Vacuum ultraviolet (VUV) photoionization of small water clusters

Tunable vacuum ultraviolet (VUV) photoionization studies of water clusters are performed using 10-14 eV synchrotron radiation and analyzed by reflectron time-of-flight (TOF) mass spectrometry. Photoionization efficiency (PIE) curves for protonated water clusters (H2O)(n)H+ are measured with 50 meV energy resolution. The appearance energies of a series of protonated water clusters are determined from the photoionization threshold for clusters composed of up to 79 molecules. These appearance energies represent an upper limit of the adiabatic ionization energy of the corresponding parent neutral water cluster in the supersonic molecular beam. The experimental results show a sharp drop in the appearance energy for the small neutral water clusters (from 12.62 +/- 0.05 to 10.94 +/- 0.06 eV, for H2O and (H2O)4, respectively), followed by a gradual decrease for clusters up to (H2O)23 converging to a value of 10.6 eV (+/-0.2 eV). The dissociation energy to remove a water molecule from the corresponding neutral water cluster is derived through thermodynamic cycles utilizing the dissociation energies of protonated water clusters reported previously in the literature. The experimental results show a gradual decrease of the dissociation energy for removal of one water molecule for small neutral water clusters (3 相似文献   

Electronic structure of the Mn4OxCa cluster in the S0 and S2 states of the oxygen-evolving complex of photosystem II based on pulse 55Mn-ENDOR and EPR spectroscopy

The heart of the oxygen-evolving complex (OEC) of photosystem II is a Mn4OxCa cluster that cycles through five different oxidation states (S0 to S4) during the light-driven water-splitting reaction cycle. In this study we interpret the recently obtained 55Mn hyperfine coupling constants of the S0 and S2 states of the OEC [Kulik et al. J. Am. Chem. Soc. 2005, 127, 2392-2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a "structure filter" that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821-825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 A Mn-Mn distance in S0 to 2.75 A in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459-7471] corresponds to a deprotonation of a mu-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the mu3-oxo bridged moiety of the cluster. We summarize our results in a molecular model for the S0 --> S1 and S1 --> S2 transitions.     

Matrix isolation and ab initio study of the HXeCCH...CO2 complex

The HXeCCH...CO2 complex is studied experimentally and computationally. The complex is prepared in a low-temperature xenon matrix using UV photolysis of propiolic acid (HCCCOOH) and thermal mobilization of H atoms at 45 K. Photolysis of propiolic acid leads to the HCCH...CO2 complex as one of the photolysis products. The HCCH...CO2 complex is further photolyzed to the HCC...CO2 complex. Thermal annealing leads to the formation of HXeCCH complexed with CO2. The H-Xe stretching absorption of the HXeCCH...CO2 complex is blueshifted (+31.9 and +5.8 cm(-1)) from the value of the HXeCCH monomer in a xenon matrix. In the calculations, three HXeCCH...CO2 structures were found (one parallel and two linear structures) corresponding to the true energy minima on the potential energy surface. For the H-Xe stretching mode, the calculations give blueshifted values of +19.2 or +19.5 cm(-1) depending on the computational level [MP2/6-311++G(2d,2p) and MP2/aug-cc-pVDZ] for the parallel structure and +19.4 or +27.9 cm(-1) for one linear structure. For the second linear structure, the H-Xe stretching frequency is redshifted by -8.6 or -9.4 cm(-1) at these levels of theory. Based on the calculations, the experimental band shifted by +5.8 cm(-1) (1492.2 cm(-1)) most likely corresponds to the HXeCCH...CO2 parallel structure. The band with larger blueshift of +31.9 cm(-1) (1518.3 cm(-1)) can be due to another matrix site of the same structure or to the blueshifting linear structure.     

Facile coupling of 2‐(1‐ethylthioethenyl)pyrroles with amines: A route to 2‐(1‐aminoethenyl)pyrroles and 1‐amino‐3‐iminopyrrolizines

2‐(2‐Cyano‐1‐ethylthioethenyl)pyrroles are readily coupled (50–55°) with primary and secondary amines at the position 1 of the ethenyl moiety to eliminate ethanethiol and afford 2‐(1‐amino‐2‐cyanoethenyl)pyrroles and/or their cyclic isomers ‐ functionalized 1‐amino‐3‐iminopyrrolizines in good to high yields.     

Symmetric low-frequency motion in incompressible transversely isotropic elastic plates

The problem of long-wave low-frequency extensional (symmetric) motion in a layer composed of incompressible, transversely isotropic elastic material is investigated. Motivated by appropriate approximations of the dispersion relation, a hierarchy of asymptotically approximate boundary value problems is set up and solved. A leading order system of equations is obtained for the governing extensions, together with a refined system for their second order counterparts. A one-dimensional model problem, involving impact edge loading, is set up and solved in order to illustrate the derived theory.     

A Degenerate Bifurcation Structure in the Dynamics of Coupled Oscillators with Essential Stiffness Nonlinearities

We study the degenerate bifurcations of the nonlinear normal modes(NNMs) of an unforced system consisting of a linear oscillator weaklycoupled to a nonlinear one that possesses essential stiffnessnonlinearity. By defining the small coupling parameter , we study thedynamics of this system at the limit 0. The degeneracy in the dynamics ismanifested by a 'bifurcation from infinity' where a bifurcation point isgenerated at high energies, as perturbation of a state of infiniteenergy. Another (nondegenerate) bifurcation point is generated close tothe point of exact 1:1 internal resonance between the linear andnonlinear oscillators. The degenerate bifurcation structure can bedirectly attributed to the high degeneracy of the uncoupled system inthe limit 0, whose linearized structure possesses a double zero, and aconjugate pair of purely imaginary eigenvalues. First we construct localanalytical approximations to the NNMs in the neighborhoods of thebifurcation points and at other energy ranges of the system. Then, we`connect' the local approximations by global approximants, and identifyglobal branches of NNMs where unstable and stable mode and inverse modelocalization between the linear and nonlinear oscillators take place fordecreasing energy.     

Transition waves in bistable structures. II. Analytical solution: wave speed and energy dissipation

We consider dynamics of chains of rigid masses connected by links described by irreversible, piecewise linear constitutive relation: the force-elongation diagram consists of two stable branches with a jump discontinuity at the transition point. The transition from one stable state to the other propagates along the chain and excites a complex system of waves. In the first part of the paper (Cherkaev et al., 2004, Transition waves in bistable structures. I. Delocalization of damage), the branches could be separated by a gap where the tensile force is zero, the transition wave was treated as a wave of partial damage. Here we assume that there is no zero-force gap between the branches. This allows us to obtain steady-state analytical solutions for a general piecewise linear trimeric diagram with parallel and nonparallel branches and an arbitrary jump at the transition. We derive necessary conditions for the existence of the transition waves and compute the speed of the wave. We also determine the energy of dissipation which can be significantly increased in a structure characterized by a nonlinear discontinuous constitutive relation. The considered chain model reveals some phenomena typical for waves of failure or crushing in constructions and materials under collision, waves in a structure specially designed as a dynamic energy absorber and waves of phase transitions in artificial and natural passive and active systems.     

New analytical approach to energy pumping problem in strongly nonhomogeneous 2dof systems

We present new analytical approach to the problem of energy pumping in strongly non- homogeneous nonlinear two-degree-of-freedom (2DOF) systems with single anchor spring under condition of initial impact. Energy pumping is a passive, almost irreversible transfer of mechanical energy from the main substructure of the system to the light auxiliary attachment. The mechanism of energy pumping in the system under consideration is a resonance capture. The approach is based on application of Laplace transformation to the principal asymptotic approximation of the equations of motion in complex form and using the power expansion of the solution in terms of time. Obtained temporal dependence of the system energetic characteristics gives a tool for estimation of energy pumping efficiency. In particular, we show that the system without an anchor spring in attachment is more efficient than the system with such a spring. Numerical simulations confirm the analytical results.     

Highly Efficient Phase Boundary Biocatalysis with Enzymogel Nanoparticles

The enzymogel nanoparticle made of a magnetic core and polymer brush shell demonstrates a novel type of remote controlled phase‐boundary biocatalysis that involves remotely directed binding to and engulfing insoluble substrates, high mobility, and stability of the catalytic centers. The mobile enzymes reside in the polymer brush scaffold and shuttle between the enzymogel interior and surface of the engulfed substrate in the bioconversion process. Biocatalytic activity of the mobile enzymes is preserved in the enzymogel while the brush‐like architecture favors the efficient interfacial interaction when the enzymogel spreads over the substrate and extends substantially the reaction area as compared with rigid particles.