Density functional theory redox potential

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. 

AMI semi-empirical and B3LYP/6-31G(d)/AMl density functional theory (DFT) computational studies were performed with the purpose of determining which variously substituted 1,3,4-oxadiazoles would participate in Diels-Alder reactions as dienes and under what conditions. Also, bond orders for 1,3,4-oxadiazole and its 2,5-diacetyl, 2,5-dimethyl, 2,5-di(trifluoromethyl), and 2,5-di(methoxycarbonyl) derivatives were calculated <1998JMT153>. The AMI method was also used to evaluate the electronic properties of 2,5-bis[5-(4,5,6,7-tetrahydrobenzo[A thien-2-yl)thien-2-yl]-l,3,4-oxadiazole 8. The experimentally determined redox potentials were compared with the calculated highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) energies. The performance of the available parameters from AMI was verified with other semi-empirical calculations (PM3, MNDO) as well as by ab initio methods <1998CEJ2211>. 

The insight provided by studying 8-oxo-guanine, and the ability to substitute DNA with a nucleobase that could be selectively oxidized by a low-potential complex, prompted us to search for other minimally substituted, redox-active nucleobases [92]. We therefore developed a library of nucleobases that were investigated using density functional theory (DFT) [93, 94] calculations self-consistently coupled to the conductorlike solvation model (COSMO) [95, 96]. The case of oxidation of nucleobases, particularly guanine. 

Recently, a number of efforts have sought to use new theoretical methods, particularly density functional theory (DFT), to predict redox potentials in solution. While considerable progress has been made toward predicting gas-phase ionization potentials, the role of solvation and coupled chemical reactions are of high importance to solution chemists. Baik and Friesner have recently discussed the ability of new methods for incorporating solvation effects into DFT calculations. Using these solvation methods, DFT calculations can be used to determine solution redox potentials to within 150mV.i ... 

Cheng, J., Sulpizi, M., Sprik, M. Redox potentials and pKa for benzoquinone from density functional theory based molecular dynamics. J. Chem. Phys. 2009,131,154504. 

Cu-ATSM is selectively trapped in highly reducing hypoxic tissue but not in less reducing normal tissue. On the other hand, Cu-PTSM is reduced in both normoxic and hypoxic tissue. Hypoxia selectivity has been correlated to the reduction potential of the molecule that is in turn related to the alkyl group substitution. The reduction potential of Cu-ATSM is about 100 mV lower than that of Cu-PTSM. Density Functional Theory and chemical reactivity studies attempt to correlate the structure and redox properties of bis(thiosemicarbazones) with the characteristics of the LUMOs (metal or ligand based) and chemical reactivity. The fast and selective uptake of jjj hypoxic... 

Table 1. Comparison of NC reactivity values from HPLC assays, and redox potential (RP) values obtained from density functional theory calculations.

The redox potential of the aryl radical is an important parameter in the electrochani-cal grafting. At more negative potentials, the radical wiU be reduced to an anion (Figure 3.5 [R14]). Several valnes have been estimated for this radical, either by experimentally or by density functional theory (DFT) calculations, and are listed in Table 3.2. 

Steele H, GuiUaumont D, Moisy P. Density Functional Theory Calculations of the Redox Potentials of Actinide(VI)/Actinide( V) Couple in Water. J Phys Chem A. 2013 117 4500-4505. 

The probability of these processes is a function of the density of states in the conductivity and valence band respectively at the potentials corresponding to the redox potential of the adsorbed species. In the electronic theory of catalysis in the later fifties only general thermodynamic rules were considered, but the conditions of the electron transfer were never applied to analyze the behaviour of different oxide catalysts in the oxidation of hydrocarbons. No quantitative data are available to make such analysis, although recently an attempt was made to interpret the changes of the rate of ethanol oxidation in terms of the density of states (36). The relative positions of the energy bands in the solid and the redox potential of the reacting molecule may be adjusted by a) formation of one or more oxide/oxide interfaces with such values of the contact potentials that the conductivity band will... 

J. Li, C. L. Fisher, J. L. Chen, D. Bashford, and L. Noodleman. Calculation of redox potentials and pKa values of hydrated transition metal cations by a combined density functional and continuum dielectric theory. Inorg. Chem., 35(16] 4694-4702,1996. 

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