期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 107, 期 1, 页码 331-337出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp026596p
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The influence of ortho sulfur substitution in the modified tyrosyl radical in apo-galactose oxidase on the g tensor and the spin-density distribution has been studied by calculations on various model systems using an accurate DFT approach. Computed g tensors agree well with experimental observation, and they are intermediate between the extremely large substituent effect found in a previous DFT study and the very small changes found in MCSCF calculations. The origin of the substituent effects has been studied by fragment analyses of the spin-orbit/orbital-Zeeman g-tensor contributions, and it is discussed in relation to the spin-density distributions. The influence of hydrogen bonding on g tensors is studied by appropriate model complexes with water. Further calculations on radicals including heavier chalcogen substituents XH (X = O, S, Se, Te) predict very large g, and g, components with selenium- and tellurium-substituted systems due to large, direct substituent spin-orbit contributions. In view of an unexpectedly large gauge dependence of the g-tensor orientation in several cases, a recently developed implementation of gauge-including atomic orbitals (GIAO) has been applied.
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