Self-consistent field , redox

J Li, MR Nelson, CY Peng, D Bashford, L Noodleman. Incorporating protein environments in density functional theory A self-consistent reaction field calculation of redox potentials of [2Ee2S] clusters in feiTedoxm and phthalate dioxygenase reductase. J Phys Chem A 102 6311-6324, 1998. 

Ziegler and co-workers reported DFT with self-consistent reaction field calculations on multielectron redox reactions for dinuclear iron complexes [Fe2(CO)6(/x2-PR2)2]° (R=CH3, CF3). They did calculations on all three oxidation states for the complexes to construct energy profiles for the addition of two electrons to the = 0 oxidation state. It was found that inclusion of solvent and/or ion pairing effects was necessary to predict the experimentally observed disproportionation reaction of the singly reduced complex. It was also found that CO ligands are important in the deloealization of added electron density due to reduction. Interestingly, the authors also conclude that ion pairing with the anionic complexes should be modeled to produce the most realistic calculations. 

The calculation of redox potentials for bacteriochlorophyll and bacteriopheophytin molecules described in Ref. 43 at the HF 6-3 Ig level using the PS-GVB solvation module represents the largest tJt initio self-consistent reaction field calculation to date. The calculations performed an a workstation involved up to 889 basis functions and were successful in predicting the correct relative redox energies. 

---