HOD on Ni(111): Ab Initio molecular dynamics prediction of molecular beam experiments.

The dissociation of water on a transition-metal catalyst is a fundamental step in relevant industrial processes such as the water-gas shift reaction and steam reforming. Although many theoretical studies have been performed, quantitative agreement between theoretical simulations and molecular beam experiments has not yet been achieved. In this work, we present a predictive ab initio molecular dynamics study on the dissociation of mono-deuterated water (HOD) on Ni(111). The analysis of the trajectories gives useful insight into the full-dimensional dynamics of the process and suggests that rotational steering plays a key role in the dissociation. The computed reaction probability suggests that, in combination with accurate molecular beam experiments, the specific reaction parameter density functional developed for CHD3 (SRP32-vdW) represents a good starting point for developing a semi-empirical functional able to achieve chemical accuracy for HOD on Ni(111).