Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields

We apply Density Functional Theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an eV. The DFT+U technique, parameterized to B3LYP predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP, and ~ 0.1 Angstrom, changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first row transition metal ion complexes in a condensed-matter setting.Comment: 14 pages, 6 figure

The ion seeps tonight: Assessing ionic transport in multilayered nanocomposites

Figure 6 – Schematic of cation (M+) transport through an organized multilayered composite. Controlling ion transport across membranes and interfaces is one of the central themes challenging technological pursuits ranging from corrosion to energy storage and chemical separations. Here, we present several examples in which we have studied the application of multilayer nanocomposites to regulate ion transport. These composites comprise organized layers of functional or structural elements, integrated within composites such that the specific nanostructure and composition of the materials play important roles in defining ionic interactions and mobility. In cases such as corrosion inhibition, thin film composite coatings are intended to block ionic transport, retarding deleterious corrosion reactions. We show that by manipulating the materials chemistry of highly organized polymer clay nanocomposite thin film barriers, it is possible to significantly increase corrosion resistance of steel samples in a simulated sea water environment. In contrast, for energy storage applications such as batteries, composite separators capable of rapid ionic diffusion are desired for high current performance. We explore how layered composite structures may provide effective ion diffusion planes, leading to promising ionic conductivity in new solid state separators. Finally, in chemical separations, the selective transport of ions becomes important. We examine how manipulating the chemical and electrostatic composition of layered polyelectrolyte materials leads to preferential cation transport through these composite structures, a key property for an effective separations membrane. These different technologies exemplify how the principles governing ion transport through multilayered materials can be adapted for widely varied applications, and they illustrate the potential for this materials development strategy to enable new classes of functional composite materials. Please click Additional Files below to see the full abstract

Flight Crew Alertness and Sleep Relative to Timing of In-Flight Rest Periods in Long-Haul Flights

BACKGROUND: In-flight breaks are used during augmented long-haul flight operations, allowing pilots a sleep opportunity. The U.S. Federal Aviation Administration duty and rest regulations restrict the pilot flying the landing to using the third rest break. It is unclear how effective these restrictions are on pilots’ ability to obtain sleep. We hypothesized there would be no difference in self-reported sleep, alertness, and fatigue between pilots taking the second vs. third rest breaks. METHODS: Pilots flying augmented operations in two U.S.-based commercial airlines were eligible for the study. Volunteers completed a survey at top-of-descent (TOD), including self-reported in-flight sleep duration, and Samn-Perelli fatigue and Karolinska Sleepiness Scale ratings. We compared the second to third rest break using noninferiority analysis. The influence of time of day (home-base time; HBT) was evaluated in 4-h blocks using repeated measures ANOVA. RESULTS: From 787 flights 500 pilots provided complete data. The second rest break was noninferior to the third break for self-reported sleep duration (1.5 6 0.7 h vs. 1.4 6 0.7 h), fatigue (2.0 6 1.0 vs. 2.9 6 1.3), and sleepiness (2.6 6 1.4 vs. 3.8 6 1.8) at TOD for landing pilots. Measures of sleep duration, fatigue, and sleepiness were influenced by HBT circadian time of day. DISCUSSION: We conclude that self-reported in-flight sleep, fatigue, and sleepiness from landing pilots taking the second in-flight rest break are equivalent to or better than pilots taking the third break. Our findings support providing pilots with choice in taking the second or third in-flight rest break during augmented operations

Polarization instabilities in a two-photon laser

We describe the operating characteristics of a new type of quantum oscillator that is based on a two-photon stimulated emission process. This two-photon laser consists of spin-polarized and laser-driven $^{39}$K atoms placed in a high-finesse transverse-mode-degenerate optical resonator, and produces a beam with a power of $\sim$0.2 $\mu$W at a wavelength of 770 nm. We observe complex dynamical instabilities of the state of polarization of the two-photon laser, which are made possible by the atomic Zeeman degeneracy. We conjecture that the laser could emit polarization-entangled twin beams if this degeneracy is lifted.Comment: Accepted by Physical Review Letters. REVTeX 4 pages, 4 EPS figure

Mathematical modeling of sleep state dynamics in a rodent model of shift work

Millions of people worldwide are required to work when their physiology is tuned for sleep. By forcing wakefulness out of the body’s normal schedule, shift workers face numerous adverse health consequences, including gastrointestinal problems, sleep problems, and higher rates of some diseases, including cancers. Recent studies have developed protocols to simulate shift work in rodents with the intention of assessing the effects of night-shift work on subsequent sleep (Grønli et al., 2017). These studies have already provided important contributions to the understanding of the metabolic consequences of shift work (Arble et al., 2015; Marti et al., 2016; Opperhuizen et al., 2015) and sleep-wake-specific impacts of night-shift work (Grønli et al., 2017). However, our understanding of the causal mechanisms underlying night-shift-related sleep disturbances is limited. In order to advance toward a mechanistic understanding of sleep disruption in shift work, we model these data with two different approaches. First we apply a simple homeostatic model to quantify differences in the rates at which sleep need, as measured by slow wave activity during slow wave sleep (SWS) rises and falls. Second, we develop a simple and novel mathematical model of rodent sleep and use it to investigate the timing of sleep in a simulated shift work protocol (Grønli et al., 2017). This mathematical framework includes the circadian and homeostatic processes of the two-process model, but additionally incorporates a stochastic process to model the polyphasic nature of rodent sleep. By changing only the time at which the rodents are forced to be awake, the model reproduces some key experimental results from the previous study, including correct proportions of time spent in each stage of sleep as a function of circadian time and the differences in total wake time and SWS bout durations in the rodents representing night-shift workers and those representing day-shift workers. Importantly, the model allows for deeper insight into circadian and homeostatic influences on sleep timing, as it demonstrates that the differences in SWS bout duration between rodents in the two shifts is largely a circadian effect. Our study shows the importance of mathematical modeling in uncovering mechanisms behind shift work sleep disturbances and it begins to lay a foundation for future mathematical modeling of sleep in rodents

Sisyphus Cooling of Electrically Trapped Polyatomic Molecules

The rich internal structure and long-range dipole-dipole interactions establish polar molecules as unique instruments for quantum-controlled applications and fundamental investigations. Their potential fully unfolds at ultracold temperatures, where a plethora of effects is predicted in many-body physics, quantum information science, ultracold chemistry, and physics beyond the standard model. These objectives have inspired the development of a wide range of methods to produce cold molecular ensembles. However, cooling polyatomic molecules to ultracold temperatures has until now seemed intractable. Here we report on the experimental realization of opto-electrical cooling, a paradigm-changing cooling and accumulation method for polar molecules. Its key attribute is the removal of a large fraction of a molecule's kinetic energy in each step of the cooling cycle via a Sisyphus effect, allowing cooling with only few dissipative decay processes. We demonstrate its potential by reducing the temperature of about 10^6 trapped CH_3F molecules by a factor of 13.5, with the phase-space density increased by a factor of 29 or a factor of 70 discounting trap losses. In contrast to other cooling mechanisms, our scheme proceeds in a trap, cools in all three dimensions, and works for a large variety of polar molecules. With no fundamental temperature limit anticipated down to the photon-recoil temperature in the nanokelvin range, our method eliminates the primary hurdle in producing ultracold polyatomic molecules. The low temperatures, large molecule numbers and long trapping times up to 27 s will allow an interaction-dominated regime to be attained, enabling collision studies and investigation of evaporative cooling toward a BEC of polyatomic molecules

A Thalamocortical Neural Mass Model of the EEG during NREM Sleep and Its Response to Auditory Stimulation

Few models exist that accurately reproduce the complex rhythms of the thalamocortical system that are apparent in measured scalp EEG and at the same time, are suitable for large-scale simulations of brain activity. Here, we present a neural mass model of the thalamocortical system during natural non-REM sleep, which is able to generate fast sleep spindles (12–15 Hz), slow oscillations (<1 Hz) and K-complexes, as well as their distinct temporal relations, and response to auditory stimuli. We show that with the inclusion of detailed calcium currents, the thalamic neural mass model is able to generate different firing modes, and validate the model with EEG-data from a recent sleep study in humans, where closed-loop auditory stimulation was applied. The model output relates directly to the EEG, which makes it a useful basis to develop new stimulation protocols

Cerebral Lactate Dynamics Across Sleep/Wake Cycles

Cerebral metabolism varies dramatically as a function of sleep state. Brain concentration of lactate, the end product of glucose utilization via glycolysis, varies as a function of sleep state, and like slow wave activity (SWA) in the electroencephalogram (EEG), increases as a function of time spent awake or in rapid eye movement sleep and declines as a function of time spent in slow wave sleep (SWS). We sought to determine whether lactate concentration exhibits homeostatic dynamics akin to those of SWA in SWS. Lactate concentration in the cerebral cortex was measured by indwelling enzymatic biosensors. A set of equations based conceptually on Process S (previously used to quantify the homeostatic dynamics of SWA) was used to predict the sleep/wake state-dependent dynamics of lactate concentration in the cerebral cortex. Additionally, we applied an iterative parameter space-restricting algorithm (the Nelder-Mead method) to reduce computational time to find the optimal values of the free parameters. Compared to an exhaustive search, this algorithm reduced the computation time required by orders of magnitude. We show that state-dependent lactate concentration dynamics can be described by a homeostatic model, but that the optimal time constants for describing lactate dynamics are much smaller than those of SWA. This disconnect between lactate dynamics and SWA dynamics does not support the concept that lactate concentration is a biochemical mediator of sleep homeostasis. However, lactate synthesis in the cerebral cortex may nonetheless be informative with regard to sleep function, since the impact of glycolysis on sleep slow wave regulation is only just now being investigated