Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Effect of structural relaxation on deformation behaviour of Zr-based metallic glass

Structural relaxation through isothermal annealing at tempertature below glass transition is conducted on Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy-4) bulk metallic glass. Defect concentration is correlated with the annealing time t according to differential scanning calorimetry thermalgrams. The effects of structural relaxation on mechanical properties and deformation behaviour are investigated by using instrumented nanoindentation. It is found that as-cast alloy exhibits pronounced serration flow during the loading process of nanoindentation, and the size and number of serrations decrease with the annealing time. The change of the deformation behaviour with structural relaxation is explained using a free volume model.

Behaviour of a puff of resuspended sediment: a conceptual model

The particulate matter concentration above the seabed is usually assumed to decrease with height, following an exponential or Rouse profile. Many particulate matter concentration profiles with a peak were found on the North Mediterranean bottom water at a few tens of metres above the bottom. A particle size signal at the same altitude was found in this area and on the New York Eight shelf. It is assumed that this unexpected shape is due to a cloud of resuspended cohesive sediments originating from an impulse resuspension process. A simplified three-dimensional numerical model is proposed to describe the behaviour of resuspended particulate matter that originates from a sediment impulse vertically injected in the bottom water. This model reproduces the concentration profile shape observed, and it gives indications concerning the length and time characteristics of such a cloud, depending on the water velocity and bottom boundary layer properties.

A New Modified Expanding Cavity Model for Characterizing the Spherical Indentation Behaviour of Bulk Metallic Glass with Pile-up

Spherical nanoindentation tests were performed on Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass and pile-ups were observed around the indenter. A new modified expanding cavity model was developed to characterize the indentation deformation behavior of strain-hardening and pressure-dependent materials. By using this model, the representative stress-strain response of this bulk metallic glass to hardness and indentation in the elastic-plastic regime were obtained taking into consideration the effect of pile-up.

On failure modes and strength characterization of brittle disordered materials under uniaxial compression and tension

With a newly developed Material Failure Process Analysis code (MFPA(2D)), influence of hetero geneity on fracture processes and strength characterization of brittle disorder materials such as rock or concrete is numerically studied under uniaxial compression and tension conditions. It is found th at, due to the heterogeneity of the disordered material, relatively more diffused micro-fractures appear in the early stage of loading. Different from homogeneous materials such as glass, macro-crack nucleation starts well before the peak stress is reached and the crack propagation and coalescence can be traced, which can be taken as a precursory to predict the macro-fracture of the material. The presence of residual strength in the post-peak region and the resemblance in the stress-strain curves between tension and compression are significant results and are found to be dependent on the heterogeneity of the specimens. Examples showing the tentative applications of MFPA(2D) in modeling failure of composite materials and rock or civil engineering problem are also given in this paper.

Fracture Mechanisms And Size Effects Of Brittle Metallic Foams: In Situ Compression Tests Inside Sem

In situ compressive tests on specially designed small samples made from brittle metallic foams were accomplished in a loading device equipped in the scanning electron microscopy (SEM). Each of the small samples comprises only several cells in the effective test zone (ETZ), with one major cell in the middle. In such a system one can not only obtain sequential collapse-process images of a single cell and its cell walls with high resolution, but also correlate the detailed failure behaviour of the cell walls with the stress-strain response, therefore reveal the mechanisms of energy absorption in the mesoscopic scale. Meanwhile, the stress-strain behaviour is quite different from that of bulk foams in dimensions of enough large, indicating a strong size effect. According to the in situ observations, four failure modes in the cell-wall level were summarized, and these modes account for the mesoscopic mechanisms of energy absorption. Paralleled compression tests on bulk samples were also carried out, and it is found that both fracturing of a single cell and developing of fracture bands are defect-directed or weakness-directed processes. The mechanical properties of the brittle aluminum foams obtained from the present tests agree well with the size effect model for ductile cellular solids proposed by Onck et al. (C) 2008 Elsevier Ltd. All rights reserved.

Time-dependent monoenergetic neutron transport in two adjacent semi-infinite media

An exact solution to the monoenergetic Boltzmann equation is obtained for the case of a plane isotropic burst of neutrons introduced at the interface separating two adjacent, dissimilar, semi-infinite media. The method of solution used is to remove the time dependence by a Laplace transformation, solve the transformed equation by the normal mode expansion method, and then invert to recover the time dependence.

The general result is expressed as a sum of definite, multiple integrals, one of which contains the uncollided wave of neutrons originating at the source plane. It is possible to obtain a simplified form for the solution at the interface, and certain numerical calculations are made there.

The interface flux in two adjacent moderators is calculated and plotted as a function of time for several moderator materials. For each case it is found that the flux decay curve has an asymptotic slope given accurately by diffusion theory. Furthermore, the interface current is observed to change directions when the scattering and absorption cross sections of the two moderator materials are related in a certain manner. More specifically, the reflection process in two adjacent moderators appears to depend initially on the scattering properties and for long times on the absorption properties of the media.

This analysis contains both the single infinite and semi-infinite medium problems as special cases. The results in these two special cases provide a check on the accuracy of the general solution since they agree with solutions of these problems obtained by separate analyses.

Density-potential mapping in the standard and quantum electrodynamical time-dependent density functional theory

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Size-dependent trajectories of DNA macromolecules due to insulative dielectrophoresis in submicrometer-deep fluidic channels.

In this paper, we demonstrate for the first time that insulative dielectrophoresis can induce size-dependent trajectories of DNA macromolecules. We experimentally use lambda (48.5 kbp) and T4GT7 (165.6 kbp) DNA molecules flowing continuously around a sharp corner inside fluidic channels with a depth of 0.4 mum. Numerical simulation of the electrokinetic force distribution inside the channels is in qualitative agreement with our experimentally observed trajectories. We discuss a possible physical mechanism for the DNA polarization and dielectrophoresis inside confining channels, based on the observed dielectrophoresis responses due to different DNA sizes and various electric fields applied between the inlet and the outlet. The proposed physical mechanism indicates that further extensive investigations, both theoretically and experimentally, would be very useful to better elucidate the forces involved at DNA dielectrophoresis. When applied for size-based sorting of DNA molecules, our sorting method offers two major advantages compared to earlier attempts with insulative dielectrophoresis: Its continuous operation allows for high-throughput analysis, and it only requires electric field strengths as low as approximately 10 Vcm.

Anomalous n-type electrical behaviour of Pd-contacted CNTFET fabricated on small-diameter nanotube.

A Pd-contacted dopant-free CNTFET with small-diameter (0.57 nm) carbon nanotube showing an anomalous n-type electrical characteristic is reported for the first time. This observed behaviour is attributed to a carbon nanotube work function higher than (or close to) palladium as well as a large hole-to-electron effective mass ratio of approximately 2.5 predicted by hybridization in small-diameter nanotubes. A variation of the conduction type with temperature is also observed and is attributed to an increase of the palladium work function and decrease of the CNT work function with increasing temperature.

Predatory behaviour of a snakehead fish (Channa striatus Bloch)

The predatory behaviour of a snake-head, Channa striatus (Bloch) on Labeo rohita fingerlings was studied in the laboratory. The study was conducted with six C. striatus (120 to 210 g and 22 to 28 cm) over 24h a day for 3 weeks. Three different sizes prey of large (2.00g and 5.8cm), medium (1.30g and 4.5cm) and small (0.72g and 3.5cm) were used for the first week and then medium size prey for 2nd and 3rd weeks. All the predators preferred eating the small group of L. rohita although all three size groups of L. rohita offered were available. It was found that the prey fishes remained together aside of the aquarium from the predator. Predator first targeted a prey, drove fast towards it, the prey tried to escape from the predator's attack using a specific route and finally the predator grasped the prey on head first and then engulfed. The handling time ranged between 45 and 50 sec. The time of peak feeding was found in the morning and in the evening of day. When 2 or 3 predators were kept in one aquarium, they engaged in fighting, head on, followed by an attack on the mouth region by the dominant one, and subsequently on the pectoral fin and caudal fin of the defeating one. After 2-3 days they became habituated to remain together and did not involve themselves in fighting.

Influence of light on diurnal behaviour of Carangids in the Wadge Bank trawl fishery

Adequate data on the Wadge Bank fishery relating to several groups of fish, including Carangids, taken in bottom trawls are available for study. Analysis of this data indicated that the variation in Carangid catches was related to the time of day. In this paper, the available Wadge Bank fishery data is analysed and discussed to show the diurnal changes in Carangid catches and the probable influence of light in affecting these changes.

Predatory behaviour of a perch, Nandus nandus (Ham.)

Predatory behaviour of Nandus nandus was studied by offering Cyprinus carpio as prey. The study was conducted with six N. namdus (8.2 ±0.2 cm and 7.60 ±0.3g) represented as P 1, P 2, P 3, P 4, P 5 and P 6. Three size categories of prey (C. carpio) such as small (2.0 ±0.1 cm and 0.23 ±0.01g), large (3.6 ±0.1 cm and 0.57 ±O.O.lg) and mixed group consisting of both small and large prey were used for 14 days of trial. Predatory behavior was classified as targeting, driving, catching, handling, resting and next attempt of catching prey. After introduction of prey into the aquarium predators followed the movement of preys by eye movements and tried to target smaller one first. The predator grasped the head of the prey by its jaws by a drive and engulfed it wholly into the mouth. The average handling time (time taken to manipulate and swallow prey from capture to ceasation of pharyngeal movement) was 42±2 sec and 47±2 sec for small and large prey respectively. N. nandus were ingested more small prey than large prey though the size classes were equally available in case of mixed prey used. Although the prey consumption was higher in number when small prey were ingested but in weight the consumption was higher when ingested large size of prey. The study indicated that N. nandus, ingested more small prey and grasped the headfirst.

On the behaviour of marine crustaceans in an electrical field of alternating current

The minimum flow of current essential to produce electro-narcosis and fixation in marine crustaceans, Metapenaeus affinis, Parapenaeopsis stylifera, Panulirus ornatus and Neptunus sanguinofentus in an AC field of specific strength varied with the lengths of animals tested, except in case of the last one where the increase in size of animals showed no significant effect on the effective period for different reactions. M. affinis in interrupted AC required threshold pulses for narcosis and fixation, which varied inversely with the length of the organism. Animals subjected to current of higher effective period required longer time for recovery in interrupted AC of 50 c/s. The period for narcosis and recovery of M. affinis did not vary significantly with repeated stimulations on the same organism.

Temporal behaviour of marine landing in Karnataka 2. Seasonal patterns

Seasonal patterns of 21 fisheries in Karnataka (after isolation from time-series components) are presented. Depending on the pattern of seasonal fluctuation in landings, 19 fisheries have been grouped into five patterns, A, B, C, D and E. Ribbon fishes and 'other clupeids' did not exhibit any significant seasonal pattern. Pattern A with highest landings in the 4th quarter (October to December), followed by the 1, 2 and 3 quarters, is the most common in 10 species/groups (comprising 78% of the total landings). Harmonic analysis has been carried out using the seasonal indices.