ETS-NOCV decomposition of the reaction force for double-proton transfer in formamide-derived systems

The analysis of the electronic-structure changes along IRC paths for double-proton-transfer reactions in the formamide dimer (R1), formamide–thioformamide system (R2), and the thioformamide dimer (R3) was performed based on the extended-transition-state natural orbitals for chemical valence (ETS-NOCV) partitioning of the reaction force, considering the intra-fragments strain and the inter-fragments interaction terms, and further—the electrostatic, Pauli-repulsion and orbital interaction components, with the latter being decomposed into the NOCV components. Two methods of the system partitioning into the fragments were considered (‘reactant perspective’/bond-formation, ‘product perspective’ / bond-breaking). In agreement with previous studies, the results indicate that the major changes in the electronic structure occur in the transition state region; the bond-breaking processes are, however, initiated already in the reactant region, prior to entering the TS region. The electrostatic contributions were identified as the main factor responsible for the increase in the activation barrier in the order R1 < R2 < R3. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s00894-017-3564-9) contains supplementary material, which is available to authorized users.