Electronic structure aspects of the complete O2 transfer reaction between Ni(ii) and Mn(ii) complexes with cyclam ligands
文献情報
Jhon Zapata-Rivera, Rosa Caballol, Carmen J. Calzado
This work explores the electronic structure aspects involving the complete intermolecular O2 transfer between Ni(II) and Mn(II) complexes, both containing N-tetramethylated cyclams (TMC). The energy of the low-lying states of reactants, intermediates and products is established at the CASSCF level and also the DDCI level when possible. The orthogonal valence bond analysis of the wave functions obtained from CASSCF and DDCI calculations indicates the dominant superoxide nature of all the adducts participating in the reaction, and consequently that the whole reaction can be described as the transfer of the superoxide O2− between Ni(II) and Mn(II) complexes, without any additional change in the electronic structure of the fragments.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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