Why Ultrafast Photo-induced CO Desorption Dominates over Oxidation on Ru(0001)

TL;DR

This study uses advanced simulations to clarify why ultrafast laser pulses cause CO desorption to dominate over oxidation on Ru(0001), revealing detailed reaction dynamics and spectral changes.

Contribution

The paper introduces ab initio molecular dynamics with electronic friction to accurately simulate ultrafast photo-induced reactions on Ru(0001), explaining the dominance of CO desorption.

Findings

Successfully reproduces experimental oxidation and desorption phenomena

Quantifies the large desorption to oxidation ratio

Identifies spectral signatures of initial oxidation stages

Abstract

CO oxidation on Ru(0001) is a long-standing example of a reaction that, being thermally forbidden in ultra-high vacuum, can be activated by femtosecond laser pulses. In spite of its relevance, the precise dynamics of the photo-induced oxidation process as well as the reasons behind the dominant role of the competing CO photo-desorption remain unclear. Here we use ab initio molecular dynamics with electronic friction that account for the highly excited and non-equilibrated system created by the laser to investigate both reactions. Our simulations successfully reproduce the main experimental findings: the existence of photo-induced oxidation and desorption, the large desorption to oxidation branching ratio, and the changes in the O K-edge X-ray absorption spectra attributed to the initial stage of the oxidation process. Now, we are able to monitor in detail the ultrafast CO desorption and CO oxidation occurring in the highly-excited system and to disentangle what causes the unexpected inertness to the otherwise energetically favored oxidation.