Circularly polarized light-induced potentials and the demise of excited states.

In the presence of strong electric fields, the excited states of single-electron molecules and molecules with large transient dipoles become unstable because of anti-alignment, the rotation of the molecular axis perpendicular to the field vector, where bond hardening is not possible. We show how to overcome this problem by using circularly polarized electromagnetic fields. Using a full quantum description of the electronic, vibrational, and rotational degrees of freedom, we characterize the excited electronic state dressed by the field and analyze its dependence on the bond length and angle and the stability of its vibro-rotational eigenstates. Although the dynamics is metastable, most of the population remains trapped in this excited state for hundreds of femtoseconds, allowing quantum control. Contrary to what happens with linearly polarized fields, the photodissociation occurs along the initial molecular axis, not perpendicular to it.

Obesity and impairment of pancreatic ß-cell function in early adulthood, independent of obesity age of onset: The Santiago Longitudinal Study.

AIM: We investigated the relation of time of onset and length of obesity with biomarkers of ß-cell function in early adulthood in an infancy cohort. MATERIAL AND METHODS: In 1039 23-year-olds, body-mass index (BMI) was measured at multiple time-points from enrollment. BMI trajectories were interpolated with cubic polynomials. Fasting glucose, insulin and adiponectin were measured at 23 years. Homeostatic model assessment-insulin resistance (HOMA-IR), HOMA-S, HOMA-ß, HOMA-adiponectin (AD) and disposition index (DI) were estimated. IR and non-alcoholic fatty liver (NAFL) were diagnosed. According to the BMI trajectory, five groups were defined: participants who were never obese (NOB); participants with obesity starting in adolescence and remained obese into adulthood (recent-onset obesity, ROB); participants who were obese in early childhood but transitioned to non-obesity as preadolescents (former obesity, FOB); participants who were obese in early childhood and remained obese into adulthood (persistent obesity, POB); participants with obesity starting in preadolescence and transitioned to non-obesity as adolescents (transient obesity; TOB). RESULTS: Obesity was present in 47% of participants during at least one time-point. ROBs and POBs had higher insulin, HOMA-IR and HOMA-ß, lower HOMA-S and DI, and higher prevalence of IR and NAFL at 23 years than NOBs, TOBs and FOBs. No differences were found in the ß-cell functionality of NOBs, TOBs and FOBs. CONCLUSIONS: Persistent and recent obesity are both related to IR, NAFL and a decline of ß-cell function in emerging adulthood. Defeating obesity in childhood or adolescence allows reaching emerging adulthood with ß-cell functioning similar to that of subjects who were NOB.

Thermal Sensitivity on Eccentric Gold Hollow Nanoparticles: A Perspective from Atomistic Simulations.

Eccentricity is a common feature consequence of several synthesis protocols of hollow nanoshells. Despite the crescent interest in these nanoparticles, it is still unclear how an irregular layer on the nanoparticle impacts the macroscopic properties. Here, we study the thermal stability of eccentric hollow nanoparticles (hNPs) for different sizes and eccentricity values by means of classical molecular dynamics simulations. Our results reveal that eccentricity displays a significant role in the thermal stability of hNPs. We attribute this behavior to the irregular shell contour, which collapses due to the thermal-activated diffusive process from the nanoparticle shell's most thin region. The mechanism is driven at low temperature by the nucleation of stacking faults until the amorphization for larger temperature values. Besides, for some particular eccentric hNPs, the shell suffers a surface reconstruction process, transforming the eccentric hNP into a concentric hNP. We believe that our study on thermal effects in eccentric hNPs has relevance because of their outstanding applications for plasmonic and sensing.

Anti-alignment driven dynamics in the excited states of molecules under strong fields.

We develop two novel models of the H2+ molecule and its isotopes from which we assess quantum-mechanically and semi-classically whether the molecule anti-aligns with the field in the first excited electronic state. The results from both models allow us to predict anti-alignment dynamics even for the HD+ isotope, which possesses a permanent dipole moment. The molecule dissociates at angles perpendicular to the field polarization in both the excited and the ground electronic state, as the population is exchanged through a conical intersection. The quantum mechanical dispersion of the initial state is sufficient to cause full dissociation. We conclude that the stabilization of these molecules in the excited state through bond-hardening under a strong field is highly unlikely.

Simulations suggest that navigation software may not be as efficient as expected for city traffic.

We suggest a theoretical framework to study the dynamics of an open city, with cars entering at a certain rate and leaving as they reach their destinations. In particular, we assess through simulations some unexpected consequences of the massive use of GPS (global positioning system) navigation systems in the overall dynamics. One of our main interest is to identify what type of measurements would be the most relevant for an experimental study of this system, specifically, the ones useful for city traffic administrators. To do so, we solve the microdynamics using a cellular automaton model considering three different navigation strategies based on the minimization of the individual paths (unweighted strategy) or travel times (weighted strategies). Although the system is inherently stochastic, we found in our simulations an equivalent saddle-node bifurcation for all strategies where the input rate acts as a bifurcation parameter. There is also evidence of additional bifurcations for travel time minimization based strategies. Although we found that weighted strategies are more efficient in terms of car motion, there is a destabilization phenomenon that makes, in an unexpected way, a variation of the unweighted strategy more optimal at certain densities from the fuel efficiency of the overall city traffic point of view. These results bring new insight into the intrinsic dynamics of cities and the perturbations that individual traffic routing can produce on the city as a whole.

Multifractal Characteristics of Geomagnetic Field Fluctuations for the Northern and Southern Hemispheres at Swarm Altitude.

This paper explores the spatial variations of the statistical scaling features of low to high latitude geomagnetic field fluctuations at Swarm altitude. The data for this study comes from the vector field magnetometer onboard Swarm A satellite, measured at low resolution (1 Hz) for one year (from 9 March 2016, to 9 March 2017). We estimated the structure-function scaling exponents using the p-leaders discrete wavelet multifractal technique, from which we obtained the singularity spectrum related to the magnetic fluctuations in the North-East-Center (NEC) coordinate system. From this estimation, we retain just the maximal fractal subset, associated with the Hurst exponent H. Here we present thresholding for two levels of the Auroral Electrojet index and almost the whole northern and southern hemispheres, the Hurst exponent, the structure-function scaling exponent of order 2, and the multifractal p-exponent width for the geomagnetic fluctuations. The latter quantifies the relevance of the multifractal property. Sometimes, we found negative values of H, suggesting a behavior similar to wave breaking or shocklet-like propagating front. Furthermore, we found some asymmetries in the magnetic field turbulence between the northern and southern hemispheres. These estimations suggest that different turbulent regimes of the geomagnetic field fluctuations exist along the Swarm path.

Thermal Stability of Hollow Porous Gold Nanoparticles: A Molecular Dynamics Study.

Hollow nanoparticle structures play a major role in nanotechnology and nanoscience since their surface to volume ratio is significantly larger than that of filled ones. While porous hollow nanoparticles offer a significant improvement of the available surface area, there is a lack of theoretical understanding, and scarce experimental information, on how the porosity controls or dominates the stability. Here we use classical molecular dynamics simulations to shed light on the particular characteristics and properties of gold porous hollow nanoparticles and how they differ from the nonporous ones. Adopting gold as a prototype, we show how, as the temperature increases, the porosity introduces surface stress and minor transitions that lead to various scenarios, from partial shrinkage for small filling factors to abrupt compression and the loss of spherical shape for large filling. Our work provides new insights into the stability limits of porous hollow nanoparticles, with important implications for the design and practical use of these enhanced geometries.

Long-term vs. recent-onset obesity: their contribution to cardiometabolic risk in adolescence.

BACKGROUND: The contribution of long-term vs. recent-onset obesity to cardiometabolic risk in adolescence remains controversial. Here, we aimed to investigate the association of time of onset and length of obesity with the cardiometabolic profile of adolescence. METHODS: Prospective study in 678 16-year-olds. BMI was measured at birth-1-5-10-16 years and BMI trajectories were interpolated using cubic splines. BMI > 2 SD at <6 years was defined as early obesity. Waist circumference (WC), blood pressure, lipid and glucose profiles were measured at 16 years. A cardiometabolic risk score was computed (MetS_score). According to the BMI trajectory, four groups were defined: participants who were never obese (NOB), participants with obesity during adolescence (recent-onset obese (ROB)), participants who were obese in early childhood but transitioned to normal/overweight as preadolescents (formerly obese (FOB)), and participants who were obese in early childhood and remained obese (persistently obese (POB)). RESULTS: ROBs and POBs had significantly unhealthier cardiometabolic profile than NOBs. No differences were observed in the cardiometabolic profile of ROBs compared to POBs. Although FOBs had higher WC and MetS_score than NOBs, no differences were found in other biomarkers. FOBs were in healthier cardiometabolic condition than ROBs and POBs. CONCLUSIONS: Both long-term and recent-onset obesity increase the cardiometabolic risk in adolescents.

Modeling interacting city traffic with finite acceleration and braking capacities.

Understanding the fundamental interactions in the complex behavior of one car moving in a sequence of traffic lights necessarily implies the inclusion of finite braking and accelerating capabilities. This characteristic is usually not considered in the standard cellular automaton models, where car interactions are the main concern. Therefore, here we develop a model which includes interactions and finite braking and accelerating capabilities, filling the gap between a standard cellular automaton model that considers car interactions but infinite braking and accelerating capabilities and the continuous one car model that includes finite braking and accelerating capabilities but does not consider, as the name indicates, car interactions. The proposed new model bridge these two seemingly different approaches in an effort to investigate how the traffic jams are produced. We found that, in the appropriate limits, we can reproduce the complex behavior of the one car continuous model and the dynamics close to the resonance induced by the interacting cars, forced by the traffic lights. In the processes of introducing car interactions, we observe how the average velocity decreases to finally obtain traffic jams, which are an emergent state in which the traffic lights control the generation of pulses of cars but do not control its average speed. This model is expected to improve our understanding of the complexity that appears in city traffic situations, as the finite braking and accelerating capabilities are necessary to describe the vehicle dynamics, the control strategy of traffic light synchronization, the motion of buses in segregated lights, and the whole urban design.

Au13-nAgn clusters: a remarkably simple trend.

The planar to three dimensional transition of Au13-nAgn clusters is investigated. To do so the low lying energy configurations for all possible concentrations (n values) are evaluated. Many thousands of possible conformations are examined. They are generated using the procedure developed by Rogan et al. in combination with the semi-empirical Gupta potential. A large fraction of these (the low lying energy ones) are minimized by means of Density Functional Theory (DFT) calculations. We employ the Tao, Perdew, Staroverov, and Scuseria (TPSS) meta-GGA functional and the Perdew, Burke and Ernzerhof (PBE) GGA functional, and compare their results. The effect of spin-orbit coupling is studied as well as the s-d hybridization. As usual in this context the results are functional-dependent. However, both functionals lead to agreement as far as trends are concerned, yielding just two relevant motifs, but their results differ quantitatively.

Modeling a bus through a sequence of traffic lights.

We propose a model of a bus traveling through a sequence of traffic lights, which is required to stop between the traffic signals to pick up passengers. A two dimensional model, of velocity and traveled time at each traffic light, is constructed, which shows non-trivial and chaotic behaviors for realistic city traffic parameters. We restrict the parameter values where these non-trivial and chaotic behaviors occur, by following analytically and numerically the fixed points and period 2 orbits. We define conditions where chaos may arise by determining regions in parameter space where the maximum Lyapunov exponent is positive. Chaos seems to occur as long as the ratio of the braking and accelerating capacities are greater than about ∼3.

Atomistic study of CoCrCuFeNi high entropy alloy nanoparticles: Role of chemical complexity.

High entropy alloy nanoparticles are envisaged as one of the most interesting materials compared to monoatomic materials due to their modulated properties in terms of their convenient surface-to-volume ratio. However, studies are still missing to unveil how composition or nanoparticle size can influence nanoparticle morphology. Based on molecular dynamics simulations, we perform a structural characterization as a function of nanoparticle size and the chemical composition of high entropy alloy nanoparticles subject to multiple annealing cycles. After the multiple thermal loads, we observe a substantial migration of copper atoms towards the np surface, consistent with the experimental results of Cu-based high entropy alloys. The resulting high entropy alloy nanoparticle behaves as a core-shell nanostructure with a rich fcc phase on the surface (50% of Cu) and 5% fcc phase in the nanoparticle core. Inspecting the nanoparticle surface, it is observed that high entropy alloy nanoparticles have a lack of surface facets, leading to a more spherical shape, quite different from mono-metallic nanoparticles with a high number of facets. Performing an average atoms simulation, it showed that nanoparticles are prone to form 111 surface facets independent of the nanoparticle size, suggesting that for high entropy alloy nanoparticles, the chemical complexity avoids the formation of surface facets. The latter can be explained in terms of the lattice distortion inducing tensile/compressive stress that drives the surface reconstruction. All in all our results match extremely well with experimental evidence of FeNiCrCoCu nanocrystalline materials, explaining the Cu segregation in terms of surface energy and mixing enthalpy criteria. We believe that our results provide a detailed characterization of high entropy nanoparticles focusing on how chemical complexity induces morphological changes compared to mono-crystalline nanoparticles. Besides, our findings are valuable for experimental works aimed at designing the shape and composition of multicomponent nanoparticles.

A strategy to find minimal energy nanocluster structures.

An unbiased strategy to search for the global and local minimal energy structures of free standing nanoclusters is presented. Our objectives are twofold: to find a diverse set of low lying local minima, as well as the global minimum. To do so, we use massively the fast inertial relaxation engine algorithm as an efficient local minimizer. This procedure turns out to be quite efficient to reach the global minimum, and also most of the local minima. We test the method with the Lennard-Jones (LJ) potential, for which an abundant literature does exist, and obtain novel results, which include a new local minimum for LJ13 , 10 new local minima for LJ14 , and thousands of new local minima for 15≤N≤65. Insights on how to choose the initial configurations, analyzing the effectiveness of the method in reaching low-energy structures, including the global minimum, are developed as a function of the number of atoms of the cluster. Also, a novel characterization of the potential energy surface, analyzing properties of the local minima basins, is provided. The procedure constitutes a promising tool to generate a diverse set of cluster conformations, both two- and three-dimensional, that can be used as an input for refinement by means of ab initio methods.

Three-dimensional non-approximate Coulomb interaction between two trapped quantum particles.

The two trapped quantum particles interacting problem is generalized to three dimensions, and the exact Coulomb potential is used. The system is solved by expanding the wavefunction in terms of the isotropic harmonic oscillator eigenfunctions and Hydrogen atom eigenfunctions independently, showing that each one results in a prime approximation for different domains of the normalized coupling constant of the relative interactions, suggesting that the combination of the basis is enough to build a well-suited base for the non-approximate problem. The results are compared to previous works that use a model of approximate finite-rage soft-core interaction model of the problem to give insights into the many-body states of strongly correlated ultracold bosons and fermions. We conclude that the proposed three-dimensional approach facilitates the distinction between bosons and fermions while the solutions given by the expansions better define the behavior of the particles for repulsive potentials. In addition, we discuss the substantial differences between our work and the previous approximate model.

Probing the Mechanical Properties of Porous Nanoshells by Nanoindentation.

In this contribution, we present a study of the mechanical properties of porous nanoshells measured with a nanoindentation technique. Porous nanoshells with hollow designs can present attractive mechanical properties, as observed in hollow nanoshells, but coupled with the unique mechanical behavior of porous materials. Porous nanoshells display mechanical properties that are dependent on shell porosity. Our results show that, under smaller porosity values, deformation is closely related to the one observed for polycrystalline and single-crystalline nanoshells involving dislocation activity. When porosity in the nanoparticle is increased, plastic deformation was mediated by grain boundary sliding instead of dislocation activity. Additionally, porosity suppresses dislocation activity and decreases nanoparticle strength, but allows for significant strain hardening under strains as high as 0.4. On the other hand, Young's modulus decreases with the increase in nanoshell porosity, in agreement with the established theories of porous materials. However, we found no quantitative agreement between conventional models applied to obtain the Young's modulus of porous materials.

Resolving early obesity leads to a cardiometabolic profile within normal ranges at 23 years old in a two-decade prospective follow-up study.

Obesity is the most important predisposing factor for cardiovascular disease and type-2 diabetes. We explored the relationship between the age at onset of obesity and selected cardiometabolic parameters in young adults. Longitudinal study of n = 1,039 participants (48% males) in their early twenties. BMI was measured at birth, 1-5-10-12-14-16-23 years. BMI trajectories were interpolated. Five groups were identified: never obese (never-OB); early childhood obesity transitioning to non-obesity before adolescence (former-OB); obesity starting in preadolescence transitioning to non-obesity as adolescents (transient-OB); obesity from adolescence into early adulthood (recent-onset-OB); participants who were obese in early childhood and remained obese into adulthood (persistent-OB). Waist circumference (WC), blood pressure, lipids, glucose, and insulin were measured at 23 years. HOMA-IR and the Metabolic Syndrome Risk Z-Score were estimated. In the sample, 47% were obese during at least one time-point. Mean obesity duration was 20.7 years, 8.5 years, 6.2 years, and 3.3 years in persistent-OBs, recent-onset-OBs, former-OBs, and transient-OBs, respectively. The cardiometabolic profile was more adverse in recent-onset-OBs (12%) and persistent-OBs (15%) compared to never-OB participants (53%). Although former-OBs (15%) and transient-OBs (4%) had higher WC values than never-OBs, no differences were seen in other biomarkers. Both persistent and recent-onset obesity led to a cardiometabolic profile of risk in early adulthood, as suggested by values of WC, HOMA-IR, and hs-CRP above normal limits and HDL-chol values below normal limits. Participants who had obesity in early childhood or preadolescence but transitioned to a non-obesity status had a cardiometabolic profile similar to participants who were never obese and within normal limits. Obesity leads to risky values in a number of cardiometabolic biomarkers in young adulthood independent of age at obesity onset. Likewise, overcoming obesity during the pediatric age leads to a cardiometabolic profile within normal ranges at 23 years of age.

Stability and robustness of asymptotic autocatalytic systems.

Here, we address the consequences of the extension in the space of a simple model of a system that is closed to efficient causation: the (M,R)-system model. To do so, we use a diffusion term to describe the collective motion of the nutrients' concentration across the compartmentalized space that defines the organism. We show that the non-trivial stable steady state remains despite such generalization, as long as the system is small enough to deal with the transport of the precursors to feed the entire protocell and dispose of a sufficient concentration of it in its surroundings. Such consideration explains the emergence of a bifurcation with two parameters that we characterize. Finally, we show that the robustness of the system under catastrophic losses of catalysts also remains, preserving the original's model character.

Diversity driven unbiased search of minimum energy cluster configurations.

The determination of the spatial distributions that atoms adopt to form condensed matter is a problem of crucial importance, since most physical properties depend on the atomic arrangement. This is especially relevant for clusters, where periodicity is nonexistent. Several optimization procedures have been implemented to tackle this problem, with ever increasing success. Here we put forward a search scheme which preserves as large a diversity as allowed by the use of phenomenological potentials, generating in an unbiased fashion a bank of configurations to be explored; a procedure we denominate diversity driven unbiased search (DDUS). It consists in the generation, using phenomenological potentials, of a data bank of putative minima rather than a single, or just a few, configurations which are based on the conformational space annealing method (CSA). All of the configurations in the bank are thereafter refined by means of DFT computations. Certainly, in spite of our efforts to generate a bank as diverse as possible, not all relevant structures might be included in it, since quantum effects are ignored. The procedure is applied to several examples of rhodium, palladium, silver, platinum and gold clusters, between 5 and 23 atoms in size. The main conclusion we reach is that unbiased search, among a significant number of candidates, quite often leads to rather unexpectedly low symmetry configurations, which turn out to be the lowest energy ones within our scheme.

Speeding up maximum population transfer in periodically driven multi-level quantum systems.

A fast and robust approach to controlling the quantum state of a multi-level quantum system is investigated using a twofrequency time-varying potential. A comparison with other related approaches in the context of a two-level system is also presented, showing similar times and fidelities. As a concrete example, we study the problem of a particle in a box with a periodically oscillating infinite square-well potential, from which we obtain results that can be applied to systems with periodically oscillating boundary conditions. We show that the transition between the ground and first excited state is about 20 times faster than the one performed using a single frequency, both with fidelity of 99.97%. The transition time is about 3.5 times the minimum allowed by quantum mechanics. A test of the robustness of the approach is presented, concluding that, counter-intuitively, it is not only faster but also easier to tune up two frequencies than one. This robustness makes the approach suitable for real applications.

Quantitative description of realistic wealth distributions by kinetic trading models.

Data on wealth distributions in trading markets show a power law behavior x(-)(1+alpha) at the high end, where, in general, alpha is greater than 1 (Pareto's law). Models based on kinetic theory, where a set of interacting agents trade money, yield power law tails if agents are assigned a saving propensity. In this paper we are solving the inverse problem, that is, in finding the saving propensity distribution which yields a given wealth distribution for all wealth ranges. This is done explicitly for two recently published and comprehensive wealth datasets.