Defect Formation,T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling

We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively.     

General local convergence theory for a class of iterative processes and its applications to Newton’s method

General local convergence theorems with order of convergence r≥1$r\ge 1$ are provided for iterative processes of the type _xn+1=T_xn$x_{n+1}=T{x}_n$, where T:D⊂X→X$T:D\subset X\to X$ is an iteration function in a metric space X$X$. The new local convergence theory is applied to Newton iteration for simple zeros of nonlinear operators in Banach spaces as well as to Schröder iteration for multiple zeros of polynomials and analytic functions. The theory is also applied to establish a general theorem for the uniqueness ball of nonlinear equations in Banach spaces. The new results extend and improve some results of [K. Do?ev, Über Newtonsche Iterationen, C. R. Acad. Bulg. Sci. 36 (1962) 695–701; J.F. Traub, H. Wo?niakowski, Convergence and complexity of Newton iteration for operator equations, J. Assoc. Comput. Mach. 26 (1979) 250–258; S. Smale, Newton’s method estimates from data at one point, in: R.E. Ewing, K.E. Gross, C.F. Martin (Eds.), The Merging of Disciplines: New Direction in Pure, Applied, and Computational Mathematics, Springer, New York, 1986, pp. 185–196; P. Tilli, Convergence conditions of some methods for the simultaneous computation of polynomial zeros, Calcolo 35 (1998) 3–15; X.H. Wang, Convergence of Newton’s method and uniqueness of the solution of equations in Banach space, IMA J. Numer. Anal. 20 (2000) 123–134; I.K. Argyros, J.M. Gutiérrez, A unified approach for enlarging the radius of convergence for Newton’s method and applications, Nonlinear Funct. Anal. Appl. 10 (2005) 555–563; M. Giusti, G. Lecerf, B. Salvy, J.-C. Yakoubsohn, Location and approximation of clusters of zeros of analytic functions, Found. Comput. Math. 5 (3) (2005) 257–311], and others.     

Electronic Structure of an [FeFe] Hydrogenase Model Complex in Solution Revealed by X-ray Absorption Spectroscopy Using Narrow-Band Emission Detection

High-resolution X-ray absorption spectroscopy with narrow-band X-ray emission detection, supported by density functional theory calculations (XAES-DFT), was used to study a model complex, ([Fe(2)(μ-adt)(CO)(4)(PMe(3))(2)] (1, adt = S-CH(2)-(NCH(2)Ph)-CH(2)-S), of the [FeFe] hydrogenase active site. For 1 in powder material (1(powder)), in MeCN solution (1'), and in its three protonated states (1H, 1Hy, 1HHy; H denotes protonation at the adt-N and Hy protonation of the Fe-Fe bond to form a bridging metal hydride), relations between the molecular structures and the electronic configurations were determined. EXAFS analysis and DFT geometry optimization suggested prevailing rotational isomers in MeCN, which were similar to the crystal structure or exhibited rotation of the (CO) ligands at Fe1 (1(CO), 1Hy(CO)) and in addition of the phenyl ring (1H(CO,Ph), 1HHy(CO,Ph)), leading to an elongated solvent-exposed Fe-Fe bond. Isomer formation, adt-N protonation, and hydride binding caused spectral changes of core-to-valence (pre-edge of the Fe K-shell absorption) and of valence-to-core (K?(2,5) emission) electronic transitions, and of Kα RIXS data, which were quantitatively reproduced by DFT. The study reveals (1) the composition of molecular orbitals, for example, with dominant Fe-d character, showing variations in symmetry and apparent oxidation state at the two Fe ions and a drop in MO energies by ～1 eV upon each protonation step, (2) the HOMO-LUMO energy gaps, of ～2.3 eV for 1(powder) and ～2.0 eV for 1', and (3) the splitting between iron d(z(2)) and d(x(2)-y(2)) levels of ～0.5 eV for the nonhydride and ～0.9 eV for the hydride states. Good correlations of reduction potentials to LUMO energies and oxidation potentials to HOMO energies were obtained. Two routes of facilitated bridging hydride binding thereby are suggested, involving ligand rotation at Fe1 for 1Hy(CO) or adt-N protonation for 1HHy(CO,Ph). XAES-DFT thus enables verification of the effects of ligand substitutions in solution for guided improvement of [FeFe] catalysts.     

Surface interaction and self-assembly of cyclodextrins with organic dyes

The interaction of seven novel substituted merocyanine dyes, i.e. 1-methyl-4-[2-(3-methoxy-4-hydroxyphenyl)ethenyl)]pyridinium iodide, 1-methyl-4-[2-(3,5-dimethoxy-4-hydroxyphenyl)ethenyl)]pyridinium iodide, 1-methyl-4-[2-(4-dimethylaminophenyl)ethenyl)]pyridinium iodide, their quinoide forms as well as 1-methyl-4-[2-(3-methoxy-4-oxocyclohexadienilydene)ethylidene]-1,4-dihydropyridine, 1-methyl-4-[2-(3,5-dimethoxy-4-oxocyclohexadienilydene)ethylidene]-1,4-dihydropyridine, with α-CD, γ-CD as well as functionalized γ-cyclodextrin phosphate sodium salt is studied by the methods such as UV–Vis and fluorescence spectroscopy, linear-polarized infrared (IR-LD) spectroscopy of oriented colloids in nematic host, ¹H- and ¹³C-NMR spectroscopy, HPLC ESI tandem mass spectrometry, scanning electron and tunneling microscopy, powder X-ray diffraction as well as thermal methods. A formation of the 1D and 2D “supramolecular polymers” with nanosizes is found. The dyes are adsorbed on the CDs surface and form a hexagonal microcrystalline sub-structures. Remarkable fluorescence properties depending of the type of the substituent in the dyes, in solid-state are observed.     

Chelate effect in cyclodextrin dimers: a computational (MD, MM/PBSA, and MM/GBSA) study

The complexation of an adamantyl-phosphate derivative with one beta-cyclodextrin, with two beta-cyclodextrins, and with two beta-cyclodextrins dimerized with a disulfide bridge was studied by computational methods (MD, MM/PBSA, and MM/GBSA) to analyze and rationalize the chelate effect. Although this effect is usually explained by invoking favorable entropy contribution due to the preorganization of the ligand, it has been determined experimentally that in this case it is enthalpy-driven. The computational results are in accord with this finding, although the entropy contribution due to the solvent structural organization around the complex is crucial for the final estimates of the free energy of complexation.     

Structure, stability, electronic and magnetic properties of Ni4 clusters containing impurity atoms

Using a gradient-corrected density functional method, we studied computationally how single impurity atoms affect the structure and the properties of a Ni4 cluster. H and O atoms coordinate at a Ni-Ni bond, inducing small changes to the structure of bare Ni4 which is essentially a tetrahedron. For a C impurity, we found three stable structures at a Ni4 cluster. In the most stable geometry, the carbon atom cleaves a Ni-Ni bond of Ni4, binding to all Ni atoms. Inclusion of the impurity atom leads to a partial oxidation of the metal atoms and, in the most stable structures, reduces the spin polarization of the cluster compared to bare Ni4. An H impurity interacts mainly with the Ni 4s orbitals, whereas the Ni 3d orbitals participate strongly in the bonding with O and C impurity atoms. For these impurity atoms, Ni 3d contributions dominate the character of the HOMO of the ligated cluster, in contrast to the HOMO of bare Ni4 where Ni 4s orbitals prevail. We also discuss a simple model which relates the effect of a H impurity on the magnetic state of metal clusters to the spin character (minority or majority) of the LUMO or HOMO of the bare metal cluster.     

Luminescence rings in quantum well structures

We review the results of an extensive study of the novel luminescence rings found in GaAs and InGaAs double quantum well structures. We propose that the rings define the edge of a metastable population of carriers between the laser excitation spot and the ring. This population carries wavelike excitations at supersonic speeds. Evidence for and against associating this effect with excitonic superfluidity is reviewed. The effect cannot be easily understood in terms of a Kosterlitz-Thouless transition to a superfluid state. We examine the effects of free carriers in the system and suggest a possible mechanism for the luminescence ring effect.     

N-trifluoromethylazoles

A method for synthesizing N-trifluoromethylazole derivatives has been developed via the reaction of their sodium salts with dibromodifluoromethane and substitution of bromine by fluorine. The first ionic liquids with a trifluoromethyl group on an imidazole nitrogen atom have been synthesized. L. M. Yagupolskii (Deceased.) Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 550–556, April, 2009.