The adaptive kinetic Monte Carlo method was used to calculate the decomposition dynamics of a methanol molecule on Cu(100) at room temperature over a time scale of minutes. Mechanisms of reaction were found using minimum mode following saddle point searches based on forces and energies from density functional theory. Rates of reaction were calculated with harmonic transition state theory. The dynamics followed a pathway from CH3OH, CH3O, CH2O, HCO, and finally to CO. Our calculations confirm that methanol decomposition starts with breaking the O–H bond followed by breaking C–H bonds in the dehydrogenated intermediates until CO is produced. The bridge site on the Cu(100) surface is the active site for scissoring chemical bonds. Reaction intermediates are mobile on the surface which allows them to find this active reaction site. This study illustrates how the adaptive kinetic Monte Carlo method can model the dynamics of surface chemistry from first principles.

1.
T.
Engel
and
G.
Ertl
,
Adv. Catal.
28
,
1
(
1979
).
2.
R. J.
Behm
,
P. A.
Thiel
,
P. R.
Norton
, and
G.
Ertl
,
J. Chem. Phys.
78
,
7437
(
1983
).
3.
P. L. J.
Gunter
,
J. W.
Niemantsverdriet
,
F. H.
Ribeiro
, and
G. A.
Somorjai
,
Catal. Rev.-Sci. Eng.
39
,
77
(
1997
).
4.
T. S.
Askgaard
,
J. K.
Nørskov
,
C. V.
Ovesen
, and
P.
Stoltze
,
J. Catal.
156
,
229
(
1995
).
5.
B.
Uberuaga
,
M.
Levskovar
,
A. P.
Smith
,
H.
Jónsson
, and
M.
Olmstead
,
Phys. Rev. Lett.
84
,
2441
(
2000
).
6.
K.
Judai
,
A. S.
Worz
,
S.
Abbet
,
J. M.
Antonietti
,
U.
Heiz
,
A. D.
Vitto
,
L.
Giordano
, and
G.
Pacchioni
,
Phys. Chem. Chem. Phys.
7
,
955
(
2005
).
7.
K.
Honkala
,
A.
Hellman
,
I. N.
Remediakis
,
A.
Logadottir
,
A.
Carlsson
,
S.
Dahl
,
C.
Christensen
, and
J. K.
Nørskov
,
Science
307
,
555
(
2005
).
8.
M. P.
Andersson
,
E.
Abild-pedersen
,
I. N.
Remediakis
,
T.
Bligaard
,
G.
Jones
,
J.
Engbwk
,
O.
Lytken
,
S.
Horch
,
J. H.
Nielsen
,
J.
Sehested
,
J. R.
Rostrup-nielsen
,
J. K.
Nørskov
, and
I.
Chorkendorff
,
J. Catal.
255
,
6
(
2008
).
9.
H.
Eyring
,
J. Chem. Phys.
3
,
107
(
1935
).
10.
E.
Wigner
,
Trans. Faraday Soc.
34
,
29
(
1938
).
11.
C.
Wert
and
C.
Zener
,
Phys. Rev.
76
,
1169
(
1949
).
12.
G. H.
Vineyard
,
J. Phys. Chem. Solids
3
,
121
(
1957
).
13.
A. B.
Bortz
,
M. H.
Kalos
, and
J. L.
Lebowitz
,
J. Comput. Phys.
17
,
10
(
1975
).
14.
D. T.
Gillespie
,
J. Comput. Phys.
22
,
403
(
1976
).
15.
D.
Mei
,
Q.
Ge
,
M.
Neurock
,
L.
Kieken
, and
J.
Lerou
,
Mol. Phys.
102
,
361
(
2004
).
16.
K.
Reuter
,
D.
Frenkel
, and
M.
Scheffler
,
Phys. Rev. Lett.
93
,
116105
(
2004
).
17.
L.
Xu
,
C. T.
Campbell
,
H.
Jónsson
, and
G.
Henkelman
,
Surf. Sci.
601
,
3133
(
2007
).
18.
M. R.
Sørensen
and
A. F.
Voter
,
J. Chem. Phys.
112
,
9599
(
2000
).
19.
G.
Henkelman
and
H.
Jónsson
,
Phys. Rev. Lett.
90
,
116101
(
2003
).
20.
B. P.
Uberuaga
,
R.
Smith
,
A. R.
Cleave
,
F.
Montalenti
,
G.
Henkelman
,
R. W.
Grimes
,
A. F.
Voter
, and
K. E.
Sickafus
,
Phys. Rev. Lett.
92
,
115505
(
2004
).
21.
B. P.
Uberuaga
,
R. G.
Hoagland
,
A. F.
Voter
, and
S. M.
Valone
,
Phys. Rev. Lett.
99
,
135501
(
2007
).
22.
L.
Xu
,
G.
Henkelman
,
C. T.
Campbell
, and
H.
Jónsson
,
Phys. Rev. Lett.
95
,
146103
(
2005
).
23.
A. F.
Voter
,
F.
Montalenti
, and
T. C.
Germann
,
Annu. Rev. Mater. Res.
32
,
321
(
2002
).
24.
H.
Jónsson
,
G.
Mills
, and
K. W.
Jacobsen
, in
Classical and Quantum Dynamics in Condensed Phase Simulations
, edited by
B. J.
Berne
,
G.
Ciccotti
, and
D. F.
Coker
(
World Scientific
,
Singapore
,
1998
), pp.
385
404
.
25.
G.
Henkelman
and
H.
Jónsson
,
J. Chem. Phys.
113
,
9978
(
2000
).
26.
G.
Henkelman
,
B. P.
Uberuaga
, and
H.
Jónsson
,
J. Chem. Phys.
113
,
9901
(
2000
).
27.
G.
Henkelman
and
H.
Jónsson
,
J. Chem. Phys.
111
,
7010
(
1999
).
28.
L. J.
Munro
and
D. J.
Wales
,
Phys. Rev. B
59
,
3969
(
1999
).
29.
R.
Malek
and
N.
Mousseau
,
Phys. Rev. E
62
,
7723
(
2000
).
30.
D.
Mei
,
L.
Xu
, and
G.
Henkelman
,
J. Catal.
258
,
44
(
2008
).
31.
D.
Mei
,
L.
Xu
, and
G.
Henkelman
,
J. Phys. Chem. C
113
,
4522
(
2009
).
32.
L.
Xu
and
G.
Henkelman
,
J. Chem. Phys.
129
,
114104
(
2008
).
33.
G.
Henkelman
and
H.
Jónsson
,
J. Chem. Phys.
115
,
9657
(
2001
).
34.
I.
Wachs
and
R.
Madix
,
J. Catal.
53
,
208
(
1978
).
35.
B. A.
Sexton
,
Surf. Sci.
88
,
299
(
1979
).
36.
J. J. N.
Russell
,
S.
Gates
, and
J. J. T.
Yates
,
Surf. Sci.
163
,
516
(
1985
).
37.
R.
Ryberg
,
Phys. Rev. Lett.
49
,
1579
(
1982
).
38.
R.
Ryberg
,
J. Electron Spectrosc. Relat. Phenom.
29
,
59
(
1983
).
39.
R.
Ryberg
,
J. Chem. Phys.
82
,
567
(
1985
).
40.
A.
Peremans
,
F.
Maseri
,
J.
Darville
, and
J. M.
Gilles
,
J. Vac. Sci. Technol. A
8
,
3224
(
1990
).
41.
X. D.
Jiang
,
J. E.
Parmeter
,
C. A.
Estrada
, and
D. W.
Goodman
,
Surf. Sci.
249
,
44
(
1991
).
42.
D. B.
Clarke
,
D. K.
Lee
,
M. J.
Sandoval
, and
A. T.
Bell
,
J. Catal.
150
,
81
(
1994
).
43.
T. H.
Ellis
and
H.
Wang
,
Langmuir
10
,
4083
(
1994
).
44.
L.
Domokos
,
T.
Katona
, and
A.
Molnar
,
Catal. Lett.
40
,
215
(
1996
).
45.
J. P.
Camplin
and
E. M.
Mccash
,
Surf. Sci.
360
,
229
(
1996
).
46.
Z. M.
Hu
,
K.
Takahashi
, and
H.
Nakatsuji
,
Surf. Sci.
442
,
90
(
1999
).
47.
M. A.
Karolewski
and
R. G.
Cavell
,
Appl. Surf. Sci.
173
,
151
(
2001
).
48.
K.
Mudalige
and
M.
Trenary
,
J. Phys. Chem. B
105
,
3823
(
2001
).
49.
C.
Ammon
,
A.
Bayer
,
G.
Held
,
B.
Richter
,
T.
Schmidt
, and
H. P.
Steinruck
,
Surf. Sci.
507-510
,
845
(
2002
).
50.
S.
Polmann
,
A.
Bayer
,
C.
Ammon
, and
H. P.
Steinruck
,
Z. Phys. Chem.
218
,
957
(
2004
).
51.
J. R. B.
Gomes
and
J. A. N. F.
Gomes
,
Surf. Sci.
471
,
59
(
2001
).
52.
J.
Greeley
and
M.
Mavrikakis
,
J. Catal.
208
,
291
(
2002
).
53.
S.
Sakong
and
A.
Gross
,
J. Catal.
231
,
420
(
2005
).
54.
S.
Sakong
,
C.
Sendner
, and
A.
Gross
,
J. Mol. Struct.: THEOCHEM
771
,
117
(
2006
).
55.
C.
Sendner
,
S.
Sakong
, and
A.
Gross
,
Surf. Sci.
600
,
3258
(
2006
).
56.
S.
Sakong
and
A.
Gross
,
J. Phys. Chem. A
111
,
8814
(
2007
).
57.
R. A.
Olsen
,
G. J.
Kroes
,
G.
Henkelman
,
A.
Arnaldsson
, and
H.
Jónsson
,
J. Chem. Phys.
121
,
9776
(
2004
).
58.
A.
Heyden
,
A. T.
Bell
, and
F. J.
Keil
,
J. Chem. Phys.
123
,
224101
(
2005
).
59.
G.
Kresse
and
J.
Hafner
,
Phys. Rev. B
47
,
558
(
1993
).
60.
J. P.
Perdew
, in
Electronic Structure of Solids
, edited by
P.
Ziesche
and
H.
Eschrig
(
Akademie
,
Berlin
,
1991
), pp.
11
20
.
61.
D.
Vanderbilt
,
Phys. Rev. B
41
,
7892
(
1990
).
62.
G.
Kresse
and
J.
Joubert
,
Phys. Rev. B
59
,
1758
(
1999
).
63.
B. A.
Sexton
and
A. E.
Hughes
,
Surf. Sci.
140
,
227
(
1984
).
64.
G.
Fratesi
,
P.
Gava
, and
S. D.
Gironcoli
,
J. Phys. Chem. C
111
,
17015
(
2007
).
65.
M. A. N.
Santiago
,
M. A.
Sanchez-castillo
,
R. D.
Cortright
, and
J. A.
Dumesic
,
J. Catal.
193
,
16
(
2000
).
66.
B.
Hammer
,
M.
Scheffler
,
K. W.
Jacobsen
, and
J. K.
Nørskov
,
Phys. Rev. Lett.
73
,
1400
(
1994
).
67.
P.
Kratzer
,
B.
Hammer
, and
J. K.
Norskov
,
Surf. Sci.
359
,
45
(
1996
).
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