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Reactivity of molecular oxygen on the surface of ionic crystals
Author(s) -
Mikheikin I. D.,
Vorontsova I. K.,
Abronin I. A.
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.10196
Subject(s) - chemistry , ionic bonding , singlet state , ab initio , basis set , multiplicity (mathematics) , electronic correlation , computational chemistry , chemical physics , molecule , ion , density functional theory , atomic physics , excited state , physics , mathematical analysis , mathematics , organic chemistry
A possibility of multiplicity change for ground‐state molecular oxygen adsorbed on the surface of regular and doped broad‐gap ionic crystals was considered in the framework of cluster approximation by using SCF MO LCAO quantum chemical methods [semiempirical INDO approximation and ab initio calculation with the 6‐311G** basis set taking into account the correlation effects on the level of second‐order Meller–Plesset perturbation theory (MP2)]. The formation energetics of cyclic products of addition reactions of dioxygen in different multiplet states to furan and cis ‐butadiene in the gas phase and on the surface of ionic crystals was considered. (These reactions are typical for the O 2 singlet state in the gas phase.) It is shown that the presence of sites with high effective charge on the crystal surface can result in a situation not requiring, as in the gas phase, multiplicity change in the transition of a system from an initial to the final state, which can significantly affect the kinetic parameters of the reactions. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002