Biomedical Engineering Reference
In-Depth Information
The rebound mechanism, though in a modified version, has been recently supported
by theoretical calculations of KIF using the density functional theory (Yoshizawa et al.,
2000). The calculations demonstrate that the transition state for the H-atom abstraction
from ethane involves a linear [FeO....H...C] array; a resultant radical species with a spin
density of nearly one is bound to an iron-hydroxy complex, followed by recombination
and release of product ethanol. According to the calculation of the reaction energy
profile, the carbon radical species is not a stable reaction intermediate with a finite
lifetime. The calculated KIF at 300 K is in the range of 7-13 in accord with experimental
data and is predicted to be significantly dependent on temperature and substituents. It
was also shown from femtosecond dynamic calculations in the
system that the
direct abstraction mechanism can occur in 100-200 fs.
The role of medium polarization in the vicinity of the model compound I-like the
ferryl species, [Por (HS)-Fe (IV) O], and the effect of hydrogen bonding of the fifth
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