ETS-NOCV Decomposition of the Reaction Force: The HCN/CNH Isomerization Reaction Assisted by Water.

Autor: Díaz S; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, 30-060, Poland.; Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile., Brela MZ; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, 30-060, Poland., Gutiérrez-Oliva S; Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile., Toro-Labbé A; Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile.; Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs Universität Freiburg, Albertstr. 19, Freiburg, 79104, Germany., Michalak A; Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, 30-060, Poland.
Jazyk: angličtina
Zdroj: Journal of computational chemistry [J Comput Chem] 2017 Sep 15; Vol. 38 (24), pp. 2076-2087. Date of Electronic Publication: 2017 Jul 18.
DOI: 10.1002/jcc.24856
Abstrakt: The partitioning of the reaction force based on the extended-transition-state natural orbital for chemical valence (ETS-NOCV) scheme has been proposed. This approach, together with the analysis of reaction electronic flux (REF), has been applied in a description of the changes in the electronic structure along the IRC pathway for the HCN/CNH isomerization reaction assisted by water. Two complementary ways of partitioning the system into molecular fragments have been considered ("reactant perspective" and "product perspective"). The results show that the ETS-NOCV picture is fully consistent with REF and bond-order changes. In addition, proposed ETS-NOCV decomposition of the reaction force allows for the quantitative assessment of the influence of the observed bond-breaking and bond-formation processes, providing detailed information about the reaction-driving and reaction-retarding force components within the assumed partitioning scheme. © 2017 Wiley Periodicals, Inc.
(© 2017 Wiley Periodicals, Inc.)
Databáze: MEDLINE
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