title: Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree-Fock and Transition State Theory Approaches.
abstract: The present paper concludes our series of kinetics studies on the reactions involved in the complex mechanism of nitrogen trifluoride decomposition. Two other related reactions that, along with this mechanism, take part in an efficient boron nitride growth process are also investigated. We report results concerning two abstraction reactions, namely NF2 + N ⇄ 2NF and NF3 + NF ⇄ 2NF2, and two dissociations, N2F4 ⇄ 2NF2 and N2F3 ⇄ NF2 + NF. State-of-the-art electronic structure calculations at the CCSD(T)/cc-pVTZ level of theory were considered to determine geometries and frequencies of reactants, products, and transition states. Extrapolation of the energies to the complete basis set limit was used to obtain energies of all the species. We applied transition state theory to compute thermal rate constants including Wigner, Eckart, Bell, and deformed theory corrections in order to take tunneling effects into account. The obtained results are in good agreement with the experimental data available in the literature and are expected to provide a better phenomenological understanding of the NF3 decomposition role in the boron nitride growth for a wide range of temperature values.
authors.affiliation: Quantum Theory Project, Gainesville, Florida 32611-2085, United States.
authors.forename: D
authors.initials: D
authors.lastname: Claudino
authors.affiliation: Institute of Physics, University of Brasilia , Brasilia, 70.919-970, Brazil.
authors.forename: R
authors.initials: R
authors.lastname: Gargano
authors.affiliation: Grupo de Química Teórica e Estrutural de Anápolis, Ciências Exatas e Tecnológicas, Universidade Estadual de Goiás , CP 459, Anápolis, 75001-970, Brazil.
authors.forename: Valter H
authors.initials: VH
authors.lastname: Carvalho-Silva
authors.affiliation: Institute of Physics, University of Brasilia , Brasilia, 70.919-970, Brazil.
authors.forename: Geraldo M
authors.initials: GM
authors.lastname: E Silva
authors.affiliation: Quantum Theory Project, Gainesville, Florida 32611-2085, United States.|Institute of Physics, University of Brasilia , Brasilia, 70.919-970, Brazil.
authors.forename: W F
authors.initials: WF
authors.lastname: da Cunha