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A Study to control chemical reactions using Si:2p core ionization; Site-specific fragmentation

Nagaoka, Shinichi*; Fukuzawa, Hironobu*; Pr$"u$mper, G.*; Takemoto, Mai*; Takahashi, Osamu*; Yamaguchi, Takuhiro*; Kakiuchi, Takuhiro*; Tabayashi, Kiyohiko*; Suzuki, Isao*; Harries, J.; Tamenori, Yusuke*; Ueda, Kiyoshi*

In an aim to create a sharp molecular knife, we have studied site-specific fragmentation caused by Si:2p core photoionization of bridged trihalosilyl-trimethylsilyl molecules in the vapor phase. Highly site-specific bond-dissociation has been found to occur around the core-ionized Si site in some of the molecules studied. The site-specificity in fragmentation and the 2p binding-energy difference between the two Si sites depend in similar ways on the inter-site bridge and the electronegativities of the included halogen atoms. The present experimental and computational results show that for efficient cutting, the following conditions for the two atomic sites to be separated by the knife should be satisfied. First, the sites should be located far from each other and connected by a chain of saturated bonds so that inter-site electron migration can be reduced. Secondly, the chemical environments of the atomic sites should be as different as possible.

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