** Reference to paper:

J. Chem. Phys. 144, 044702 (2016)

** DOI:

10.1063/1.4939520

** Title:

Methane dissociation on Pt(111): Searching for a specific reaction parameter density functional

** Authors:

Francesco Nattino, Davide Migliorini, Matteo Bonfanti and Geert-Jan Kroes

** Contact e-mail:

f.nattino@chem.leidenuniv.nl

** Abstract:

The theoretical description of methane dissociating on metal surfaces
is a current frontier in the field of gas-surface dynamics. Dynamical
models that aim at achieving a highly accurate description of this
reaction rely on potential energy surfaces based on density functional
theory calculations at the generalized gradient approximation.
We focus here on the effect that the exchange-correlation functional has on the
reactivity of methane on a metal surface, using CHD$_{3}$ + Pt(111)
as a test case. We present new \emph{ab initio} molecular dynamics calculations performed
with various density functionals,  looking also at  functionals that
account for the van der Waals (vdW) interaction. While searching for a semi-empirical
specific reaction parameter density functional for this system, we find that the use of
a weighted average of the PBE and the RPBE exchange functionals
together with a vdW-corrected correlation functional leads to an improved
agreement with quantum state-resolved experimental data for
the sticking probability, compared to previous PBE calculations.
With this semi-empirical density functional we
have also investigated the surface temperature dependence of the
methane dissociation reaction and the influence of the rotational alignment on the
reactivity, and compared our results with experiments.

** Description per file:

Manuscript_vs9_Resubmit.pdf is the paper in pdf (preprint format).
The material is divided in directories corresponding to the various 
tables/figures in the paper. Most of the figure files are xmgrace files (.agr).