MRCI investigation of Ni2O2 and Ni2O2+

文献情報

出版日 2009-02-10

DOI 10.1039/B819433E

インパクトファクター 3.676

著者

Olaf Hübner, Hans-Jörg Himmel

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要旨

The geometrical and electronic structures of rhombic Ni2O2 and Ni2O2+ are investigated by multireference configuration interaction (MRCI) calculations using natural atomic orbital basis sets. The ground term of Ni2O2 is a 1Ag term with a Ni–O distance of 178.9 pm and a Ni–O–Ni angle of 79.6°. At energies below 1 eV there are at least 21 further terms of singlet, triplet, and quintet multiplicity. The lowest-lying term of Ni2O2+ is a 2B1 term with a distorted C2v symmetric structure with two non-equivalent Ni centres and Ni–O distances of 170.6 and 182.6 pm. A 4B2 term is found at an energy higher by only 0.02 eV. At energies below 0.6 eV there are at least 6 further terms of doublet and quartet multiplicity. The lowest-lying sextet terms appear at about 0.6 eV. The calculated Ni–O–Ni angle of Ni2O2 is in very close agreement with the value derived from IR spectra. The fact of a doublet ground state of Ni2O2+ does not support the assumption that spin restrictions are the reason for the absence of any observable reaction of Ni2O2+ with H2 and CH4.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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