Electronic Structure of the Aqueous Vanadyl Ion Probed by 9 and 94 GHz EPR and Pulsed ENDOR Spectroscopies and Density Functional Theory Calculations.
The aqueous vanadyl ion ([VO(H(2)O)(5)](2+)) has been investigated by X-band EPR, 94 GHz W-band EPR, and ESE-ENDOR. These experiments reveal information about the hyperfine (|A(xx)| = 208.5 MHz, |A(yy)| = 208.5 MHz, |A(zz)| = 547.0 MHz), and nuclear quadrupole coupling (|e(2)qQ| = 5.6 MHz) of the (51)V nucleus. The measured nuclear quadrupole coupling parameters are compared to values determined by density functional theory calculations (|e(2)qQ| = 5.2 MHz). These theoretical calculations illustrate that axial ligands and molecular distortions can alter the magnitude of the nuclear quadrupole interaction.
Department of Chemistry, University of California, Davis, California 95616, and Institute of Molecular Biophysics, Florida State University, Tallahassee, Florida 32306.
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Grant
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Cope
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Ball
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Maresch
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Gaffney
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Fink
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Britt