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.

The Characterization Of Creep And Time-Dependent Properties Of Bulk Metallic Glasses Using Nanoindentation

Viscoelastic deformation and creep behavior of La- and Ce-based bulk metallic glasses (BMGs) with low glass transition temperature are investigated through nanoindentation at room temperature. Creep compliance and retardation spectra are derived to study the creep mechanism. The time-dependent displacement can be well described by a generalized Kelvin model. A modification is proposed to determine the elastic modulus from the generalized Kelvin model. The results are in excellent agreement with the elastic modulus determined by uniaxial compression tests. (c) 2007 Published by Elsevier B.V.

“Deborah Numbers”, Coupling Multiple Space and Time Scales and Governing Damage Evolution to Failure

Two different spatial levels are involved concerning damage accumulation to eventual failure. nucleation and growth rates of microdamage nN* and V*. It is found that the trans-scale length ratio c*/L does not directly affect the process. Instead, two independent dimensionless numbers: the trans-scale one * * ( V*)including the * **5 * N c V including mesoscopic parameters only, play the key role in the process of damage accumulation to failure. The above implies that there are three time scales involved in the process: the macroscopic imposed time scale tim = /a and two meso-scopic time scales, nucleation and growth of damage, (* *4) N N t =1 n c and tV=c*/V*. Clearly, the dimensionless number De*=tV/tim refers to the ratio of microdamage growth time scale over the macroscopically imposed time scale. So, analogous to the definition of Deborah number as the ratio of relaxation time over external one in rheology. Let De be the imposed Deborah number while De represents the competition and coupling between the microdamage growth and the macroscopically imposed wave loading. In stress-wave induced tensile failure (spallation) De* < 1, this means that microdamage has enough time to grow during the macroscopic wave loading. Thus, the microdamage growth appears to be the predominate mechanism governing the failure. Moreover, the dimensionless number D* = tV/tN characterizes the ratio of two intrinsic mesoscopic time scales: growth over nucleation. Similarly let D be the “intrinsic Deborah number”. Both time scales are relevant to intrinsic relaxation rather than imposed one. Furthermore, the intrinsic Deborah number D* implies a certain characteristic damage. In particular, it is derived that D* is a proper indicator of macroscopic critical damage to damage localization, like D* ∼ (10–3~10–2) in spallation. More importantly, we found that this small intrinsic Deborah number D* indicates the energy partition of microdamage dissipation over bulk plastic work. This explains why spallation can not be formulated by macroscopic energy criterion and must be treated by multi-scale analysis.

The relationship between otolith increments and time for yellowfin and skipjack tuna marked with tetracycline

ENGLISH: The rate at which increments are deposited on the sagittal otoliths of yellowfin (Thunnus albacares) and skipjack (Katsuwonus p elamis) tunas is determined by a markrecapture experiment using tetracycline. During growth in fork length from 40 to 110 em, and for a period of up to 389 days, yellowfin of the Revillagigedo Islands- Baja California region deposit one increment per day in either the postrostrum or rostrum position of the otolith. For skipjack of the same region, rostrum increments underestimate time by approximately 24 percent during growth from 42 to 64 cm and over the maximum interval of 249 days. The growth rate of each species is estimated from the recapture fork length and the linear change in an otolith dimension following tetracycline injection. Over specific ranges in fork length the rates are 3.06 and 1.15 em per month for yellowfin and skipjack, respectively. SPANISH: La rapidez (tasa) en la que se depositan los incrementos en los otolitos sagitales del aleta amarilla (Thunnus albacares) y el barrilete (Katsuwonus pelamis) se determina mediante un experimento al recapturar los peces que han sido marcados con tetraciclina. Durante el crecimiento de la longitud de horquilla de 40 a 110 cm y por un período hasta de 389 días, se forma en el aleta amarilla de la región de las Islas Revillagigedo-Baja California, un incremento diario ya sea en el parte del postrostrum o rostrum de los otolitos. Con respecto al barrilete de la misma region los incrementos en el rostrum subestiman aproximadamente el tiempo en un 24 por ciento durante el crecimiento de 42 a 64 cm y sobre un intervalo máximo de 249 días. El índice de crecimiento de cada especie se estima en la recaptura según la longitud de horquilla y el cambio lineal en la dimensión de un otolito después de la inyección de tetraciclina. La variación específica sobre la longitud de horquilla de los índices son 3.06 y 1.15 cm por mes para el aleta amarilla y el barrilete, respectivamente. (PDF contains 54 pages.)

General-domain compressible Navier-Stokes solvers exhibiting quasi-unconditional stability and high-order accuracy in space and time

This thesis presents a new class of solvers for the subsonic compressible Navier-Stokes equations in general two- and three-dimensional spatial domains. The proposed methodology incorporates: 1) A novel linear-cost implicit solver based on use of higher-order backward differentiation formulae (BDF) and the alternating direction implicit approach (ADI); 2) A fast explicit solver; 3) Dispersionless spectral spatial discretizations; and 4) A domain decomposition strategy that negotiates the interactions between the implicit and explicit domains. In particular, the implicit methodology is quasi-unconditionally stable (it does not suffer from CFL constraints for adequately resolved flows), and it can deliver orders of time accuracy between two and six in the presence of general boundary conditions. In fact this thesis presents, for the first time in the literature, high-order time-convergence curves for Navier-Stokes solvers based on the ADI strategy---previous ADI solvers for the Navier-Stokes equations have not demonstrated orders of temporal accuracy higher than one. An extended discussion is presented in this thesis which places on a solid theoretical basis the observed quasi-unconditional stability of the methods of orders two through six. The performance of the proposed solvers is favorable. For example, a two-dimensional rough-surface configuration including boundary layer effects at Reynolds number equal to one million and Mach number 0.85 (with a well-resolved boundary layer, run up to a sufficiently long time that single vortices travel the entire spatial extent of the domain, and with spatial mesh sizes near the wall of the order of one hundred-thousandth the length of the domain) was successfully tackled in a relatively short (approximately thirty-hour) single-core run; for such discretizations an explicit solver would require truly prohibitive computing times. As demonstrated via a variety of numerical experiments in two- and three-dimensions, further, the proposed multi-domain parallel implicit-explicit implementations exhibit high-order convergence in space and time, useful stability properties, limited dispersion, and high parallel efficiency.

Effects of rhFSH regimen and time interval on ovarian responses to repeated stimulation cycles in rhesus monkeys during a physiologic breeding season

We studied the effects of repeated stimulation by recombinant human FSH (rhFSH) at various time intervals during a physiologic breeding season in rhesus monkeys. Ovarian recovery and responses were assessed by ultrasonography, serum steroid concentrations

Standardization of setting temperature and time for fish meat

Meat to water ratio used for washing was 1:3 for oil sardine and mackerel; but for pink perch and croaker, it was 1:2. Again the washing process was repeated three times for oil sardine and mackerel; but two times for pink perch and croaker. The washed meat was mixed with 2.5% NaC1 and set at +5°C and +40°C for 1, 2 and 3hrs. The gel strength and expressible water content was measured. Basing on this study, setting temperature at +40°C was selected and with respect to time 1hr for sardine and mackerel and 3hrs for pink perch and croaker was selected.

Comparison of Image-Based and Time-of-Flight-Based Technologies for 3D Reconstruction of Infrastructure

Image-based (i.e., photo/videogrammetry) and time-of-flight-based (i.e., laser scanning) technologies are typically used to collect spatial data of infrastructure. In order to help architecture, engineering, and construction (AEC) industries make cost-effective decisions in selecting between these two technologies with respect to their settings, this paper makes an attempt to measure the accuracy, quality, time efficiency, and cost of applying image-based and time-of-flight-based technologies to conduct as-built 3D reconstruction of infrastructure. In this paper, a novel comparison method is proposed, and preliminary experiments are conducted. The results reveal that if the accuracy and quality level desired for a particular application is not high (i.e., error < 10 cm, and completeness rate > 80%), image-based technologies constitute a good alternative for time-of-flight-based technologies and significantly reduce the time and cost needed for collecting the data on site.

Comparison of Image-Based and Time-of-Flight-Based Technologies for Three-Dimensional Reconstruction of Infrastructure

Image-based (i.e., photo/videogrammetry) and time-of-flight-based (i.e., laser scanning) technologies are typically used to collect spatial data of infrastructure. In order to help architecture, engineering, and construction (AEC) industries make cost-effective decisions in selecting between these two technologies with respect to their settings, this paper makes an attempt to measure the accuracy, quality, time efficiency, and cost of applying image-based and time-of-flight-based technologies to conduct as-built 3D reconstruction of infrastructure. In this paper, a novel comparison method is proposed, and preliminary experiments are conducted. The results reveal that if the accuracy and quality level desired for a particular application is not high (i.e., error < 10 cm, and completeness rate > 80%), image-based technologies constitute a good alternative for time-of-flight-based technologies and significantly reduce the time and cost needed for collecting the data on site.

A dependent partition-valued process for multitask clustering and time evolving network modelling

The fundamental aim of clustering algorithms is to partition data points. We consider tasks where the discovered partition is allowed to vary with some covariate such as space or time. One approach would be to use fragmentation-coagulation processes, but these, being Markov processes, are restricted to linear or tree structured covariate spaces. We define a partition-valued process on an arbitrary covariate space using Gaussian processes. We use the process to construct a multitask clustering model which partitions datapoints in a similar way across multiple data sources, and a time series model of network data which allows cluster assignments to vary over time. We describe sampling algorithms for inference and apply our method to defining cancer subtypes based on different types of cellular characteristics, finding regulatory modules from gene expression data from multiple human populations, and discovering time varying community structure in a social network.

The rhythm of fountains: The length and time scales of rise height fluctuations at low and high Froude numbers

The magnitude and frequency of vertical fluctuations of the top of an axisymmetric miscible Boussinesq fountain forms the focus of this work. We present measurements of these quantities for saline-aqueous fountains in uniform quiescent surroundings. Our results span source Froude numbers 0.3 ≤ Fr 0 ≤ 40 and, thereby, encompass very weak, weak, intermediate and forced classes of fountain. We identify distinct scalings, based on known quantities at the fountain source, for the frequency of fountain height fluctuations which collapse our data within bands of Fr0. Notably, our scalings reveal that the (dimensionless) frequency takes a constant value within each band. These results highlight characteristic time scales for the fluctuations which we decompose into a single, physically apparent, length scale and velocity scale within each band. Moreover, within one particular band, spanning source Froude numbers towards the lower end of the full range considered, we identify unexpectedly long-period fluctuations indicating a near balance of inertia and (opposing) buoyancy at the source. Our analysis identifies four distinct classes of fluctuation behaviour (four bands of Fr 0) and this classification matches well with existing classifications of fountains based on rise heights. As such, we show that an analysis of the behaviour of the fountain top alone, rather than the entire fountain, provides an alternative approach to classifying fountains. The similarity of classifications based on the two different methods confirms that the boundaries between classes mark tangible changes in the physics of fountains. For high Fr0 we show that the dominant fluctuations occur at the scale of the largest eddies which can be contained within the fountain near its top. Extending this, we develop a Strouhal number, Strtop, based on experimental measures of the fountain top, defined such that Strtop = 1 would suggest the dominant fluctuations are caused by a continual cycle of eddies forming and collapsing at this largest physical scale. For high- Fr 0 fountains we find Strtop ≈ 0. 9. © 2013 Cambridge University Press.