Visualizing On-Surface Decomposition Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy.

Chemical imaging of molecular decomposition processes at solid-liquid interfaces is a long-standing problem in achieving mechanistic understanding. Conventional analytical tools fail to meet this challenge due to the lack of required chemical sensitivity and specificity at the nanometer scale. In this work, we demonstrate that high-resolution hyperspectral tip-enhanced Raman spectroscopy (TERS) imaging can be a powerful analytical tool for studying on-surface decomposition chemistry at the nanoscale. Specifically, we present a TERS-based hyperspectral approach to visualize the on-surface decomposition process of a pyridine-4-thiol self-assembled monolayer on atomically flat Au(111) surfaces under ambient conditions. Reactive intermediates involved in the degradation process are spectroscopically detected with 5 nm spatial resolution. With supporting density functional theory simulations, a key species could be assigned to the disulfide reaction intermediate. This work opens a new application area for studying on-surface decomposition chemistry and related dynamics quantitatively at solid-liquid interfaces with nanometer spatial resolution.