The adsorption of O2 on Ag(111) between 300 and 500 K has been studied with temperature-programmed desorption (TPD) and scanning tunneling microscopy (STM). At the first stage of adsorption, the disordered local oxide phase (commonly looking in STM as an array of black spots) is formed on the surface irrespective of the substrate temperature. The maximum concentration of black spots was found to be ≈0.11 ML, which corresponds to an oxygen coverage of ≈0.66 ML. Taking into account that the nucleation of the Ag(111)-p(4 × 4)-O phase starts after the saturation of the disordered phase, one can conclude that its coverage is at least not less than 0.66 ML. The analysis of STM and TPD data shows that the thermodesorption peak (m/e = 32) at 570 K is related exclusively to the decomposition of the p(4 × 4) phase, while the local oxide phase does not contribute to desorption.

1.
J. G.
Serafin
,
A. C.
Liu
, and
S. R.
Seyedmonir
,
J. Mol. Catal.
131
,
157
(
1998
).
2.
G.
Rovida
,
F.
Pratesi
,
M.
Maglietta
, and
E.
Ferroni
,
J. Vac. Sci. Technol.
9
,
796
(
1972
).
3.
G.
Rovida
,
F.
Pratesi
,
M.
Maglietta
, and
E.
Ferroni
,
Surf. Sci.
43
,
230
(
1974
).
4.
C. T.
Campbell
,
Surf. Sci.
157
,
43
(
1985
).
5.
S. R.
Bare
,
K.
Griffiths
,
W. N.
Lennard
, and
H. T.
Tang
,
Surf. Sci.
342
,
185
(
1995
).
6.
J.
Schnadt
,
A.
Michaelides
,
J.
Knudsen
,
R. T.
Vang
,
K.
Reuter
,
E.
Lægsgaard
,
M.
Scheffler
, and
F.
Besenbacher
,
Phys. Rev. Lett.
96
,
146101
(
2006
).
7.
J.
Schnadt
,
X. L. H. J.
Knudsen
,
A.
Michaelides
,
R. T.
Vang
,
K.
Reuter
,
Z.
Li
,
E.
Lægsgaard
,
M.
Scheffler
, and
F.
Besenbacher
,
Phys. Rev. B
80
,
075424
(
2009
).
8.
J.
Derouin
,
R. G.
Farber
,
S. L.
Heslop
, and
D. R.
Killelea
,
Surf. Sci.
641
,
L1
(
2015
).
9.
J.
Derouin
,
R. G.
Farber
,
M. E.
Turano
,
E. V.
Iski
, and
D. R.
Killelea
,
ACS Catal.
6
,
4640
(
2016
).
10.
B. V.
Andryushechkin
,
V. M.
Shevlyuga
,
T. V.
Pavlova
,
G. M.
Zhidomirov
, and
K. N.
Eltsov
,
Phys. Rev. Lett.
117
,
056101
(
2016
).
11.
C. I.
Carlisle
,
M. L. B. D. A.
King
,
J.
Cerdá
, and
P.
Sautet
,
Phys. Rev. Lett.
84
,
3899
(
2000
).
12.
C.
Carlisle
,
T.
Fujimoto
,
W.
Sim
, and
D.
King
,
Surf. Sci.
470
,
15
(
2000
).
13.
M.
Schmid
,
A.
Reicho
,
A.
Stierle
,
I.
Costina
,
J.
Klikovits
,
P.
Kostelnik
,
O.
Doubay
,
G.
Kresse
,
J.
Gustafson
,
E.
Lundgren
,
J. N.
Anderson
,
H.
Dosch
, and
P.
Varga
,
Phys. Rev. Lett.
96
,
146102
(
2006
).
14.
R.
Reichelt
,
S.
Günther
,
J.
Wintterlin
,
W.
Moritz
,
L.
Aballeb
, and
T. O.
Mentes
,
J. Chem. Phys.
127
,
134706
(
2007
).
15.
N. M.
Martin
,
S.
Klacar
,
H.
Grönbeck
,
J.
Knudsen
,
J.
Schnadt
,
S.
Blomberg
,
J.
Gustafson
, and
E.
Lundgren
,
J. Phys. Chem. C
118
,
15324
(
2014
).
16.

1 ML corresponds to 1 O atom per Ag atom in the top layer of clean Ag(111).

17.
A.
Michaelides
,
M.-L.
Bocquet
,
P.
Sautet
,
A.
Alavi
, and
D.
King
,
Chem. Phys. Lett.
367
,
344
(
2003
).
18.
J.
Pal
,
T. B.
Rawal
,
M.
Smerieri
,
S.
Hong
,
M.
Alatalo
,
L.
Savio
,
L.
Vattuone
,
T. S.
Rahman
, and
M.
Rocca
,
Phys. Rev. Lett.
118
,
226101
(
2017
).
19.
See http://www.sigmascan.ru for technical details.
20.
R.
Reichelt
,
S.
Günther
, and
J.
Wintterlin
,
J. Phys. Chem. C
115
,
17417
(
2011
).
21.
A.
Klust
and
R. J.
Madix
,
J. Chem. Phys.
126
,
084707
(
2007
).
22.
V. I.
Bukhtiyarov
,
A. I.
Nizovskii
,
H.
Bluhm
,
M.
Hävecker
,
E.
Kleimenov
,
A.
Knop-Gericke
, and
R.
Schlögl
,
J. Catal.
238
,
260
(
2006
).
23.

To estimate the fraction of the surface occupied by the p(4 × 4) phase, a series of panoramic STM images with a frame up to 10 000 × 10 000 Å2 were acquired in both topographic and conductance (dI/dV) modes. The use of conductance mode allows to increase the contrast between p(4 × 4) and disordered phases, and to avoid the problems in the recognition of surface phases related with atomic steps. After STM measurements, the sample was directly transferred to the face of the mass-spectrometer for thermodesorption.

24.
W.-X.
Li
,
C.
Stampfl
, and
M.
Scheffler
,
Phys. Rev. B
67
,
045408
(
2003
).
25.
A.
Raukema
,
R. J.
Dirksen
, and
A. W.
Kleyn
,
J. Chem. Phys.
103
,
6217
(
1995
).
26.
I.
Goikoetxea
,
J.
Meyer
,
J. I.
Juaristi
,
M.
Alducin
, and
K.
Reuter
,
Phys. Rev. Lett.
112
,
156101
(
2014
).
27.
M.
Rocca
,
L.
Savio
,
L.
Vattuone
,
U.
Burghaus
,
V.
Palomba
,
N.
Novelli
,
F.
Buatier de Mongeot
,
U.
Valbusa
,
R.
Gunnella
,
G.
Comelli
,
A.
Baraldi
,
S.
Lizzit
, and
G.
Paolucci
,
Phys. Rev. B
61
,
213
(
2000
).
28.
C.
Backx
,
C. D.
Groot
, and
P.
Biloen
,
Surf. Sci.
104
,
300
(
1981
).
29.
W. S.
Epling
,
G. B.
Hoflund
, and
G. N.
Salaita
,
J. Phys. Chem. B
102
,
2263
(
1998
).
30.
J. F.
Weaver
and
G. B.
Hoflund
,
Chem. Mater.
6
,
1693
(
1994
).
31.
J. F.
Weaver
and
G. B.
Hoflund
,
J. Phys. Chem.
98
,
8519
(
1994
).
32.
T.
Hashizume
,
M.
Taniguchi
,
K.
Motai
,
H.
Lu
,
K.
Tanaka
, and
T.
Sakurai
,
Jpn. J. Appl. Phys., Part 2
30
,
L1529
(
1991
).
33.
G.
Dorenbos
and
D. O.
Boerma
,
Surf. Sci.
287
,
443
(
1993
).
34.
L.
Savio
,
C.
Giallombardo
,
L.
Vattuone
,
A.
Kokalj
, and
M.
Rocca
,
Phys. Rev. Lett.
101
,
266103
(
2008
).
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