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Theoretical studies on hydrogen activation by iridium dimers
Author(s) -
Castillo S.,
Bertin V.,
SolanoReyes E.,
LunaGarcía H.,
Cruz A.,
Poulain E.
Publication year - 1998
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/(sici)1097-461x(1998)70:4/5<1029::aid-qua50>3.0.co;2-x
Subject(s) - iridium , chemistry , dimer , ab initio , computational chemistry , catalysis , organic chemistry , biochemistry
The basic and fundamental mechanisms governing the catalytic reaction of small iridium clusters with H 2 are presented here with the purpose to determine its behavior in hydrogenation reactions. The iridium dimer/s lowest states in interaction with H 2 potential energy surface were obtained using ab initio multiconfigurational self‐consistent‐field calculations (MC–SCF), with relativististic pseudopotentials. The electronic correlation contribution was included by configurations interaction (CI) calculations, which considered a variational part plus a second‐order perturbative part. The Ir 2 +H 2 reactions were developed in the C 2 v symmetry. The Ir 2 's five lowest electronic states were determined, 5 Π g , 3 Π g , 1 Σ g + , 3 Σ u + , and 5 Σ g , and studied when reacted with H 2 . It was found that the iridium dimer, in these five states, might capture and break the HH bond, spontaneously in certain cases and after surmounting activation barriers in other cases. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 1029–1035, 1998