Abstract
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...
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