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At least 73 records · Page 4

Characteristics of finite amplitude stationary gravity waves in the atmosphere of Venus

This paper extends the study of stationary gravity waves generated near the surface of Venus reported previously by Young et al. to include finite amplitude effects associated with large amplitude waves. Waves are forced near the surface of Venus by periodic forcing. The height-dependent profiles of static stability and mean wind in the Venus atmosphere play a very important role in the evolution of the nonlinear behavior of the waves, just as they do in the linear wave solutions. Certain wave properties are qualitatively consistent with linear wave theory, such as wave trapping, resonance, and wave evanescence for short horizontal wavelenghts. However, the finite amplitude solutions also exhibit many other interesting features. In particular, for forcing amplitudes representative of those that could be expected in mountainous regions such as Aphrodite Terra, waves generated near the surface can reach large amplitudes at and above cloud levels, with clear signatures in the circulation pattern. At still higher levels, the waves can reach large enough amplitude to break, unless damping rates above the clouds are sufficient to limit wave amplitude growth. Well below cloud levels the waves develop complex flow patterns as the result of finite amplitude wave-wave interactions, and waves are generated having considerably shorter horizontal wavelenghts than that associated with the forcing near the surface. Nonlinear interactions can excite waves that are resonant with the background wind and static stability fields even when the primary surface forcing does not, and these waves can dominate the wave spectrum near cloud levels. A global map of Venus topographic slopes derived from Magellan altimetry data shows that slopes of magnitude comparable to or exceeding that used to force the model are ubiquitous over the surface.

Young, Richard E.↗

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

Myerson, Allan S.↗

Diffusion models for Jupiter's radiation belt

Solutions are given for the diffusion of trapped particles in a planetary magnetic field in which the first and second adiabatic invariants are preserved but the third is not, using as boundary conditions a fixed density at the outer boundary (the magnetopause) and a zero density at an inner boundary (the planetary surface). Losses to an orbiting natural satellite are included and an approximate evaluation is made of the effects of the synchrotron radiation on the energy of relativistic electrons. Choosing parameters appropriate to Jupiter, the electrons required to produce the observed synchrotron radiation are explained. If a speculative mechanism in which the diffusion is driven by ionospheric wind is the true explanation of the electrons producing the synchrotron emission it can be concluded that Jupiter's inner magnetosphere is occupied by an energetic proton flux that would be a serious hazard to spacecraft.

Jacques, S. A.↗

The Coronae of Moderate-Mass Giants in the Hertzsprung Gap and the Clump

We have used the Roentgensatellit (ROSAT), the Extreme Ultraviolet Explorer (EUVE), and the Hubble Space Telescope (HST) to measure X-ray and ultraviolet emissions of moderate-mass (APPROX. 2-3 solar mass) giants in the Hertzsprung gap (spectral types early F to mid-G) and the post-helium flash "clump" (approx. G8-K0). Our motivation was to document the evolution of hot coronae (T greater than 10(exp 6)K) along the post-main-sequence trajectories traveled by such stars in order to gain insight concerning the "X-ray deficiency" of the F-GO giants and the strong braking of stellar rotation at the red edge of the Hertzsprung gap. With few exceptions, Hertzsprung gap and clump giants observed by ROSAT PSPC show hot (T approx. 10(exp 7)K) coronal energy distributions, regardless of any X-ray deficiency, EUVE spectra of gap star 31 Com (G0 111) indicate a broad coronal emission measure hump at approx. 10(exp 7.2)K, while the active clump giant beta Ceti (K0 III) displays a sharp peak at approx. 10(exp 6.8)K, as seen previously in the mixed clump/gap binary Capella (alpha Aur: G8 III + G0 III). The gap giants upsilon Peg (F8 III) and 24 UMa (G4 III) have EUV emissions of intermediate temperature (approx. 10(exp 7.0)K). The stars 31 Com, psi(sup 3) Psc (G0 III), and beta Cet exhibit redshifted transition zone (TZ: approx. 10(exp 5)K) lines in HST GHRS spectra, as reported earlier in Procyon (alpha CMi: F5 IV-V) and Capella G0. Such redshifts on the Sun are thought to signify flows in magnetic loops. beta Cas (F2 III)-a rare soft coronal source among the gap stars-displays blueshifts of C iv and 0 iv], although emissions at cooler and hotter temperatures are near the photospheric velocity. The remarkably broad line profiles of the fastest rotating gap giants suggest that the 10(exp 5) K "subcoronal " emission zones extend to h approx. R(sub *) above the photosphere, about 50 scale heights. In contrast to the TZ line redshifts, the upper chromospheric emissions (e.g., Mg II and Si III) of 31 Com and upsilon(sup 3) Psc have blueshifted cores. Blue-asymmetric peaks in the solar Mg a lines are thought to indicate dynamical heating in the chromosphere. Observations of the H(sub I) Ly(alpha) feature of 31 Com taken 9 months apart reveal striking profile changes, reminiscent of those noted previously in the Ly(alpha) blue peak of the Capella G0 star. We used the far-ultraviolet diagnostics, in combination with ROSAT X-ray photometry and EUVE high-excitation line strengths, to constrain physical models of the stellar outer atmospheres. Quasi-static magnetic loops can simulate the empirical coronal emission measures of the giant stars, but the inferred pressures for sensible loop lengths conflict with direct measurements of subcoronal densities. Furthermore, the high rate of emission at approx. 10(exp 5) K cannot be explained by thermal conduction down the legs of hot quasi-static loops. On the other hand, the possible existence of elongated (l - R(sub *) emission structures on the gap giants leads to a speculative scenario to explain the X-ray deficiency. It is based on the increased importance of the dynamical filling phase ("explosive evaporation") of the loop life cycle; conductive cooling, yielding TZ emissions at the footpoints, when the heating is interrupted; and the possibility for transitions between " hot " and " cool " energy balance solutions owing to dynamical suspension and centrifugal trapping of the cooling gas. The long loops might represent a vestigial global " magnetosphere " inherited from the main-sequence phase, which ultimately is disrupted near approx. G0 by the deepening convective envelope and growth of a more solar-like dynamo. Coronal emissions might be boosted temporarily as the X-ray deficiency is removed but soon would be quenched by wind braking previously inhibited by the magnetospheric "dead zone."

Ayres, Thomas R.↗

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

Ultraviolet (UV) photolysis of nitrite ions (NO 2 – ) in aqueous solutions produces a suite of radicals, viz., NO · , O – , · OH, and · NO 2 . The O – and NO · radicals are initially formed from the dissociation of photoexcited NO 2 – . The O – radical undergoes reversible proton transfer with water to generate · OH. Both · OH and O – oxidize the NO 2 – to · NO 2 radicals. The reactions of · OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO · , · OH, and · NO 2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO 2 – solvation were determined to alter the initial yields of · NO and · OH radicals as well as alter the reactivity of NO 2 – toward · OH, impacting the production of · NO 2 . The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adaptive, problem-tailored variational quantum eigensolver mitigates rough parameter landscapes and barren plateaus

Abstract Variational quantum eigensolvers (VQEs) represent a powerful class of hybrid quantum-classical algorithms for computing molecular energies. Various numerical issues exist for these methods, however, including barren plateaus and large numbers of local minima. In this work, we consider the Adaptive, Problem-Tailored Variational Quantum Eiegensolver (ADAPT-VQE) ansätze, and examine how they are impacted by these local minima. We find that while ADAPT-VQE does not remove local minima, the gradient-informed, one-operator-at-a-time circuit construction accomplishes two things: First, it provides an initialization strategy that can yield solutions with over an order of magnitude smaller error compared to random initialization, and which is applicable in situations where chemical intuition cannot help with initialization, i.e., when Hartree-Fock is a poor approximation to the ground state. Second, even if an ADAPT-VQE iteration converges to a local trap at one step, it can still “burrow” toward the exact solution by adding more operators, which preferentially deepens the occupied trap. This same mechanism helps highlight a surprising feature of ADAPT-VQE: It should not suffer optimization problems due to barren plateaus and random initialization. Even if such barren plateaus appear in the parameter landscape, our analysis suggests that ADAPT-VQE avoids such regions by design.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Contributions of biofilm-induced flow heterogeneities to solute retention and anomalous transport features in porous media

We report that microbial biofilms are ubiquitous within porous media and the dynamics of their growth influence surface and subsurface flow patterns which impacts the physical properties of porous media and large-scale transport of solutes. Here, a two-dimensional pore-scale numerical model was used to evaluate the impact of biofilm-induced flow heterogeneities on conservative transport. Our study integrates experimental biofilm images of Paenibacillus 300A strain in a microfluidic device packed with cylindrical grains in a hexagonal distribution, with mathematical modeling. Biofilm is represented as a synthetic porous structure with locally varying physical properties that honors the impact of biofilm on the porous medium. We find that biofilm plays a major role in shaping the observed conservative transport dynamics by enhancing anomalous characteristics. More specifically, when biofilm is present, the pore structure in our geometry becomes more spatially correlated. We observe intermittent behavior in the Lagrangian velocities that switches between fast transport periods and long trapping events. Our results suggest that intermittency enhances solute spreading in breakthrough curves which exhibit extreme anomalous slope at intermediate times and very marked late solute arrival due to solute retention. The efficiency of solute retention by the biofilm is controlled by a transport regime which can extend the tailing in the concentration breakthrough curves. These results indicate that solute retention by the biofilm exerts a strong control on conservative solute transport at pore-scale, a role that to date has not received enough attention.

54 ENVIRONMENTAL SCIENCES↗

Protein Crystallization

Nucleation, growth and perfection of protein crystals will be overviewed along with crystal mechanical properties. The knowledge is based on experiments using optical and force crystals behave similar to inorganic crystals, though with a difference in orders of magnitude in growing parameters. For example, the low incorporation rate of large biomolecules requires up to 100 times larger supersaturation to grow protein, rather than inorganic crystals. Nucleation is often poorly reproducible, partly because of turbulence accompanying the mixing of precipitant with protein solution. Light scattering reveals fluctuations of molecular cluster size, its growth, surface energies and increased clustering as protein ages. Growth most often occurs layer-by-layer resulting in faceted crystals. New molecular layer on crystal face is terminated by a step where molecular incorporation occurs. Quantitative data on the incorporation rate will be discussed. Rounded crystals with molecularly disordered interfaces will be explained. Defects in crystals compromise the x-ray diffraction resolution crucially needed to find the 3D atomic structure of biomolecules. The defects are immobile so that birth defects stay forever. All lattice defects known for inorganics are revealed in protein crystals. Contribution of molecular conformations to lattice disorder is important, but not studied. This contribution may be enhanced by stress field from other defects. Homologous impurities (e.g., dimers, acetylated molecules) are trapped more willingly by a growing crystal than foreign protein impurities. The trapped impurities induce internal stress eliminated in crystals exceeding a critical size (part of mni for ferritin, lysozyme). Lesser impurities are trapped from stagnant, as compared to the flowing, solution. Freezing may induce much more defects unless quickly amorphysizing intracrystalline water.

Chernov, Alexander A.↗

Bonding and reactivity of isostructural uranyl and neptunyl peroxide phases

Understanding the reactivity of actinide peroxides is critical for predicting the behavior of spent nuclear fuel in radiolytic environments. Herein, we report the synthesis and characterization of a lithium neptunyl(VI) hydroxo peroxo compound (LiNp), which is isostructural to the uranyl analogue (LiU). Single-crystal X-ray diffraction reveals that LiNp contains both [NpO 2 (O 2 ) 3 ] 4- and [NpO 2 (OH) 4 ] 2- units stabilized by Li + and hydrogen bonding and Raman spectroscopy shows systematic redshifts in neptunyl vibrational modes relative to uranyl. DFT calculations highlight the importance of secondary coordination in reproducing vibrational and structural features, but challenges remain with correctly modeling strong sigma donors. Solid-state EPR spectroscopy and DFT confirm superoxide stabilization within LiU and calculations suggest favorability of the analogous radical species in LiNp. Solution state EPR spectroscopy with the radical spin trap 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO) reveal evidence of superoxide in the LiU and LiNp phases and suggests stabilization of superoxide within actinyl triperoxide complexes, forming [AnO 2 (O 2 ) 2 (O) 2 • ] 3- .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Black hole horizons from the double copy

We describe a procedure for locating black hole horizons in 'Kerr–Schild' spacetimes in the double copy paradigm. Using only single- and zeroth-copy data on flat spacetime, our procedure predicts the existence of trapped surfaces in the double-copy gravitational solution. We show explicitly how this procedure locates the horizon of the Schwarzschild black hole and the general Myers–Perry black hole.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Crystal growth and crystallography

Selected topics that may be of interest for both crystal-structure and crystal-growth communities are overviewed. The growth of protein crystals, along with that of some other compounds, is one of the topics, and recent insights into related phenomena are considered as examples of applications of general principles. The relationship between crystal growth shape and structure is reviewed and an attempt to introduce semiquantitative characterization of binding for proteins is made. The concept of kinks for complex structures is briefly discussed. Even at sufficiently low supersaturations, the fluctuation of steps may not be sufficient to implement the Gibbs-Thomson law if the kink density is low enough. Subsurface ordering of liquids and growth of rough interfaces from melts is discussed. Crystals growing in microgravity from solution should be more perfect if they preferentially trap stress-inducing impurities, thus creating an impurity-depleted zone around themselves. Evidently, such a zone is developed only around the crystals growing in the absence of convection. Under terrestrial conditions, the self-purified depleted zone is destroyed by convection, the crystal traps more impurity and grows stressed. The stress relief causes mosaicity. In systems containing stress-inducing but poorly trapped impurities, the crystals grown in the absence of convection should be worse than those of their terrestrial counterparts.

Review, Tutorial↗

Electrical sensing, tracking, and actuation of droplets

Devices, techniques, and processes are disclosed that use electrical impedance to detect of the presence and contents of droplets including cells, nucleic acids, proteins, or solute concentrations in an array of retrievable, trackable, trapped droplets in a fluidic system. Electrodes may be positioned underneath individual droplet traps in a microchannel to assay droplet contents and/or actuating droplets for the release of the droplets from corresponding traps. The disclosed technology may be used for detection of the results of solvent extraction processes including time-dependent quantification of metal ion concentration in the aqueous and organic phases, for wastewater treatment, heavy metal detection, pharmaceutical industry, and/or biotechnology, or for environmental monitoring of wastewater for toxic metal, monitoring of biological cell viability and proliferation, monitoring of extraction processes used in heavy metal mining, monitoring of extraction processes used in nuclear fuel processing, monitoring kinetics of enzyme processes, and/or assessing pharmacodynamics and drug efficacy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Benchmarking the multiconfigurational Hartree method by the exact wavefunction of two harmonically trapped bosons with contact interaction

Highlights: • Comparison of exact and numerical single-particle density matrices. • Benchmark for multiconfigurational Hartree. • Convergence for large number of orbitals. We consider two bosons in a one-dimensional harmonic trap, interacting by a contact potential, and compare the exact solution of this problem to a self-consistent numerical solution by using the multiconfigurational time-dependent Hartree (MCTDH) method. We thereby benchmark the predictions of the MCTDH method with a few-body problem that has an analytical solution for the most commonly experimentally realized interaction potential in ultracold quantum gases. It is found that exact ground state energy and first order correlations are accurately reproduced by MCTDH up to the intermediate dimensionless coupling strengths corresponding to typical background scattering lengths of magnetically trapped ultracold dilute Bose gases. For larger couplings, established for example by (a combination of) Feshbach resonances and optical trapping, the MCTDH approach overestimates the depth of the trap-induced correlation dip of first order correlations in position space, as well as overestimates the fragmentation, defined as the average relative occupation of orbitals other than the energetically lowest one. We anticipate that qualitatively similar features in the correlation function may arise for larger particle numbers, paving the way for a quantitative assessment of the accuracy of MCTDH by experiments with ultracold atoms.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

An example of branching in a variational problem

In an experiment in space it was found that when a cubical frame was slowly withdrawn from a soap solution, the wire frame retained practically a full cube of liquid. Removed from the frame (by shaking), the faces of the cube became progressively more concave, until adjacent faces became tangential. In the present paper a mathematical model describing the shape a liquid takes due to its surface tension while suspended on a wire frame in zero-g is solved by use of Lagrange multipliers. It is shown how the configuration of soap films so bounded is dependent upon the volume of liquid trapped in the films. A special case of the solution is a soap film naturally formed on a cubical wire frame.

Darbro, W.↗

Supersaturated Electrolyte Solutions: Theory and Experiment

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

Izmailov, Alexander F.↗

Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity

In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $^+_2$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $^+_2$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $^+_2$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗