Thiols and disulfides on the Au(111) surface:: The headgroup-gold interaction
Thiols and disulfides on the Au(111) surface:: The headgroup-gold interaction
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DOI：
10.1021/ja993622x
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发表时间：
2000-04-26
影响因子：
15
通讯作者：
Andreoni, W
中科院分区：
文献类型：
--
作者：
Grönbeck, H;Curioni, A;Andreoni, W
硫醇和二硫化物如何结合到金表面形成自组装单分子膜是一个长期存在的开放问题。特别是，确定锚基团本身的性质以及它们与金属的相互作用是一个优先问题，迄今为止，这只是用过于简化的模型来处理的。我们提出了从头计算的吸附构型（解离和不）的甲硫醇和二甲基二硫在Au（1 1 1）在低覆盖度，这是基于密度泛函理论，使用梯度校正的交换相关泛函。它们的结构，结合能，和类型的键合得到一个完整的表征。它是建立，解离显然有利于二硫化物与随后形成的强烈结合的硫醇盐，在协议与实验证据，而硫醇中的S-H键裂解产生的硫醇盐可以与吸附的“完整”的物种共存，并成为有利的，如果伴随着形成分子氢。
How thiols and disulfides bind to gold surfaces to form self-assembled monolayers is a long-standing open question. In particular, determining the nature itself of the anchor groups and of their interaction with the metal is a priority issue, which has so far been approached only with oversimplified models. We present ab initio calculations of the adsorption configurations (dissociative and not) of methanethiol and dimethyl disulfide on Au(1 1 1) at low coverage, which are based on density functional theory using gradient-corrected exchange-correlation functionals. A complete characterization of their structure, binding energies, and type of bonding is obtained. It is established that dissociation is clearly favored for the disulfide with subsequent formation of strongly bound thiolates, in agreement with experimental evidence, whereas thiolates resulting from S-H bond cleavage in thiols can coexist with the adsorbed "intact" species and become favored if accompanied by the formation of molecular hydrogen.