How useful are vibrational frequencies of isotopomeric O2 fragments for assessing local symmetry? Some simple systems and the vexing case of a galactose oxidase model |
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Authors: | Christopher R Kinsinger Benjamin F Gherman Laura Gagliardi Christopher J Cramer |
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Institution: | (1) Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA;(2) Department of Physical Chemistry, “F. Accascina” University of Palermo, Viale delle Scienze, Parco d‘Orleans II Pad 17, 90128 Palermo, Italy |
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Abstract: | The tendency for mixed-isotope O2 fragments to exhibit different stretching frequencies in asymmetric environments is examined with various levels of electronic
structure theory for simple peroxides and peroxyl radicals, as well as for a variety of monocopper–O2 complexes. The study of the monocopper species is motivated by their relevance to the active site of galactose oxidase. Extensive
theoretical work with an experimental model characterized by Jazdzewski et al. (J. Biol. Inorg. Chem. 8:381–393, 2003) suggests that the failure to observe a splitting between 16O18O and 18O16O isotopomers cannot be taken as evidence against end-on O2 coordination. Conformational analysis on an energetic basis, however, is complicated by biradical character inherent in all
of the copper–O2 singlet structures.
Electronic Supplementary Material Supplementary material is available for this article at . |
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Keywords: | Copper superoxide Copper peroxide Raman spectroscopy Galactose oxidase Density functional theory |
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