Formation of Stabilized Ketene Intermediates in the Reaction of O(3P) with Oligo(phenylene ethynylene) Thiolate Self-Assembled Monolayers on Au(111)
Formation of Stabilized Ketene Intermediates in the Reaction of O(3P) with Oligo(phenylene ethynylene) Thiolate Self-Assembled Monolayers on Au(111)
复制标题
O(3P) 与 Au(111) 上低聚（亚苯基乙炔基）硫醇盐自组装单层反应形成稳定的乙烯酮中间体
DOI：
10.1021/jp504466r
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发表时间：
2014
影响因子：
3.7
通讯作者：
S. Sibener
中科院分区：
文献类型：
--
作者：
Wenxin Li;Grant G. Langlois;Natalie A. Kautz;S. Sibener
我们已经采取步骤开发了一种方法，通过在有序的自组装单分子膜(SAM)暴露于超音速原子试剂束期间对反应物和产物进行光谱监测，来量化双分子反应的动力学和动力学。SAM的使用稳定了双分子反应在真空/薄膜界面形成的高能中间体，这是由于与SAM基质的快速热平衡，否则在气相中的单碰撞条件下不易观察到这些中间体。在本文中，我们将通过监测低聚(苯乙炔)SAM与O(3P)在具有特定初始反应方向的碰撞条件下的化学和结构变化，来阐明O(3P)与苯基取代炔键之间的基本反应的机理细节。利用超高真空条件下的时间分辨反射吸收红外光谱(RAIRS)和扫描隧道显微镜(STM)对样品进行了表征。
We have taken steps to develop a methodology for quantifying the kinetics and dynamics of bimolecular reactions through spectroscopic monitoring of reactants and products during exposure of well-ordered self-assembled monolayers (SAMs) to supersonic beams of atomic reagents. The use of a SAM stabilizes highly energetic intermediates formed from bimolecular reactions at the vacuum/film interface due to rapid thermal equilibration with the SAM matrix that are otherwise not readily observed under single-collision conditions in the gas phase. In this paper, we will discuss the elucidation of the mechanistic details for the fundamental reaction between O(3P) and phenyl-substituted alkyne bonds by monitoring chemical and structural changes in an oligo(phenylene ethynylene) SAM reacting with O(3P) under collision conditions having specified initial reaction orientation. Utilizing time-resolved reflection–absorption infrared spectroscopy (RAIRS) and scanning tunneling microscopy (STM) under ultrahigh vacuum condi...