Publication details
Comparative density-functional study of the electron paramagnetic resonance parameters of amavadin
| Authors | |
|---|---|
| Year of publication | 2005 |
| Type | Article in Periodical |
| Magazine / Source | Journal of Physical Chemistry B |
| MU Faculty or unit | |
| Citation | |
| Field | Physical chemistry and theoretical chemistry |
| Keywords | TRANSITION-METAL-COMPLEXES; SPIN-ORBIT OPERATORS; MOLECULAR HYPERFINE INTERACTIONS; EXCHANGE-CORRELATION POTENTIALS; KOHN-SHAM THEORY; G-TENSORS; AMANITA-MUSCARIA; SHIELDING CONSTANTS; VANADIUM COMPOUND; COUPLING TENSORS |
| Description | Electronic g tensors and hyperfine coupling tensors have been calculated for amavadin, an unusual eight-coordinate vanadium(IV) complex isolated from Amanita muscaria mushrooms. Different density-functional methods have been compared, ranging from local via gradient-corrected to hybrid functionals with a variable Hartree-Fock exchange admixture. For both electron paramagnetic resonance (EPR) properties, hybrid functionals with an appreciable exact-exchange admixture provide the closest agreement with experimental data. Second-order spin-orbit corrections provide non-negligible contributions to the V-51 hyperfine tensor. The orientation of g and A tensors relative to each other also depends on spin-orbit corrections to the A tensor. A rationalization for the close resemblance of the EPR parameters of amavadin to those of the structurally rather different vanadyl complexes is provided, based on the nature of the relevant frontier orbitals. |
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