Iida Kenji, Noda Masashi, Ishimura Kazuya, Nobusada Katsuyuki
Department of Theoretical and Computational Molecular Science, Institute for Molecular Science , Okazaki, 444-8585, Japan.
J Phys Chem A. 2014 Nov 26;118(47):11317-22. doi: 10.1021/jp5088042. Epub 2014 Nov 13.
Cluster-size dependence of localized surface plasmon resonance (LSPR) for Aun nanoclusters (n = 54, 146, 308, 560, 922, 1414) is investigated by using our recently developed computational program of first-principles calculations for photoinduced electron dynamics in nanostructures. The size of Au1414 (3.9 nm in diameter) is unprecedentedly large in comparison with those addressed in previous first-principles calculations of optical response in nanoclusters. These computations enable us to clearly see that LSPR gradually grows and the LSPR peaks red shift with increasing cluster size. The growth of LSPR is visualized in real space, demonstrating that electron charge distributions oscillate in a collective manner around the outermost surface region of the clusters. We further illustrate that the core d electrons screen the collective oscillation of the conduction-like s electrons.
通过使用我们最近开发的用于纳米结构中光致电子动力学的第一性原理计算程序，研究了Aun纳米团簇（n = 54、146、308、560、922、1414）的局域表面等离子体共振（LSPR）的团簇尺寸依赖性。与先前关于纳米团簇光学响应的第一性原理计算中所涉及的那些相比，Au1414（直径3.9 nm）的尺寸空前大。这些计算使我们能够清楚地看到，随着团簇尺寸的增加，LSPR逐渐增强且LSPR峰发生红移。LSPR的增强在实空间中可视化，表明电子电荷分布在团簇最外层表面区域周围以集体方式振荡。我们进一步说明，核心d电子屏蔽了类传导s电子的集体振荡。
