Ultrafast excited-state intermolecular proton transfer of cyanine fluorochrome dyes

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.     

A quantum dot close to Stoner instability: The role of the Berry phase

The physics of a quantum dot with electron–electron interactions is well captured by the so called “Universal Hamiltonian” if the dimensionless conductance of the dot is much higher than unity. Within this scheme interactions are represented by three spatially independent terms which describe the charging energy, the spin-exchange and the interaction in the Cooper channel. In this paper we concentrate on the exchange interaction and generalize the functional bosonization formalism developed earlier for the charging energy. This turned out to be challenging as the effective bosonic action is formulated in terms of a vector field and is non-abelian due to the non-commutativity of the spin operators. Here we develop a geometric approach which is particularly useful in the mesoscopic Stoner regime, i.e., when the strong exchange interaction renders the system close to the Stoner instability. We show that it is sufficient to sum over the adiabatic paths of the bosonic vector field and, for these paths, the crucial role is played by the Berry phase. Using these results we were able to calculate the magnetic susceptibility of the dot. The latter, in close vicinity of the Stoner instability point, matches very well with the exact solution [I.S. Burmistrov, Y. Gefen, M.N. Kiselev, JETP Lett. 92 (2010) 179].     

On recurrence and transience of self-interacting random walks

Let µ₁,...,µ _k be d-dimensional probabilitymeasures in ? ^d with mean 0. At each time we choose one of the measures based on the history of the process and take a step according to that measure. We give conditions for transience of such processes and also construct examples of recurrent processes of this type. In particular, in dimension 3 we give the complete picture: every walk generated by two measures is transient and there exists a recurrent walk generated by three measures.     

Nonamenable products are not treeable

LetX andY be infinite graphs such that the automorphism group ofX is nonamenable and the automorphism group ofY has an infinite orbit. We prove that there is no automorphism-invariant measure on the set of spanning trees in the direct productX×Y. This implies that the minimal spanning forest corresponding to i.i.d. edge-weights in such a product has infinitely many connected components almost surely. Research partially supported by NSF grant DMS-9803597.     

Intersection-equivalence of Brownian paths and certain branching processes

We show that sample paths of Brownian motion (and other stable processes) intersect the same sets as certain random Cantor sets constructed by a branching process. With this approach, the classical result that two independent Brownian paths in four dimensions do not intersect reduces to the dying out of a critical branching process, and estimates due to Lawler (1982) for the long-range intersection probability of several random walk paths, reduce to Kolmogrov's 1938 law for the lifetime of a critical branching process. Extensions to random walks with long jumps and applications to Hausdorff dimension are also derived.     

Biased Random Walks, Lyapunov Functions, and Stochastic Analysis of Best Fit Bin Packing

We study the average case performance of the Best Fit algorithm for on-line bin packing under the distributionU{j, k}, in which the item sizes are uniformly distributed in the discrete range {1/k, 2/k,…,j/k}. Our main result is that, in the casej = k − 2, the expected waste for an infinite stream of items remains bounded. This settles an open problem posed by Coffmanet al.[[4]]. It is also the first result which involves a detailed analysis of the infinite multidimensional Markov chain underlying the algorithm.     

Visibility preserving terrain simplification— an experimental study

The terrain surface simplification problem has been studied extensively, as it has important applications in geographic information systems and computer graphics. The goal is to obtain a new surface that is combinatorially as simple as possible, while maintaining a prescribed degree of similarity with the original input surface. Generally, the approximation error is measured with respect to distance (e.g., Hausdorff) from the original or with respect to visual similarity. In this paper, we propose a new method of simplifying terrain surfaces, designed specifically to maximize a new measure of quality based on preserving inter-point visibility relationships. Our work is motivated by various problems of terrain analysis that rely on inter-point visibility relationships, such as optimal antenna placement.

We have implemented our new method and give experimental evidence of its effectiveness in simplifying terrains according to our quality measure. We experimentally compare its performance with that of other leading simplification methods.     

Fractional products of sets

For integers d > 1 and arbitrary 1 ? α ? d, α-products in d-fold Cartesian products are produced by probabilistic methods. Some explicit constructions are given by solutions of instances of the Turán problem for graphs.