Atomic spectral-product representations of molecular electronic structure: metric matrices and atomic-product composition of molecular eigenfunctions

Recent progress is reported in development of ab initio computational methods for the electronic structures of molecules employing the many-electron eigenstates of constituent atoms in spectral-product forms. The approach provides a universal atomic-product description of the electronic structure of matter as an alternative to more commonly employed valence-bond- or molecular-orbital-based representations. The Hamiltonian matrix in this representation is seen to comprise a sum over atomic energies and a pairwise sum over Coulombic interaction terms that depend only on the separations of the individual atomic pairs. Overall electron antisymmetry can be enforced by unitary transformation when appropriate, rather than as a possibly encumbering or unnecessary global constraint. The matrix representative of the antisymmetrizer in the spectral-product basis, which is equivalent to the metric matrix of the corresponding explicitly antisymmetric basis, provides the required transformation to antisymmetric or linearly independent states after Hamiltonian evaluation. Particular attention is focused in the present report on properties of the metric matrix and on the atomic-product compositions of molecular eigenstates as described in the spectral-product representations. Illustrative calculations are reported for simple but prototypically important diatomic (H_2, CH) and triatomic (H_3, CH_2) molecules employing algorithms and computer codes devised recently for this purpose. This particular implementation of the approach combines Slater-orbital-based one- and two-electron integral evaluations, valence-bond constructions of standard tableau functions and matrices, and transformations to atomic eigenstate-product representations. The calculated metric matrices and corresponding potential energy surfaces obtained in this way elucidate a number of aspects of the spectral-product development, including the nature of closure in the representation, the general redundancy or linear dependence of its explicitly antisymmetrized form, the convergence of the apparently disparate atomic-product and explicitly antisymmetrized atomic-product forms to a common invariant subspace, and the nature of a chemical bonding descriptor provided by the atomic-product compositions of molecular eigenstates. Concluding remarks indicate additional studies in progress and the prognosis for performing atomic spectral-product calculations more generally and efficiently

Measurement and Calculation of Absolute Single and Multiple Charge Exchange Cross Sections for Fe^(q+) Ions Impacting H_2O

Charge exchange (CE) plays a fundamental role in the collisions of solar- and stellar-wind ions with lunar and planetary exospheres, comets, and circumstellar clouds. Reported herein are absolute cross sections for single, double, triple, and quadruple CE of Fe^(q+) (q = 5-13) ions with H_2O at a collision energy of 7q keV. One measured value of the pentuple CE is also given for Fe^(9+) ions. An electron cyclotron resonance ion source is used to provide currents of the highly charged Fe ions. Absolute data are derived from knowledge of the target gas pressure, target path length, and incident and charge-exchanged ion currents. Experimental cross sections are compared with new results of the n-electron classical trajectory Monte Carlo approximation. The radiative and non-radiative cascades following electron transfers are approximated using scaled hydrogenic transition probabilities and scaled Auger rates. Also given are estimates of cross sections for single capture, and multiple capture followed by autoionization, as derived from the extended overbarrier model. These estimates are based on new theoretical calculations of the vertical ionization potentials of H_2O up to H_2O^(10+)

Noise-aided gradient descent bit-flipping decoders approaching maximum likelihood decoding

International audienceIn the recent literature, the study of iterative LDPC decoders implemented on faulty-hardware has led to the counter-intuitive conclusion that noisy decoders could perform better than their noiseless version. This peculiar behavior has been observed in the finite codeword length regime, where the noise perturbating the decoder dynamics help to escape the attraction of fixed points such as trapping sets. In this paper, we will study two recently introduced LDPC decoders derived from noisy versions of the gradient descent bit-flipping decoder (GDBF). Although the GDBF is known to be a simple decoder with limited error correction capability compared to more powerful soft-decision decoders, it has been shown that the introduction of a random perturbation in the decoder could greatly improve the performance results, approaching and even surpassing belief propagation or min-sum based decoders. For both decoders, we evaluate the probability of escaping from a Trapping set, and relate this probability to the parameters of the injected noise distribution, using a Markovian model of the decoder transitions in the state space of errors localized on isolated trapping sets. In a second part of the paper, we present a modified scheduling of our algorithms for the binary symmetric channel, which allows to approach maximum likelihood decoding (MLD) at the cost of a very large number of iterations

A comparison of similar aerosol measurements made on the NASA P3-B, DC-8, and NSF C-130 aircraft during TRACE-P and ACE-Asia

Two major aircraft experiments occurred off the Pacific coast of Asia during spring 2001: the NASA sponsored Transport and Chemical Evolution over the Pacific (TRACE-P) and the National Science Foundation (NSF) sponsored Aerosol Characterization Experiment-Asia (ACE-Asia). Both experiments studied emissions from the Asian continent (biomass burning, urban/industrial pollution, and dust). TRACE-P focused on trace gases and aerosol during March/April and was based primarily in Hong Kong and Yokota Air Force Base, Japan, and involved two aircraft: the NASA DC-8 and the NASA P3-B. ACE-Asia focused on aerosol and radiation during April/May and was based in Iwakuni Marine Corps Air Station, Japan, and involved the NSF C-130. This paper compares aerosol measurements from these aircraft including aerosol concentrations, size distributions (and integral properties), chemistry, and optical properties. Best overall agreement (generally within RMS instrumental uncertainty) was for physical properties of the submircron aerosol, including condensation nuclei concentrations, scattering coefficients, and differential mobility analyzer and optical particle counter (OPC) accumulation mode size distributions. Larger differences (typically outside of the RMS uncertainty) were often observed for parameters related to the supermicron aerosols (total scattering and absorption coefficients, coarse mode Forward Scattering Spectrometer Probe and OPC size distributions/integral properties, and soluble chemical species usually associated with the largest particles, e.g., Na+, Cl−, Ca2+, and Mg2+), where aircraft sampling is more demanding. Some of the observed differences reflect different inlets (e.g., low-turbulence inlet enhancement of coarse mode aerosol), differences in sampling lines, and instrument configuration and design. Means and variances of comparable measurements for horizontal legs were calculated, and regression analyses were performed for each platform and allow for an assessment of instrument performance. These results provide a basis for integrating aerosol data from these aircraft platforms for both the TRACE-P and ACE-Asia experiments

Spectral aerosol extinction (SpEx): a new instrument for in situ ambient aerosol extinction measurements across the UV/visible wavelength range

We introduce a new instrument for the measurement of in situ ambient aerosol extinction over the 300– 700 nm wavelength range, the spectral aerosol extinction (SpEx) instrument. This measurement capability is envisioned to complement existing in situ instrumentation, allowing for simultaneous measurement of the evolution of aerosol optical, chemical, and physical characteristics in the ambient environment. In this work, a detailed description of the instrument is provided along with characterization tests performed in the laboratory. Measured spectra of NO2 and polystyrene latex spheres (PSLs) agreed well with theoretical calculations. Good agreement was also found with simultaneous aerosol extinction measurements at 450, 530, and 630 nm using CAPS PMex instruments in a series of 22 tests including nonabsorbing compounds, dusts, soot, and black and brown carbon analogs. SpEx measurements are expected to help identify the presence of ambient brown carbon due to its 300 nm lower wavelength limit compared to measurements limited to longer UV and visible wavelengths. Extinction spectra obtained with SpEx contain more information than can be conveyed by a simple power law fit (typically represented by Ångström exponents). Planned future improvements aim to lower detection limits and ruggedize the instrument for mobile operation

The impact of local sources and long-range transport on aerosol properties over the northeast U.S. region during INTEX-NA

We use data collected aboard the NASA DC-8 aircraft during the summer 2004, Intercontinental Transport and Chemical Evolution Experiment over North America (INTEX-NA) field campaign to examine the origin, composition, physical and optical properties of aerosols within air masses sampled over and downwind of the northeastern U.S. We note that aerosol concentrations within the region exhibited steep vertical gradients and significant variability in both time and space. An examination of air mass chemical signatures and backward trajectories indicates that transport from four, significantly different source regions contributed to the variability: the subtropical Atlantic Ocean (AO); the U.S. west coast and eastern Pacific (WCP); the U.S. east coast and Midwestern states (EC); and northwest Canada and Alaska (CA). AO air masses were typically confined to below 2 km altitude, exhibited low pollutant contents, contained enhanced levels of sea salt, and were typically observed when the Bermuda High strengthened. The most common air mass present in the upper troposphere, WCP air often contained weak dust and aged pollution enhances from convective input occurring over the central part of the continent. CA air exhibited enhancements in anthropogenic pollution tracers below 2 km and contained some black-carbon rich haze layers between 3 and 5 km that could be traced to forest fires burning in western Canada and Alaska. EC air was prevalent at lower elevations throughout the study area and exhibited enhanced scattering along with elevated levels of sulfate aerosols and combustion tracers. There is an overall balance between the observed cations and anions for all cases, except EC air mass below 4 km

Observational evidence for the convective transport of dust over the central United States

Bulk aerosol composition and aerosol size distributions measured aboard the DC-8 aircraft during the Deep Convective Clouds and Chemistry Experiment mission in May/June 2012 were used to investigate the transport of mineral dust through nine storms encountered over Colorado and Oklahoma. Measurements made at low altitudes (\u3c5 km mean sea level (MSL)) in the storm inflow region were compared to those made in cirrus anvils (altitude \u3e 9 km MSL). Storm mean outflow Ca2+ mass concentrations and total coarse (1 µm \u3c diameter \u3c 5 µm) aerosol volume (Vc) were comparable to mean inflow values as demonstrated by average outflow/inflow ratios greater than 0.5. A positive relationship between Ca2+, Vc, ice water content, and large (diameter \u3e 50 µm) ice particle number concentrations was not evident; thus, the influence of ice shatter on these measurements was assumed small. Mean inflow aerosol number concentrations calculated over a diameter range (0.5 µm \u3c diameter \u3c 5.0 µm) relevant for proxy ice nuclei (NPIN) were ~15–300 times higher than ice particle concentrations for all storms. Ratios of predicted interstitial NPIN (calculated as the difference between inflow NPIN and ice particle concentrations) and inflow NPIN were consistent with those calculated for Ca2+ and Vc and indicated that on average less than 10% of the ingested NPIN were activated as ice nuclei during anvil formation. Deep convection may therefore represent an efficient transport mechanism for dust to the upper troposphere where these particles can function as ice nuclei cirrus forming in situ

Elastic electron scattering from 3-hydroxytetrahydrofuran: experimental and theoretical studies

We report the results of measurements and calculations for elastic electron scattering from 3-hydroxytetrahydrofuran (C4H8O2). The measurements are performed with a crossed electron-target beam apparatus and the absolute cross-sections are determined using the relative flow technique. The calculations are carried out using the Schwinger multichannel method in the static-exchange plus polarization (SEP) approximation. A set of angular differential cross-sections (DCS) is provided at five incident energies (6.5, 8, 10, 15 and 20 eV) over an angular range of 20–130°, and the energy dependence of the elastic DCS at a scattering angle of 120° is also presented. Integral elastic and elastic momentum transfer cross-sections have also been derived and calculated. The results are compared with those of recent measurements and calculations for the structurally similar molecule tetrahydrofuran (C4H8O)