Selecting between two transition states by which water oxidation intermediates on an oxide surface decay

While catalytic mechanisms on electrode surfaces have been proposed for decades, the pathways by which the product's chemical bonds evolve from the initial charge-trapping intermediates have not been resolved in time. Here, we discover a reactive population of charge-trapping intermediates with states in the middle of a semiconductor's band-gap to reveal the dynamics of two parallel transition state pathways for their decay. Upon photo-triggering the water oxidation reaction from the n-SrTiO3 surface with band-gap, pulsed excitation, the intermediates' microsecond decay reflects transition state theory (TST) through: (1) two distinct and reaction dependent (pH, T, Ionic Strength, and H/D exchange) time constants, (2) a primary kinetic salt effect on each activation barrier and an H/D kinetic isotope effect on one, and (3) realistic activation barrier heights (0.4 - 0.5 eV) and TST pre-factors (10^11 - 10^12 Hz). A photoluminescence from midgap states in n-SrTiO3 reveals the reaction dependent decay; the same spectrum was previously assigned by us to hole-trapping at parallel Ti-O(dot)-Ti (bridge) and perpendicular Ti-O(dot) (oxyl) O-sites using in situ ultrafast vibrational and optical spectroscopy. Therefore, the two transition states are naturally associated with the decay of these respective intermediates. Furthermore, we show that reaction conditions select between the two pathways, one of which reflects a labile intermediate facing the electrolyte (the oxyl) and the other a lattice oxygen (the bridge). Altogether, we experimentally isolate an important activation barrier for water oxidation, which is necessary for designing water oxidation catalysts with high O2 turn over. Moreover, in isolating it, we identify competing mechanisms for O2 evolution at surfaces and show how to use reaction conditions to select between them

Time delays and energy transport velocities in three dimensional ideal cloaking

We obtained the energy transport velocity distribution for a three dimensional ideal cloak explicitly. Near the operation frequency, the energy transport velocity has rather peculiar distribution. The velocity along a line joining the origin of the cloak is a constant, while the velocity approaches zero at the inner boundary of the cloak. A ray pointing right into the origin of the cloak will experience abrupt changes of velocities when it impinges on the inner surface of the cloak. This peculiar distribution causes infinite time delays for the ideal cloak within a geometric optics description.Comment: A scaling factor is added to convert the parameter \tau into the physical tim

Analysis of a Classical Matrix Preconditioning Algorithm

We study a classical iterative algorithm for balancing matrices in the $L_\infty$ norm via a scaling transformation. This algorithm, which goes back to Osborne and Parlett \& Reinsch in the 1960s, is implemented as a standard preconditioner in many numerical linear algebra packages. Surprisingly, despite its widespread use over several decades, no bounds were known on its rate of convergence. In this paper we prove that, for any irreducible $n\times n$ (real or complex) input matrix~$A$, a natural variant of the algorithm converges in $O(n^3\log(n\rho/\varepsilon))$ elementary balancing operations, where $\rho$ measures the initial imbalance of~$A$ and $\varepsilon$ is the target imbalance of the output matrix. (The imbalance of~$A$ is $\max_i |\log(a_i^{\text{out}}/a_i^{\text{in}})|$, where $a_i^{\text{out}},a_i^{\text{in}}$ are the maximum entries in magnitude in the $i$th row and column respectively.) This bound is tight up to the $\log n$ factor. A balancing operation scales the $i$th row and column so that their maximum entries are equal, and requires $O(m/n)$ arithmetic operations on average, where $m$ is the number of non-zero elements in~$A$. Thus the running time of the iterative algorithm is $\tilde{O}(n^2m)$. This is the first time bound of any kind on any variant of the Osborne-Parlett-Reinsch algorithm. We also prove a conjecture of Chen that characterizes those matrices for which the limit of the balancing process is independent of the order in which balancing operations are performed.Comment: The previous version (1) (see also STOC'15) handled UB ("unique balance") input matrices. In this version (2) we extend the work to handle all input matrice

Applications of diffraction theory to aeroacoustics

A review is given of the fundamentals of diffraction theory and the application of the theory to several problems of aircraft noise generation, propagation, and measurement. The general acoustic diffraction problem is defined and the governing equations set down. Diffraction phenomena are illustrated using the classical problem of the diffraction of a plane wave by a half-plane. Infinite series and geometric acoustic methods for solving diffraction problems are described. Four applications of diffraction theory are discussed: the selection of an appropriate shape for a microphone, the use of aircraft wings to shield the community from engine noise, the reflection of engine noise from an aircraft fuselage and the radiation of trailing edge noise

Two-dimensional arrays of low capacitance tunnel junctions: general properties, phase transitions and Hall effect

We describe transport properties of two-dimensional arrays of low capacitance tunnel junctions, such as the current voltage characteristic and its dependence on external magnetic field and temperature. We discuss several experiments in which the small capacitance of the junctions plays an important role. In arrays where the junctions have a relatively large charging energy, (i.e. when they have a low capacitance) and a high normal state resistance, the low bias resistance increases with decreasing temperature and eventually at very low temperature the array becomes insulating even though the electrodes in the array are superconducting. This transition to the insulating state can be described by thermal activation. In an intermediate region where the junction resistance is of the order of the quantum resistance and the charging energy is of the order of the Josephson coupling energy, the arrays can be tuned between a superconducting and an insulating state with a magnetic field. We describe measurements of this magnetic-field-tuned superconductor insulator transition, and we show that the resistance data can be scaled over several orders of magnitude. Four arrays follow the same universal function. At the transition the transverse (Hall) resistance is found to be very small in comparison with the longitudinal resistance. However, for magnetic field values larger than the critical value.we observe a substantial Hall resistance. The Hall resistance of these arrays oscillates with the applied magnetic field. features in the magnetic field dependence of the Hall resistance can qualitatively be correlated to features in the derivative of the longitudinal resistance, similar to what is found in the quantum Hall effect.Comment: 29 pages, 16 eps figures, uses aipproc.sty and epsfig.sty, contribution to Euroschool on "Superconductivity in Networks and Mesoscopic Systems", held in Siena, Italy (8-20 september 1997

Correction of the definition of mass-flow parameter in dynamic inflow modelling

No abstract available

Transformation media that rotate electromagnetic fields

We suggest a way to manipulate electromagnetic wave by introducing a rotation mapping of coordinates that can be realized by a specific transformation of permittivity and permeability of a shell surrounding an enclosed domain. Inside the enclosed domain, the information from outside will appear as if it comes from a different angle. Numerical simulations were performed to illustrate these properties.Comment: 5 pages, 3 figure

Using LIP to Gloss Over Faces in Single-Stage Face Detection Networks

This work shows that it is possible to fool/attack recent state-of-the-art face detectors which are based on the single-stage networks. Successfully attacking face detectors could be a serious malware vulnerability when deploying a smart surveillance system utilizing face detectors. We show that existing adversarial perturbation methods are not effective to perform such an attack, especially when there are multiple faces in the input image. This is because the adversarial perturbation specifically generated for one face may disrupt the adversarial perturbation for another face. In this paper, we call this problem the Instance Perturbation Interference (IPI) problem. This IPI problem is addressed by studying the relationship between the deep neural network receptive field and the adversarial perturbation. As such, we propose the Localized Instance Perturbation (LIP) that uses adversarial perturbation constrained to the Effective Receptive Field (ERF) of a target to perform the attack. Experiment results show the LIP method massively outperforms existing adversarial perturbation generation methods -- often by a factor of 2 to 10.Comment: to appear ECCV 2018 (accepted version