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Mechanism of the oxidation reaction of Cu with N 2 O via nonadiabatic electron transfer
Author(s) -
Kryachko Eugene S.,
Tishchenko Oksana,
Nguyen Minh Tho
Publication year - 2002
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.10296
Subject(s) - chemistry , arrhenius equation , electron transfer , work (physics) , reaction mechanism , atom (system on chip) , molecule , activation energy , quantum , quantum chemical , electron , computational chemistry , redox , chemical physics , atomic physics , thermodynamics , physics , catalysis , inorganic chemistry , quantum mechanics , organic chemistry , computer science , embedded system
We treat the present work as an attempt to elucidate the mechanism of the oxidation reaction of the Cu atom by nitrous oxide based on our recent work (Kryachko, E. S.; Vinckier, C.; Nguyen, M. T. J Chem Phys 2001, 114, 7911) on the electron attachment to this molecule. We suggest that the title reaction in its Arrhenius regime occurs via the nonadiabatic electron transfer from Cu to the oxygen atom at the crossing of the potential energy surfaces Cu(4 s 2 S 1/2 ) + N 2 O( X 1 Σ + ) and Cu + + N 2 O − , where the latter is linked to the complex N 2 O − originated from the higher‐energy T‐shape N 2 O molecule and discovered in the aforementioned work. The calculations performed in the present work using a variety of quantum chemical methods support the proposed model. We also show the existence of other reaction pathways of the title reaction that, we believe, contribute to its non‐Arrhenius behavior observed experimentally at T > 1190 K. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002