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Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward a comprehensive model for feedback by active galactic nuclei: New insights from M87 observations by LOFAR, Fermi, and H.E.S.S

Feedback by active galactic nuclei (AGNs) appears to be critical in balancing radiative cooling of the low-entropy gas at the centers of galaxy clusters and in mitigating the star formation of elliptical galaxies. New observations of M87 enable us to put forward a comprehensive model for the physical heating mechanism. Low-frequency radio observations by LOFAR revealed the absence of fossil cosmic-ray (CR) electrons in the radio halo surrounding M87. This puzzle can be resolved by accounting for the CR release from the radio lobes and the subsequent mixing of CRs with the dense ambient intracluster gas, which thermalizes the electrons on a timescale similar to the radio halo age of 40 Myr. Hadronic interactions of similarly injected CR protons with the ambient gas should produce an observable gamma-ray signal in accordance with the steady emission of the low state of M87 detected by Fermi and H.E.S.S. Hence, we normalize the CR population to the gamma-ray emission, which shows the same spectral slope as the CR injection spectrum probed by LOFAR, thereby supporting a common origin. We show that CRs, which stream at the Alfvén velocity with respect to the plasma rest frame, heat the surrounding thermal plasma at a rate that balances that of radiative cooling on average at each radius. However, the resulting global thermal equilibrium is locally unstable and allows for the formation of the observed cooling multi-phase medium through thermal instability. Provided that CR heating balances cooling during the emerging 'cooling flow', the collapse of the majority of the gas is halted around 1 keV—in accordance with X-ray data. We show that both the existence of a temperature floor and the similar radial scaling of the heating and cooling rates are generic predictions of the CR heating model.

79 ASTRONOMY AND ASTROPHYSICS↗

Witnessing Spin-Orbital Entanglement Using Resonant Inelastic X-Ray Scattering

Entanglement plays a central role in quantum technologies, yet its characterization and control in materials remain challenging. Recent developments in spectrum-based entanglement witnesses have enabled new strategies for quantifying many-body entanglement in macroscopic materials. Here, in this work, we develop a protocol for detecting spin-orbital entanglement using experiment-accessible resonant inelastic x-ray scattering. Central to our approach is the construction of a Hermitian generator from measurable spectra, which allows us to compute the quantum Fisher information (QFI) available in spin-orbital systems. The resulting QFI provides upper bounds for 𝑘-producible states and thus serves as a robust witness of spin-orbital entanglement. To account for realistic experimental limitations, we further extend our framework to include relaxed QFI bounds applicable to measurements lacking full polarization resolution.

entanglement detection↗

Backscattering cascade of beam modes off ambient density fluctuations

The effects of a given nonthermal low-frequency density-fluctuation spectrum on the amplification of Langmuir waves by a 'bump-on-tail' beam of electrons are studied. The density-fluctuation spectrum is assumed to contain a uniform distribution of wavelengths ranging from much shorter than the beam mode wavelength to of the same order. This permits multiple large-angle (back) scattering to occur. One-dimensional numerical solutions of the kinetic equations are found which yield criteria for linear saturation of the beam instability of a cascade of backscattering to high wavenumber. The relevant time scales and spectral shapes are also determined in both the stable and unstable regions. Linear damping and Cerenkov emission by a possible nonthermal tail of electrons is taken into account. An application is made to the beam modes observed simultaneously with density fluctuations off the Jovian bow shock. It is shown that the observed level of density fluctuations is sufficient to saturate the unstable Langmuir waves, although nonthermal Landau damping may prevent a cascade to very high wavenumbers.

Russell, D. A.↗

The Mimas ghost revisited - An analysis of the electron flux and electron microsignatures observed in the vicinity of Mimas at Saturn

An analysis of the electron-absorption signature observed by the cosmic-ray system on Voyager 2 near the orbit of Mimas is presented. It is found that these observations cannot be explained as the absorption signature of Mimas. By combining Pioneer 11 and Voyager 2 measurements of the electron flux at Mimas's orbit (L = 3.1), an electron spectrum is found in which most of the flux above about 100 keV is concentrated near 1 to 3 MeV. This spectral form is qualitatively consistent with the bandpass filter model of Van Allen et al. (1980). The expected Mimas absorption signature is calculated from this spectrum neglecting radial diffusion. Since no Mimas absorption signature was observed in the inbound Voyager 2 data, a lower limit on the diffusion coefficient for MeV electrons at L = 3.1 of D greater than 10 to the -8th sq Saturn radii/sec is obtained. With a diffusion coefficient this large, both the Voyager 2 and the Pioneer 11 small-scale electron-absorption-signature observations in Mimas's orbit are enigmatic. Thus the mechanism for producing these signatures is referred to as the Mimas ghost. A cloud of material in orbit with Mimas may account for the observed electron signature if the cloud is at least 1-percent opaque to electrons across a region extending over a few hundred kilometers.

Chenette, D. L.↗

Coupling between radiative flux divergence and turbulence near the surface

Near‐surface turbulent flux and radiation divergence field observations are analysed over a grass‐covered surface located at the Wageningen observatory, the Netherlands. Net radiative flux divergence appears to be a large component of the energy budget near the surface, accounting for a cooling rate of several tens of degrees per day. Long‐wave radiation divergence dominates this radiation divergence flux. We show here that long‐wave flux divergence near the surface is strongly coupled to sensible heat flux, except in high relative humidity (>90%) and foggy conditions. The net long‐wave radiative flux divergence exhibits a sharp gradient within the first 20 m above the surface. This flux divergence is itself strongly coupled to sensible heat flux through adjustments in surface‐layer profiles. Nonetheless, no systematic effect of radiation is witnessed on the turbulent temperature spectrum so that the main effect of near‐surface radiation is on the mean heat budget. As typical flux‐gradient relationships are derived based on observations taken in the near‐surface boundary‐layer region where sharp long‐wave divergence is present, we suspect that those relationships implicitly represent some of the long‐wave divergence term. A modification of Monin–Obukhov Similarity Theory to include the effect of radiative divergence is proposed and discussed. This calls for independent measurements of turbulent fluxes and radiative flux divergence near the surface to re‐derive turbulent flux‐gradient relationships independently of radiative effects.

Gentine, Pierre↗

X-ray cluster constraints on non-Gaussianity

We report constraints on primordial non-Gaussianity from the abundance of X-ray detected clusters. Our analytic prescription for adding non-Gaussianity to the cluster mass function takes into account moments beyond the skewness, and we demonstrate that those moments should not be ignored in most analyses of cluster data. We constrain the amplitude of the skewness for two scenarios that have different overall levels of non-Gaussianity, characterized by how amplitudes of higher cumulants scale with the skewness. We find that current data can constrain these one-parameter non-Gaussian models at a useful level, but are not sensitive to adding further details of the corresponding inflation scenarios. Combining cluster data with Cosmic Microwave Background constraints on the cosmology and power spectrum amplitude, we find the dimensionless skewness to be 10{sup 3}M{sub 3} = −1{sub −28}{sup +24} for one of our scaling scenarios, and 10{sup 3}M{sub 3} = −4±7 for the other. These are the first constraints on non-Gaussianity from Large Scale Structure that can be usefully applied to any model of primordial non-Gaussianity. The former constraint, when applied to the standard local ansatz (where the n-th cumulant scales as M{sub n}∝M{sub 3}{sup n−2}), corresponds to f{sub NL}{sup local} = −3{sub −91}{sup +78}. When applied to a model with a local-shape bispectrum but higher cumulants that scale as M{sub n}∝M{sub 3}{sup n/3} (the second scaling scenario), the amplitude of the local-shape bispectrum is constrained to be f{sub NL}{sup local*} = −14{sub −21}{sup +22}. For this second scaling (which occurs in various well-motivated models of inflation), we also obtain strong constraints on the equilateral and orthogonal shapes of the bispectrum, f{sub NL}{sup equil} = −52{sub −79}{sup +85} and f{sub NL}{sup orth} = 63{sub −104}{sup +97}. This sensitivity implies that cluster counts could be used to distinguish qualitatively different models for the primordial fluctuations that have identical bispectra.

79 ASTRONOMY AND ASTROPHYSICS↗

Probing neutrinos from Planck and forthcoming galaxy redshift surveys

We investigate how much the constraints on the neutrino properties can be improved by combining the CMB, the photometric and spectroscopic galaxy redshift surveys which include the CMB lensing, galaxy lensing tomography, galaxy clustering and redshift space distortion observables. We pay a particular attention to the constraint on the neutrino mass in view of the forthcoming redshift surveys such as the Euclid satellite and the LSST survey along with the Planck CMB lensing measurements. Combining the transverse mode information from the angular power spectrum and the longitudinal mode information from the spectroscopic survey with the redshift space distortion measurements can determine the total neutrino mass with the projected error of O(0.02) eV. Our analysis fixes the mass splittings among the neutrino species to be consistent with the neutrino oscillation data, and we accordingly study the sensitivity of our parameter estimations on the minimal neutrino mass. The cosmological measurement of the total neutrino mass can distinguish between the normal and inverted mass hierarchy scenarios if the minimal neutrino mass ∼<0.005 eV with the predicted 1–σ uncertainties taken into account.

79 ASTRONOMY AND ASTROPHYSICS↗

Dielectric function and plasmons in graphene: A self-consistent-field calculation within a Markovian master equation formalism

We introduce a method for calculating the dielectric function of nanostructures with an arbitrary band dispersion and Bloch wave functions. The linear response of a dissipative electronic system to an external electromagnetic field is calculated by a self-consistent-field approach within a Markovian master equation formalism (SCF-MMEF) coupled with full-wave electromagnetic equations. The SCF-MMEF accurately accounts for several concurrent scattering mechanisms. The method captures interband electron-hole-pair generation, as well as the interband and intraband electron scattering with phonons and impurities. We employ the SCF-MMEF to calculate the dielectric function, complex conductivity, and loss function for supported graphene. From the loss-function maximum, we obtain plasmon dispersion and propagation length for different substrate types [nonpolar diamondlike carbon (DLC) and polar SiO 2 and hBN], impurity densities, carrier densities, and temperatures. Plasmons on the two polar substrates are suppressed below the highest surface phonon energy, while the spectrum is broad on the nonpolar DLC. Plasmon propagation lengths are comparable on polar and nonpolar substrates and are on the order of tens of nanometers, considerably shorter than previously reported. As a result, they improve with fewer impurities, at lower temperatures, and at higher carrier densities.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Magnetic Excitations across the Metal-Insulator Transition in the Pyrochlore Iridate Eu 2 Ir 2 O 7 [Evolution of Magnetic Excitations across the Metal-Insulator Transition in the Pyrochlore Iridate Eu 2 Ir 2 O 7 ]

Here, we report a resonant inelastic x-ray scattering study of the magnetic excitation spectrum in a highly insulating Eu 2 Ir 2 O 7 single crystal that exhibits a metal-insulator transition at T MI = 111(7) K. A propagating magnon mode with a 20 meV bandwidth and a 28 meV magnon gap is found in the excitation spectrum at 7 K, which is expected in the all-in-all-out magnetically ordered state. This magnetic excitation exhibits substantial softening as the temperature is raised towards T MI and turns into a highly damped excitation in the paramagnetic phase. Remarkably, the softening occurs throughout the whole Brillouin zone including the zone boundary. This observation is inconsistent with the magnon renormalization expected in a local moment system and indicates that the strength of the electron correlation in Eu 2 Ir 2 O 7 is only moderate, so that electron itinerancy should be taken into account in describing its magnetism.

74 ATOMIC AND MOLECULAR PHYSICS↗

Laying the Foundation for a Predictive Theory of Electroweak Nuclear Phenomena

Reliable model-independent predictions of nuclear processes such as beta-decay and neutrinonucleus scattering are important for many fundamental science and mission-related investigations; For example, accurate descriptions of as beta-decay are required for modeling the anti-neutrino spectrum of nuclear reactor, whether for trying to detect new physics such as sterile neutrinos, or remotely identifying the purpose of that reactor. For these activities, we need accurate calculations, as well as careful and thorough analyses of theoretical error and uncertainty in the underlying models and the many-body methods and codes used in solving that model. Unfortunately, modern theoretical calculations of these processes are inadequate for this task. At the heart of this inadequacy is the interaction between nucleons and other particles known as nuclear currents. Historically, descriptions of nuclear currents took into account only the simplest of particle interactions. Recently, the development of an effective field theory known as chiral EFT has been used to derive large corrections to these particle interactions. However, the complex nature of these corrections inhibited their use in ab initio methods of predicting nuclear processes. We developed a novel method to address these complexities and applied it in a series of benchmark and demonstrative calculations using state-of-the-art quantum few-nucleon solvers. Specifically, we studied the role of two-nucleon currents in electroweak processes using light nuclei (i.e., nuclei containing fewer than five nucleons) as a workbench to compute these processes and quantify their uncertainties using Bayesian extensions of the EFT.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Auroral zone electric fields from DE 1 and 2 at magnetic conjunctions

Nearly simultaneous measurements of auroral zone electric fields are obtained by the Dynamics Explorer spacecraft at altitudes below 900 km and above 4,500 km during magnetic conjunctions. The measured electric fields are usually perpendicular to the magnetic field lines. The north-south meridional electric fields are projected to a common altitude by a mapping function which accounts for the convergence of the magnetic field lines. When plotted as a function of invariant latitude, graphs of the projected electric fields measured by both DE-1 and DE-2 show that the large-scale electric field is the same at both altitudes, as expected. Superimposed on the large-scale fields, however, are small-scale features with wavelengths less than 100 km which are larger in magnitude at the higher altitude. Fourier transforms of the electric fields show that the magnitudes depend on wavelength. Outside of the auroral zone the electric field spectrums are nearly identical. But within the auroral zone the high and low altitude electric fields have a ratio which increases with the reciprocal of the wavelength. The small-scale electric field variations are associated with field-aligned currents. These currents are measured with both a plasma instrument and magnetometer on DE-1.

Weimer, D. R.↗

Large Torque Variations in Two Soft Gamma Repeaters

We have monitored the pulse frequencies of the two soft gamma repeaters SGR 1806-20 and SGR 1900+14 through the beginning of year 2001 using primarily Rossi X-ray Timing Explorer Proportional Counter Array observations. In both sources, we observe large changes in the spin-down torque up to a factor of approximately 4, which persist for several months. Using long baseline phase-connected timing solutions as well as the overall frequency histories, we construct torque noise power spectra for each SGR. The power spectrum of each source is very red (power-law slope approximately -3.5). These power spectra are consistent in normalization with some accreting systems, yet much steeper in slope than any known accreting source. To the best of our knowledge, torque noise power spectra with a comparably steep frequency dependence have only been seen in young, glitching radio pulsars (e.g. Vela). The observed changes in spin-down rate do not correlate with burst activity, therefore, the physical mechanisms behind each phenomenon are also likely unrelated. Within the context of the magnetar model, seismic activity cannot account for both the bursts and the long-term torque changes unless the seismically active regions are decoupled from one another.

Woods, Peter M.↗

Meridional component of oceanic Rossby wave propagation

A three-dimensional spectral analysis of Topex altimeter data reveals a large meridional component k(y) of the wavevector k for baroclinic Rossby waves of all timescales. Its existence necessitates some refinements in our estimates of certain basic properties of the Rossby wave field. In particular, by taking into account an actual off-zonal direction of k (often exceeding 70 degrees), one finds that the wavelength, phase speed, and group velocity of mid-latitude Rossby waves (with periods less than 2 years) are much smaller than they appear to be on the assumption of a purely zonal wavenumber vector. Because of a shorter wavelength (yielding U as high as 0.6, where L is the Rossby radius of deformation), these waves are essentially dispersive. Their group velocity vector may depart from zonal by more than 30 degrees. An important intrinsic feature of the wave spectrum confirmed by our analysis is a broadband distribution with respect to k(y). Some of the dynamical implications of the large k(y)/k(x), ratio are discussed.

Satellite altimetry↗

Shaping Diffraction-Grating Grooves to Optimize Efficiency

A method of shaping diffraction-grating grooves to optimize the spectral efficiency, spectral range, and image quality of a spectral imaging instrument is under development. The method is based on the use of an advanced design algorithm to determine the possibly complex shape of grooves needed to obtain a desired efficiency-versus-wavelength response (see figure). Then electron- beam fabrication techniques are used to realize the required groove shape. The method could be used, for example, to make the spectral efficiency of the grating in a given wavelength range proportional to the inverse of the spectral efficiency of a photodetector array so that the overall spectral efficiency of the combination of the grating and the photodetector array would be flat. The method has thus far been applied to one-dimensional gratings only, but in principle, it is also applicable to two-dimensional gratings. The algorithm involves calculations in the spatial-frequency domain. The spatial-frequency spectrum of a grating is represented as a diffraction-order spectral-peak-width function multiplied by an efficiency function for a single grating groove. This representation affords computational efficiency and accuracy by making it possible to consider only the response from one grating groove (one period of the grating), instead of from the whole grating area, in determining the response from the entire grating. This combination of efficiency and accuracy is crucial for future extensions of the algorithm to two-dimensional designs and to designs in which polarization must also be taken into account. The algorithm begins with the definition of target values of relative efficiency that represent the desired spectral response of the grating in certain spectral frequencies calculated from the diffraction order and wavelength. The grating period is divided into a number of cells - typically, 100. The phase contribution from each cell is determined from the phase of the incident electromagnetic wave and the height of the grating surface in the cell. The total contribution from all cells to each target value is then calculated. Then a method known to specialists as the optimum-rotation-angle method is used to adjust the height of each cell so that the total response from all cells is optimized. The computation is iterative and continues until the desired response is obtained. In the event that the desired response is unphysical, the algorithm nevertheless strives to generate a grating-grove profile for which the response approximates the desired one as closely as possible.

Backlund, John↗

The 2.5-12 micrometers spectrum of comet Halley from the IKS-VEGA experiment

The infrared instrument IKS flown on board the VEGA space probes was designed for the detection of emission bands of parent molecules, and for a measurement of the size and temperature of the thermal emitting nuclear region. The instrument had three channels with cooled detectors: an "imaging channel" designed to modulate the signal of the nucleus and two spectroscopic channels operating at 2.5-5 and 6-12 micrometers, respectively, equipped with circular variable filters of resolving power approximately 50. This paper presents and discusses the results from the spectral channels. On VEGA 1, usable spectra were obtained at distances D from the comet nucleus ranging from 250,000 to 40,000 km corresponding to fields of view 4000 and 700 km in diameter, respectively. The important internal background signal caused by the instrument itself, which could not be cooled, had to be eliminated. Since no sky chopping was performed, we obtain difference spectra between the current spectrum and a reference spectrum with little or no cometary signal taken at the beginning of the observing sequence (D approximately 200,000 km). Final discrimination between cometary signal and instrumental background is achieved using their different time evolution, since the instrumental background is proportional to the slow temperature drift of the instrument, and the cometary signal due to parent molecules or dust grains is expected to vary in first order as D-1. The 2.5-5 micrometers IKS spectra definitely show strong narrow signals at 2.7 and 4.25 micrometers, attributed to the nu 3 vibrational bands of H2O and CO2, respectively, and a broader signal in the region 3.2-3.5 micrometers, which may be attributed to CH-bearing molecules. All these signals present the expected D-1 intensity variation. Weaker emission features at 3.6 and 4.7 micrometers could correspond to the nu 1 and nu 5 bands of H2CO and the (1 - 0) band of CO, respectively. Molecular production rates are derived from the observed emissions, assuming that they are due to resonance fluorescence excited by the Sun's infrared radiation. For the strong bands of H2O and CO2, the rovibrational lines are optically thick, and radiative transfer is taken into account. We derive production rates, at the moment of the VEGA 1 flyby, of approximately 10(30) sec-1 for H2O, approximately 2.7 x 10(28) sec-1 for CO2, approximately 5 x 10(28) sec-1 for CO, and 4 x 10(28) sec-1 for H2CO, if attributions to CO and H2CO are correct. The production rate of carbon atoms in CH-bearing molecules is approximately 9 x 10(29) sec-1 assuming fluorescence of molecules in the gas phase, but could be much less if the 3.2-3.5 micrometers emission is attributed to C-H stretch in polycyclic aromatic hydrocarbons or small organic grains. In addition, marginal features are present at 4.85 and 4.45 micrometers, tentatively attributed to OCS and molecules with the CN group, respectively. Broad absorption at 2.8-3.0 micrometers, as well as a narrow emission at 3.15 micrometers, which follow well the D-1 intensity variation, might be due to water ice. Emission at 2.8 micrometers is also possibly present, and might be due to OH created in vibrationally excited states after water photodissociation. The 6-12 micrometers spectrum does not show any molecular emission, nor emission in the 7.5-micrometers region. The spectrum is dominated by silicate emission showing a double structure with maxima at 9.0 and 11.2 micrometers, which suggests the presence of olivine.

NASA Discipline Number 52-10↗

Baryonic matter perturbations in decaying vacuum cosmology

We consider the perturbation dynamics for the cosmic baryon fluid and determine the corresponding power spectrum for a Λ(t)CDM model in which a cosmological term decays into dark matter linearly with the Hubble rate. The model is tested by a joint analysis of data from supernovae of type Ia (SNIa) (Constitution and Union 2.1), baryonic acoustic oscillations (BAO), the position of the first peak of the anisotropy spectrum of the cosmic microwave background (CMB) and large-scale-structure (LSS) data (SDSS DR7). While the homogeneous and isotropic background dynamics is only marginally influenced by the baryons, there are modifications on the perturbative level if a separately conserved baryon fluid is included. Considering the present baryon fraction as a free parameter, we reproduce the observed abundance of the order of 5% independently of the dark-matter abundance which is of the order of 32% for this model. Generally, the concordance between background and perturbation dynamics is improved if baryons are explicitly taken into account.

79 ASTRONOMY AND ASTROPHYSICS↗

A summary of the history of the development of automated remote sensing for agricultural applications

An historical account is given of the development of technology for the processing of satellite-acquired multispectral data aimed at the identification of the type, condition, and ontogenic stages of agricultural areas. During 1972 and 1973, research established the feasibility of automating digital classification for the processing of large volumes of Landsat MSS data. This capability was successfully demonstrated during the Large Area Crop Inventory Experiment, which estimated wheat crop production on a global basis. This achievement in turn led to the Agriculture and Resources Inventory Surveys Through Aerospace Remote Sensing, which investigated other portions of the electromagnetic spectrum and expanded the study of key commercial crops in important agricultural areas.

Macdonald, R. B.↗