Microkinetic modeling of surface chemical reactions still relies heavily on the mean-field based rate equation approach. This approach is expected to be most accurate for systems without appreciable lateral interactions among the adsorbed chemicals, and there in particular for the uniform adlayers resulting in poisoned regimes with predominant coverage of one species. Using first-principles kinetic Monte Carlo simulations and the CO oxidation at RuO2(110) as a showcase, we demonstrate that even in this limit mean-field rate equations fail to predict the catalytic activity by orders of magnitude. This deficiency is traced back to the inability to account for the vacancy pair formation that is kinetically driven by the ongoing reactions.

1.
H.
Lynggaard
,
A.
Andreasen
,
C.
Stegelmann
, and
P.
Stoltze
,
Prog. Surf. Sci.
77
,
71
(
2004
).
2.
C. W.
Gardiner
,
Handbook of Stochastic Methods
, ed. (
Springer-Verlag
,
Berlin
,
2003
).
3.
K.
Reuter
, in
Modeling Heterogeneous Catalytic Reactions: From the Molecular Process to the Technical System
, edited by
O.
Deutschmann
(
Wiley-VCH
,
Weinheim
,
2011
).
4.
I.
Chorkendorff
and
H.
Niemantsverdriet
,
Concepts of Modern Catalysis and Kinetics
(
Wiley-VCH
,
Weinheim
,
2003
).
5.
B.
Temel
,
H.
Meskine
,
K.
Reuter
,
H.
Metiu
, and
M.
Scheffler
,
J. Chem. Phys.
126
,
204711
(
2007
).
6.
K.
Reuter
and
M.
Scheffler
,
Phys. Rev. B
73
,
045433
(
2006
).
7.
A. C.
Hindmarsh
, in
Scientific Computing
, edited by
R. S.
Stepleman
(
North-Holland
,
Amsterdam
,
1983
).
8.
H.
Meskine
,
S.
Matera
,
M.
Scheffler
,
K.
Reuter
, and
H.
Metiu
,
Surf. Sci.
603
,
1724
(
2009
).
9.
M.
Rieger
,
J.
Rogal
, and
K.
Reuter
,
Phys. Rev. Lett.
100
,
016105
(
2008
).
You do not currently have access to this content.