Reaction mechanisms of dissociative chemisorption of HI, I2, and CH3I on a magic cluster Al

✍ Scribed by Jong Chan Kim; Kyoung Hoon Kim; Jaehoon Jung; Young-Kyu Han

• Book ID: 102304028
• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 273 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20921

✦ Synopsis

Abstract

We have investigated the transition‐state structures and reaction mechanisms for the dissociative chemisorption reactions of HI, I~2~, and CH~3~I on the magic cluster Al. The HI, I~2~, and CH~3~I molecules approach Al with an end‐on orientation rather than a side‐on orientation because of the more effective orbital overlap in the end‐on orientation. The reactions of Al with HI and I~2~ would produce Al~13~HI^–^ and Al~13~I~2~^−^, respectively, because of large exothermic energy changes and relatively small activation energies. The reaction of Al with CH~3~I is unlikely to take place because of the low mobility of CH~3~ on Al and the high activation barrier for the S~N~2‐type reaction. The dissociative chemisorption reactions are preferred thermodynamically to the abstractive chemisorption reactions. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008