Experimental and Computational Analysis of Para-Hydroxy Methylcinnamate following Photoexcitation

Para-hydroxy methylcinnamate is part of the cinnamate family of molecules. Experimental and computational studies have suggested conflicting non-radiative decay routes after photoexcitation to its S₁(ππ*) state. One non-radiative decay route involves intersystem crossing mediated by an optically dark singlet state, whilst the other involves direct intersystem crossing to a triplet state. Furthermore, irrespective of the decay mechanism, the lifetime of the initially populated S₁(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S₁(ππ*) lifetime for the s-cis conformer of para-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S₁(ππ*) state lifetime of s-cis para-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [¹ππ*→¹nπ*→³ππ*→S₀] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as para-coumaric acid and methylcinnamate.     

Atypical behaviour of the surface hardness and the elastic modulus of a phosphate glass matrix under 193 nm laser irradiation

The effect of 193 nm excimer laser radiation on the Knoop hardness and the elastic modulus of an ultra-phosphate glass is presented here. The experimental results reveal that the glass matrix undergoes a significant softening and volume dilation process for highly accumulated energy doses, where the Knoop hardness reduces by more than 15%, while following a single photon absorption rule. Further, during the early stages of the exposure a slight hardening process is observed. Finally, the elastic modulus is correlated with respect to the measured Knoop hardness.     

An improved grid method for the computation of the pseudospectra of matrix polynomials

Pseudospectra of matrix polynomials have been systematically investigated in recent years, since they provide important insights into the sensitivity of polynomial eigenvalue problems. An accurate approximation of the pseudospectrum of a matrix polynomial $P\left(\lambda \right)$ by means of the standard grid method is highly demanding computationally. In this paper, we propose an improvement of the grid method, which reduces the computational cost and retains the robustness and the parallelism of the method. In particular, after giving two lower bounds for the distance from a point to the boundary of the pseudospectrum of $P\left(\lambda \right)$, we present two algorithms for the estimation of the pseudospectrum, using exclusion discs. Furthermore, two illustrative examples and an application of pseudospectra on elliptic (quadratic) eigenvalue problems are given.     

An EEG study of brain connectivity dynamics at the resting state

We investigated the dynamical behavior of resting state functional connectivity using EEG signals. Employing a recently introduced methodology that considers the time variations of phase coupling among signals from different channels, a sequence of functional connectivity graphs (FCGs) was constructed for different frequency bands and analyzed based on graph theoretic tools. In the first stage of analysis, hubs were detected in the FCGs based on local and global efficiency. The probability of each node to be identified as a hub was estimated. This defined a topographic function that showed widespread distribution with prominence over the frontal brain regions for both local and global efficiency. Hubs consistent across time were identified via a summarization technique and found to locate over forehead. In the second stage of analysis, the modular structure of each single FCG was delineated. The derived time-dependent signatures of functional structure were compared in a systematic way revealing fluctuations modulated by frequency. Interestingly, the evolution of functional connectivity can be described via abrupt transitions between states, best described as short-lasting bimodal functional segregations. Based on a distance function that compares clusterings, we discovered that these segregations are recurrent. Entropic measures further revealed that the apparent fluctuations are subject to intrinsic constraints and that order emerges from spatially extended interactions.     

Computational electromagnetic methods for interconnects and small structures

The continual advances in speed and integration scale of electronic circuits have created enormous demands for high-speed, high-density packages which ensure reduced interconnection delays and improved electrical performance. Such structures usually involve a large number of planar transmission lines at various levels within the package, whereas the geometrical orientation of these lines is not necessarily uniform. Also, the existence of multiple dielectric layers, discontinuities, bends, and wire bounds adds considerable complexity to the package. It is therefore essential that full-wave computational electromagnetic (CEM) techniques, such as the finite element method (FEM) and the finite-difference time-domain (FDTD) method, be developed and used to accurately model the electrical performance of these devices and circuits.     

Observation of ultrafast NH3 (Ã) state relaxation dynamics using a combination of time-resolved photoelectron spectroscopy and photoproduct detection

The ultrafast excited state relaxation of ammonia is investigated by resonantly exciting specific vibrational modes of the electronically excited NH(3) (?) state using three complementary femtosecond (fs) pump-probe techniques: time-resolved photoelectron, ion-yield and photofragment translational spectroscopy. Ammonia can be seen as a prototypical system for studying non-adiabatic dynamics and therefore offers a benchmark species for demonstrating the advantages of combining the aforementioned techniques to probe excited state dynamics, whilst simultaneously illuminating new aspects of ammonia's photochemistry. Time-resolved photoelectron spectroscopy (TRPES) provides direct spectroscopic evidence of σ* mediated relaxation of the NH(3) (?) state which manifests itself as coupling of the umbrella (ν(2)) and symmetric N-H stretch (ν(1)) modes in the photoelectron spectra. Time-resolved ion yield (TRIY) and time-resolved photofragment translation spectroscopy (TRPTS) grant a measure of the dissociation dynamics through analysis of the H and NH(2) photodissociation co-fragments. Initial vibrational level dependent TRIY measurements reveal photoproduct formation times of between 190 and 230 fs. Measurement of H-atom photoproduct kinetic energies enables investigation into the competition between adiabatic and non-adiabatic dissociation channels at the NH(3) (?)/NH(3) (X?) conical intersection and has shown that upon non-adiabatic dissociation into NH(2) (X?) + H, the NH(2) (X[combining tilde]) fragment is predominantly generated with significant fractions of internal vibrational energy.     

Conservation of ultrafast photoprotective mechanisms with increasing molecular complexity in sinapoyl malate derivatives

Sinapoyl malate is a natural plant sunscreen molecule which protects leaves from harmful ultraviolet radiation. Here, the ultrafast dynamics of three sinapoyl malate derivatives, sinapoyl L-dimethyl malate, sinapoyl L-diethyl malate and sinapoyl L-di-t-butyl malate, have been studied using transient electronic absorption spectroscopy, in a dioxane and methanol solvent environment to investigate how well preserved these dynamics remain with increasing molecular complexity. In all cases it was found that, upon photoexcitation, deactivation occurs via a trans-cis isomerisation pathway within ∼20–30 ps. This cis-photoproduct, formed during photodeactivation, is stable and longed-lived for all molecules in both solvents. The incredible levels of conservation of the isomerisation pathway with increased molecular complexity demonstrate the efficacy of these molecules as ultraviolet photoprotectors, even in strongly perturbing solvents. As such, we suggest these molecules might be well-suited for augmentations to further improve their photoprotective efficacy or chemical compatibility with other components of sunscreen mixtures, whilst conserving their underlying photodynamic properties.     

A Scalable Parallel Interior Point Algorithm for Stochastic Linear Programming and Robust Optimization

We present a computationally efficient implementation of an interior point algorithm for solving large-scale problems arising in stochastic linear programming and robust optimization. A matrix factorization procedure is employed that exploits the structure of the constraint matrix, and it is implemented on parallel computers. The implementation is perfectly scalable. Extensive computational results are reported for a library of standard test problems from stochastic linear programming, and also for robust optimization formulations.The results show that the codes are efficient and stable for problems with thousands of scenarios. Test problems with 130 thousand scenarios, and a deterministic equivalent linear programming formulation with 2.6 million constraints and 18.2 million variables, are solved successfully.     

String tension in the three-dimensional Abelian Higgs model

We measure the expectation values of the Wilson loops for the radially active Abelian Higgs Model in three dimensions with Higgs chargeq=1 andq=2. We observe a drastic fall-off of the area term as we pass to the Higgs phase, as well as a peak of the perimetric term at the phase transition. Implications of our results for other Higgs models are also discussed.     

Consecutive k-out-of-n systems with maintenance

A consective k-out-of-n system consists of n linearly or cycliccally ordered components such that the system fails if and only if at least k consecutive components fail. In this paper we consider a maintained system where each component is repaired independently of the others according to an exponential distribution. Assuming general lifetime distributions for system's components we prove a limit theorem for the time to first failure of both linear and circular systems.