Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular for polyatomic-surface reactions. Here we report, to the best of our knowledge, the first full-dimensional quantum dynamics study for the dissociative chemisorption of H₂O on rigid Cu(111) with all the nine molecular degrees of freedom fully coupled, based on an accurate full-dimensional potential energy surface. The full-dimensional quantum mechanical reactivity provides the dynamics features with the highest accuracy, revealing that the excitations in vibrational modes of H₂O are more efficacious than increasing the translational energy in promoting the reaction. The enhancement of the excitation in asymmetric stretch is the largest, but that of symmetric stretch becomes comparable at very low energies. The full-dimensional characterization also allows the investigation of the validity of previous reduced-dimensional and approximate dynamical models.

Nature Communications 7, Article number: 11953 doi:10.1038/ncomms11953
Received 11 March 2016 Accepted 13 May 2016 Published 10 June 2016

http://www.nature.com/ncomms/2016/160610/ncomms11953/full/ncomms11953.html