Density functional theory calculations of the lowest energy quintet and triplet states of model hemes: role of functional, basis set, and zero-point energy corrections

We investigated the effect of several computational variables, including the choice of the basis set, application of symmetry constraints, and zero-point energy (ZPE) corrections, on the structural parameters and predicted ground electronic state of model 5-coordinate hemes (iron(II) porphines axially coordinated by a single imidazole or 2-methylimidazole). We studied the performance of B3LYP and B3PW91 with eight Pople-style basis sets (up to 6-311+G*) and B97-1, OLYP, and TPSS functionals with 6-31G and 6-31G* basis sets. Only hybrid functionals B3LYP, B3PW91, and B97-1 reproduced the quintet ground state of the model hemes. With a given functional, the choice of the basis set caused up to 2.7 kcal/mol variation of the quintet-triplet electronic energy gap (DeltaEel), in several cases, resulting in the inversion of the sign of DeltaEel. Single-point energy calculations with triple-zeta basis sets of the Pople (up to 6-311G++(2d,2p)), Ahlrichs (TZVP and TZVPP), and Dunning (cc-pVTZ) families showed the same trend. The zero-point energy of the quintet state was approximately 1 kcal/mol lower than that of the triplet, and accounting for ZPE corrections was crucial for establishing the ground state if the electronic energy of the triplet state was approximately 1 kcal/mol less than that of the quintet. Within a given model chemistry, effects of symmetry constraints and of a "tense" structure of the iron porphine fragment coordinated to 2-methylimidazole on DeltaEel were limited to 0.3 kcal/mol. For both model hemes the best agreement with crystallographic structural data was achieved with small 6-31G and 6-31G* basis sets. Deviation of the computed frequency of the Fe-Im stretching mode from the experimental value with the basis set decreased in the order: nonaugmented basis sets, basis sets with polarization functions, and basis sets with polarization and diffuse functions. Contraction of Pople-style basis sets (double-zeta or triple-zeta) affected the results insignificantly for iron(II) porphyrin coordinated with imidazole. Poor performance of a "locally dense" basis set with a large number of basis functions on the Fe center was observed in calculation of quintet-triplet gaps. Our results lead to a series of suggestions for density functional theory calculations of quintet-triplet energy gaps in ferrohemes with a single axial imidazole; these suggestions are potentially applicable for other transition-metal complexes.     

Simple dimer containing dissociatively stable mono-imidazole ligated ferrohemes

In weakly coordinating solvents FeII meso-(N-methylimidazol-2-yl)porphine Fe exists as a stable dimer (Kd=50+/-30 nM) that binds ligands without undergoing dissociation and is presently the simplest complex in which the mono-imidazole ligation of a ferroheme is enforced without excess imidazole in solution.     

Macrocyclic Disulfides for Studies of Sensitized Photolysis of the S?S Bond

Sensitized photolysis : We describe a series of macrocyclic disulfides containing stiff stilbene (see scheme) as the intramolecular photosensitizer designed for fundamental mechanistic studies of sensitized photolysis of the S? S bond. Preliminary studies revealed weak temperature dependence of the quantum yields, which decreased exponentially with Boltzmann‐weighted average separation between the S? S bond and stiff stilbene.

     

Solubility and Binding of Water in Toluene Solutions of Asphaltenes

The solubility of water in toluene solutions of asphaltenes is determined, and the state of water molecules in these solutions is studied spectroscopically. A number of water molecules bound to an asphaltene molecule is estimated from the experimental data. Aggregation in the system asphaltene-water-toluene is simulated using the pseudophase approximation, and the Flory-Huggins parameters are estimated for the pair asphaltene-water. The potentiality of this model for simulation of mixed aggregates in the asphaltene-water-toluene systems is discussed.