Reaction dynamics, a molecule at a time
Subtitle: scanning tunneling microscopy (STM) studies of self-assembly and of induced reaction at silicon surfaces.
Contributors: University of Toronto.  Dept. of Chemistry.
Published: 2005
Language: eng
Number of pages: 85
Description: Scanning tunneling microscopy (STM) has been used to study the self-assembled patterning and also the subsequent reaction of halogenated organic molecules on Si(111) 7 x 7 surface at various temperatures. A method of imprinting Br, as covalently-bound Br-Si(s), at Si(111) 7 x 7 from self-assembled monolayer (SAM) of CH3Br(ad) is described; physisorbed methyl bromide molecules self-assemble to form bright circular patterns at 50 K, following charge-transfer of an electron, induced by UV irradiation, or a tunneling electron induces C-Br bond breaking in CH3Br(ad). Post irradiation STM imaging of the surface structure illustrated that the photo-induced bond cleavage leads to a highly localised pattern of chemisorbed Br (as Br-Si). This pattern is strongly correlated to the initial physisorption pattern of CH3Br and thus gives evidence for a fast reaction involving either direct photo-cleavage of the Br or photo-induced electron transfer to create highly reactive Br - intermediate. The adsorption and the dissociation of bromobenzene at Si(111) 7 x 7 surface is also investigated. The STM studies find that adsorption is site-selective. The faulted middle adatoms are most favored, followed by a preference for faulted corner adatoms, unfaulted middle adatoms, and unfaulted corner adatoms in diminishing order of importance. Surprisingly, subsequent substrate heating produces only one brominated corner adatom per corner hole. This suggests that the 'corner hole' acts as a highly reactive adsorption site for bromobenzene en route to thermal surface brominations. Related studies of physisorbed self-assembled patterns of chlorobenzene on a Si(111) 7 x 7 surface have been observed at &lt;100 K. Four patterns were noted of which the most studied consisted of triangles which were shown to change to circles by scanning at a surface voltage of -2.5 V. With the STM tip over an adsorbate, the pattern of molecule changes from triangles to circles at &lt;-2.5 V. This effect leads to effectively "switching off" the current, with a subsequent temperature-controllable rate of thermal reversion to the "switching on" condition.
Notes: Advisor: John Polanyi

Thesis (Ph.D.)--University of Toronto, 2005.

Electronic version licensed for access by U. of T. users.

Source: Dissertation Abstracts International, Volume: 66-06, Section: B, page: 3152.