Rustam Z Khaliullin | PubMed Health

PubMed2006

An efficient self-consistent field method for large systems of weakly interacting components.

An efficient method for removing the self-consistent field (SCF) diagonalization bottleneck is proposed for systems of weakly interacting components. The method is based on the equations of the locally projected SCF for molecular interactions (SCF MI) which utilize absolutely localized nonorthogonal molecular orbitals expanded in local subsets of the atomic basis set. A generalization of direct inversion in the iterative subspace for nonorthogonal molecular orbitals is formulated to increase the rate of convergence of the SCF MI equations. Single Roothaan step perturbative corrections are developed to improve the accuracy of the SCF MI energies. The resulting energies closely reproduce the conventional SCF energy. Extensive test calculations are performed on water clusters up to several hundred molecules. Compared to conventional SCF, speedups of the order of (N/O)2 have been achieved for the diagonalization step, where N is the size of the atomic orbital basis, and O is the number of occupied molecular orbitals.

Journal Article↗

PubMed2005

A density functional theory study of the mechanism of free radical generation in the system vanadate/PCA/H2O2.

Experimental studies by Shul'pin and co-workers have shown that vanadate anions in combination with pyrazine-2-carboxylic acid (PCA identical with pcaH) produce an exceptionally active complex that promotes the oxidation of alkanes and other organic molecules. Reaction of this complex with H2O2 releases HOO* free radicals and generates V(IV) species, which are capable of generating HO* radicals by reaction with additional H2O2. The oxidation of alkanes is initiated by reaction with the HO* radicals. The mechanism of hydrocarbon oxidation with vanadate/PCA/H2O2 catalyst has been studied using density functional theory. The proposed model reproduces the major experimental observations. It is found that a vanadium complex with one pca (PCA identical with pcaH) and one H2O2 ligand is the precursor to the species responsible for HOO* generation. It is also found that species containing two pca ligands and an H2O2 molecule do not exist in the solution, in contradiction to previous interpretations of experimental observations. Calculated dependences of the oxidation rate on initial concentrations of PCA and H2O2 have characteristic maxima, the shapes of which are determined by the equilibrium concentration of the active species. Conversion of the precursors requires hydrogen transfer from H2O2 to a vanadyl group. Our calculations show that direct transfer has a higher barrier than pca-assisted indirect transfer. Indirect transfer occurs by migration of hydrogen from coordinated H2O2 to the oxygen of a pca ligand connected to the vanadium atom. The proposed mechanism demonstrates the important role of the cocatalyst in the reaction and explains why H2O2 complexes without pca are less active. Our work shows that the generation of HOO* radicals cannot occur via cleavage of a V-OOH bond in the complex formed directly from the precursors, as proposed before. The activation barrier for this process is too high. Instead, HOO* radicals are formed via a sequence of additional steps involving lower activation barriers. The new mechanism for free radical generation underestimates the observed rate of hexane oxidation by less than an order of magnitude; however, the calculated activation energy (67-81 kJ/mol) agrees well with that determined experimentally (63-80 kJ/mol).

Adsorption↗