Kinetic analysis of the reaction between (V2O5)n=1,2+ and ethylene

A systematic experimental and theoretical investigation of the influence of reactant energy on the reactivity of (V(2)O(5))(n)=1,2(+) clusters with ethylene (Justes, D. R.; Mitri?, R.; Moore, N. A.; Bonaci?-Koutecky, V.; Castleman, A. W., Jr. J. Am. Chem. Soc., 2003, 125, 6289) provided evidence of the rate controlling steps in the reaction. Herein, we present further experimental and theoretical evidence for our recently proposed radical cation mechanism for oxygen atom transfer from (V(2)O(5))(n)=1,2(+) clusters to ethylene. In particular the results of ab initio molecular dynamics simulations are found to further support the radical cation mechanism. Experimental reaction cross sections at the zero pressure limit and rate coefficients show that the energy dependence of the reaction cross section is in accord with the Langevin formula. Evidence is presented that ion-molecule association is the rate determining step, whereas subsequent hydrogen transfer and formation of acetaldehyde proceed without significant barriers. We propose a kinetic model for the reaction cross section that fully accounts for the experimental findings. The model offers the prospect of elucidating the details of the general reaction mechanisms through a study of the energy dependence of the reaction cross sections.     

Hydrogen molecule in the small dodecahedral cage of a clathrate hydrate: quantum five-dimensional calculations of the coupled translation-rotation eigenstates

We report quantum five-dimensional (5D) calculations of the energy levels and wave functions of the hydrogen molecule, para-H2 and ortho-H2, confined inside the small dodecahedral (H2O)20 cage of the sII clathrate hydrate. All three translational and the two rotational degrees of freedom of H2 are included explicitly, as fully coupled, while the cage is treated as rigid. The 5D potential energy surface (PES) of the H2-cage system is pairwise additive, based on the high-quality ab initio 5D (rigid monomer) PES for the H2-H2O complex. The bound state calculations involve no dynamical approximations and provide an accurate picture of the quantum 5D translation-rotation dynamics of H2 inside the cage. The energy levels are assigned with translational (Cartesian) and rotational quantum numbers, based on calculated root-mean-square displacements and probability density plots. The translational modes exhibit negative anharmonicity. It is found that j is a good rotational quantum number, while the threefold degeneracy of the j = 1 level is lifted completely. There is considerable translation-rotation coupling, particularly for excited translational states.     

Defects in ZnO nanorods prepared by a hydrothermal method

ZnO nanorod arrays were fabricated using a hydrothermal method. The nanorods were studied by scanning electron microscopy, photoluminescence (PL), time-resolved PL, X-ray photoelectron spectroscopy, and positron annihilation spectroscopy before and after annealing in different environments and at different temperatures. Annealing atmosphere and temperature had significant effects on the PL spectrum, while in all cases the positron diffusion length and PL decay times were increased. We found that, while the defect emission can be significantly reduced by annealing at 200 degrees C, the rods still have large defect concentrations as confirmed by their low positron diffusion length and short PL decay time constants.     

Improved density functional theory/electrostatic calculation of the His291 protonation state in cytochrome C oxidase: self-consistent charges for solvation energy calculation

The protonation state of His291 in cytochrome c oxidase (CcO), a ligand to the Cu(B) center of the enzyme, has been recently studied in this group by using combined density functional theory (DFT)/electrostatic (QM/MM) calculations. On the basis of these calculations, a model of the proton pumping mechanism of CcO has been proposed. Due to certain technical difficulties, the procedure used in the previous calculation to find partial atomic charges of the QM system for the solvation energy evaluation was not entirely satisfactory; i.e., it was not self-consistent. Here, we describe a procedure that resolves the problem and report on the improved calculations of the protonation state of the His residue. The new procedure fits the protein and reaction field potentials in the region of the QM system with artificial point charges placed on a surface of a sphere surrounding the QM system and a few charges inside the sphere and allows one to perform DFT calculations that involve an inhomogeneous dielectric environment in a self-consistent way. The procedure improves the accuracy of calculations in comparison with previous work. The improved results show, however, that although the absolute energies change significantly the relative energies of the protonated and deprotonated states of His291 remain close to the previously reported ones and therefore do not change significantly the pK(a) values reported earlier. Therefore, our new improved calculations support for the proposed His291 model of the CcO pump.     

Template-directed synthesis of mechanically interlocked molecular bundles using dynamic covalent chemistry

Mixing the dipyrido[24]crown-8 derivatives carrying one or two formyl group(s) on the 4 position(s) of their pyridine ring(s) with a 3-fold symmetrical trisammonium ion template in a 3:1 ratio in CD3NO2 results in the formation of thermodynamically stable [4]pseudorotaxanes which, upon addition of a 1,3,5-trisaminobenzene cap, form mechanically interlocked molecular bundles with one and two caps, respectively, by virtue of dynamic imine bond formation.     

Thermal collapse of spin polarization in half-metallic ferromagnets

We propose two novel approaches to study the temperature dependence of the magnetization and the spin polarization at the Fermi level in magnetic compounds, and apply them to half-metallic ferromagnets. We reveal a new mechanism, where the hybridization of states forming the half-metallic gap depends on thermal spin fluctuations and the polarization can drop abruptly at temperatures much lower than the Curie point. We verify this for NiMnSb by ab initio calculations. The thermal properties are studied by mapping ab initio results to an extended Heisenberg model which includes longitudinal fluctuations and is solved by a Monte Carlo method.     

On Li’s coefficients for the Rankin–Selberg <Emphasis Type="Italic">L</Emphasis>-functions

We define a generalized Li coefficient for the L-functions attached to the Rankin–Selberg convolution of two cuspidal unitary automorphic representations π and π ^′ of GL_m(\mathbbA_F)GL_{m}(\mathbb{A}_{F}) and GL_m^￠(\mathbbA_F)GL_{m^{\prime }}(\mathbb{A}_{F}) . Using the explicit formula, we obtain an arithmetic representation of the n th Li coefficient l_p,p^￠(n)\lambda _{\pi ,\pi ^{\prime }}(n) attached to L(s,p_f×[(p)\tilde]_f^￠)L(s,\pi _{f}\times \widetilde{\pi}_{f}^{\prime }) . Then, we deduce a full asymptotic expansion of the archimedean contribution to l_p,p^￠(n)\lambda _{\pi ,\pi ^{\prime }}(n) and investigate the contribution of the finite (non-archimedean) term. Under the generalized Riemann hypothesis (GRH) on non-trivial zeros of L(s,p_f×[(p)\tilde]_f^￠)L(s,\pi _{f}\times \widetilde{\pi}_{f}^{\prime }) , the nth Li coefficient l_p,p^￠(n)\lambda _{\pi ,\pi ^{\prime }}(n) is evaluated in a different way and it is shown that GRH implies the bound towards a generalized Ramanujan conjecture for the archimedean Langlands parameters μ _π (v,j) of π. Namely, we prove that under GRH for L(s,p_f×[(p)\tilde]_f)L(s,\pi _{f}\times \widetilde{\pi}_{f}) one has |Rem_p(v,j)| ￡ \frac14|\mathop {\mathrm {Re}}\mu_{\pi}(v,j)|\leq \frac{1}{4} for all archimedean places v at which π is unramified and all j=1,…,m.