Considerably Increased Dynamics of CO-Water Complexes over CO and Water Alone.

Abstract

Solvents are increasingly known to influence chemical reactivity. However, the microscopic origin of solvent effects is scarcely understood, particularly at the individual molecule level. To shed light on this, we explored a well-defined model system of water (D2O) and carbon monoxide on a single-crystal copper surface with time-lapsed low-temperature scanning tunneling microscopy (STM) and ab initio calculations. Through detailed measurements on a time scale of minutes to hours at the limit of single-molecule solvation, we find that at cryogenic temperatures CO-D2O complexes are more mobile than individual CO or water molecules. We also obtain detailed mechanistic insights into the motion of the complex. In diffusion-limited surface reactions, such a solvent-triggered increase in mobility would substantially increase the reaction yield.