Deciphering the Structural Evolution and Electronic Properties of Magnesium Clusters: An Aromatic Homonuclear Metal Mg17Cluster.
The structures and electronic properties of low-energy neutral and anionic Mgn(n = 3-20) clusters have been studied by utilizing a widely adopted CALYPSO structure searching method coupled with density functional theory calculations. A large number of low-energy isomers are optimized at the B3PW91 functional with the 6-311+G(d) basis set. The optimized geometries clearly indicate that a structural transition from hollow three-dimensional configurations to filled-cage-like structures occurs at n = 16 for both neutral and anionic clusters. Based on the anionic ground state structures, photoelectron spectra are simulated using time-dependent density functional theory (TD-DFT) and compared with experimental results. The good agreement validates that the current ground state structures, obtained from the symmetry-unconstrained searches, are true global minima. A detailed chemical bonding analysis distinctly indicates that the Mg17cluster is the first neutral locally π-aromatic homonuclear all-metal cluster, which perfectly satisfies Hückel's well-known 4N + 2 rule.
Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610065, China.|Department of Physics, Nanyang Normal University , Nanyang 473061, China.
Xinxin
X
Xia
Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610065, China.
Xiaoyu
X
Kuang
Department of Physics, Nanyang Normal University , Nanyang 473061, China.|Department of Physics and High Pressure Science and Engineering Center, University of Nevada , Las Vegas, Nevada 89154, United States.
Cheng
C
Lu
Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610065, China.
Yuanyuan
Y
Jin
Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610065, China.
Xiaodong
X
Xing
Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida , Km 6 Antigua Carretera a Progreso, Apdo. Postal 73, Cordemex, 97310 Mérida, Yucatán, Mexico.
Gabriel
G
Merino
Centre for Science at Extreme Conditions and SUPA, School of Physics and Astronomy, The University of Edinburgh , Edinburgh EH9 3JZ, United Kingdom.
Andreas
A
Hermann