| Full text | |
| Author(s): |
Total Authors: 2
|
| Affiliation: | [1] Univ Sao Paulo, Inst Quim, Dept Biochem, BR-05508900 Sao Paulo, SP - Brazil
[2] CEA CNRS Univ Joseph Fourier, IBS, F-38044 Grenoble 9 - France
Total Affiliations: 2
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| Document type: | Journal article |
| Source: | Journal of Physical Chemistry A; v. 119, n. 39, p. 10084-10090, OCT 1 2015. |
| Web of Science Citations: | 2 |
| Abstract | |
The stability and reactivity of iron-sulfur clusters are fundamental properties for the biological function of these prosthetic groups. Here, we investigate the ferric-thiolate bond dissociation of model iron-sulfur tetrahedral complexes with high-level ab initio multiconfigurational electronic structure calculations. We find that the reaction mechanism is homolytic with a spin-crossing from the sextet state in the reactant to quartet state in the product. We also compare several density functionals and semiempirical configuration interaction with the high-level ab initio results to find an accurate but computationally more efficient method to describe the reaction. The functionals M06 and those based on the OPTX exchange functional show the best performance and may reasonably describe the various electron correlation effects involved in ferric-thiolate bond dissociation. (AU) | |
| FAPESP's process: | 14/21900-2 - Development and application of computer simulation and spectroscopical analysis to study metalloenzymes and flexible proteins |
| Grantee: | Guilherme Menegon Arantes |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 12/02501-4 - Computer simulation and spectroscopic analysis of proteins involved in bioenergetics and in molecular recognition |
| Grantee: | Guilherme Menegon Arantes |
| Support Opportunities: | Regular Research Grants |