Diffusion of ammonia was studied over the smooth Re(001) surface utilizing optical second harmonic diffraction from surface coverage grating. The decay of the first order diffraction peak as a function of surface temperature for different initial coverages was measured and then simulated by numerical solution of Fick’s second diffusion equation, employing a coverage dependent diffusion constant. For the first time the second order diffracted second harmonic signal was monitored during the diffusion process, supporting the calculated initial coverage profile and the diffusion model. The resulting diffusivity D(θ)=D0exp[−Em(θ)/RT], is defined by a barrier for diffusion Em(θ)=E0−ωZθ, with activation energy at zero coverage E0=3.4±0.6 kcal/mol, D0=2.8×10−3 cm2 sec−1 and the repulsion energy between the pair of nearest neighbor molecules ω=0.2±0.06 kcal/mol. The magnitude and effect of the repulsive interactions on diffusion are compared to their strong effect on the activation energy for desorption.

1.
(a)
G.
Ehrlich
and
K.
Stolt
,
Ann. Rev. Phys. Chem.
31
,
603
(
1980
);
(b)
D. A.
Reed
and
G.
Ehrlich
,
Surf. Sci.
102
,
588
(
1981
).
2.
R.
Gomer
,
Rep. Prog. Phys.
53
,
917
(
1990
).
3.
R.
Viswanathan
,
D. R.
Burgess
,
P. C.
Stair
, and
E.
Weitz
,
J. Vac. Sci. Technol.
20
,
605
(
1982
).
4.
S. M.
George
,
A. M.
DeSantolo
, and
R. B.
Hall
,
Surf. Sci.
159
,
L425
(
1985
).
5.
C. H.
Mak
,
J. L.
Brand
,
A. A.
Deckert
, and
S. M.
George
,
J. Chem. Phys.
85
,
1676
(
1986
).
6.
E. G.
Seebauer
and
L. D.
Schmidt
,
Chem. Phys. Lett.
123
,
129
(
1985
).
7.
B.
Roop
,
S. A.
Costello
,
D. R.
Mullins
, and
J. M.
White
,
J. Chem. Phys.
86
,
3003
(
1987
).
8.
(a)
Xu-Dong
Xiao
,
X. D.
Zhu
,
W.
Daum
and
Y. R.
Shen
,
Phys. Rev. B
46
,
9732
(
1992
);
Xu-Dong
Xiao
,
X. D.
Zhu
,
W.
Daum
and
Y. R.
Shen
, (b)
Surf. Sci.
271
,
295
(
1992
).
9.
X. D.
Zhu
,
Th.
Rasing
, and
Y. R.
Shen
,
Phys. Rev. Lett.
61
,
2883
(
1988
).
10.
T.
Suzuki
and
T. F.
Heinz
,
Opt. Lett.
14
,
1201
(
1989
).
11.
G. A.
Reider
,
U.
Hofer
, and
T. F.
Heinz
,
Phys. Rev. Lett.
66
,
1994
(
1991
).
12.
X. D.
Zhu
,
A.
Lee
, and
A.
Wong
,
Appl. Phys. A
52
,
317
(
1991
).
13.
X. D.
Zhu
,
A.
Lee
,
A.
Wong
, and
U.
Linke
,
Phys. Rev. Lett.
68
,
1862
(
1992
).
14.
Z.
Rosenzweig
and
M.
Asscher
,
Surf. Sci.
204
,
L880
(
1988
).
15.
Z.
Rosenzweig
and
M.
Asscher
,
Surf. Sci.
225
,
249
(
1990
).
16.
Z.
Rosenzweig
and
M.
Asscher
,
J. Chem. Phys.
96
,
4040
(
1992
).
17.
Z. Rosenzweig and M. Asscher, in Surface Science of Catalysis, ACS Symposium Series No. 482, edited by D. J. Dwyer and F. M. Hoffman (American Chemical Society, Washington, DC, 1992).
18.
J. H.
Bechtel
,
J. Appl. Phys.
46
,
1585
(
1975
).
19.
R. D.
Burgess
,
P. C.
Stair
, and
E.
Weitz
,
J. Vac. Sci. Technol. A
4
,
1362
(
1986
).
20.
Y. S. Toulukian, R. W. Powell, C. Y. Ho, and M. C. Nicolaou, Thermal Properties of Matter (Plenum, New York, 1970), Vols. 1, 4, and 10.
21.
M.
Bowker
and
D. A.
King
,
Surf. Sci.
71
,
583
(
1978
).
22.
M.
Bowker
and
D. A.
King
,
Surf. Sci.
72
,
208
(
1978
).
23.
C.
Uebing
and
R.
Gomer
,
J. Chem. Phys.
95
,
7626
(
1991
).
24.
M. C.
Tringides
and
R.
Gomer
,
Surf. Sci.
265
,
283
(
1992
).
25.
R.
Butz
and
H.
Wagner
,
Surf. Sci.
63
,
448
(
1977
).
26.
S. S.
Mann
,
T.
Seto
,
C. J.
Barnes
, and
D. A.
King
,
Surf. Sci.
261
,
155
(
1991
).
27.
D. A.
Arthur
,
D. L.
Meixner
,
M.
Boudart
, and
S. M.
George
,
J. Chem. Phys.
95
,
8521
(
1991
).
28.
T. M.
Lu
,
G.-C.
Wang
, and
M. G.
Lagally
,
Phys. Rev. Lett.
39
,
411
(
1977
).
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