Optimization of Spin-Unrestricted Density Functional Theory for Redox Properties of Rubredoxin Redox Site Analogues.

ABSTRACT: Quantum chemical calculations of metal clusters in proteins for redox studies require both computational feasibility as well as accuracies of at least ∼50 mV for redox energies but only ∼0.05 Å for bond lengths. Thus, optimization of spin-unrestricted density functional theory (DFT) methods, especially the hybrid generalized gradient approximation functionals, for energies while maintaining good geometries is essential. Here, different DFT functionals with effective core potential (ECP) and full core basis sets for [Fe(SCH(3))(4)](2-/1-) and [Fe(SCH(3))(3)](1-/0), which are analogs of the iron-sulfur protein rubredoxin, are investigated in comparison to experiment as well as other more computationally intensive electron correlation methods. In particular, redox energies are calibrated agai

SUBMITTER: Niu S 

PROVIDER: S-EPMC2701694 | biostudies-literature | 2009 May

REPOSITORIES: biostudies-literature