Quantum and non-Markovian effects in the electron transfer reaction dynamics in the Marcus inverted region

Electron transfer reactions in large molecules may often be coupled to both the polar solvent modes and the intramolecular vibrational modes of the molecule. This can give rise to a complex dynamics which may in some systems, like betaine, be controlled more by vibrational rather than by solvent effects. Additionally, a significant contribution from an ultrafast relaxation component in the solvation dynamics may enhance the complexity. To explain the wide range of behavior that has been observed experimentally, Barbara et al. recently proposed that a model of an electron transfer reaction should minimally consist of a low-frequency classical solvent mode (X), a low-frequency vibrational mode (Q), and a high-frequency quantum mode (q) (J. Phys. Chem. 1991, 96, 3728). In the present work, a theoretical study of this model is described. This study generalizes earlier work by including the biphasic solvent response and the dynamics of the low-frequency vibrational mode in the presence of a delocalized, extended reaction zone. A novel Green's function technique has been developed which allowed us to study the non-Markovian dynamics on a multidimensional surface. The contributions from the high-frequency vibrational mode and the ultrafast component in the non-Markovian solvent dynamics are found to be primarily responsible for the dramatic increase in charge transfer rate over the prediction of the classical theories that neglect both these factors. These, along with a large coupling between the reactant and the product states, may combine to render the electron transfer rate both very large and constant over a wide range of solvent relaxation rates. A study on the free energy gap dependence of the electron transfer rate reveals that the rates are sensitive to changes in the quantum frequency particularly when the free energy gap is very large.

Reaction of diisopropoxytitanium(III) tetrahydroborate with selected organic compounds containing representative functional groups

Diisopropoxytitanium(III) tetrahydroborate, ((PrO)-Pr-1)(2)TiBH4), generated in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium borohydride in a 1:2 ratio selectively reduces aldehydes, ketones, acid chlorides, carboxylic acids, and N-Boc-protected amino acids to the corresponding alcohols in excellent yield under very mild reaction conditions (-78 to 25 degrees C).

The reaction of lambda 3-cyclotriphosphazanes with tetrachloro-ortho-benzoquinone: An unusual ring contraction-rearrangement

Oxidative addition of tetrachloro-ortho-benzoquinone to lambda(3)-cyclotriphosphazanes, [EtNP(OR)](3) results in an unprecedented ring contraction-rearrangement to give diazadiphosphetidines (EtN)(2)[P(OR)(O2C6Cl4)] [P(O2C6Cl4)-[N(Et)P(OR)(2)}] (R = C6H4Br-4 or C(6)H(3)Me(2)-2,6), a process indicated to be thermodynamically favourable on the basis of PM3 calculations.

The intercalation reaction of pyridine with manganese thiophosphate, MnPS3

The intercalation of pyridine in the layered manganese thiophosphate, MnPS3, has been examined in detail by a variety of techniques. The reaction is interesting since none of the anticipated changes in optical and electrical properties associated with intercalation of electron donating molecules is observed. The only notable change in the properties of the host lattice is in the nature of the low-temperature magnetic ordering; while MnPS3 orders antiferromagnetically below 78 K, the intercalated compound shows weak ferromagnetism probably due to a canted spin structure. Vibrational spectra clearly show that the intercalated species are pyridinium ions solvated by neutral pyridine molecules. The corresponding reduced sites of the host lattice, however, were never observed. The molecules in the solvation shell are exchangeable. Although the reaction appears to be topotactic and reversible, from XRD, a more detailed analysis of the products of deintercalation reveal that it is not so. The intercalation proceeds by an ion exchange/intercalation mechanism wherein the intercalated species are pyridinium ions solvated by neutral molecules with charge neutrality being preserved not by electron transfer but by a loss of Mn2+ ions from the lattice. The experimental evidence leading to this conclusion is discussed and it is shown that this model can account satisfactorily for the observed changes (or lack of it) in the optical, electrical, vibrational, and magnetic properties.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Intramolecular Reactivity - Keto Participation in the Hydrolysis of N-Methyl-N-(9-Oxobicyclo[3.3.1]Nonan-2-Alpha-YL) Morpholinium Iodide, and A Cannizzaro-Type Reaction of 3-(2-Oxocyclohexyl)Propanal

Mechanistic studies of two intramolecular processes, nucleophilic displacement of N-methylmorpholinium in N-methyl-N-{9-oxobicyclo[3,3,1]nonan-2 alpha-yl}morpholinium iodide, anchimerically assisted by keto carbonyl, and a Cannizzaro-type reaction of 3-(2-oxocyclohexyl)propanal, occurring via axial hydride transfer onto the cyclohexanone, are reported.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Carbothermal reduction and nitridation reaction of SiOx and preoxidized SiOx: Formation of α-Si3N4 fibers

The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40reaction with SrCO3 to form Sr2CeO4 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Ru(4+) ion in CeO(2) (Ce(0.95)Ru(0.05)O(2-delta)): A non-deactivating, non-platinum catalyst for water gas shift reaction

Hydrogen is a clean energy carrier and highest energy density fuel. Water gas shift (WGS) reaction is an important reaction to generate hydrogen from steam reforming of CO. A new WGS catalyst, Ce(1-x)Ru(x)O(2-delta) (0 <= x <= 0.1) was prepared by hydrothermal method using melamine as a complexing agent. The Catalyst does not require any pre-treatment. Among the several compositions prepared and tested, Ce(0.95)Ru(0.05)O(2-delta) (5% Ru(4+) ion substituted in CeO(2)) showed very high WGS activity in terms of high conversion rate (20.5 mu mol.g(-1).s(-1) at 275 degrees C) and low activation energy (12.1 kcal/mol). Over 99% conversion of CO to CO(2) by H(2)O is observed with 100% H(2) selectivity at >= 275 degrees C. In presence of externally fed CO(2) and H(2) also, complete conversion of CO to CO(2) was observed with 100% H(2) selectivity in the temperature range of 305-385 degrees C. Catalyst does not deactivate in long duration on/off WGS reaction cycle due to absence of surface carbon and carbonate formation and sintering of Ru. Due to highly acidic nature of Ru(4+) ion, surface carbonate formation is also inhibited. Sintering of noble metal (Ru) is avoided in this catalyst because Ru remains in Ru(4+) ionic state in the Ce(1-x)Ru(x)O(2-delta) catalyst.

An oxidative cross-dehydrogenative-coupling reaction in water using molecular oxygen as the oxidant: vanadium catalyzed indolation of tetrahydroisoquinolines

An aerobic oxidative cross-dehydrogenative coupling reaction between sp(3) C-H and sp(2) C-H bonds is developed by employing a vanadium catalyst (10 mol%) in an aqueous medium using molecular oxygen as the oxidant. This environmentally benign strategy exhibits larger substrate scope and shows high regioselectivity.

SOS films and interfaces: chemical aspects

The possible chemical reactions that take place during the growth of single crystal films of silicon on sapphire (SOS) are analyzed thermodynamically. The temperature for the growth of good quality epitaxial films is dependent on the extent of water vapor present in the carrier gas. The higher the water vapor content the higher the temperature needed to grow SOS films. Due to the interaction of silicon with sapphire at elevated temperatures, SOS films are doped with aluminum. The extent of doping is dependent on the conditions of film growth. The doping by aluminum from the substrate increases with increasing growth temperatures and decreasing growth rates. The equilibrium concentrations of aluminum at the silicon-sapphire interface are calculated as a function of deposition temperature, assuming that SiO2 or Al6Si2O13 are the products of reaction. It is most likely that the product could be a solid solutio n of Al2O3 in SiO2. The total amount of aluminum released due to the interaction between silicon and sapphire will account only for the formation of not more than one monolayer of reaction product unless the films are annealed long enough at elevated temperatures. This value is in good agreement with the recently reported observations employing high resolution transmission electron microscopy.

Physically consistent simulation of mesoscale chemical kinetics: The non-negative FIS-alpha method

Biochemical pathways involving chemical kinetics in medium concentrations (i.e., at mesoscale) of the reacting molecules can be approximated as chemical Langevin equations (CLE) systems. We address the physically consistent non-negative simulation of the CLE sample paths as well as the issue of non-Lipschitz diffusion coefficients when a species approaches depletion and any stiffness due to faster reactions. The non-negative Fully Implicit Stochastic alpha (FIS alpha) method in which stopped reaction channels due to depleted reactants are deleted until a reactant concentration rises again, for non-negativity preservation and in which a positive definite Jacobian is maintained to deal with possible stiffness, is proposed and analysed. The method is illustrated with the computation of active Protein Kinase C response in the Protein Kinase C pathway. (C) 2011 Elsevier Inc. All rights reserved.

Production of niobium powder by electronically mediated reaction (EMR) using calcium as a reductant

Explored in this study is an electronically mediated reaction (EMR) route for the production of niobium powder using calcium as a reductant for niobium oxide (Nb2O5). Feed material, Nb2O5, and reductant calcium alloy containing aluminum and nickel were charged into electronically isolated locations in a molten salt (e.g. CaCl2) at 1173 K. The current flow through an external path between the feed and reductant locations was monitored. A current approximately 0.4 A was measured during the reaction in the external circuit connecting cathode and anode location. Niobium powder with low aluminum and nickel content was obtained although liquid Ca–Al–Ni alloy was used as the reductant. This clearly demonstrates that niobium metal powder can be produced by an electronically mediated reaction (EMR), without direct physical contact between feed (Nb2O5) and reductant (calcium). Mechanism of calciothermic reduction of Nb2O5 in the molten salt is discussed using an isothermal chemical potential diagram.