Surface Oxidation of Supported,Size-Selected Silver Clusters

We use surface second harmonic generation spectroscopy to study the oxidation of supported, size-selected silver clusters under ultra-high vacuum conditions. The oxidation reaction of small silver clusters between \(Ag_{9}\) and \(Ag_{55}\) is monitored by means of their localized surface plasmon resonance. We observe a rapid decline of the SH-intensity, as soon as cluster samples are exposed to an oxygen partial pressure of \(5 \cdot 10^{-6}\) mbar, which is attributed to the formation of silver–oxygen-bonds. The evolution of the SH-intensity under exposure to oxygen shows a double-exponential character for all investigated cluster sizes. Since the oxidation of single crystalline silver surfaces follow single-exponential Langmuir-kinetics, the two independent pathways of SH-intensity loss are attributed to a surface- and an interface-oxidation of supported clusters, respectiveley. For small cluster sizes, a complete loss of the SH intensity is obtained, which suggests the complete oxidation of the clusters. For larger clusters a plasmonic resonance is still observed after oxidation, indicating a residual free-electron density.     

The Strong Variant of a Barbashin Theorem on Stability of Solutions for Non-autonomous Differential Equations in Banach Spaces

Among others we shall prove that an exponentially bounded evolution family U = {U(t, s)} _t≥s≥0 of bounded linear operators acting on a Banach space X is uniformly exponentially stable if and only if there exists q [1, ∞) such that

The Erdős–Pósa Property For Long Circuits

We show that, for every l, the family of circuits of length at least l satisfies the Erdős–Pósa property, with f(k)=13l(k−1)(k−2)+(2l+3)(k−1), thereby sharpening a result of C. Thomassen. We obtain as a corollary that graphs without k disjoint circuits of length l or more have tree-width O(lk²).     

J/psi production versus transverse momentum and rapidity in p+p collisions at square root s=200 GeV

J/psi production in p+p collisions at square root s=200 GeV has been measured by the PHENIX experiment at the BNL Relativistic Heavy Ion Collider over a rapidity range of -2.2相似文献   

Interacting anyons in topological quantum liquids: the golden chain

We discuss generalizations of quantum spin Hamiltonians using anyonic degrees of freedom. The simplest model for interacting anyons energetically favors neighboring anyons to fuse into the trivial ("identity") channel, similar to the quantum Heisenberg model favoring neighboring spins to form spin singlets. Numerical simulations of a chain of Fibonacci anyons show that the model is critical with a dynamical critical exponent z=1, and described by a two-dimensional (2D) conformal field theory with central charge c=7/10. An exact mapping of the anyonic chain onto the 2D tricritical Ising model is given using the restricted-solid-on-solid representation of the Temperley-Lieb algebra. The gaplessness of the chain is shown to have topological origin.     

Evidence for a long-range component in the pion emission source in Au+Au collisions at sqrt sNN=200 GeV

Emission source functions are extracted from correlation functions constructed from charged pions produced at midrapidity in Au+Au collisions at sqrt[s(NN)]=200 GeV. The source parameters extracted from these functions at low k(T) give first indications of a long tail for the pion emission source. The source extension cannot be explained solely by simple kinematic considerations. The possible role of a halo of secondary pions from resonance emissions is explored.     

Power-efficient Fourier domain optical coherence tomography setup for selection in the optical path difference sign using Talbot bands

A power-efficient Fourier domain optical coherence tomography fiber system is presented free of mirror terms. The object and reference beams from the interferometer are spatially separated to illuminate different parts of the diffraction grating in the spectrometer according to a method inspired from the use of Talbot bands. In this way, the system is made sensitive to only one sign of the optical path difference in the interferometer.     

Coupling of replica exchange simulations to a non-Boltzmann structure reservoir

Computing converged ensemble properties remains challenging for large biomolecules. Replica exchange molecular dynamics (REMD) can significantly increase the efficiency of conformational sampling by using high temperatures to escape kinetic traps. Several groups, including ours, introduced the idea of coupling replica exchange to a pre-converged, Boltzmann-populated reservoir, usually at a temperature higher than that of the highest temperature replica. This procedure reduces computational cost because the long simulation times needed for extensive sampling are only carried out for a single temperature. However, a weakness of the approach is that the Boltzmann-weighted reservoir can still be difficult to generate. We now present the idea of employing a non-Boltzmann reservoir, whose structures can be generated through more efficient conformational sampling methods. We demonstrate that the approach is rigorous and derive a correct statistical mechanical exchange criterion between the reservoir and the replicas that drives Boltzmann-weighted probabilities for the replicas. We test this approach on the trpzip2 peptide and demonstrate that the resulting thermal stability profile is essentially indistinguishable from that obtained using very long (>100 ns) standard REMD simulations. The convergence of this reservoir-aided REMD is significantly faster than for regular REMD. Furthermore, we demonstrate that modification of the exchange criterion is essential; REMD simulations using a standard exchange function with the non-Boltzmann reservoir produced incorrect results.     

Tunneling and classical paths for proton transfer in an enzyme reaction dominated by tunneling: oxidation of tryptamine by aromatic amine dehydrogenase

Proton tunneling dominates the oxidative deamination of tryptamine catalyzed by the enzyme aromatic amine dehydrogenase. For reaction with the fast substrate tryptamine, a H/D kinetic isotope effect (KIE) of 55 +/- 6 has been reported-one of the largest observed in an enzyme reaction. We present here a computational analysis of this proton-transfer reaction, applying combined quantum mechanics/molecular mechanics (QM/MM) methods (PM3-SRP//PM3/CHARMM22). In particular, we extend our previous computational study (Masgrau et al. Science 2006, 312, 237) by using improved energy corrections, high-level QM/MM methods, and an ensemble of paths to estimate the tunneling contributions. We have carried out QM/MM molecular dynamics simulations and variational transition state theory calculations with small-curvature tunneling corrections. The results provide detailed insight into the processes involved in the reaction. Transfer to the O2 oxygen of the catalytic base, Asp128beta, is found to be the favored reaction both thermodynamically and kinetically, even though O1 is closer in the reactant complex. Comparison of quantum and classical models of proton transfer allows estimation of the contribution of hydrogen tunneling in lowering the barrier to reaction in the enzyme. A reduction of the activation free energy due to tunneling of 3.1 kcal mol-1 is found, which represents a rate enhancement due to tunneling by 2 orders of magnitude. The calculated KIE of 30 is significantly elevated over the semiclassical limit, in agreement with the experimental observations; a semiclassical value of 6 is obtained when tunneling is omitted. A polarization of the C-H bond to be broken is observed due to the close proximity of the catalytic aspartate and the (formally) positively charged imine nitrogen. A comparison is also made with the related quinoprotein methylamine dehydrogenase (MADH)-the much lower KIE of 11 that we obtain for the MADH/methylamine system is found to arise from a more endothermic potential energy surface for the MADH reaction.