A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster

The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented [Ti^IV₃(μ₃‐O)(O)₂(COO)₆] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one Ti^IV center per cluster can be photoreduced to Ti^III while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found.     

Hill‐climbing to Pasch valleys

Exhaustive enumeration of Steiner Triple Systems is not feasible, due to the combinatorial explosion of instances. The next‐best hope is to quickly find a sample that is representative of isomorphism classes. Stinson's Hill‐Climbing algorithm [ 20 ] is widely used to produce random Steiner Triple Systems, and certainly finds a sample of systems quickly, but the sample is not uniformly distributed with respect to the isomorphism classes of STS with ν ≤ 19, and, in particular, we find that isomorphism classes with a large number of Pasch configurations are under‐represented. No analysis of the non‐uniformity of the distribution with respect to isomorphism classes or the intractability of obtaining a representative sample for ν > 19 is known. We also exhibit a modification to hill‐climbing that makes the sample if finds closer to the uniform distribution over isomorphism classes in return for a modest increase in running time. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 405–419, 2007     

The algebraic structure of cohomological field theory

The algebraic foundation of cohomological field theory is presented. It is shown that these theories are based upon realizations of an algebra which contains operators for both BRST and vector supersymmetry. Through a localization of this algebra, we construct a theory of cohomological gravity in arbitrary dimensions. The observables in the theory are polynomial, but generally non-local operators, and have a natural interpretation in terms of a universal bundle for gravity. As such, their correlation functions correspond to cohomology classes on moduli spaces of Riemannian connections. In this uniformization approach, different moduli spaces are obtained by introducing curvature singularities on codimension two submanifolds via a puncture operator. This puncture operator is constructed from a naturally occuring differential form of co-degree two in the theory, and we are led to speculate on connections between this continuum quantum field theory, and the discrete Regge calculus.     

Extreme value copula estimation based on block maxima of a multivariate stationary time series

The core of the classical block maxima method consists of fitting an extreme value distribution to a sample of maxima over blocks extracted from an underlying series. In asymptotic theory, it is usually postulated that the block maxima are an independent random sample of an extreme value distribution. In practice however, block sizes are finite, so that the extreme value postulate will only hold approximately. A more accurate asymptotic framework is that of a triangular array of block maxima, the block size depending on the size of the underlying sample in such a way that both the block size and the number of blocks within that sample tend to infinity. The copula of the vector of componentwise maxima in a block is assumed to converge to a limit, which, under mild conditions, is then necessarily an extreme value copula. Under this setting and for absolutely regular stationary sequences, the empirical copula of the sample of vectors of block maxima is shown to be a consistent and asymptotically normal estimator for the limiting extreme value copula. Moreover, the empirical copula serves as a basis for rank-based, nonparametric estimation of the Pickands dependence function of the extreme value copula. The results are illustrated by theoretical examples and a Monte Carlo simulation study.     

Edge searching weighted graphs

In traditional edge searching one tries to clean all of the edges in a graph employing the least number of searchers. It is assumed that each edge of the graph initially has a weight equal to one. In this paper we modify the problem and introduce the Weighted Edge Searching Problem by considering graphs with arbitrary positive integer weights assigned to its edges. We give bounds on the weighted search number in terms of related graph parameters including pathwidth. We characterize the graphs for which two searchers are sufficient to clear all edges. We show that for every weighted graph the minimum number of searchers needed for a not-necessarily-monotonic weighted edge search strategy is enough for a monotonic weighted edge search strategy, where each edge is cleaned only once. This result proves the NP-completeness of the problem.     

Analysis of several subcycling schemes in partitioned simulations of a strongly coupled fluid-structure interaction

Fluid-structure interaction (FSI) simulations are used extensively to calculate the vibration of structures subjected to an internal or external flow. In the case of partitioned FSI simulations, separate flow and structure solvers are used, which requires some kind of coupling between both. The time step in both solvers is typically taken the same, but this unnecessarily leads to long calculation times when the time step is small due to stability reasons in one of the two solvers. Subcycling, the procedure where the time step of one solver is chosen smaller than the time step used in the other solver, may reduce the computational cost of the FSI simulation. The subcycling procedure can be either explicit or implicit, the latter implying the use of coupling iterations in each time step. Contrary to explicit subcycling, no stability analyses of implicit subcycling schemes are found in the literature. In this paper, the temporal stability of the implicit subcycling procedure is investigated. The one-dimensional flow in an elastic cylindrical tube is studied analytically. The results of this analysis are subsequently compared to a partitioned two-dimensional axisymmetric FSI calculation with implicit coupling between the flow and structure solvers.     

The puzzle of contrast inversion in DNA STM imaging

DNA has been at the center of an imaging effort since the invention of the scanning tunneling microscope (STM). In some of the STM imaging reports the molecules appeared with negative contrast, i.e., "submerged" under the metal background and darker. We demonstrate the phenomenon of contrast inversion in DNA STM imaging by controlled and spontaneous contrast inversions and by the dependence of the DNA apparent height with respect to the surface on the imaging bias voltage. Using these characterizations, we formulate a model explaining the above phenomenon by resonant tunneling through virtual states in the vacuum between the STM tip and the DNA molecule.     

Bundle Gerbes for Chern-Simons and Wess-Zumino-Witten Theories

We develop the theory of Chern-Simons bundle 2-gerbes and multiplicative bundle gerbes associated to any principal G-bundle with connection and a class in H⁴(BG, ℤ) for a compact semi-simple Lie group G. The Chern-Simons bundle 2-gerbe realises differential geometrically the Cheeger-Simons invariant. We apply these notions to refine the Dijkgraaf-Witten correspondence between three dimensional Chern-Simons functionals and Wess-Zumino-Witten models associated to the group G. We do this by introducing a lifting to the level of bundle gerbes of the natural map from H⁴(BG, ℤ) to H³(G, ℤ). The notion of a multiplicative bundle gerbe accounts geometrically for the subtleties in this correspondence for non-simply connected Lie groups. The implications for Wess-Zumino-Witten models are also discussed.The authors acknowledge the support of the Australian Research Council. ALC thanks MPI für Mathematik in Bonn and ESI in Vienna and BLW thanks CMA of Australian National University for their hospitality during part of the writing of this paper.