title: Reaction mechanisms of dissociative chemisorption of HI, I2, and CH3I on a magic cluster Al13-.
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.
authors.affiliation: Computational Chemistry Laboratory, Corporate R&D, LG Chemical Ltd., Research Park, 104-1 Moonji-dong, Yusung-gu, Daejeon 305-380, Republic of Korea.
authors.forename: Jong Chan
authors.initials: JC
authors.lastname: Kim
authors.forename: Kyoung Hoon
authors.initials: KH
authors.lastname: Kim
authors.forename: Jaehoon
authors.initials: J
authors.lastname: Jung
authors.forename: Young-Kyu
authors.initials: YK
authors.lastname: Han