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Hydrogenation and hydration of carbon dioxide: a detailed characterization of the reaction mechanisms based on the reaction force and reaction electronic flux analyses

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Abstract

A computational DFT study of the reaction mechanism of hydrogenation and hydration of carbon dioxide is presented. It has been found that hydrogenation and hydration are endoenergetic reactions that are carried out in two steps, passing by a stable intermediate that is surrounded by energy barriers of 70 kcal/mol and 10 kcal/mol for hydrogenation and 50 kcal/mol and 10 kcal/mol for hydration. Using the reaction force analysis, we were able to characterize the physical nature of the activation barriers and found that activation energies are mostly due to structural rearrangements. An interesting difference in the reaction mechanisms disclosed by the reaction force and electronic flux analyses is that while in the hydrogenation reaction the mechanisms is conditioned by the H2 cleavage with a high energy barrier, in the hydration reaction the formation of a transient four member ring structure favoring an attractive local hydrogen bond interaction pushes the reaction toward the product with a considerably lower energy barrier.

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Acknowledgements

This work is dedicated to our dear friend Professor Pratim K. Chattaraj, one of the most brilliant minds that we had the chance to meet along this travel through quantum chemistry. We are deeply thankful to him for showing us the many and often mysterious ways of conceptual DFT. This work was supported by FONDECYT through the project N°1181072. DGA thanks financial support from CONICYT-PCHA/Doctorado Nacional for a Ph.D. fellowship (N° 2016-21161202).

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Authors and Affiliations

  1. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, Chile

    Daniela Guzmán-Angel, Soledad Gutiérrez-Oliva & Alejandro Toro-Labbé

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  1. Daniela Guzmán-Angel
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  2. Soledad Gutiérrez-Oliva
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  3. Alejandro Toro-Labbé
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Correspondence to Alejandro Toro-Labbé.

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This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

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Guzmán-Angel, D., Gutiérrez-Oliva, S. & Toro-Labbé, A. Hydrogenation and hydration of carbon dioxide: a detailed characterization of the reaction mechanisms based on the reaction force and reaction electronic flux analyses. J Mol Model 25, 16 (2019). https://doi.org/10.1007/s00894-018-3891-5

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  • DOI: https://doi.org/10.1007/s00894-018-3891-5

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