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The 3-butenal + H reactions: an application of the multipath canonical variational theory
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  • Maiara Passos,
  • Igor Lins,
  • Mateus Venâncio,
  • Tiago Vinicius Alves
Maiara Passos
Universidade Federal da Bahia
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Igor Lins
Universidade Federal da Bahia
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Mateus Venâncio
Universidade Federal da Bahia
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Tiago Vinicius Alves
Universidade Federal da Bahia
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Abstract

Thermal rate coefficients for the hydrogen abstraction reactions of 3-butenal by hydrogen atom were obtained, for the first time, with the application of the multipath canonical variational theory with small-curvature tunneling (MP-CVT/SCT). Torsional anharmonicity due to the hindered rotors was taken into account with the calculation of the rovibrational partition function using the extended two-dimensional torsional method (E2DT). In contrast with the (E)-2-butenal reactions, the abstraction reactions of 3-butenal proceed via five reaction channels, (R1)–(R5). In the conformational search, 48 distinguishable structures of transition states were found, including enantiomers, and separated into six conformational reaction channels (CRC). The individual reactive paths were constructed, variational and recrossing coefficients estimated, and the multipath rate constants obtained. The torsional anharmonicity is responsible for increased the rate constants for (R2). In the case of (R1), (R3), (R4), and (R5), this effect decreased the velocity of reactions. Compared to the overall (E)-2-butenal + H reaction, the thermal rate constants of this study are faster in a wide range of temperatures. The analysis of the contributions of each conformer of the transition state shows an important contribution of the high energy rotamers in the total flux of (R1)–(R5). After fitting of rate constants in a four-parameters equation, the activation energy estimation shown strong temperature dependence.

Peer review status:UNDER REVIEW

30 Sep 2020Submitted to International Journal of Quantum Chemistry
01 Oct 2020Submission Checks Completed
01 Oct 2020Assigned to Editor
01 Oct 2020Reviewer(s) Assigned
16 Oct 2020Review(s) Completed, Editorial Evaluation Pending
19 Oct 2020Editorial Decision: Revise Major
14 Dec 20201st Revision Received
15 Dec 2020Submission Checks Completed
15 Dec 2020Assigned to Editor
23 Dec 2020Reviewer(s) Assigned