Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.
Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.
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DOI：
10.1063/1.1862239
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发表时间：
2005-03
期刊：
影响因子：
--
通讯作者：
D. Yuan;Yang Wang;Z. Zeng
中科院分区：
文献类型：
--
作者：
D. Yuan;Yang Wang;Z. Zeng
本文采用第一性原理方法，基于密度泛函理论，报道了掺杂铂族原子Au(N)M （N = 1-7, M = Ni, Pd, Pt）的金团簇的基态几何和电子结构。掺镍金团簇的稳定性和电子性能与纯金团簇相似，但键强度有所提高。由于杂质与金原子之间的d-d或s-d相互作用是由相对论效应引起的，以及掺杂剂离域s-电子在Pd和pt掺杂金团簇中的独特性质，掺杂原子显著改变了金团簇的几何和电子性质，并且在掺杂pt的团簇中发现了更强的键能。通过杂质的Mulliken居群分析、键能的详细分解以及最稳定的掺杂金团簇的各种态密度，了解单个掺杂原子对掺杂金团簇成键和电子性能的不同影响。从掺杂金团簇的电子性质出发，预测了过渡金属掺杂金团簇与纯金团簇相比对O(2)、CO或NO分子的不同化学反应性。
Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.