Binding at molecule/gold transport interfaces. II. Orbitals and density of states

被引:21
作者
Basch, H
Ratner, MA
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[2] Northwestern Univ, Ctr Nanofabricat & Mol Self Assembly, Evanston, IL 60208 USA
[3] Bar Ilan Univ, Dept Chem, IL-52900 Ramat Gan, Israel
关键词
D O I
10.1063/1.1613942
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
The density of states diagrams, and the associated orbital populations and structure, are analyzed for the discrete models for dithiol bridged molecular junctions discussed in the previous paper. The orbitals closest to the Fermi surface are generally dominated by the high s and d densities of metal atoms. Some orbitals are mixed metal/sulfur/hydrocarbon, and a few (generally lower-lying occupied) are dominantly within the hydrocarbon itself. These orbital populations suggest that the frontier orbitals are, in themselves, not adequate for quantitative description of transport, essentially because the Green's functions of slightly lower-lying orbitals give large contributions to the mixing between electrodes that dominates the transport. Effects of different spin multiplicities and charges, as well as different choices of density functional, are also presented: the major conclusions seem robust, and are not strongly effected by these modifications. (C) 2003 American Institute of Physics.
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页码:11943 / 11950
页数:8
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