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Title: The lowest doublet and quartet potential energy surfaces involved in the N(4S) + O2 reaction. II. Ab initio study of the C2v-symmetry insertion mechanism
Author: González Pérez, Miguel
Oliva, Carolina
Sayós Ortega, Ramón
Keywords: Compostos de nitrogen
Reaccions químiques
Teoria del funcional de densitat
Teoria quàntica
Nitrogen compounds
Chemical reactions
Density functionals
Quantum theory
Issue Date: 24-Feb-2002
Publisher: American Institute of Physics
Abstract: In the present work we have carried out ab initio complete active space self-consistent field (CASSCF) and second-order perturbation theory on CASSCF wave function (CASPT2) calculations and also some density functional theory calculations with the aug-cc-pVTZ Dunning's basis set on the lowest A1, B1, A2 and B2 doublet and quartet potential energy surfaces (PESs) that could be involved in the title reaction. Thus, several minima, transition states and surface crossings have been found for the C2v-insertion reaction mechanism. The results agree very well with available experimental data (i.e., for NO2 (2A1), MIN2 (2B2), NO2 (2∏u)) and with other previous ab initio calculations. Six A' / A' and four A' / A' type surface crossings were located and classified for these PESs, whose only one (i.e., 2B2 / 2A1) has been previously reported in theoretical and experimental studies. High-energy barriers were found for the direct C2v-insertion mechanism (3.11 and 2.54 eV for the lowest doublet and quartet PESs at the CASPT2/aug-cc-pVTZ level, respectively), clearly showing that this competitive mechanism is much less favorable than the direct Cs-abstraction or the indirect Cs-insertion reaction mechanisms reported in paper I.
Note: Reproducció del document publicat a:
It is part of: Journal of Chemical Physics, 2002, vol. 117, num. 2, p. 680-692
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ISSN: 0021-9606
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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