A Study To Control Chemical Reactions Using Si:2p Core Ionization: Site-Specific Fragmentation

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• 作者：Shin-ichi Nagaoka ; Hironobu Fukuzawa ; Georg Pru虉mper ; Mai Takemoto ; Osamu Takahashi ; Katsuhiro Yamaguchi ; Takuhiro Kakiuchi ; Kiyohiko Tabayashi ; Isao H. Suzuki ; James R. Harries ; Yusuke Tamenori ; Kiyoshi Ueda
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：August 18, 2011
• 年：2011
• 卷：115
• 期：32
• 页码：8822-8831
• 全文大小：1029K
• 年卷期：v.115,no.32(August 18, 2011)
• ISSN：1520-5215

文摘

In an aim to create a 鈥渟harp鈥?molecular knife, we have studied site-specific fragmentation caused by Si:2p core photoionization of bridged trihalosilyltrimethylsilyl 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 intersite bridge and the electronegativities of the included halogen atoms. The present experimental and computational results show that for efficient 鈥渃utting鈥?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 intersite electron migration can be reduced. Second, the chemical environments of the atomic sites should be as different as possible.