The adsorption of uracil on Au(111) and Au(100) from sulfuric acid sol
ution has been studied by in-situ scanning tunneling microscopy (STM).
Depending on the potential applied to the Au(hkl) electrode, uracil f
orms highly ordered two-dimensional physisorbed as well as chemisorbed
adlayers, which were imaged with molecular resolution in-situ. ''Stea
dy-state'' and time-dependent experiments were performed in order to f
ollow structural changes of the respective substrate surfaces in the p
resence of these organic layers. The physisorbed films on Au(111)-(p x
root 3), Au(100)-(hex), and Au(100)-(1 x 1) are rather similar. They
display characteristic properties of a hydrogen-bonded network of plan
ar oriented uracil molecules. The influence of the substrate surface g
eometry for these systems was primarily reflected in the dimensions of
the respective coincidence cells. At sufficiently positive electrode
potentials, uracil deprotonates and forms highly ordered chemisorbed,
perpendicularly oriented surface coordination complexes. The organic m
olecule occupies (root 3 x root 3)R30 degrees-positions of the Au(111)
-(1 x 1) lattice. An additional experimentally observed contrast patte
rn between adjacent rows of molecules is explained by the formation of
interdigitated rows of molecules rotated +45 degrees and -45 degrees
with respect to the [110] direction of the substrate surface. The chem
isorbed uracil film on Au(100)-(1 x 1) is of oblique symmetry and cons
ists of interdigitated regular arrays of stacks, each containing four
molecules.