We report scanning tunneling microscopy observations on the restructuring of a Ag(110) surface induced by the molecule 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA). Our data reveal that the surface undergoes a mesoscopic step faceting following exposure to submonolayer coverages and thermal activation. A sawtooth arrangement evolves implying long-range mass transport of substrate atoms and forming a regular arrangement of kink sites. Its formation is associated with the molecules’ functional headgroups forming carboxylates with {100} Ag microfacets at step edges, and eventually operating to reshape the surface morphology. Interestingly, the resulting microfacets act as chiral templates for the growth of supramolecular PVBA structures. Theoretical modeling based on ab initio results indicates that chiral recognition processes discriminating between the two enantiomers of adsorbed PVBA molecules occur in this process.

1.
H.-U.
Baiker
,
Tetrahedron: Asymmetry
2
,
843
(
1991
).
2.
Chiral Reactions in Heterogeneous Catalysis, edited by G. Jannes and V. Dubois (Plenum, New York, 1995).
3.
A. Baiker and H. U. Blaser, in Handbook of Heterogeneous Catalysis, edited by G. Ertl, H. Knözinger, and J. Weitkamp (VCH, Weinheim, 1997), Vol. 5, p. 2422.
4.
C. A.
Orne
et al.,
Nature (London)
411
,
775
(
2001
).
5.
V.
Humblot
et al.,
Nature (London)
404
,
376
(
2002
).
6.
C. F.
McFadden
,
P. S.
Cremer
, and
A. J.
Gellman
,
Langmuir
12
,
2483
(
1996
).
7.
D. S.
Sholl
,
Langmuir
12
,
862
(
1998
).
8.
A.
Ahmadi
,
G.
Attard
,
J.
Feliu
, and
A.
Rodes
,
Langmuir
15
,
2420
(
1999
).
9.
G.
Attard
et al.,
J. Phys. Chem.
103
,
1381
(
1999
).
10.
R.
Fasel
et al.,
J. Chem. Phys.
115
,
1020
(
2001
).
11.
Z.
Sljivancanin
,
K. J.
Gothelf
, and
B.
Hammer
,
J. Am. Chem. Soc.
124
,
14789
(
2002
).
12.
X.
Zhao
,
J. Am. Chem. Soc.
122
,
12584
(
2000
).
13.
M.
Schunack
et al.,
Angew. Chem., Int. Ed. Engl.
40
,
2623
(
2001
).
14.
M.
Schunack
et al.,
Phys. Rev. Lett.
86
,
456
(
2001
).
15.
C.
Cai
et al.,
Adv. Mater. (Weinheim, Ger.)
11
,
745
(
1999
).
16.
C.
Cai
et al.,
Adv. Mater. (Weinheim, Ger.)
11
,
750
(
1999
).
17.
C. Cai et al., in Anisotropic Materials—Approaches to Polar Order, edited by R. Glaser and P. Kaszynski (ACS Symposium Series, 2001), p. 34.
18.
H.-P.
Rust
,
J.
Buisset
,
E. K.
Schweizer
, and
L.
Cramer
,
Rev. Sci. Instrum.
68
,
129
(
1997
).
19.
J. V.
Barth
et al.,
Angew. Chem., Int. Ed. Engl.
39
,
1230
(
2000
).
20.
J.
Weckesser
et al.,
Phys. Rev. Lett.
87
,
096101
(
2001
).
21.
J. V.
Barth
et al.,
J. Am. Chem. Soc.
124
,
7991
(
2002
).
22.
T.
Zambelli
,
J. V.
Barth
, and
J.
Wintterlin
,
Phys. Rev. B
58
,
12663
(
1998
).
23.
R. C. Mehrotra and R. Bohra, Metal Carboxylates (Academic, London, 1983).
24.
C. C.
Perry
,
S.
Haq
,
B. G.
Frederick
, and
N. V.
Richardson
,
Surf. Sci.
409
,
512
(
1998
).
25.
Q.
Chen
et al.,
Surf. Sci.
446
,
63
(
2000
).
26.
N.
Lin
et al.,
Angew. Chem., Int. Ed. Engl.
41
,
4779
(
2002
).
27.
J. V.
Barth
et al.,
Appl. Phys. A
76
,
645
(
2003
).
28.
M.
Böhringer
,
R.
Berndt
, and
W.-D.
Schneider
,
Phys. Rev. B
55
,
1384
(
1997
).
29.
X.
Zhao
et al.,
Surf. Sci.
424
,
L347
(
1999
).
30.
Q.
Chen
,
D. J.
Frankel
, and
N. V.
Richardson
,
Langmuir
17
,
8276
(
2001
).
31.
R. S.
Cahn
,
C. K.
Ingold
, and
V.
Prelog
,
Angew. Chem.
78
,
413
(
1966
).
32.
F.
Rosei
et al.,
Science
296
,
328
(
2002
).
33.
F.
Moresco
et al.,
Phys. Rev. Lett.
91
,
036601
(
2003
).
34.
We model the electrostatic interaction between PVBA monomers using effective point charges sitting on each atoms of the molecule, fitted on electronic charge distribution obtained via ab intio dft plane waves calculations, cf.
M.
Böhringer
et al.,
Phys. Rev. Lett.
83
,
324
(
1999
).
35.
J. I.
Pascual
et al.,
Surf. Sci.
502–503
,
1
(
2002
).
36.
J.
Weckesser
et al.,
Surf. Sci.
431
,
168
(
1999
).
37.
J.
Weckesser
,
J. V.
Barth
, and
K.
Kern
,
J. Chem. Phys.
110
,
5351
(
1999
).
This content is only available via PDF.
You do not currently have access to this content.