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A theoretical study on the hyperfine coupling constant of the radical cations of aliphatic ethers

Theoretica Chimica Acta, ISSN: 0040-5744, Vol: 81, Issue: 4-5, Page: 291-301
1992
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The hyperfine coupling constants of the radical cations of dimethylether, oxetane (oxacyclobutane), and tetrahydrofuran (oxacyclopentane) are studied by ab-initio molecular orbital theories. The extraordinarily large hyperfine coupling constants of the β protons of the ethers that have been found experimentally are analyzed to conclude that an important mechanism of the hole delocalization is the spin polarization in the H-C-O-C-H σ bond. It is also found that for the ethereal systems conventional molecular orbital calculations give glaringly small spin densities but the SAC-CI calculation gives remarkably improved values. © 1992 Springer-Verlag.

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