Physisorption and reaction at silicon surfaces of a series of brominated organic molecules: bromoethane, 1,2-dibromoethane, 1-bromopropane, 1-bromobutane and 1-bromopentane were examined by Scanning Tunneling Microscopy (STM). On Si(111)-7×7, a widely-spaced “one-per-corner-hole” pattern was observed, formed by the physisorption and reaction of several alkyl bromides. This “one-per-corner-hole” pattern suggested long-range repulsion between the adsorbates. Density Functional Theory (DFT) calculations, performed by others in parallel with these experiments, showed that this long-range repulsion was due to lateral charge transfer in the Si(111)-7×7 surface consequent on the physisorption of an alkyl bromide or chemisorption of a Br atom. The reaction rate of bromine ‘abstraction’ (transfer of a Br-atom from the adsorbate to the silicon) was examined for two physisorbed states of 1 bromopentane on Si(111)-7×7, one vertical and one horizontal, each distinguishable by STM. The energy barrier was found to be significantly lower for abstraction of Br-atom from the vertical than for the horizontal 1 bromopentane, both for thermal and electron-induced reaction. This finding accords with previous DFT calculations for methyl bromide, for which theory exhibited a clear preference for a vertical transition state in the bromination of Si(111)-7×7. The effect of alkyl chain-length on the rate of thermally-induced dissociative attachment reactions was investigated for a series of primary bromo-alkanes (bromoethane, 1-bromopropane and 1-bromobutane) on a different face of silicon; Si(100)-c(4×2). These three bromo-alkanes all physisorbed exclusively ‘inter-row’, bridging the gap between Si dimer-rows of Si(100)-c(4×2). Thermal reaction was highly ‘localized’, i.e. the chemisorbed Br-atom was formed directly below the parent bromo-alkane. The thermal barrier heights were found experimentally to increase systematically with chain length. This trend was interpreted, on the basis of DFT calculations performed by the author, as being due to the extra energy required to lift the alkyl group in going from the initial physisorbed state to the more-nearly vertical transition state.

Physisorption and reaction at silicon surfaces of a series of brominated organic molecules: bromoethane, 1,2-dibromoethane, 1-bromopropane, 1-bromobutane and 1-bromopentane were examined by Scanning Tunneling Microscopy (STM). On Si(111)-7×7, a widely-spaced “one-per-corner-hole” pattern was observed, formed by the physisorption and reaction of several alkyl bromides. This “one-per-corner-hole” pattern suggested long-range repulsion between the adsorbates. Density Functional Theory (DFT) calculations, performed by others in parallel with these experiments, showed that this long-range repulsion was due to lateral charge transfer in the Si(111)-7×7 surface consequent on the physisorption of an alkyl bromide or chemisorption of a Br atom. The reaction rate of bromine ‘abstraction’ (transfer of a Br-atom from the adsorbate to the silicon) was examined for two physisorbed states of 1 bromopentane on Si(111)-7×7, one vertical and one horizontal, each distinguishable by STM. The energy barrier was found to be significantly lower for abstraction of Br-atom from the vertical than for the horizontal 1 bromopentane, both for thermal and electron-induced reaction. This finding accords with previous DFT calculations for methyl bromide, for which theory exhibited a clear preference for a vertical transition state in the bromination of Si(111)-7×7. The effect of alkyl chain-length on the rate of thermally-induced dissociative attachment reactions was investigated for a series of primary bromo-alkanes (bromoethane, 1-bromopropane and 1-bromobutane) on a different face of silicon; Si(100)-c(4×2). These three bromo-alkanes all physisorbed exclusively ‘inter-row’, bridging the gap between Si dimer-rows of Si(100)-c(4×2). Thermal reaction was highly ‘localized’, i.e. the chemisorbed Br-atom was formed directly below the parent bromo-alkane. The thermal barrier heights were found experimentally to increase systematically with chain length. This trend was interpreted, on the basis of DFT calculations performed by the author, as being due to the extra energy required to lift the alkyl group in going from the initial physisorbed state to the more-nearly vertical transition state.