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Surface-mediated chain reaction through
dissociative attachment
Tingbin Lim1,JohnC.Polanyi1*,HongGuo2and Wei Ji2
Chain reactions on a surface offer an important route to linear nanopatterning. We recently reported cooperative reactions
on a silicon surface in which the reaction of one halogen atom with a silicon atom of a silicon dimer induced the
halogenation of its neighbouring silicon atom through surface-mediated charge transfer. The reaction was unable to
propagate further but here we describe how, by chemically bridging the gaps between the rows of these silicon dimers,
this mechanism is able to form extended chains. The agents for chain growth are CH3Cl molecules that dissociatively
attach CH3groups and chlorine atoms to silicon atoms from different dimers. By means of charge transfer through the
surface, this gives rise to dangling bonds adjacent to the CH3groups and chlorine atoms (in effect, ¡®free radicals¡¯) that
dissociate further incoming CH3Cl molecules, thereby providing the growing points for chains of inde?nite length. This
versatile mechanism of chain growth is examined in experiments and using ab initio theory.
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http://www.namipan.com/d/nchem.930.pdf/
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