Solvation effects on the intracluster elimination channels in M+(L)n, where M+= Mg+ and Ca+, L = CH3OH, and NH3, and n = 2-6.
The methanol and ammonia solvated Ca (+) or Mg (+) clusters are known to go through intracluster H or CH 3 eliminations which are typically switched on just below n = 6. By first principles calculations at the B3LYP/6-311+G** level, we have identified the transition structures, activation barriers, and energy changes in these reactions for clusters with 2-6 solvent molecules. The activation barrier is crucial to explain the previously reported experimental results. While increasing number of solvent molecules stabilizes a transition structure, the increasing presence of solvent molecules in the first solvation shell makes it difficult for the metal ion to assist the bond breaking through its interaction with the departing H atom or CH 3 group. The balance of these two factors determines whether a particular elimination channel could be switched on.
Chan
Ka Wai
KW
Department of Chemistry and Centre for Scientific Modeling and Computation Chinese, University of Hong Kong, Shatin, Hong Kong, China.
Wu
Yang
Y
Liu
Zhi-Feng
ZF