We have developed an experimental and analytical setup for thermal desorption spectroscopy of solid water films on surfaces. We obtain the coverage-dependent desorption kinetics of water molecules from a well-defined ultra-thin alumina/NiAl(110) surface in the coverage range of 0–2 monolayers. We use a novel deconvolution technique to eliminate the pumping delay of water vapor in the vacuum system, which has previously hindered the accurate estimation of desorption kinetic parameters, such as activation energy and pre-exponential factor. The coverage-dependent Arrhenius analysis reveals that the desorption activation energy decreases with increasing coverage in the sub-monolayer range, indicating that the water–water interaction is not attractive. We also find that the pre-exponential factor for the second layer is higher than that for the sub-monolayer. We explain this difference in terms of transition state theory and propose that entropic effects play a significant role in water desorption kinetics.

1.
P. A.
Thiel
and
T. E.
Madey
,
Surf. Sci. Rep.
7
,
211
(
1987
).
3.
A.
Verdaguer
,
G. M.
Sacha
,
H.
Bluhm
, and
M.
Salmeron
,
Chem. Rev.
106
,
1478
(
2006
).
4.
A.
Hodgson
and
S.
Haq
,
Surf. Sci. Rep.
64
,
381
(
2009
).
5.
O.
Björneholm
,
M. H.
Hansen
,
A.
Hodgson
,
L.-M.
Liu
,
D. T.
Limmer
,
A.
Michaelides
,
P.
Pedevilla
,
J.
Rossmeisl
,
H.
Shen
,
G.
Tocci
,
E.
Tyrode
,
M.-M.
Walz
,
J.
Werner
, and
H.
Bluhm
,
Chem. Rev.
116
,
7698
(
2016
).
6.
P.
Bampoulis
,
K.
Sotthewes
,
E.
Dollekamp
, and
B.
Poelsema
,
Surf. Sci. Rep.
73
,
233
(
2018
).
7.
J.
Carrasco
,
A.
Michaelides
, and
M.
Scheffler
,
J. Chem. Phys.
130
,
184707
(
2009
).
8.
R. L. H.
Freire
,
A.
Kiejna
, and
J. L. F.
Da Silva
,
Phys. Chem. Chem. Phys.
18
,
29526
(
2016
).
9.
R. J.
Speedy
,
P. G.
Debenedetti
,
R. S.
Smith
,
C.
Huang
, and
B. D.
Kay
,
J. Chem. Phys.
105
,
240
(
1996
).
10.
R. S.
Smith
,
J.
Matthiesen
,
B. D.
Kay
, and
B. D.
Kay
,
J. Phys. Chem. A
118
,
8242
(
2014
).
12.
A. M.
de Jong
and
J. W.
Niemantsverdriet
,
Surf. Sci.
233
,
355
(
1990
).
13.
S. L.
Tait
,
Z.
Dohnálek
,
C. T.
Campbell
, and
B. D.
Kay
,
J. Chem. Phys.
122
,
164707
(
2005
).
14.
S. L.
Tait
,
Z.
Dohnálek
,
C. T.
Campbell
, and
B. D.
Kay
,
J. Chem. Phys.
122
,
164708
(
2005
).
15.
R. S.
Smith
,
Z.
Li
,
L.
Chen
,
Z.
Dohnálek
, and
B. D.
Kay
,
J. Phys. Chem. B
118
,
8054
(
2014
).
16.
E.
Habenschaden
and
J.
Küppers
,
Surf. Sci.
138
,
L147
(
1984
).
17.
J. B.
Miller
,
H. R.
Siddiqui
,
S. M.
Gates
,
J. N.
Russell
,
J. T.
Yates
,
J. C.
Tully
, and
M. J.
Cardillo
,
J. Chem. Phys.
87
,
6725
(
1987
).
19.
J. W.
Niemantsverdriet
,
P.
Dolle
,
K.
Markert
, and
K.
Wandelt
,
J. Vac. Sci. Technol. A
5
,
875
(
1987
).
20.
J.
Libuda
,
F.
Winkelmann
,
M.
Bäumer
,
H.-J.
Freund
,
T.
Bertrams
,
H.
Neddermeyer
, and
K.
Müller
,
Surf. Sci.
318
,
61
(
1994
).
21.
G.
Kresse
,
M.
Schmid
,
E.
Napetschnig
,
M.
Shishkin
,
L.
Köhler
, and
P.
Varga
,
Science
308
,
1440
(
2005
).
22.
R. M.
Jaeger
,
H.
Kuhlenbeck
,
H.-J.
Freund
,
M.
Wuttig
,
W.
Hoffmann
,
R.
Franchy
, and
H.
Ibach
,
Surf. Sci.
259
,
235
(
1991
).
23.
F.
Winkelmann
,
S.
Wohlrab
,
J.
Libuda
,
M.
Bäumer
,
D.
Cappus
,
M.
Menges
,
K.
Al-Shamery
,
H.
Kuhlenbeck
, and
H.-J.
Freund
,
Surf. Sci.
307–309
,
1148
(
1994
).
24.
G.
Tzvetkov
,
Y.
Zubavichus
,
G.
Koller
,
T.
Schmidt
,
C.
Heske
,
E.
Umbach
,
M.
Grunze
,
M. G.
Ramsey
, and
F. P.
Netzer
,
Surf. Sci.
543
,
131
(
2003
).
25.
C.-W.
Yi
and
J.
Szanyi
,
J. Phys. Chem. C
111
,
17597
(
2007
).
26.
E.
Ozensoy
,
J.
Szanyi
, and
C. H. F.
Peden
,
J. Phys. Chem. B
109
,
3431
(
2005
).
27.
U.
Leist
,
W.
Ranke
, and
K.
Al-Shamery
,
Phys. Chem. Chem. Phys.
5
,
2435
(
2003
).
28.
C.
Benndorf
and
T. E.
Madey
,
Surf. Sci.
194
,
63
(
1988
).
29.
M. B.
Hugenschmidt
,
L.
Gamble
, and
C. T.
Campbell
,
Surf. Sci.
302
,
329
(
1994
).
30.
M.
Kulawik
,
N.
Nilius
,
H.-P.
Rust
, and
H.-J.
Freund
,
Phys. Rev. Lett.
91
,
256101
(
2003
).
31.
A.
Beniya
,
S.
Yamamoto
,
K.
Mukai
,
Y.
Yamashita
, and
J.
Yoshinobu
,
J. Chem. Phys.
125
,
054717
(
2006
).
33.
Y. J.
Li
,
J.
Brndiar
,
Y.
Naitoh
,
Y.
Sugawara
, and
I.
Štich
,
Nanotechnology
26
,
505704
(
2015
).
34.
A.
Tamtögl
,
E.
Bahn
,
M.
Sacchi
,
J.
Zhu
,
D. J.
Ward
,
A. P.
Jardine
,
S. J.
Jenkins
,
P.
Fouquet
,
J.
Ellis
, and
W.
Allison
,
Nat. Commun.
12
,
3120
(
2021
).
35.
C. T.
Campbell
and
J. R. V.
Sellers
,
Chem. Rev.
113
,
4106
(
2013
).
36.
P. J.
Linstrom
,
The NIST Chemistry WebBook
(
National Institute of Standards and Technology
,
2001
).
37.
A. S.
Friedman
and
L.
Haar
,
J. Chem. Phys.
22
,
2051
(
1954
).
38.
J. W.
Niemantsverdriet
,
K.
Markert
, and
K.
Wandelt
,
Appl. Surf. Sci.
31
,
211
(
1988
).
39.
N.
Zuniga-Hansen
,
L. E.
Silbert
, and
M. M.
Calbi
,
Phys. Rev. E
98
,
032128
(
2018
).

Supplementary Material

You do not currently have access to this content.