Premium
Energetic and topological analysis of the reaction of Mo and Mo 2 with NH 3 , C 2 H 2 , and C 2 H 4 molecules
Author(s) -
Michelini Maria Del Carmen,
Russo Nino,
Alikhani Mohammad Esmaïl,
Silvi Bernard
Publication year - 2004
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.20087
Subject(s) - excited state , center (category theory) , crystallography , chemistry , ground state , metal , ligand (biochemistry) , density functional theory , acceptor , bond length , atomic physics , electronic structure , stereochemistry , physics , computational chemistry , crystal structure , condensed matter physics , biochemistry , receptor , organic chemistry
The Density functional theory has been applied to characterize the structural features of Mo 1,2 NH 3 ,C 2 H 4 , and C 2 H 2 compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo 1,2 NH 3 ), the interaction between Mo (or Mo 2 ) and C 2 H 4 (or C 2 H 2 ) are the low‐spin (MoC 2 H 4 and C 2 H 2 ) and high‐spin (Mo 2 C 2 H 4 and C 2 H 2 ) complexes. In the ground state of Mo 1,2 C 2 H 4 and C 2 H 2 , the metal‐center always reacts with the CC center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a π‐acceptor ligand correlates with a maximum charge transfer from the metal center to the CC bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the CC basin. The interaction between Mo 1,2 and C 2 H 4 (or C 2 H 2 ) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo 1,2 and NH 3 , and the partners are bound by an electrostatic interaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1647–1655, 2004