Density Functional Theory Investigations of Ferrocene-Terminated Self-Assembled Monolayers: Electronic State Changes Induced by Electric Dipole Field of Coadsorbed Species
Density Functional Theory Investigations of Ferrocene-Terminated Self-Assembled Monolayers: Electronic State Changes Induced by Electric Dipole Field of Coadsorbed Species
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DOI：
10.1021/acs.jpcc.6b00812
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发表时间：
2016-04
影响因子：
3.7
通讯作者：
Y. Yokota;Sumito Akiyama;Yuki Kaneda;A. Imanishi;K. Inagaki;Y. Morikawa;K. Fukui
中科院分区：
文献类型：
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作者：
Y. Yokota;Sumito Akiyama;Yuki Kaneda;A. Imanishi;K. Inagaki;Y. Morikawa;K. Fukui
在过去的四分之一个世纪中，二茂铁封端的自组装单层（SAM）得到了广泛的研究，以揭示化学修饰电极的电化学特性。众所周知，该系统的形式潜力很大程度上取决于二茂铁部分的局部环境。尽管二茂铁封端 SAM 的电子态应直接影响电化学性能，但有关不同局部环境的电子结构的知识非常有限。在本研究中，我们对具有不同共吸附物质的二茂铁封端的 SAM 进行了密度泛函理论计算，以揭示电子结构与二茂铁部分局部环境之间的关系。根据局部静电势，从二茂铁部分的最高占据分子轨道 (HOMO) 及其附近（HOMO-1 和 HOMO-2）衍生的态密度被发现相对于电极费米有很大的偏移......
Ferrocene-terminated self-assembled monolayers (SAMs) have been widely studied in the past quarter century to reveal the electrochemical properties of chemically modified electrodes. It has been well-known that the formal potential of the system strongly depends on the local environment of the ferrocene moiety. Although electronic states of ferrocene-terminated SAMs should directly affect the electrochemical properties, knowledge concerning electronic structures with respect to different local environment is very limited. In this study, we performed density functional theory calculations of ferrocene-terminated SAMs with different coadsorbed species to reveal the relationship between the electronic structures and the local environment of ferrocene moieties. Depending on the local electrostatic potential, density of states derived from the highest-occupied molecular orbital (HOMO) and its vicinities (HOMO–1 and HOMO–2) of the ferrocene moiety were found to largely shift with respect to the electrode Fermi ...