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Studies on CO bonding to Rh clusters using an intermediate neglect of differential overlap theory to model heterogeneous catalytic reactions
Author(s) -
Estiu Guillermina L.,
Zerner Michael C.
Publication year - 1992
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560440853
Subject(s) - rhodium , chemistry , cluster (spacecraft) , redistribution (election) , metal , chemical physics , catalysis , cluster size , computational chemistry , electronic structure , biochemistry , organic chemistry , politics , computer science , political science , law , programming language
The interaction of CO with rhodium clusters of different sizes is studied by means of Intermediate Neglect of Differential Orbital ( INDO ) calculations. Interactions of both σ and π type are well‐known to contribute to the metal CO bond formation. The relative importance of the repulsive Rh5σCO interaction with the metal and the back‐bonding to the π* CO empty orbital in the stabilization of the bond is analyzed as a function of the cluster size and the coordination geometry. It is found that the shift of charge in the larger metal clusters brings about a reduction of the Rh5σ CO repulsion, and this redistribution is important to change the optimal CO bonding geometry from bridge to on top . © 1992 John Wiley & Sons, Inc.