LAUSR

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.