Deciphering Dynamic Structural and Mechanistic Complexity in Cu/CeO2/ZSM-5 Catalysts for the Reverse Water-Gas Shift Reaction
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99 GENERAL AND MISCELLANEOUS↗
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Theoretical Prediction and Interpretation of 237 Np Mössbauer Isomer Shifts
Different theoretical approaches for the calculation of 237 Np Mössbauer isomer shifts are investigated. The traditional contact density route is compared to a previously proposed alternative approach that uses energy derivatives with respect to the nuclear radius. Both approaches yield similar results as long as suitable basis sets augmented with large exponents and relativistic methods are used. Density functional theory (DFT) calculations do not show a strong dependency of the 237 Np isomer shift on the chosen functional. Wavefunction calculations show that dynamic electron correlation can be important when covalent bonding influences the isomer shift. Effects from spin–orbit coupling are small. The isomer shifts of ionic solids and Np(III) organometallic complexes are largely governed by the oxidation state of Np. Isomer shifts of organometallic Np(IV) complexes are strongly affected by donation bonding. Furthermore, detailed analysis of the wavefunction results with different active spaces demonstrates that correlation among the outer core Np and occupied ligand frontier orbitals contributes significantly to isomer shifts of Np(IV) compounds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DISCOVR strain pipeline screening – Part II: Winter and summer season areal productivities and biomass compositional shifts in climate-simulation photobioreactor cultures
Assessing the seasonal biomass productivity and compositional shift dynamics under simulated outdoor culture conditions of the top 22 algae strains selected during Tier I flask screening is an important step in the further prioritization of strains with regard to outdoor pond cultivation. These top 22 strains were subjected to Tier II testing in the PNNL Laboratory Environmental Algae Pond Simulator (LEAPS) photobioreactors, simulating light and temperature conditions of 20 cm deep outdoor ponds during the Arizona winter and summer season. All strains were grown in two consecutive nutrient-replete batch culture experiments at their particular optimal medium salinity to quantify their respective seasonal linear-phase areal biomass productivities. To determine biomass compositional shifts in response to nutrient-depletion, the LEAPS cultures were allowed to enter a 9-day nutrient depletion phase at the end of the second batch run. The following strains were evaluated in winter-season climate-simulated cultures and are listed in the order from highest (7.9 g m -2 day -1 ) to lowest (2.3 g m -2 day -1 ) areal N-replete biomass productivity: Monoraphidium minutum 26B-AM, Tetraselmis striata LANL1001, Chlorella vulgaris LRB AZ-1201, Micractinium reisseri NREL14-F2, Monoraphidium sp. MONOR1, Chlorella vulgaris NREL4-C12, Scenedesmus obliquus UTEX393, Scenedesmus acutus LRB-AP-0401, Nannochloropsis oceanica CCAP849/10, and Stichococcus minutus CCALA727. The following strains were evaluated in summer-season climate-simulated cultures and are listed in the order from highest (31.8 g m -2 day -1 ) to lowest (14.2 g m -2 day -1 ) areal N-replete biomass productivity: Picochlorum renovo NREL39-A8, Scenedesmus obliquus UTEX393, Porphyridium cruentum CCMP675, Picochlorum celeri TG2-WT-CSM/EMRE, Chlorella sorokiniana DOE1116, Stichococcus minor CCMP819, Picochlorum oklahomensis CCMP2329, Chlorella sorokiniana DOE1412 (UTEXB3016), Scenedesmus rubescens NREL46B-D3, Picochlorum soloecismus DOE101, Tetraselmis striata LANL1001, Scenedesmus obliquus DOE 0152.z, and Agmenellum quadruplicatum UTEX2268. All LEAPS cultures experienced a significant reduction in areal biomass productivity in response to nutrient-depletion, from 7-16% in the winter season simulation and up to 1-60% in the summer season simulation. Finally, for 10 of the strains tested, the carbohydrate content more than doubled upon nutrient depletion, and for 9 strains, the lipid content increased by over 50% of the initial content.
09 BIOMASS FUELS↗
237 Np Mössbauer Isomer Shifts: A Lesson About the Balance of Static and Dynamic Electron Correlation in Heavy Element Complexes
A large set of neptunium compounds with different oxidation states (III to VII) was assembled to study the Mössbauer isomer shift by wave function calculations and better understand covalency in f-elements complexes. The contact density approach was used to calculate the isomer shift using complete active space self-consistent field (CASSCF) multiconfiguration wave functions, as well as matrix product states [from Density Matrix Renormalization Group (DMRG) algorithms] for large active spaces. Dynamic correlation effects for the isomer shifts were treated via CASPT2 energy derivatives with respect to the nuclear radius. The CASSCF calculations appear to produce different orbital overlocalization errors for low and high Np oxidation states. For compounds with low Np oxidation numbers, the errors can be attributed to the overlocalization of the 5f orbitals. For the compounds with high Np oxidation numbers, the main errors arise from an overlocalization of ligand orbitals and concomitant to weak donation bonding. Attempts to mitigate the overlocalization errors with large active spaces using DMRG were only partially successful, showing that explicit treatment of dynamic correlation is necessary for accurate predictions of Mössbauer isomer shifts. The CASPT2 calculations perform very satisfactorily. For a subset of Np compounds, both static and dynamic correlation effects were substantial. Furthermore, a rational active space selection based on orbital entanglement diagrams proved beneficial for determining the optimal reference wave function.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Expected number of blue-shifts and red-shifts of ejected sources.
Doppler effect in quasar red-shifts and theoretical expected number of blue-shifts and red-shifts of ejected sources
STELLAR DOPPLER SHIFT↗
A Shift Selection Strategy for Parallel Shift-invert Spectrum Slicing in Symmetric Self-consistent Eigenvalue Computation
The central importance of large-scale eigenvalue problems in scientific computation necessitates the development of massively parallel algorithms for their solution. Recent advances in dense numerical linear algebra have enabled the routine treatment of eigenvalue problems with dimensions on the order of hundreds of thousands on the world’s largest supercomputers. In cases where dense treatments are not feasible, Krylov subspace methods offer an attractive alternative due to the fact that they do not require storage of the problem matrices. However, demonstration of scalability of either of these classes of eigenvalue algorithms on computing architectures capable of expressing massive parallelism is non-trivial due to communication requirements and serial bottlenecks, respectively. In this work, we introduce the SISLICE method: a parallel shift-invert algorithm for the solution of the symmetric self-consistent field (SCF) eigenvalue problem. The SISLICE method drastically reduces the communication requirement of current parallel shift-invert eigenvalue algorithms through various shift selection and migration techniques based on density of states estimation and k-means clustering, respectively. This work demonstrates the robustness and parallel performance of the SISLICE method on a representative set of SCF eigenvalue problems and outlines research directions that will be explored in future work.
97 MATHEMATICS AND COMPUTING↗
Extracting the Frequency-Dependent Dynamic Stokes Shift from Two-Dimensional Electronic Spectra with Prominent Vibrational Coherences
The dynamic Stokes shift is a common means for characterizing ultrafast solvation dynamics of electronically excited states. Here we extract the excitation frequency-dependent dynamic Stokes shift from two-dimensional electronic spectra (2DES) of cresyl violet, a molecule with a well-defined vibronic progression. The extracted dynamic Stokes shift function, S(t), exhibits oscillatory behavior, and the oscillatory components are assigned to intramolecular vibrational modes through DFT and TD-DFT calculations. Here, the well-characterized oscillations are incorporated into the fitting procedure of S(t). The excitation frequency dependence of the ultrafast response is examined through the analysis of S(t) obtained from slices taken at different excitation frequencies of the 2DES spectra. The extracted ultrafast timescales range from 36 to 98 fs, and we interpret the frequency dependence of the timescales in the context of other dynamic processes that also lead to lineshape changes in the 2DES spectrum, such as vibrational energy relaxation and spectral diffusion. Through comparison of the extracted timescales, we find that the fastest timescales are extracted over a range of excitation frequencies, where contributions from vibrational relaxation and spectral diffusion can be minimized.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Edge technique for measurement of laser frequency shifts including the Doppler shift
A method is disclosed for determining the frequency shift in a laser system by transmitting an outgoing laser beam. An incoming laser beam having a frequency shift is received. A first signal is acquired by transmitting a portion of the incoming laser beam to an energy monitor detector. A second signal is acquired by transmitting a portion of the incoming laser beam through an edge filter to an edge detector, which derives a first normalized signal which is proportional to the transmission of the edge filter at the frequency of the incoming laser beam. A second normalized signal is acquired which is proportional to the transmission of the edge filter at the frequency of the outgoing laser beam. The frequency shift is determined by processing the first and second normalized signals.
Korb, Larry↗
Hyperfine structures and isotopic shifts of uranium transitions using tunable laser spectroscopy of laser ablation plumes
We report isotopic shifts and hyperfine structures of selected U transitions employing tunable spectroscopy viz: laser-induced fluorescence and laser absorption spectroscopy of laser ablation plumes. The laser-produced plasmas were produced during ns laser ablation on a natural U metal which contains 0.7% 235U. Our results show that isotopic shifts between 238U and 235U are entangled with hyperfine structures of 235U. The isotopic ratio obtained using laser-induced fluorescence is affected by optical saturation effect. Time-resolved laser absorption spectroscopy is carried out for evaluating the optical absorption and estimating the hyperfine constants.
(020.3260) Isotope shifts↗
Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ 34 S records
We report total reduced inorganic S isotope ratios (δ 34 S CRS ) shift toward more negative values across much of the southern North Atlantic just before the onset of the Cenomanian-Turonian Ocean Anoxic Event (OAE-2). At the same time, there is no parallel isotopic change in the significantly larger pool of kerogen (organic) S, which indicates that the distribution and S-isotope composition of sulfide in the environment likely did not drive the change in δ 34 S CRS . Here, we investigate possible explanations for the negative shift in δ 34 S CRS values and their divergence from organic S by isolating iron sulfides for morphological identification and grain-specific isotopic analysis using secondary ion mass spectrometry (SIMS). In pre- and syn-OAE-2 sedimentary rocks from Demerara Rise, we find four distinct morphologies of iron sulfides: pyrite framboids (1–20 μm diameter), irregular pyrite aggregates (1–38 μm diameter), large cemented pyrite aggregates (~60 μm diameter), and irregular and cemented aggregates of the pyrite polymorph marcasite (1–45 μm diameter). These different textural groups have distinct S-isotopic compositions that are largely consistent through the onset of OAE-2. As such, the secular change in bulk δ 34 S CRS values likely reflects the changing proportions of these phases stratigraphically across OAE-2. All textural groups feature resolvable intra-grain δ 34 S variability, suggesting that the environments in which they formed were characterized by dynamic sulfide δ 34 S values and/or by partial closed-system distillation. We use grain-specific δ 34 S distributions to rule out shoaling of the chemocline within the sediments as a mechanism for the observed decrease in δ 34 S CRS . Instead, we propose that changes in the reactivity of the iron species delivered to Demerara Rise over the ~200 kyr leading up to the onset of OAE-2 impacted the relative contributions of pyrite with S-isotope signatures reflecting the water column, shallow sediments, and deeper sediments to the bulk sedimentary δ 34 S CRS value. Specifically, the change in iron reactivity at the onset of OAE-2 favored the production of 34 S-depleted large, cemented aggregates and framboids at the expense of more 34 S-enriched irregular aggregates. Our results underscore that bulk δ 34 S CRS measurements integrate multiple reduced phases that form via distinct reaction mechanisms and potentially in different parts of the depositional environment. Grain-specific SIMS analyses dramatically enrich our ability to interpret pyrite isotopic patterns in the geologic record.
58 GEOSCIENCES↗
Detection of the BICT State in a Borafluorene with High Stokes Shift Fluorescence
Four-coordinate aryl borafluorenes with boron–oxygen and boron–nitrogen dative bonds can exhibit very large fluorescence Stokes shifts. The large Stokes shifts are hypothesized to arise from cleavage of the boron-donor dative bond in the excited state, via a mechanism called bond-cleavage-induced intramolecular charge transfer (BICT). The primary goal of this current investigation is to directly observe the BICT state by performing transient absorption spectroscopy (TAS) on four-coordinate borafluorenes, which have improved optical stability. A novel four-coordinate aryl borafluorene was synthesized which features a dative B–O bond and two tert-butyl moieties on the aryl ring. TAS of the new borafluorene is consistent with the existence of a single, three-coordinate species in the excited state, as predicted by the BICT hypothesis. In conclusion, the TAS data is supported by fluorescence lifetime measurements and DFT calculations.
Absorption↗
Comparative Evaluation of the Single-Phase Shift and Extended-Phase Shift Control for Isolated DC-DC Converter
Abstract: This paper presents a comparative evaluation of the Single-Phase Shift (SPS) and Extended-Phase Shift (EPS) controls for the isolated DC-DC Converter. The analysis is based on the power regulation range, flexibility of operation, current stress on power devices, system efficiency while focusing on the issue of backflow power, control complexity, design and implementation overhead, and stability of the entire system. It is also examined how the backflow influences power circulation and increases current stress. Here, the Dual Active Bridge (DAB) Converter is employed to assess the performance of the control methods. Compared to SPS control, EPS offers a wider power regulation range, greater flexibility, lower current stress, and better system efficiency. However, EPS has increased control complexity, design and implementation overhead, and often requires sophisticated feedback control loops. The comparison is made through mathematical modeling of power transfer, backflow, and current stress. Simulation results validate the comparative analysis presented.
Amir, Aamir [The University of Alabama (UA)]↗
Concatenated shift registers generating maximally spaced phase shifts of PN-sequences
A large class of linearly concatenated shift registers is shown to generate approximately maximally spaced phase shifts of pn-sequences, for use in pseudorandom number generation. A constructive method is presented for finding members of this class, for almost all degrees for which primitive trinomials exist. The sequences which result are not normally characterized by trinomial recursions, which is desirable since trinomial sequences can have some undesirable randomness properties.
Hurd, W. J.↗
A generalization of binary minimum shift keying and staggered quadriphase shift keying modulation
A generalized modulation scheme, which includes minimum shift keying (MSK) and staggered quadriphase shift keying (SQPSK) as special cases, is analyzed. The general modulator is realized as a one-input, two-output sequence transducer whose outputs select the carrier signal for each band. This form of the modulator has the practical advantage of not requiring any RF filtering since there is no actual mixing of the carriers with the modulating signals. It is shown that the optimum demodulator (whether hard-decision or soft-decision) always can make its decisions from the received waveform over two bands when the interference is additive white Gaussian noise, thus generalizing a well-known result for hard decision demodulation of MSK and SQPSK signals. The power spectra of MSK and SQPSK signals are derived to isolate the role played by coherency between the modulating signals and the carriers.
Massey, J. L.↗
Doppler phase shifting using dual, switched phase shifting devices
A system of inducing a phase shift using moving reflector elements. The moving reflectors can be moving mirrors or an acousto-optical filter. The moving reflectors oscillate i.e. the move first in a first direction and then in a second direction. Two different reflectors are used so that the light can be switched between the reflectors. During a first portion of the cycle the light is coupled to the first modulator which moves the reflector in the first direction. The second modulator is out of phase with the first modulator, and the light is switched to that second modulator during a second portion of the cycle. The second modulator is also moving in the first direction when the light is applied thereto. In this way, the light obtains a constant direction Doppler shift.
Gutierrez, Roman C.↗
Effect of cobalt addition on platinum supported on multi-walled carbon nanotubes for water-gas shift
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Mitchell, Garrett M.↗