Ferric-Thiolate Bond Dissociation Studied with Electronic Structure Calculations

Autor(es)

Arantes, Guilherme Menegon ^[1] ; Field, Martin J. ^[2]

Afiliação do(s) autor(es)

^[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

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry A; v. 119, n. 39, p. 10084-10090, OCT 1 2015.
• Citações Web of Science: 2

Resumo

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)

• Processo FAPESP: 14/21900-2 - Desenvolvimento e aplicação de simulação computacional e análise espectroscópica para o estudo de metaloenzimas e de proteínas flexíveis
• Beneficiário: Guilherme Menegon Arantes
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 12/02501-4 - Simulação computacional e análise espectroscópica de proteínas envolvidas em bioenergética e em reconhecimento molecular
• Beneficiário: Guilherme Menegon Arantes
• Modalidade de apoio: Auxílio à Pesquisa - Regular