Jie Lu, Lian-Rui Hu, Xi-Ling Xu, Hong-Guang Xu, Hui Chen, Wei-Jun Zheng


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Abstract

Gold-doped germanium clusters, AuGen− (n = 2–12), were investigated by using anion photoelectron spectroscopy in combination with ab initio calculations. Their geometric structures were determined by comparison of the theoretical calculations with the experimental results. The results show that the most stable isomers of AuGen− with n = 2–10 are all exohedral structures with the Au atom capping the vertex, edge or face of Gen clusters, while AuGe11− is found to be the critical size of the endohedral structure. Interestingly, AuGe12− has an Ih symmetric icosahedral structure with the Au atom located at the center. The molecular orbital analysis of the AuGe12− cluster suggests that the interactions between the 5d orbitals of the Au atom and the 4s4p hybridized orbitals of the Ge atoms may stabilize the Ih symmetric icosahedral cage and promote the Au atom to be encapsulated in the cage of Ge12. The NICS(0) and NICS(1) values are calculated to be −143.7 ppm and −36.3 ppm, respectively, indicating that the icosahedral AuGe12− cluster is significantly aromatic.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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