Vibrational stark effect of the electric-field reporter 4-mercaptobenzonitrile as a tool for investigating electrostatics at electrode/SAM/solution interfaces.
Vibrational stark effect of the electric-field reporter 4-mercaptobenzonitrile as a tool for investigating electrostatics at electrode/SAM/solution interfaces.
复制标题
DOI：
10.3390/ijms13067466
复制
发表时间：
2012
影响因子：
5.6
通讯作者：
Hildebrandt P
中科院分区：
文献类型：
--
作者：
Schkolnik G;Salewski J;Millo D;Zebger I;Franzen S;Hildebrandt P
利用表面增强红外吸收和拉曼光谱研究了Au和Ag电极上自组装单层（SAMs）中4-巯基苯腈（MBN）的拉伸频率与利用振动斯塔克效应（VSE）的局部电场之间的关系。在不同的金属/SAM界面上使用MBN - SAM，我们整理了控制腈拉伸频率的主要因素，除了外电场外，还包括金属-MBN键、表面电位和氢键相互作用。基于丁腈拉伸与电极电位之间的线性关系，提出了界面电位分布的静电描述，可以确定SAM表面的电场强度以及SAM涂层金属的零电荷有效电位。将后一个量与从文献数据中得出的计算值进行比较，我们注意到Au/MBN的计算值非常吻合，但Ag/MBN的计算值存在明显偏差，这可能反映了模型的近似和简化，或者反映了Ag/MBN报道的结构参数的不确定性。目前的静电模型一致地解释了MBN在Ag和Au上的SAMs以及噻吩和巯基己酸SAMs的电场强度，其中MBN作为VSE报告因子。
4-mercaptobenzonitrile (MBN) in self-assembled monolayers (SAMs) on Au and Ag electrodes was studied by surface enhanced infrared absorption and Raman spectroscopy, to correlate the nitrile stretching frequency with the local electric field exploiting the vibrational Stark effect (VSE). Using MBN SAMs in different metal/SAM interfaces, we sorted out the main factors controlling the nitrile stretching frequency, which comprise, in addition to external electric fields, the metal-MBN bond, the surface potential, and hydrogen bond interactions. On the basis of the linear relationships between the nitrile stretching and the electrode potential, an electrostatic description of the interfacial potential distribution is presented that allows for determining the electric field strengths on the SAM surface, as well as the effective potential of zero-charge of the SAM-coated metal. Comparing this latter quantity with calculated values derived from literature data, we note a very good agreement for Au/MBN but distinct deviations for Ag/MBN which may reflect either the approximations and simplifications of the model or the uncertainty in reported structural parameters for Ag/MBN. The present electrostatic model consistently explains the electric field strengths for MBN SAMs on Ag and Au as well as for thiophenol and mercaptohexanoic acid SAMs with MBN incorporated as a VSE reporter.
登录
查看更多内容
影响因子：
4.4
作者：
Akinaga, Y;Nakajima, T;Hirao, K
通讯作者：
Hirao, K
影响因子：
3.3
作者：
Lecomte, S;Hildebrandt, P;Soulimane, T
通讯作者：
Soulimane, T
影响因子：
15
作者：
Gershevitz, O;Sukenik, CN
通讯作者：
Sukenik, CN
影响因子：
15
作者：
Oklejas, V;Sjostrom, C;Harris, JM
通讯作者：
Harris, JM
影响因子：
3.7
作者：
Alloway, Dana M.;Graham, Amy L.;Armstrong, Neal R.
通讯作者：
Armstrong, Neal R.