Zhao Shuang, Li Zhen-Hua, Wang Wen-Ning, Liu Zhi-Pan, Fan Kang-Nian, Xie Yaoming, Schaefer Henry F
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Center for Theoretical Chemical Physics, Fudan University, Shanghai 200433, People's Republic of China.
J Chem Phys. 2006 May 14;124(18):184102. doi: 10.1063/1.2193512.
Twenty-three density functional theory (DFT) methods, including the second- and the third-generation functionals, are tested in conjunction with two basis sets (LANL2DZ and SDD) for studying the properties of neutral and ionic silver clusters. We find that DFT methods incorporating the uniform electron gas limit in the correlation functional, namely, those with Perdew's correlation functionals (PW91, PBE, P86, and TPSS), Becke's B95, and the Van Voorhis-Scuseria functional VSXC, generally perform better than the other group of functionals, e.g., those incorporating the LYP correlation functional and variations of the B97 functional. Strikingly, these two groups of functionals can produce qualitatively different results for the Ag3 and Ag4 clusters. The energetic properties and vibrational frequencies of Ag(n) are also evaluated by the different functionals. The present study shows that the choice of DFT methods for heavy metals may be critical. It is found that the exact-exchange-incorporated PBE functional (PBE1PBE) is among the best for predicting the range of properties.
二十三种密度泛函理论（DFT）方法，包括第二代和第三代泛函，与两种基组（LANL2DZ和SDD）结合使用，以研究中性和离子态银团簇的性质。我们发现，在相关泛函中纳入均匀电子气极限的DFT方法，即那些采用佩德韦相关泛函（PW91、PBE、P86和TPSS）、贝克的B95以及范·沃尔希斯-斯库西亚泛函VSXC的方法，通常比其他泛函组表现更好，例如那些采用LYP相关泛函和B97泛函变体的方法。令人惊讶的是，这两组泛函对于Ag3和Ag4团簇可能会产生定性不同的结果。不同泛函还对Ag(n)的能量性质和振动频率进行了评估。本研究表明，对于重金属，DFT方法的选择可能至关重要。发现纳入精确交换的PBE泛函（PBE1PBE）在预测性质范围方面是最佳的之一。
