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Reaction mechanisms of dissociative chemisorption of HI, I 2 , and CH 3 I on a magic cluster Al 13 −
Author(s) -
Kim Jong Chan,
Kim Kyoung Hoon,
Jung Jaehoon,
Han YoungKyu
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20921
Subject(s) - chemisorption , chemistry , exothermic reaction , activation barrier , cluster (spacecraft) , activation energy , orientation (vector space) , crystallography , computational chemistry , density functional theory , adsorption , organic chemistry , computer science , programming language , geometry , mathematics
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 13 − . The HI, I 2 , and CH 3 I molecules approach Al 13 −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 13 −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 13 −with CH 3 I is unlikely to take place because of the low mobility of CH 3 on Al 13 −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