** Reference to paper:

J. Chem. Phys. 142, 104702 (2015) 

** DOI:

10.1063/1.4913979 

** Title:

N2 dissociation on W(110): An ab initio molecular dynamics study on the effect of phonons

** Authors:

Francesco Nattino, Francesca Costanzo and Geert-Jan Kroes

** Contact e-mail:

f.nattino@chem.leidenuniv.nl

** Abstract:

Accurately modeling the chemisorption dynamics of N$_{2}$ on metal
surfaces is of both practical and fundamental interest. The factors
that may have hampered this achievement so far are the lack of an
accurate density functional and the use of approximate methods to
deal with surface phonons and non-adiabatic effects. In the current
work, the dissociation of molecular nitrogen on W(110) has been studied
using ab initio molecular dynamics (AIMD) calculations, simulating both 
surface temperature effects, such as lattice distortion, and surface motion 
effects, like recoil. The forces were calculated using density functional theory, 
and two density functionals were tested, namely the PBE and the RPBE functionals. 
The computed dissociation probability considerably differs from earlier
static surface results, with AIMD predicting a much larger contribution
of the indirect reaction channel, in which molecules dissociate after 
being temporally trapped in the proximity of the surface. 
Calculations suggest that the surface motion effects play a role here, 
since the energy transfer to the lattice does not
allow molecules that have been trapped into potential wells close
to the surface to find their way back to the gas phase. In comparison
to experimental data, AIMD results overestimate the dissociation probability
at the lowest energies investigated, where trapping dominates,
suggesting a failure of both tested exchange-correlation functionals
in describing the potential energy surface in the area sampled by
trapped molecules. 

** Description per file:

Manuscript_vs7_And_SM.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).