** Reference to paper:

J. Chem. Phys. 145, 144701 (2016)

** DOI:

10.1063/1.4964486

** Title:

Dynamics of H2 dissociation on the close-packed (111) surface of the noblest metal: H2 + Au(111)

** Authors:

Mark Wijzenbroek, Darcey Helstone, Joerg Meyer and Geert-Jan Kroes

** Contact e-mail:

g.j.kroes@chem.leidenuniv.nl

** Abstract:

We have performed calculations on the dissociative chemisorption of H2 on un-reconstructed and
reconstructed Au(111) with density functional theory, and dynamics calculations on this process
on un-reconstructed Au(111). Due to a very late barrier for dissociation, H2 + Au(111) is a
candidate H2-metal system for which the dissociative chemisorption could be considerably affected
by the energy transfer to electron-hole pairs. Minimum barrier geometries and potential energy
surfaces were computed for six density functionals. The functionals tested yield minimum barrier
heights in the range of 1.15-1.6 eV, and barriers that are even later than found for the similar
H2 + Cu(111) system. The potential energy surfaces have been used in quasi-classical trajectory
calculations of the initial (v,J) state resolved reaction probability for several vibrational
states v and rotational states J of H2 and D2. Our calculations may serve as predictions for
state-resolved associative desorption experiments, from which initial state-resolved dissociative
chemisorption probabilities can be extracted by invoking detailed balance. The vibrational
efficacy η_{v=0→1} reported for D2 dissociating on un-reconstructed Au(111) (about 0.9) is
similar to that found in earlier quantum dynamics calculations on H2 + Ag(111), but larger than
found for D2 + Cu(111). With the two functionals tested most extensively, the reactivity of H2
and D2 exhibits an almost monotonic increase with increasing rotational quantum number J. Test
calculations suggest that, for chemical accuracy (1 kcal/mol), the herringbone reconstruction of
Au(111) should be modeled.

** Description per file:

JCP2016_Accepted_Manuscript.pdf contains the Accepted Manuscript format of the manuscript.
JCP2016_Supporting_information_vs2.pdf contains the supporting information in pdf format.