Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series

Electrochemically driven efficient enzymatic conversion of CO2 to formic acid with artificial cofactors

Enzymatic reduction of CO2 to formic acid with the enzyme formate dehydrogenase (FDH) and a cofactor is a promising method for CO2 conversion and utilization. However, the natural cofactor nicotinamide adenine dinucleotide (NADH) shows some drawbacks such as a low reduction efficiency and forms isomers or dimers (1,6 - NADH or NAD dimer) in the regeneration reaction. To overcome them and to improve the production of formic acid, in this work, the artificial cofactors, i.e., the bipyridinium-based salts of methyl viologen (MV2+), 1,1’-dicarboxymethyl-4,4’-bipyridinium bromine (DC2+), and 1,1’-diaminoethyl-4,4’-bipyridinium bromine (DA2+), were used to replace NADH, and the effect of different functional groups on the electrochemical regeneration and catalytic performance in the enzymatic reaction was studied systematically. Also, studies using the natural cofactor NADH were carried out for comparison. It was found that the cofactor with amino groups showed the highest catalytic efficiency (kcat/Km) of 0.161 mM-1min-1, which is 536 times higher than that of the natural cofactor NADH. Molecular Dynamics simulations were conducted to give further molecular insight into the behavior of the cofactors. Analyzing the free energy profiles of the complexes between CO2 in the FDH active site with different artificial cofactors indicated that the artificial cofactor with the amino groups had the highest affinity for CO2, being consistent with the experimental observations

Magnon Broadening Effect by Magnon-Phonon Interaction in Colossal Magnetoresistance Manganites

In order to study the magnetic excitation behaviors in colossal magnetoresistance manganites, a magnon-phonon interacting system is investigated. Sudden broadening of magnon linewidth is obtained when a magnon branch crosses over an optical phonon branch. Onset of the broadening is approximately determined by the magnon density of states. Anomalous magnon damping at the brillouine zone boundary observed in low Curie temperature manganites is explained.Comment: 4 pages incl. 4 figs. New e-mail: [email protected]

SOLVENT EFFECTS ON THE ABSORPTION AND FLUORESCENCE SPECTRA OF Er(III) (AZO-DYES AND SCHIFF BASES) COMPLEXES: DETERMINATION OF GROUND AND EXCITED STATE DIPOLE MOMENT

Absorption and fluorescence emission spectra of some thermally stable Er(III) mononuclear complexes of azo dyes, namely o, o` -dihydroxy azobenzene (DAB), o, o` -dihydroxy 4-Cl-phenylazonaphatalene (P1) and Schiff bases o, o` -dihydroxy phenylazomethinnaphatalene (D2), o-hidroxy -o` -carboxy (D3), were recorded in solvents with different solvent dielectric constant ε and refractive index n. The solvatochromic shift method was used to determine the experimental ground and excited state dipole moments of the complexes. All the complexes were proved to be more polar in the excited state as compared with the ground state

The Structure of Nanoscale Polaron Correlations in La1.2Sr1.8Mn2O7

A system of strongly-interacting electron-lattice polarons can exhibit charge and orbital order at sufficiently high polaron concentrations. In this study, the structure of short-range polaron correlations in the layered colossal magnetoresistive perovskite manganite, La1.2Sr1.8Mn2O7, has been determined by a crystallographic analysis of broad satellite maxima observed in diffuse X-ray and neutron scattering data. The resulting q=(0.3,0,1) modulation is a longitudinal octahedral-stretch mode, consistent with an incommensurate Jahn-Teller-coupled charge-density-wave fluctuations, that implies an unusual orbital-stripe pattern parallel to the directions.Comment: Reformatted with RevTe

Spin Dynamics of the Magnetoresistive Pyrochlore Tl_2Mn_2O_7

Neutron scattering has been used to study the magnetic order and spin dynamics of the colossal magnetoresistive pyrochlore Tl_2Mn_2O_7. On cooling from the paramagnetic state, magnetic correlations develop and appear to diverge at T_C (123 K). In the ferromagnetic phase well defined spin waves are observed, with a gapless ($\Delta <0.04$ meV) dispersion relation E=Dq^{2} as expected for an ideal isotropic ferromagnet. As T approaches T_C from low T, the spin waves renormalize, but no significant central diffusive component to the fluctuation spectrum is observed in stark contrast to the La$_{1-x}$(Ca,Ba,Sr)$_x$MnO$_3$ system. These results argue strongly that the mechanism responsible for the magnetoresistive effect has a different origin in these two classes of materials.Comment: 4 pages (RevTex), 4 figures (encapsulated postscript), to be published in Phys. Rev. Let

Novel stripe-type charge ordering in the metallic A-type antiferromagnet Pr{0.5}Sr{0.5}MnO{3}

We demonstrate that an A-type antiferromagnetic (AFM) state of Pr{0.5}Sr{0.5}MnO{3} exhibits a novel charge ordering which governs the transport property. This charge ordering is stripe-like, being characterized by a wave vector q ~ (0,0,0.3) with very anisotropic correlation parallel and perpendicular to the stripe direction. This charge ordering is specific to the manganites with relatively wide one-electron band width (W) which often exhibit a metallic A-type AFM state, and should be strictly distinguished from the CE-type checkerboard-like charge ordering which is commonly observed in manganites with narrower W such as La{1-x}Ca{x}MnO{3} and Pr{1-x}Ca{x}MnO{3}.Comment: REVTeX4, 5 pages, 4 figure

A novel spin wave expansion, finite temperature corrections and order from disorder effects in the double exchange model

The magnetic excitations of the double exchange (DE) model are usually discussed in terms of an equivalent ferromagnetic Heisenberg model. We argue that this equivalence is valid only at a quasi--classical level -- both quantum and thermal corrections to the magnetic properties of DE model differ from any effective Heisenberg model because its spin excitations interact only indirectly, through the exchange of charge fluctuations. To demonstrate this, we perform a novel large S expansion for the coupled spin and charge degrees of freedom of the DE model, aimed at projecting out all electrons not locally aligned with core spins. We generalized the Holstein--Primakoff transformation to the case when the length of the spin is by itself an operator, and explicitly constructed new fermionic and bosonic operators to fourth order in 1/\sqrt{S}. This procedure removes all spin variables from the Hund coupling term, and yields an effective Hamiltonian with an overall scale of electron hopping, for which we evaluate corrections to the magnetic and electronic properties in 1/S expansion to order O(1/S^2). We also consider the effect of a direct superexchange antiferromagnetic interaction between core spins. We find that the competition between ferromagnetic double exchange and an antiferromagnetic superexchange provides a new example of an "order from disorder" phenomenon -- when the two interactions are of comparable strength, an intermediate spin configuration (either a canted or a spiral state) is selected by quantum and/or thermal fluctuations.Comment: 21 pages revtex, 11 eps figure