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At least 91 records · Page 5

Fully Suspended, Five-Axis, Three-Magnetic-Bearing Dynamic Spin Rig With Forced Excitation

The Five-Axis, Three-Magnetic-Bearing Dynamic Spin Rig, a significant advancement in the Dynamic Spin Rig (DSR), is used to perform vibration tests of turbomachinery blades and components under rotating and nonrotating conditions in a vacuum. The rig has as its critical components three magnetic bearings: two heteropolar radial active magnetic bearings and a magnetic thrust bearing. The bearing configuration allows full vertical rotor magnetic suspension along with a feed-forward control feature, which will enable the excitation of various natural blade modes in bladed disk test articles. The theoretical, mechanical, electrical, and electronic aspects of the rig are discussed. Also presented are the forced-excitation results of a fully levitated, rotating and nonrotating, unbladed rotor and a fully levitated, rotating and nonrotating, bladed rotor in which a pair of blades was arranged 180 degrees apart from each other. These tests include the bounce mode excitation of the rotor in which the rotor was excited at the blade natural frequency of 144 Hz. The rotor natural mode frequency of 355 Hz was discerned from the plot of acceleration versus frequency. For nonrotating blades, a blade-tip excitation amplitude of approximately 100 g/A was achieved at the first-bending critical (approximately 144 Hz) and at the first-torsional and second-bending blade modes. A blade-tip displacement of 70 mils was achieved at the first-bending critical by exciting the blades at a forced-excitation phase angle of 908 relative to the vertical plane containing the blades while simultaneously rotating the shaft at 3000 rpm.

Morrison, Carlos R.

Excitations for Rapidly Estimating Flight-Control Parameters

A flight test on an F-15 airplane was performed to evaluate the utility of prescribed simultaneous independent surface excitations (PreSISE) for real-time estimation of flight-control parameters, including stability and control derivatives. The ability to extract these derivatives in nearly real time is needed to support flight demonstration of intelligent flight-control system (IFCS) concepts under development at NASA, in academia, and in industry. Traditionally, flight maneuvers have been designed and executed to obtain estimates of stability and control derivatives by use of a post-flight analysis technique. For an IFCS, it is required to be able to modify control laws in real time for an aircraft that has been damaged in flight (because of combat, weather, or a system failure). The flight test included PreSISE maneuvers, during which all desired control surfaces are excited simultaneously, but at different frequencies, resulting in aircraft motions about all coordinate axes. The objectives of the test were to obtain data for post-flight analysis and to perform the analysis to determine: 1) The accuracy of derivatives estimated by use of PreSISE, 2) The required durations of PreSISE inputs, and 3) The minimum required magnitudes of PreSISE inputs. The PreSISE inputs in the flight test consisted of stacked sine-wave excitations at various frequencies, including symmetric and differential excitations of canard and stabilator control surfaces and excitations of aileron and rudder control surfaces of a highly modified F-15 airplane. Small, medium, and large excitations were tested in 15-second maneuvers at subsonic, transonic, and supersonic speeds. Typical excitations are shown in Figure 1. Flight-test data were analyzed by use of pEst, which is an industry-standard output-error technique developed by Dryden Flight Research Center. Data were also analyzed by use of Fourier-transform regression (FTR), which was developed for onboard, real-time estimation of the derivatives.

Moes, Tim

Comparing the Performance of Hyperbolic and Circular Rod Quadrupole Mass Spectrometers with Applied Higher Order Auxiliary Excitation

This work applies higher order auxiliary excitation techniques to two types of quadrupole mass spectrometers (QMSs): commercial systems and spaceborne instruments. The operational settings of a circular rod geometry commercial system and an engineering test-bed for a hyperbolic rod geometry spaceborne instrument were matched, with the relative performance of each sensor characterized with and without applied excitation using isotopic measurements of Kr+. Each instrument was operated at the limit of the test electronics to determine the effect of auxiliary excitation on extending instrument capabilities. For the circular rod sensor, with applied excitation, a doubling of the mass resolution at 1% of peak transmission resulted from the elimination of the low-mass side peak tail typical of such rod geometries. The mass peak stability and ion rejection efficiency were also increased by factors of 2 and 10, respectively, with voltage scan lines passing through the center of stability islands formed from auxiliary excitation. Auxiliary excitation also resulted in factors of 6 and 2 in peak stability and ion rejection efficiency, respectively, for the hyperbolic rod sensor. These results not only have significant implications for the use of circular rod quadrupoles with applied excitation as a suitable replacement for traditional hyperbolic rod sensors, but also for extending the capabilities of existing hyperbolic rod QMSs for the next generation of spaceborne instruments and low-mass commercial systems.

Gershman, D. J.

Nonpigmented PsbR is involved in the integrity of excitation landscape in higher plant photosystem II, a case study in Arabidopsis thaliana and a mutant

PsbR is a nonpigmented 10 kDa protein in Photosystem II (PSII) in algae and plants. A recent structural study clarified its enigmatic structural location in a Photosystem II megacomplex that has baffled the community for more than four decades. Our current study interrogates whether absence of PsbR affects the overall dynamics of excitation energy migration within light harvesting complexes (LHC) and PSII super assemblies using highly-active PSII membrane particles, so-called BBY particles, isolated from a PsbR deletion mutant (ΔPsbR) of Arabidopsis thaliana. A femto-second (fs)-time-resolved transient absorption experimentation recorded at 77 K with selective excitation of Chl b which is exclusively present in LHCs enabled us to resolve the temporal differences in LHC→LHC and LHC→PSII excitation energy transfer steps. By applying specific target spectro-kinetic models to the transient absorption datasets, we demonstrated that the time constants of Chl a LHC → Chl a LHC excitation transfer significantly elongates in the ΔPsbR LHC-PSII particles, suggestive of the decreased aggregation level of photosynthetic proteins in the mutant. These findings highlight excitation energy transfer integrity in LHC-PSII assembly is not only determined by the pigmented light-harvesting complexes, but also synergistically by the nonpigmented PSII components. Furthermore, the disturbed integrity in dynamics of excitation energy transfer pathway within LHC-PSII supercomplex is discussed in the context of the altered LHC-PSII megacomplexes type I and II architectures which result from the absence of the PsbR protein in higher plant PSII.

Chlorophyll

Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3 MC Excited State in an Fe(II) Carbene Complex

The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered ( 3 MC) excited states - recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls - have to date remained elusive, with temporally isolable examples limited to the picosecond regime. Here, with this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived 3 MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn−Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a 3 MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.

carbene compounds

Search for excited tau leptons in the ττγ final state in proton-proton collisions at $\sqrt{\text{s}}$ = 13 TeV

Results are presented for a test of the compositeness of the heaviest charged lepton, τ, using data collected by the CMS experiment in proton-proton collisions at a center-of-mass energy of 13 TeV at the CERN LHC. The data were collected in 2016–2018 and correspond to an integrated luminosity of 138 fb −1 . This analysis searches for tau lepton pair production in which one of the tau leptons is produced in an excited state and decays to a ground state tau lepton and a photon. The event selection consists of two isolated tau lepton decay candidates and a high-energy photon. The mass of the excited tau lepton is reconstructed using the missing transverse momentum in the event, assuming the momentum of the neutrinos from each tau lepton decay are aligned with the visible decay products. No excess of events above the standard model background prediction is observed. This null result is used to set lower bounds on the excited tau lepton mass. For a compositeness scale Λ equal to the excited tau lepton mass, excited tau leptons with masses below 4700 GeV are excluded at 95% confidence level; for Λ = 10 TeV this exclusion is set at 2800 GeV. This is the first experimental result covering this production and decay process in the excited tau mass range above 175 GeV.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

An Attractive Way to Correct for Missing Singles Excitations in Unitary Coupled Cluster Doubles Theory

Coupled cluster methods based exclusively on double excitations are comparatively “cheap” and interesting model chemistries, as they are typically able to capture the bulk of the dynamic electron correlation effects. The trade-off in such approximations is that the effect of neglected excitations, particularly single excitations, can be considerable. Using standard and electron-pair-restricted T 2 operators to define two flavors of unitary coupled cluster doubles (UCCD) methods, we investigate the extent to which missing single excitations can be recovered from low-order corrections in many-body perturbation theory (MBPT) within the unitary coupled cluster (UCC) formalism. Here, our analysis includes the derivations of finite-order UCC energy functionals, which are used as a basis to define perturbative estimates of missed single excitations. This leads to the novel UCCD[4S] and UCCD[6S] methods, which consider energy corrections for missing single excitations through fourth- and sixth-order in MBPT, respectively. We also apply the same methodology to the electron-pair-restricted ansatz, but the improvements are only marginal. Our findings show that augmenting UCCD with these post hoc perturbative corrections can lead to UCCSD-quality results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1–Cu3) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNac Me ) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNac Me )(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state ( 3 CT) and the long-lived pyrene-centered triplet state ( 3 pyr). This TTET process is irreversible in Cu3, producing exclusively the 3 pyr state, and in Cu2, the 3 CT and 3 pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3 CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. Furthermore, these results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

14 SOLAR ENERGY

Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

Copper(I) complexes are prominent candidates to replace noble metal-based photosensitizers. We recently introduced a three-coordinate design for copper(I) charge-transfer chromophores that pair β-diketiminate ligands with aryl isocyanides. The excited-state lifetime in these compounds can be extended using a bichromophoric “triplet reservoir” strategy, which comes at the expense of a decrease in excited-state energy and reducing power. In this work, we introduce a complementary, sterically driven strategy for increasing the excited-state lifetimes of these photosensitizers, which gives a higher-energy, more strongly reducing charge-transfer triplet state than does the bichromophore approach. The compounds presented (Cu1–Cu4) have the general formula Cu(CyNacNac Me )(CN-Ar), where CyNacNac Me is a cyclohexyl-substituted β-diketiminate and CN-Ar is an aryl isocyanide with a variable steric profile. Their structural features and electrochemical and photophysical properties are described. The complexes with sterically encumbered 2,6-diisopropylphenyl or m-terphenyl isocyanide ligands (Cu2–Cu4) exhibit prolonged excited-state lifetimes relative to those of the parent 2,6-dimethylphenyl isocyanide compound Cu1. Specifically, one of the m-terphenyl isocyanide compounds, Cu3, displays an excited-state lifetime of 276 ns, approximately 30 times longer than that of Cu1 (9.3 ns). The photoluminescence quantum yield of Cu3 (0.09) also increases by two orders of magnitude compared to that of Cu1 (0.0008). Furthermore, the strong excited-state reducing power (*E ox = –2.4 V vs Fc +/0 ) and long lifetime of Cu3 lead to higher yields in photoredox and photocatalytic isomerization reactions, which include dehalogenation and/or hydrodgenation of benzophenone substrates, C–O bond activation of a lignin model substrate, and photocatalytic E/Z isomerization of stilbene.

14 SOLAR ENERGY

Nonlinear excitation of energetic particle driven geodesic acoustic mode by resonance overlap with Alfvén instability in ASDEX Upgrade

The Alfvén instability nonlinearly excited the energetic-particle-driven geodesic acoustic mode on the ASDEX-Upgrade tokamak, as demonstrated experimentally. The mechanism of the energetic-particle-driven geodesic acoustic mode excitation and the mode nonlinear evolution is not yet fully understood. In the present work, a first-principles simulation using the MEGA code investigated the mode properties in both the linear growth and nonlinear saturated phases. Here we show that the simulation successfully reproduced the excitation and coexistence of these two modes, and agreed with the experimental results well. Conclusive evidence showed that the resonance overlap is the excitation mechanism of the energetic-particle-driven geodesic acoustic mode. In the linear growth phase, energetic particles that satisfied different resonance conditions excited the Alfvén instability, which then caused energetic particle redistribution in phase space. These redistributed energetic particles caused resonance overlap, exciting the energetic-particle-driven geodesic acoustic mode in the nonlinear phase.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

An improved guess for the variational calculation of charge-transfer excitations in large systems

Ab initio quantum-chemical methods that perform well for computing the electronic ground state are not straightforwardly transferable to electronically excited states, particularly in large molecular systems. Wave function theory offers high accuracy, but is often prohibitively expensive. Methods based on time-dependent density functional theory (TD-DFT) are crucially sensitive to the chosen exchange-correlation functional (XCF) parameterization, and system-specific tuning protocols were therefore proposed to address the method's robustness. Methods based on the variational relaxation of the excited-state electron density showcased promising results for the calculation of charge-transfer excitations, but the complex shape of the electronic hypersurface makes convergence to a specific excited state much more difficult than for the ground state when standard variational techniques are applied. We address the latter aspect by providing suitable initial guesses, which we obtain by two separate constrained algorithms. Combined with the squared-gradient minimization algorithm for all-electrons relaxation in a freeze-and-release scheme (FRZ-SGM), we demonstrate that orbital-optimized density functional theory (OO-DFT) calculations can reliably converge to the charge-transfer states of interest even for large molecular systems. We test the FRZ-SGM method on a phenothiazine-anthraquinone CT excitation in a supramolecular Pd(II) coordination cage complex as a function of the cage conformation. This compound has been studied experimentally prior to our work. We compare this freeze-and-release scheme to two XCF reparameterizations, which were recently proposed as low-cost TD-DFT-based alternatives to variational methods. Two dye-semiconductor complexes, which were previously investigated in the context of photovoltaic applications, serve as a second example to investigate the convergence and stability of the FRZ-SGM approach. Our results demonstrate that FRZ-SGM provides reliable convergence for charge-transfer excited states and avoids variational collapse to lower-lying electronic states, whereas time-dependent DFT calculations with an adequate tuning procedure for the range-separation parameter provide a computationally efficient initial estimate of the corresponding energies, with a computational cost comparable to that of configuration-interaction singles (CIS) calculations.

Bogo, Nicola

Deciphering the excited-state landscape of Cr(iii) tris(diimines) using [Cr(phen) 3 ] 3+

Earth-abundant Cr(III) polypyridines chromophores feature long-lived doublet ligand-field excited states. The thermally equilibrated 2 T 1 / 2 E ligand-field excited state manifold produces broad, structured UV-Vis-NIR absorption bands. Although ubiquitous across pseudo-octahedral Cr(III) diimine complexes, the dynamics and individual electronic transitions underlying these spectra have remained elusive. Here, we combine time-resolved spectroscopy and multiconfigurational calculations to assign ground- and excited-state absorption spectra of Cr(III) tris(1,10-phenanthroline), [Cr(phen) 3 ] 3+ , as a prototypical example for this class of complexes. Excited-state kinetics reveal a rapid biexponential decay of the initially prepared intraligand/ligand-to-metal charge transfer [ 4 ( 1 IL)/ 4 LMCT] excited state into the lowest 2 T 1 / 2 E state within 10 picoseconds, assigned to intersystem crossing and vibrational relaxation. Calculations identify broad excited-state absorption features associated with metal-centered ligand-field states ( 2 MC) mixed with intraligand ( 2 IL) transitions within the doublet manifold. These results provide detailed spectral assignments and highlight the need to include multiconfigurational ligand-based orbitals when modeling the spectral properties of Cr(III) coordination complexes.

Barth, Alexandra T. [North Carolina State Universi

Spin-Forbidden Excitations in the Magneto-optical Spectra of CrI 3 Tuned by Covalency

Spin-forbidden (Δ⁢𝑆 ≠0) multiplet excitations and their coupling to magnetic properties are of increasing importance for magneto-optical studies of correlated materials. Nonetheless, the mechanisms for optically brightening these transitions and their generality remain poorly understood. Here, we report magnetic circular dichroism (MCD) spectroscopy on the van der Waals ferromagnet (FM) CrI 3 . Previously unreported spin-forbidden (Δ⁢𝑆 =1) 4 𝐴 2⁢g → 2 𝐸 g / 2 𝑇 1⁢g Cr 3+ 𝑑⁢𝑑 excitations are observed near the ligand-to-metal charge-transfer excitation threshold. The assignment of these excitations and their Cr 3+ multiplet character is established through complementary Cr 𝐿 3 -edge resonant inelastic x-ray scattering measurements along with charge-transfer multiplet calculations and chemical trends in the chromium trihalide series (Cr⁢𝑋 3 , 𝑋 = Cl, Br, I). We utilize the high sensitivity of MCD spectroscopy to study the thickness-dependent optical response. The spin-forbidden excitations remain robust down to the monolayer limit, and we observe a significant magnetic-field dependence of the MCD spectrum across the antiferromagnetic-to-FM transition in few-layer samples. We preliminarily attribute this behavior to changes in the metal-ligand covalency with magnetic state. Our results clarify the magneto-optical response of CrI 3 and identify covalency as a central mechanism for the brightening and field tunability of spin-forbidden multiplet excitations.

36 MATERIALS SCIENCE

Incident excitation effects on ZnO-based photoluminescence

Zinc oxide (ZnO) is an attractive semiconductor material owing to a wide band gap, large exciton binding energy, and strong luminescent properties. Two distinct spectral regions are present in the room temperature emission of this material: a narrow line in the UV/near-UV region that is excitonic in nature and a lower energy broad emission band centered in the green/yellow region. Commercially available ZnO particles containing excess Zn and oxygen vacancy defect sites (referred to as ZnO:Zn) were excited using three light sources to study different radiative recombination regimes of the as-received powders. First, a UV LED at a center wavelength of 365 nm provided low irradiance (0.02–0.08 W/cm 2 ) with varying pulse widths (continuous operation to 16 ns). Second, the third harmonic of a pulsed Nd:YAG laser provided high irradiances (∼10 4 –10 6 W/cm 2 ) at a fixed nominal pulse width of 5 ns. Finally, a continuous polychromatic synchrotron X-ray source was also used to excite the ZnO:Zn powders. During UV LED excitation, a low number of carriers are created in the material, leading to an anticipated linear relationship between luminescence and irradiance. This held true for defect luminescence; however, there was an observed enhancement of exciton emission relative to the UV LED intensity as the pulse width was decreased, independent of irradiance. During UV laser excitation, the number of carriers was significantly increased, raising the material into a bimolecular recombination regime, which produced exciton emission much stronger than visible band emission. Finally, spectra obtained during synchrotron X-ray excitation, whose continuous illumination and higher penetration depth yielded higher emission from defect sites relative to exciton emission. A redshift in the exciton emission was also observed as excitation pulse width and sample temperature were varied, and is discussed.

Westphal, Eric Robert [Sandia National Lab. (SNL-N

Excitation of parametric instabilities by radio waves in the ionosphere.

The excitation of parametric instabilities by radio waves in a magnetoplasma is discussed. A uniform medium is assumed and linear approximations are used. Excitation by a pump wave of ordinary polarization is hardly affected by the magnetic field. Low or zero frequency ion waves and high frequency Langmuir waves are excited simultaneously. For an extraordinary pump wave, the excited high frequency electrostatic waves are in the Bernstein mode. The threshold is slightly higher and excitation can occur only within certain 'allowed' frequency bands. A new type of parametric instability in which the excited waves are electromagnetic in nature and which is more strongly affected by the inhomogeneous nature of the medium is discussed qualitatively.

Fejer, J. A.

Electron-impact excitation of the low-lying electronic states of formaldehyde

Electron-impact excitation has been observed at incident electron energies of 10.1 and 20.1 eV to the first five excited electronic states of formaldehyde lying at and below the 1B2 state at 7.10 eV. These excitations include two new transitions in the energy-loss range 5.6-6.2 eV and 6.7-7.0 eV which have been detected for the first time, either through electron-impact excitation or photon absorption. The differential cross sections of these new excitations are given at scattering angles between 15 and 135 deg. These cross-section ratios peak at large scattering angles - a characteristic of triplet - singlet excitations. The design and performance of the electron-impact spectrometer used in the above observations is outlined and discussed.

Chutjian, A.

Turbulence suppression in free shear flows by controlled excitation

The mechanism of turbulence suppression in the near field of a free shear flow under controlled acoustic excitation is investigated. The near fields of four circular air jets, a plane air jet and a large single-stream plane free air mixing layer with laminar efflux boundary layers were monitored with hot-wire anemometers. The suppression effect is found to occur over the entire frequency range in all the flows studied, with maximal suppression (as much as 80%) at about 400 initial shear layer momentum thicknesses downstream from the exit and for excitation at a Strouhal number of 0.017. Suppression is shown to be a consequence of excitation-induced modification of the shear layer instability mode and the resulting structure, and to occur at the excitation frequency corresponding to the maximally unstable disturbance frequency of the initial free shear layer. Flow visualization reveals the presence of strong, large-scale vortical structures in the unexcited flow, which are weakened and diminished by excitation. It is concluded that excitation produces rapid roll-up and early breakdown of the shear layer, thus inhibiting the formation of energetic large-scale vortices and reducing the large fluctuation intensities caused by the passage and interaction of these vortices.

Zaman, K. B. M. Q.

An experimental study of tone excited heated jets

The objective of this investigation was to obtain detailed experimental data on the effects of upstream acoustic excitation on the mixing of heated jets with the surrounding air. Based on the information gathered in the literature survey, a technical approach was developed to carry out a systematic set of mean flowfield measurements for a broad range of jet operating and acoustic excitation conditions. Most of the results were obtained at Mach numbers of 0.3 and 0.8 and total temperatures of up to 800 K. Some measurements were made also for the fully expanded supersonic jet of Mj = 1.15. The maximum level of excitation was Le equal to or less than 150 dB and a range of excitation frequencies up to fe = 4 kHz was used. The important results derived from this study can be summarized as follows: (1) the sensitivity of heated jets to upstream acoustic excitation varies strongly with the jet operating conditions, (2) the threshold excitation level increases with increasing jet temperature, and (3) the preferred Strouhal number does not change significantly with a change of the jet operating conditions.

Lepicovsky, J.