Energy-decomposition analysis of ion-neutral complexes along reaction coordinates of unimolecular proton-transfer reaction in gas phase: Comparison between 2-butanol radical ion and protonated 2-ethoxypropane ion

摘要

Graphical abstract Display Omitted Highlights ? Physical origins of ion-neutral-complex (INC) formation process were represented. ? Dispersion energy is a major attractive source in the 2-butanol radical INC. ? Electrostatic energy is a major attractive source in protonated 2-ethoxypropane INC. ? Physical origins in INC were affected by local charges and distances. Abstract An energy-decomposition analysis clarified the physical origins that change in gas-phase unimolecular proton-transfer reactions via ion-neutral complexes of the 2-butanol radical ion and protonated 2-ethoxypropane ion. In the bond cleavage and new bond-formation parts of the reaction coordinates, exchange and polarization energies provide a major source of the attraction. In the ion-neutral complex-formation part of the reaction coordinate, different major attractive sources, dispersion, and electrostatic energies were observed. The physical origins of weak interaction in the ion-neutral complexes were affected by the local charges and distances between the ion moieties and the neutral moieties. ]]>