Site-specific analysis of dielectric properties of finite systems

被引:42
作者
Jackson, K. [1 ]
Yang, M.
Jellinek, J.
机构
[1] Cent Michigan Univ, Dept Phys, Mt Pleasant, MI 48859 USA
[2] Argonne Natl Lab, Div Chem, Argonne, IL 60439 USA
关键词
D O I
10.1021/jp0719457
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A new scheme for decomposing the total dipole moment and polarizability of a system into site-specific contributions is presented. The scheme is based on partitioning the system volume into cells associated with its atoms or groups of atoms. The site-specific dipole moments and polarizabilities are computed from the charge densities within the individual cells and the responses of these densities to an external electric field. These dipole moments and polarizabilities are further partitioned into local/dipole and charge-transfer components. The utility of the scheme is illustrated through analysis of the structure4shape- and size-specific aspects of the dipole moments and polarizabilities of silicon clusters. It is shown that the polarizabilities associated with the individual constituent Si atoms vary considerably with the structure/shape of the cluster and the location.of the atom or site within a given structure. Surface atoms, and especially those at edges, have larger polari zabili ties than interior atoms. The overall contribution of the charge-transfer components to the total cluster polarizability increases with the cluster size. Finally, the anisotropy of the total polarizability correlates with the anisotropy of the cluster shape, and the charge-transfer component is the part dominantly responsible for the polarizability anisotropy.
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页码:17952 / 17960
页数:9
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