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
- 27 September 2005
- journal article
- Published by Springer Science and Business Media LLC in JBIC Journal of Biological Inorganic Chemistry
- Vol. 10 (7), 778-789
- https://doi.org/10.1007/s00775-005-0026-0
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.Keywords
This publication has 66 references indexed in Scilit:
- Reversible Binding of Dioxygen by the Copper(I) Complex with Tris(2-dimethylaminoethyl)amine (Me6tren) LigandInorganic Chemistry, 2003
- Implicit and Explicit Coverage of Multi-reference Effects by Density Functional TheoryInternational Journal of Molecular Sciences, 2002
- Can Unrestricted Density-Functional Theory Describe Open Shell Singlet Biradicals?International Journal of Molecular Sciences, 2002
- On the diagnostic value of (Ŝ2) in Kohn-Sham density functional theoryMolecular Physics, 2001
- Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW modelsThe Journal of Chemical Physics, 1998
- Density functional study of a highly correlated molecule, oxygen fluoride (FOOF)The Journal of Physical Chemistry, 1991
- DOPAMINE BETA-HYDROXYLASE OF ADRENAL CHROMAFFIN GRANULES: STRUCTURE AND FUNCTIONAnnual Review of Biochemistry, 1988
- A full coupled-cluster singles and doubles model: The inclusion of disconnected triplesThe Journal of Chemical Physics, 1982
- Resonance Raman spectroscopy with unsymmetrically isotopic ligands. Differentiation of possible structures of hemerythrin complexesJournal of the American Chemical Society, 1976
- Matrix infrared study of the chlorine superoxide radicalJournal of the American Chemical Society, 1967