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At least 163 records · Page 9

Design of Experiments for Dynamic Test Runs in Solvent-Based CO 2 Capture Pilot Plants

Test runs in the pilot plants consume significant resources, and therefore, the learning from test runs should be maximized. Test runs conducted in the pilot plants are often steady state. It takes several hours for reaching steady-state in the pilot plants, and thus, the duration of the test runs needs to be long even for collecting few steady-state data points. On the other hand, a large number of measurements can be collected through dynamic test runs in a short span of time. This paper presents a systematic design of dynamic experiments (DoDEs) for identifiability of model parameters, which is achieved by persistently exciting the inputs signals. A pseudorandom binary sequence (PRBS) is designed as the input signal for DoDE due to its efficiency in obtaining sufficient spectral content. However, due to the long sequence size of the PRBS signal, a Schroeder-phase input signal, which is a multisine signal, is also designed. Tests for both types of signals are run in the Pilot Solvent Test Unit (PSTU) at the National Carbon Capture Center in Wilsonville, Alabama. The transient data are used to solve dynamic data reconciliation and parameter estimation problem. The estimated parameters are found to be not only superior to those estimated from using data collected from hundreds of steady-state test runs in a nonreactive (air–water) system, but the parameters could be estimated by using the dynamic data collected for about 24 h from the pilot plant for the MEA-H 2 O–CO 2 system.

CO2 capture↗

Cavity Controlled Upconversion in CdSe Nanoplatelet Polaritons

Exciton-polaritons provide a versatile platform for investigating quantum electrodynamics effects in chemical systems, such as polariton-altered chemical reactivity. However, using polaritons in chemical contexts will require a better understanding of their photophysical properties under ambient conditions, where chemistry is typically performed. Here, we used cavity quality factor to control strong light–matter interactions and in particular the excited state dynamics of colloidal CdSe nanoplatelets (NPLs) coupled to a Fabry– Pérot optical cavity. With increasing cavity quality factor, we observe significant population of the upper polariton (UP) state, exemplified by the rare observation of substantial UP photoluminescence (PL). Excitation of the lower polariton (LP) states results in upconverted PL emission from the UP branch due to efficient exchange of population between the LP, UP and the reservoir of dark states present in collectively coupled polaritonic systems. In addition, we measure time scales for polariton dynamics ~100 ps, implying great potential for NPL based polariton systems to affect photochemical reaction rates. State-of-the-art quantum dynamical simulations show outstanding quantitative agreement with experiments, and thus provide important insight into polariton photophysical dynamics of collectively coupled nanocrystal-based systems. These findings represent a significant step toward the development of practical polariton photochemistry platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of polarization density waves in SrTiO 3

The nature of the incipient ferroelectric transition in SrTiO 3 has been a long-standing puzzle in condensed matter physics. One explanation involves the competition between ferroelectricity and an instability characterized by the mesoscopic modulation of the polarization. These polarization density waves, which should intensify near the quantum critical point, break local inversion symmetry and are difficult to characterize with conventional X-ray scattering methods. Here, in this study, we probe inversion symmetry breaking at finite momenta and visualize the instability of the polarization at the nanometre scale in SrTiO3 by combining a femtosecond X-ray free-electron laser with terahertz coherent control methods. We found polar-acoustic collective modes that are soft, particularly at the tens of nanometre scale. These precursor collective excitations provide evidence for the conjectured mesoscopic-modulated phase in SrTiO 3 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of mApple as a Red Fluorescent Protein for Cryogenic Single-Molecule Imaging with Turn-Off and Turn-On Active Control Mechanisms

Single-molecule superresolution microscopy is a powerful tool for the study of biological structures on size scales smaller than the optical diffraction limit. Imaging samples at cryogenic temperatures (77 K) reduces the quantum yield of photobleaching for many fluorescent labels, yielding localization precisions below 10 nm. Cryogenic imaging further enables correlation with cryogenic electron tomography. A key limitation in applying methods such as PALM and STORM to samples maintained at 77 K is the limited number of fluorophores known to undergo efficient turn-on and turn-off mechanisms necessary to control the sparsity of active emitters. Here we find that mApple, a red-emitting fluorescent protein, undergoes a novel turn-off mechanism in response to simultaneous illumination with two colors of light. This turn-off mechanism enables localization of many individual molecules in initially bright samples, but the final density of localizable emitters is limited by relatively inefficient turn-on (photoactivation). Bulk excitation and emission spectroscopy shows that mApple has access to two distinct emissive states as well as dark states accessible optically or through changes in pH. The bright and stable emission of mApple enables widefield collection of single-molecule emission spectra, which highlight the complex nature and environmental sensitivity of states observed in red fluorescent proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microscopic modeling of direct pre-equilibrium emission: Impact on exclusive and inclusive (n, x n) and fission channels

We report on a microscopic modeling of the first order of multistep direct emission based on one phonon excitations, given by the QRPA model, and an effective in-medium nucleon nucleon interaction, described within the JLM folding model. The results of our coupled channels framework for deformed target are illustrated in the case of low energy discrete state excitations in 152 Sm. Pre-equilibrium predictions and their impact on inclusive and exclusive (n,xn) cross sections and fission cross sections are discussed for actinides. We discuss the importance of i) collective excitations to describe the neutron emission spectra and of ii) spin distribution of the residual nucleus formed after the neutron pre-equilibrium emission, that is a key ingredient to model the residual nucleus decay.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Ab initio symmetry-adapted approaches to nuclear reactions

In this review, we discuss recent applications of the ab initio symmetry-adapted no-core shell-model (SA-NCSM) theory for study and prediction of structure and reactions of stable and unstable nuclei from light to medium mass range. We explore structure properties of neutron-rich He, Li, and Mg isotopes, with a focus on nuclear collectivity, clustering, and spectroscopic factors, as well as multi-particle excitations of utmost significance in the proximity of the drip lines. In addition, we present extensions of the SA-NCSM with continuum for determining the microscopic structure of reaction fragments, which enables calculations of reaction cross sections for targets from the lightest He to 40Ca, rooted in first principles. We illustrate this for neutron and proton elastic scattering, deuteron and alpha capture reactions, and alpha knock-out reactions. Furthermore, we discuss microscopic optical potentials with uncertainty quantification, a critical ingredient in many reaction models. As a result, we also discuss the impact of alpha clustering on reactions of significance to nuclear astrophysics, as well as on beta decays and beyond-the-standard-model physics.

Ab initio approaches to nuclear reactions↗

Nonresonant Raman Control of Ferroelectric Polarization

Important advances is recently made in the search for materials with complex multi-phase landscapes that host photoinduced metastable collective states with exotic functionalities. In almost all cases so far, the desired phases are accessed by exploiting light–matter interactions via the imaginary part of the dielectric function through above-bandgap or resonant mode excitation. Nonresonant Raman excitation of coherent modes is experimentally observed and proposed for dynamic material control, but the resulting atomic excursion is limited to perturbative levels. Here, in this study, this challenge is overcome by employing nonresonant ultrashort pulses with low photon energies well below the bandgap. Using mid-infrared pulses, ferroelectric reversal is induced in lithium niobate, and the large-amplitude mode displacements are characterized through femtosecond stimulated Raman scattering and second harmonic generation. This approach, validated by first-principle calculations, defines a novel method for synthesizing hidden phases with unique functional properties and manipulating complex energy landscapes at reduced energy consumption and ultrafast speeds.

Shi, Jiaojian [Stanford Univ., CA (United States);↗

Proton inelastic scattering reveals deformation in 8 He

A measurement of proton inelastic scattering of 8He at 8.25A MeV at TRIUMF shows a resonance at 3.54(6) MeV with a width of 0.89(11) MeV. The energy of the state is in good agreement with coupled cluster and no-core shell model with continuum calculations, with the latter successfully describing the measured resonance width as well. Its differential cross section analyzed with phenomenological collective excitation form factor and microscopic coupled reaction channels framework consistently reveals a large deformation parameter = 0.40(3), consistent with no-core shell model predictions of a large neutron deformation. This deformed double-closed shell at the neutron drip-line opens a new paradigm.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and ab initio calculations

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS - ), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS - ), and triflate (TF - ), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS + ), particularly at ~193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. Here we observed the lowest vertical detachment energy of 6.6 eV of pTS - in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS - , 308.1 kcal/mol for TFMBS - , and 303.2 kcal/mol for TF - , which suggest the increasing acidity strength, yet even the weakest acid pTS - is still stronger than strong acid HBr. The photolysis of TPS + -based PAG, TPS + ·pTS - , generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS - displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Edge States Drive Exciton Dissociation in Ruddlesden–Popper Lead Halide Perovskite Thin Films

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA) 2 (MA) n-1 Pb n I 3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. Furthermore, we analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ~0.18 cm 2 s –1 . We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Charge Correlations in Cuprate Superconductors

High-temperature superconductivity, with transition temperatures up to ≈134 K at ambient pressure, occurs in layered cuprate compounds. The conducting CuO 2 planes, which are universally present, are responsible for the superconductivity but also show a disposition to other competing states including spin and charge order. Charge-density-wave (CDW) order appears to be a universal property of cuprate superconductors. It has been studied via a multitude of probes including X-ray and neutron scattering, nuclear magnetic resonance, scanning probe techniques, electronic transport, and quantum oscillations. Here, we review the microscopic properties of the CDW order. We discuss the nature of the ordered state, that is, its symmetry and microscopic structure. Furthermore, we show how the CDW order is related to quenched disorder, host structure, symmetry breaking perturbations, and magnetic fields. Here, we also describe measurements of dynamic collective charge excitations that are closely related to the quasi-static CDW order. Finally, we highlight some of the debated issues in the field, including the origin of the CDW order, the relationship to spin order, and the nature of the spatial CDW correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Deciphering between enhanced light emission and absorption in multi-mode porphyrin cavity polariton samples

Abstract It remains unclear how the collective strong coupling of cavity-confined photons to the electronic transitions of molecular chromophore leverages the distinct properties of the polaritonic constituents for future technologies. In this study, we design, fabricate, and characterize multiple types of Fabry-Pérot (FP) mirco-resonators containing copper(II) tetraphenyl porphyrin (CuTPP) to show how cavity polariton formation affects radiative relaxation processes in the presence of substantial non-Condon vibronic coupling between two of this molecule’s excited electronic states. Unlike the prototypical enhancement of Q state radiative relaxation of CuTPP in a FP resonator incapable of forming polaritons, we find the light emission processes in multimode cavity polariton samples become enhanced for cavity-exciton energy differences near those of vibrations known to mediate non-Condon vibronic coupling. We propose the value of this detuning is consistent with radiative relaxation of Herzberg-Teller polaritons into collective molecular states coupled to the cavity photon coherently. We contrast the feature stemming from light emission from the HT polariton state with those that occur due to polariton-enhanced light absorption. Our results demonstrate the landscape of molecular and photonic interactions enabled by cavity polariton formation using complex chromophores and how researchers can design resonators to leverage these interactions to characterize and control polaritonic properties.

Odewale, Elizabeth O.↗

Evolution of shape and collectivity along the Ge isotopic chain: The case of 80 Ge

In this work, the shape and collectivity of 80 Ge were investigated via a sub-barrier-energy Coulomb excitation measurement using the JANUS setup at the NSCL ReA3 facility. The 80 Ge spectroscopic quadrupole moment $Q_{s}(2^{+}_{1})$ of the $2^{+}_{1}$ state was measured for the first time, and the precision of the 80 Ge $B(E2; 0^{+}_{1}$ → $2^{+}_{1}$) transition strength was increased. The experimental $Q_{s}(2^{+}_{1})$ value indicates a large, prolate deformation for 80 Ge, which is consistent with large-scale shell-model calculations performed for comparison. These results provide important benchmarks for models that try to describe nuclear shape in neutron-rich nuclei near the magic number N=50.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Spinor $GW$ Bethe-Salpeter calculations in BerkeleyGW: Implementation, symmetries, benchmarking, and performance

Computing the GW quasiparticle band structure and Bethe-Salpeter equation (BSE) absorption spectra for materials with spin-orbit coupling have commonly been done by treating GW corrections and spin-orbit coupling (SOC) as separate perturbations to density-functional theory. However, accurate treatment of materials with strong spin-orbit coupling (such as many topological materials of recent interest, and thermoelectrics) often requires a nonperturbative approach using spinor wave functions in the Kohn-Sham equation and GW/BSE. Such calculations have only recently become available, in particular for the BSE. Here, we have implemented this approach in the plane-wave pseudopotential GW/BSE code BerkeleyGW, which is highly parallelized and widely used in the electronic-structure community. We present reference results for quasiparticle band structures and optical absorption spectra of solids with different strengths of spin-orbit coupling, including Si, Ge, GaAs, GaSb, CdSe, Au, and Bi 2 Se 3 . The calculated quasiparticle band gaps of these systems are found to agree with experiment to within a few tens of meV. SOC splittings are found to be generally in better agreement with experiment, including quasiparticle corrections to band energies. The absorption spectrum of GaAs is not significantly impacted by the inclusion of spin-orbit coupling due to its relatively small value (0.2 eV) in the Λ direction, while the absorption spectrum of GaSb calculated with the spinor GW/BSE captures the large spin-orbit splitting of peaks in the spectrum. For the prototypical topological insulator Bi 2 Se 3 , we find a drastic change in the low-energy band structure compared to that of DFT, with the spinorial treatment of the GW approximation correctly capturing the parabolic nature of the valence and conduction bands after including off-diagonal self-energy matrix elements. We present the detailed methodology, approach to spatial symmetries for spinors, comparison against other codes, and performance compared to spinless GW/BSE calculations and perturbative approaches to SOC. This work aims to spur further development of spinor GW/BSE methodology in excited-state research software and enables a more accurate and detailed exploration of electronic and optical properties of materials containing elements with large atomic numbers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transient Terahertz Oscillations During Photoinduced Polarization Topology Reconfiguration in Ferroelectric Superlattices

Terahertz resonances embedded in crystalline heterostructures could close a spectral gap between conventional electronics and photonics while opening new windows on non-equilibrium lattice dynamics. We show that femtosecond optical screening of the depolarization field in epitaxial PbTiO3/SrTiO3 superlattices launches a collective polar mode that oscillates near 1 THz and coherently spans the entire mini-Brillouin zone. Wave-vector-resolved pump–probe X-ray diffraction resolves a nearly dispersion-less oscillation at 0.87 THz and 0.94 THz at the zone boundary and zone center, respectively, persisting for ~2.5 ps, corresponding to a weakly damped resonance. Dynamical phase-field simulations reveal the origin of the mode to mesoscopic rotation of closure-domain textures during the photo-excited transition from an unscreened to a screened electrostatic state. Varying the PbTiO3 and SrTiO3 ratio tunes the mode frequency continuously from 0.9 to 1.4 THz, providing a quantitative design rule for frequency-selectable THz oscillators in ferroelectric heterostructures. By coupling nanoscale polarization reconfiguration to long-wavelength coherent dynamics, this work establishes depolarization-field engineering to topology-driven THz functionality and expanding the landscape of collective lattice dynamics.

Sri Gyan, Deepankar [Univ. of Wisconsin, Madison, ↗

Canopy Level Solar Induced Fluorescence for Vegetation in Controlled Experiments

Solar induced chlorophyll fluorescence (SIF) was retrieved from high resolution reflectance spectra acquired one meter above saplings of three deciduous tree species during springtime (three weeks after leaf flush) and in late summer when foliage was mature. SIF was determined by application of the Fraunhofer Line Depth (FLD) Principal to above-canopy spectra acquired with an Analytical Spectral Devices (ASD) Fieldspec spectroradiometer (3.2 nm resolution with 1.2 nm sampling interval). SIF retrievals were made at the two atmospheric oxygen (O2) absorption features that occur in the chlorophyll fluorescence (ChlF) region (660 -780 nm). These telluric features are 02V, the broader and deeper feature centered at 760 nm, but located on the shoulder of the far-red ChlF peak at 740 nm; and 023, a narrow feature centered at 688 nm that is positioned near the red ChlF peak at 685 nm. Supporting, coincident leaf level fluorescence, reflectance, photochemical and other measurements were also made. At the leaf level, these measurements included in situ photosynthetic capacity (Pmax) and light adapted total chlorophyll fluorescence (Fs') collected at steady state under high light and controlled chamber conditions (e.g., temperature, PAR, humidity, and COz); optical properties (reflectance, transmittance, absorptance); chlorophyll and carotenoid content; specific leaf mass; carbon (C) and nitrogen (N) content; fluorescence emission spectra at multiple excitation wavelengths; the ChlF contribution to red (R) and far-red (FR) reflectance; fluorescence imagery; and fluorescence excitation-emission matrices (EEMs). The tree species examined were tulip poplar (Liriodendron tulipifera L.), red maple (Acer rubrum L.), and sweetgum (Liquidambar styraczflua L.), and each had been provided four levels of N augmentation (0, 19, 37, and 75 kg Nhectare seasonally) to simulate atmospheric deposition from air pollution. Whole-plant SIF measurements of these species were compared with SIF estimates derived using FluorMOD, a radiative transfer model that includes fluorescence properties of foliage, when provided with our supporting measurements. Simulated values for SIF were also compared with similar estimates made over three years for corn (Zea mays L) crops under N treatments (20, 50,70, and 140 kg Nhectare) and with corn and pepper (Capsicum annuum L.) plants provided dimethyl urea (DCMU, 0 and 5 x 10" M) which were grown in pots and grouped in artificial canopies for spectral measurements. For near-surface measurements of healthy and stressed vegetation, red SIF retrieved at 688 nm (023) varied between 2-7 mW/m(exp 2)/nm/sr while far-red SIF retrieved at 760 nm (O2A) varied between 0.5 and 4.0 mW/m(exp 2)/nm/sr. Typical values for the SIF red/far-red ratio ranged between 1.75 and 4.0. Relationships of SIF to spectral reflectance indices and foliar photochemical indices were examined, such as photosynthetic light use efficiency. Initial investigations of the variability in these measurements at the same leaf temperature for sunlit and shaded foliage showed us that shaded foliage produced higher ChlF and light use efficiency. Other factors that affect SIF determinations are discussed. These results will assist in determine the expected intensity of the SIF signal from vegetation near the surface, as well as to identify enhancements needed for FluorMOD (or other such models), and will assist in determining relationships of SIF to reflectance indices and carbon dynamics.

Middleton, E. M.↗

Optical suppression of defect-related photoluminescence in GeSn

Reports of photoluminescence from GeSn grown on Ge substrates by molecular beam epitaxy have been limited. We find that one limiting factor to observing photoluminescence is due to localized defect states marked by photoluminescence at 2400 nm and originating from the Ge substrate and buffer layer. In this study, we report on an optical study utilizing doped Ge(001) substrates to effectively suppress defect-related photoluminescence in GeSn layers by filling localized defect trap states. For this experiment, a GeSn layer with Sn content up to 10.5 ± 0.5% was grown on a doped Ge(001) substrate. Analysis of the physics of the photoluminescence spectrum collected from the GeSn thin film shows an emission at the expected wavelength of 2300 nm for 10.5 ± 0.5% Sn content and the absence of the typically observed defect-related signal at 2400 nm. This understanding is further confirmed using short-pulse optical excitation of the GeSn grown on undoped Ge substrates.

Chemical vapor deposition↗

Magnons and magnetic fluctuations in atomically thin MnBi 2 Te 4

Electron band topology is combined with intrinsic magnetic orders in MnBi 2 Te 4 , leading to novel quantum phases. Here we investigate collective spin excitations (i.e. magnons) and spin fluctuations in atomically thin MnBi 2 Te 4 flakes using Raman spectroscopy. In a two-septuple layer with non-trivial topology, magnon characteristics evolve as an external magnetic field tunes the ground state through three ordered phases: antiferromagnet, canted antiferromagnet, and ferromagnet. The Raman selection rules are determined by both the crystal symmetry and magnetic order while the magnon energy is determined by different interaction terms. Using non-interacting spin-wave theory, we extract the spin-wave gap at zero magnetic field, an anisotropy energy, and interlayer exchange in bilayers. We also find magnetic fluctuations increase with reduced thickness, which may contribute to a less robust magnetic order in single layers.

36 MATERIALS SCIENCE↗