Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/72619
Type: Artigo de periódico
Title: The use of the generator coordinate method for designing basis set. Application to oxo-diperoxo molybdenum complexes
Author: Sensato, FR
Custodio, R
Cass, QB
Long, E
Hernandes, MZ
Longo, RL
Andres, J
Abstract: The molecular and electronic structures of MoO(O(2))(2) (1), MoO(O(2))(2)(OPY) (2) and MOO(O(2))(2)(OPY)(H(2)O) (3) complexes were investigated at the Hartree-Fock and density functional method (B3LYP) calculation levels. The generator coordinate method (GCM) has been used to design basis sets that properly represent the electronic density on the Mo and O atoms for all electron calculations, while a variant of the GCM method has been employed to design a valence basis set for the Mo atom for the pseudopotential calculations. Compound 1 adopts a distorted tetragonal pyramid structure, where the four peroxo oxygen atoms are located in the same plane, which is perpendicular to the axis defined by the Mo and oxo oxygen atoms. An analysis based upon the geometrical and electronic parameters and the vibrational frequencies renders that 1 can be described as two peroxide fragments bonded to the MoO moiety. 2 and 3 complexes are bipyramidal pentagonal structures, with the OPy ligand occupying a quasi-equatorial position in the same plane as the two peroxo triangles while the H(2)O ligand is situated trans to the oxo group in 3. A comparison between theoretical and experimental results for the geometry and vibrational frequencies of 3 complex shows good agreement. The relationship between the reactivity of 1, 2 and 3 complexes and their coordination number has been established by analyzing the values of the vibrational frequencies, frontier molecular orbitals and the values of electron affinities. (C) 2002 Elsevier Science B.V. All rights reserved.
Subject: generator coordinate method
basis sets
oxo-diperoxo molybdenum complexes
oxygen transfer reaction
electronic structure calculations
Country: Holanda
Editor: Elsevier Science Bv
Rights: fechado
Identifier DOI: 10.1016/S0166-1280(02)00202-6
Date Issue: 2002
Appears in Collections:Unicamp - Artigos e Outros Documentos

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