作者: Milena Petković , Đura Nakarada , Mihajlo Etinski
DOI: 10.1002/JCC.25359
关键词:
摘要: Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation reactants at corresponding transition states. Although discrepancy between two barriers amounts to only 2 kJ/mol, implies that comparable probability, extent intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated procedure can be applied unravel distinct transfer routes seemingly similar mechanisms. Identification components with greatest contribution variation overall (intra-atomic terms involve hydroquinone's oxygen carbon atom covalently bound it, transferring radical's oxygen), performed using Relative gradient method. Additionally, Fragments approach shed light on nature dominant interactions among selected fragments: both Coulomb exchange-correlation contributions importance when considering all other atoms, whereas term dominates interaction methyl group aromatic ring. This study represents one first applications order saddle points. © 2018 Wiley Periodicals, Inc.