High level ab initio, DFT, and RRKM calculations for the unimolecular decomposition reaction of ethylamine

M.H. Almatarneh; M. Altarawneh; R.A. Poirier; I.A. Saraireh

doi:10.1016/j.jocs.2014.02.003

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High level ab initio, DFT, and RRKM calculations for the unimolecular decomposition reaction of ethylamine

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High level ab initio, DFT, and RRKM calculations for the unimolecular decomposition reaction of ethylamine

M.H. Almatarneh, M. Altarawneh, R.A. Poirier and I.A. Saraireh

Journal of Computational Science, Vol.5(4), pp.568-575

2014

DOI: https://doi.org/10.1016/j.jocs.2014.02.003

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Abstract

Mechanisms for the decomposition reaction of ethylamine, CH3CH2NH2, were investigated using ab initio, DFT, and RRKM calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at HF, MP2, and B3LYP levels of theory using the 6-31G(d) and 6-31+G(d) basis sets. Single point energies were also determined at G3MP2B3 and G3B3 levels of theory. Thermodynamic properties, activation energies, enthalpies and Gibbs energies of activation were calculated for each reaction pathway investigated. Intrinsic reaction coordinate (IRC) analysis was performed to characterize the transition states on the potential energy surface. The conformational change and planarity of the ethylamine moiety along with the twist angle of the amino group about the CN axis are examined. Four pathways for the decomposition reaction of ethylamine were studied. All pathways involve a 1,2-elimination reaction and 1,3-proton shift to produce ethene, ethanimine, ethenamine, and methanimine. All pathways are single-step mechanisms. Elimination of the NH3 dominates the decomposition behavior up to 1200 K whereas after this temperature, secession of the C-N gradually holds more importance. While pathways signifying departures of NH3 and NH2 exhibit pressure-dependent behavior, branching ratios for these two channels are generally not influenced by variation in pressure higher than the atmospheric pressure.

Details

Title: High level ab initio, DFT, and RRKM calculations for the unimolecular decomposition reaction of ethylamine
Authors/Creators: M.H. Almatarneh (Author/Creator) - University of Jordan
M. Altarawneh (Author/Creator) - Al-Hussein Bin Talal University
R.A. Poirier (Author/Creator) - Memorial University of Newfoundland
I.A. Saraireh (Author/Creator) - Al-Hussein Bin Talal University
Publication Details: Journal of Computational Science, Vol.5(4), pp.568-575
Publisher: Elsevier B.V
Identifiers: 991005540059407891
Murdoch Affiliation: School of Engineering and Information Technology
Language: English
Resource Type: Journal article

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Collaboration types: Domestic collaboration; International collaboration
Citation topics: 2 Chemistry; 2.15 Physical Chemistry; 2.15.3 Quantum Chemistry
Web Of Science research areas: Computer Science, Interdisciplinary Applications; Computer Science, Theory & Methods
ESI research areas: Computer Science