Thermal (300K) and electron-induced reactions of benzene (Bz), chlorobenzene
(ClPh), 1,2-dichlorobenzene (1,2-diClPh) and 1,4-dichlorbenzene (1,4-diClPh)
with Si(100)2×1 have been examined by Scanning Tunneling Microscopy (STM).
Thermal reactions of Bz yielded predominantly the
quadruply-
-bound
Tight Bridge, TB,
configuration on top of the Si dimer-rows. For ClPh and 1,2-diClPh, which
resembled one another, thermal reaction led with 45-50% yield to the
doubly-
-bound
Butterfly, BF, configuration,
also on top of the dimer-row, and with 20% yield to a novel "Displaced", D,
configuration to one side of a dimer-row. The adsorbate 1,4-diClPh was alone
in favouring a configuration in which neighbouring dimer-rows were "linked" (L)
by a bright-feature centrally located between the dimer-rows. By ab initio
calculation, we interpret D as due to the rupture of one C-Cl bond per
adsorbate molecule, and L to the rupture of two C-Cl's. The breaking of this
weak bond is followed in the former case by attachment of the aromatic ring
to one dimer-row, and in the latter to attachment to two adjacent dimer rows.
Application of a -5V voltage pulse to the STM tip substantially increased the
percentage of row-linking structures, L, for 1,4-diClPh, but neither -5V nor
+4-6V volt pulses resulted in L-type binding of Bz. The postulated L product
of 1,4-diClPh, with an aromatic ring linking the two inner Si atoms of adjacent
dimer-rows and the two Cl's on the outer Si atoms of the dimer-rows, is shown
to be in accord with ab initio simulation of the observed STM image.