Unimolecular reaction rates in solution and in the isolated molecule: Comparison of diphenyl butadiene nonradiative decay in solutions and supersonic jets

The recent study of diphenyl butadiene (DPB) in supersonic jets and in solution by Shepanski et al.(1) and by Courtney and Felming(2), respectively, provides an opportunity to compare the isomerization rates measured in the isolated molecule (jet) with those measured at very low viscosity in solution. These comparisons should shed light on the vibrational energy flows between “optical” and “reactive” modes in the isolated molecule and on the connection between activated, friction dependent, models of barrier crossing in solution,(3-5) and statistical RRK (or RRKM) theories of gas phase unimolecular reactions(6)

Carbohydrate intake and cardiometabolic risk factors in high BMI African American children.

The aim of this study was to evaluate the relationship between intakes of subgroups of energy-providing carbohydrate, and markers of cardiometabolic risk factors in high BMI African American (AA) children.A cross sectional analysis was performed on data from a sample of 9-11 year old children (n = 95) with BMI greater than the 85th percentile. Fasting hematological and biochemical values for selected markers of cardiometabolic risk factors were related to intakes of carbohydrates and sugars.After adjusting for gender, pubertal stage and waist circumference, multivariate regression analysis showed that higher intakes of carbohydrate (with fat and protein held constant) were associated with higher plasma concentrations of triglycerides (TG), VLDL-C, IDL-C, and worse insulin resistance (homeostasis model assessment of insulin resistance, HOMA-IR). After dividing carbohydrate into non-sugar versus sugar fractions, sugars were significantly related to higher TG, VLDL-C, IDL-C, lower adipocyte fatty acid insulin sensitivity (ISI-FFA), and was closely associated with increased HOMA-IR. Similar trends were observed for sugars classified as added sugars, and for sugars included in beverages. Further dividing sugar according to the food group from which it was consumed showed that consuming more sugar from the candy/soda food group was highly significantly associated with increased TG, VLDL-C, IDL-C and closely associated with increased HOMA-IR. Sugars consumed in all fruit-containing foods were significantly associated with lower ISI-FFA. Sugars consumed as fruit beverages was significantly associated with VLDL-C, IDL-C and ISI-FFA whereas sugars consumed as fresh, dried and preserved fruits did not show significant associations with these markers.Sugars consumed from in all dairy foods were significantly associated with higher TG, VLDL-C and IDL-C, and with significantly lower HDL-C and ISI-FFA. These effects were associated with sugars consumed in sweetened dairy products, but not with sugars consumed in unsweetened dairy products. This analysis suggests that increases in carbohydrate energy, especially in the form of sugar, may be detrimental to cardiometabolic health in high BMI children

Non-Markovian Dynamics and Entanglement of Two-level Atoms in a Common Field

We derive the stochastic equations and consider the non-Markovian dynamics of a system of multiple two-level atoms in a common quantum field. We make only the dipole approximation for the atoms and assume weak atom-field interactions. From these assumptions we use a combination of non-secular open- and closed-system perturbation theory, and we abstain from any additional approximation schemes. These more accurate solutions are necessary to explore several regimes: in particular, near-resonance dynamics and low-temperature behavior. In detuned atomic systems, small variations in the system energy levels engender timescales which, in general, cannot be safely ignored, as would be the case in the rotating-wave approximation (RWA). More problematic are the second-order solutions, which, as has been recently pointed out, cannot be accurately calculated using any second-order perturbative master equation, whether RWA, Born-Markov, Redfield, etc.. This latter problem, which applies to all perturbative open-system master equations, has a profound effect upon calculation of entanglement at low temperatures. We find that even at zero temperature all initial states will undergo finite-time disentanglement (sometimes termed "sudden death"), in contrast to previous work. We also use our solution, without invoking RWA, to characterize the necessary conditions for Dickie subradiance at finite temperature. We find that the subradiant states fall into two categories at finite temperature: one that is temperature independent and one that acquires temperature dependence. With the RWA there is no temperature dependence in any case.Comment: 17 pages, 13 figures, v2 updated references, v3 clarified results and corrected renormalization, v4 further clarified results and new Fig. 8-1

A High Reliability Asymptotic Approach for Packet Inter-Delivery Time Optimization in Cyber-Physical Systems

In cyber-physical systems such as automobiles, measurement data from sensor nodes should be delivered to other consumer nodes such as actuators in a regular fashion. But, in practical systems over unreliable media such as wireless, it is a significant challenge to guarantee small enough inter-delivery times for different clients with heterogeneous channel conditions and inter-delivery requirements. In this paper, we design scheduling policies aiming at satisfying the inter-delivery requirements of such clients. We formulate the problem as a risk-sensitive Markov Decision Process (MDP). Although the resulting problem involves an infinite state space, we first prove that there is an equivalent MDP involving only a finite number of states. Then we prove the existence of a stationary optimal policy and establish an algorithm to compute it in a finite number of steps. However, the bane of this and many similar problems is the resulting complexity, and, in an attempt to make fundamental progress, we further propose a new high reliability asymptotic approach. In essence, this approach considers the scenario when the channel failure probabilities for different clients are of the same order, and asymptotically approach zero. We thus proceed to determine the asymptotically optimal policy: in a two-client scenario, we show that the asymptotically optimal policy is a "modified least time-to-go" policy, which is intuitively appealing and easily implementable; in the general multi-client scenario, we are led to an SN policy, and we develop an algorithm of low computational complexity to obtain it. Simulation results show that the resulting policies perform well even in the pre-asymptotic regime with moderate failure probabilities

The Rotating-Wave Approximation: Consistency and Applicability from an Open Quantum System Analysis

We provide an in-depth and thorough treatment of the validity of the rotating-wave approximation (RWA) in an open quantum system. We find that when it is introduced after tracing out the environment, all timescales of the open system are correctly reproduced, but the details of the quantum state may not be. The RWA made before the trace is more problematic: it results in incorrect values for environmentally-induced shifts to system frequencies, and the resulting theory has no Markovian limit. We point out that great care must be taken when coupling two open systems together under the RWA. Though the RWA can yield a master equation of Lindblad form similar to what one might get in the Markovian limit with white noise, the master equation for the two coupled systems is not a simple combination of the master equation for each system, as is possible in the Markovian limit. Such a naive combination yields inaccurate dynamics. To obtain the correct master equation for the composite system a proper consideration of the non-Markovian dynamics is required.Comment: 17 pages, 0 figures

J/Psi Production from Electromagnetic Fragmentation in Z decay

The rate for $Z^{0}\to J/ \psi + \ell^{+}\ell^{-}$ is suprisingly large with about one event for every million $Z^{0}$ decays. The reason for this is that there is a fragmentation contribution that is not suppressed by a factor of $M^{2}_{\psi}/M^{2}_{Z}$. In the fragmentation limit $M_{Z}\to\infty$ with $E_{\psi}/M_{Z}$ fixed, the differential decay rate for $Z^{0}\to J/ \psi + \ell^{+}\ell^{-}$ factors into electromagnetic decay rates and universal fragmentation functions. The fragmentation functions for lepton fragmentation and photon fragmentation into $J/\psi$ are calculated to lowest order in $\alpha$. The fragmentation approximation to the rate is shown to match the full calculation for $E_{\psi}$ greater than about $3 M_{\psi}$.Comment: 16 pages and 8 figure

One-dimensional conduction in Charge-Density Wave nanowires

We report a systematic study of the transport properties of coupled one-dimensional metallic chains as a function of the number of parallel chains. When the number of parallel chains is less than 2000, the transport properties show power-law behavior on temperature and voltage, characteristic for one-dimensional systems.Comment: 4 pages, 5 figures, submitted to Phys. Rev. Let

The [4+2]‐Cycloaddition of α‐Nitrosoalkenes with Thiochalcones as a Prototype of Periselective Hetero‐Diels–Alder Reactions—Experimental and Computational Studies

The [4+2]‐cycloadditions of α‐nitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styryl‐substituted 4H‐1,5,2‐oxathiazines in moderate to good yields. Of the eight conceivable hetero‐Diels–Alder adducts only this isomer was observed, thus a prototype of a highly periselective and regioselective cycloaddition has been identified. Analysis of crude product mixtures revealed that the α‐nitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bis‐heterocyclic [4+2]‐cycloadducts. The experiments are supported by high‐level DFT calculations that were also extended to related hetero‐Diels–Alder reactions of other nitroso compounds and thioketones. These calculations reveal that the title cycloadditions are kinetically controlled processes confirming the role of thioketones as superdienophiles. The computational study was also applied to the experimentally studied thiochalcone dimerization, and showed that the 1,2‐dithiin and 2H‐thiopyran isomers are in equilibrium with the monomer. Again, the DFT calculations indicate kinetic control of this process

Empirical wind model for the middle and lower atmosphere. Part 1: Local time average

The HWM90 thermospheric wind model was revised in the lower thermosphere and extended into the mesosphere and lower atmosphere to provide a single analytic model for calculating zonal and meridional wind profiles representative of the climatological average for various geophysical conditions. Gradient winds from CIRA-86 plus rocket soundings, incoherent scatter radar, MF radar, and meteor radar provide the data base and are supplemented by previous data driven model summaries. Low-order spherical harmonics and Fourier series are used to describe the major variations throughout the atmosphere including latitude, annual, semiannual, and longitude (stationary wave 1). The model represents a smoothed compromise between the data sources. Although agreement between various data sources is generally good, some systematic differences are noted, particularly near the mesopause. Root mean square differences between data and model are on the order of 15 m/s in the mesosphere and 10 m/s in the stratosphere for zonal wind, and 10 m/s and 4 m/s, respectively, for meridional wind