Spatially Resolved Near Field Spectroscopy of Vibrational Polaritons at the Small N Limit
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Electroanalytical characterization of Np( VI )/Np( V ) redox in a pentadentate ligand environment and stabilization of [Np V O 2 ] + by hydrogen bonding
The redox chemistry of the actinyl cations (AnO 2 n+ ) heavily influences their reactivity and speciation in solution, but the redox properties of the actinyls in non-aqueous media have received far less attention than they deserve. Here, the non-aqueous electrochemistry of a chemically reversible Np(VI)/Np(V) redox manifold is reported in both protic (CH 3 OH) and aprotic (CH 3 CN) organic media. Using a neutral Np(VI) complex supported by a chelating and strongly donating pentadentate ligand that was fully characterized in prior work, a clean Np(VI)/Np(V) redox couple was found to be accessible under ambient conditions. Coupled electrochemical and spectroscopic studies, as well as simulations of cyclic voltammetry data, confirm the 1e− nature of this couple and establish it to be chemically reversible and nearly electrochemically reversible as well. Bulk electrolysis of a solution of the neutral Np(VI) complex facilitated isolation of the corresponding anionic and monomeric Np(V) species. Data from X-ray diffraction analysis as well as optical and vibrational spectroscopies provide strong evidence in support of metal-centered reduction and the Np(V) oxidation state, findings that are in accord with the measured reduction potentials. Distinctive hydrogen bonding interactions between the terminal (yl) oxo groups and water molecules appear to stabilize the isolated Np(V) species in the solid state, providing insight into the features that afford the uncommon chemically reversible redox encountered in this system.
Mikeska, Emily R.↗
Reagent-Triggered Isomerization of Fluxional Cluster Catalyst via Dynamic Coupling
Metallic cluster catalysts have many thermodynamically accessible isomers with diverse active sites and low reaction barriers, and lately a strong hypothesis emerged that the many catalyst states collectively drive the catalysis. Furthermore, it remained a hypothesis that catalyst isomerization is actually kinetically feasible under the current reaction conditions. Using high-temperature dynamics simulations and sampling, a range of orientations, and vibrational energy distributions, we probe how thermal effects and molecular events affect cluster catalyst dynamics. We show that even such a delicate affair as the dissociation or scattering of a methane molecule on the heavy and thus slow Pt 13 cluster triggers substantial isomerization of the catalyst, far beyond thermal at 700 K. A kinetic coupling between the methane activity and cluster catalyst dynamics is observed. In return, the thermal dynamics of the cluster affects the methane reaction and scattering probabilities. Hence, molecular events at the surfaces of fluxional cluster catalysts should facilitate the population of an ensemble of catalyst states under the current reaction conditions, with implications for available active sites, reaction mechanisms, and apparent rates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Application of molecular convergent close-coupling cross sections in a collisional radiative model for the triplet system of molecular hydrogen
Collisional radiative (CR) models for molecular hydrogen are of high relevance for performing qualitative and quantitative analysis of excited-state population densities measured in plasmas or predicting the dependence of plasma emission on parameter variations. Although the development of such models for H 2 started decades ago, major uncertainties still exist regarding the most important set of input parameters, namely the cross sections for electron-impact excitation. The deviations between cross sections from different datasets are particularly pronounced in the energy region close to the threshold energy, strongly increasing the uncertainty of CR models applied to low-temperature plasmas. This paper presents experimental validation of a set of newly calculated non ro-vibrationally resolved electron-impact cross sections calculated for the triplet system of H 2 using the molecular convergent close-coupling method in the adiabatic-nuclei formulation. These cross sections are implemented into a CR model based on the flexible solver Yacora. A first comparison of CR calculations with the different datasets to experimentally-determined population densities is performed at a planar ICP discharge for varying pressure (between 1 and 10 Pa) and RF power (between 700 and 1100 W). For the experimentally-accessible electron temperature and density range (2.5–10 eV and 1.8–3.3 × 10 16 m –3 , respectively), very good agreement between the model and experiment is obtained using the new data set, in contrast to previously used cross sections.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Quantum Ratcheted Photophysics in Energy Transport
In this paper, we explore the scope of vibrations as quantum ratchets that serve as nonthermal routes to achieving population transport in systems where excitation transport between molecules is otherwise energetically unfavorable. In addition to their role as channels of transport, we investigate the effect of resonance of the vibrations, which are described by Huang-Rhys mixing, with excitonic energy gaps, which leads to strongly mixed vibronic excitons. Finally, we explore the interplay of resonance and Huang-Rhys mixing with electronic coupling between the molecules, in the presence of a dissipative bath, in optimizing transport in such systems. Furthermore, we find that while resonance is desirable, a moderate electronic coupling has a stronger positive effect in contrast to a large electronic coupling, which results in delocalized excitations across molecules and hampers unidirectional transport. We also report a special resonance regime that is able to circumvent the transport problems arising from large electronic couplings.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Acoustically Induced Vibration of Structures: Reverberant Vs. Direct Acoustic Testing
Large reverberant chambers have been used for several decades in the aerospace industry to test larger structures such as solar arrays and reflectors to qualify and to detect faults in the design and fabrication of spacecraft and satellites. In the past decade some companies have begun using direct near field acoustic testing, employing speakers, for qualifying larger structures. A limited test data set obtained from recent acoustic tests of the same hardware exposed to both direct and reverberant acoustic field testing has indicated some differences in the resulting structural responses. In reverberant acoustic testing, higher vibration responses were observed at lower frequencies when compared with the direct acoustic testing. In the case of direct near field acoustic testing higher vibration responses appeared to occur at higher frequencies as well. In reverberant chamber testing and direct acoustic testing, standing acoustic modes of the reverberant chamber or the speakers and spacecraft parallel surfaces can strongly couple with the fundamental structural modes of the test hardware. In this paper data from recent acoustic testing of flight hardware, that yielded evidence of acoustic standing wave coupling with structural responses, are discussed in some detail. Convincing evidence of the acoustic standing wave/structural coupling phenomenon will be discussed, citing observations from acoustic testing of a simple aluminum plate. The implications of such acoustic coupling to testing of sensitive flight hardware will be discussed. The results discussed in this paper reveal issues with over or under testing of flight hardware that could pose unanticipated structural and flight qualification issues. Therefore, it is of paramount importance to understand the structural modal coupling with standing acoustic waves that has been observed in both methods of acoustic testing. This study will assist the community to choose an appropriate testing method and test setup in the planning stages.
Reverberant acoustic field↗
Magnetoelastic effects in the hyperhoneycomb Kitaev spin liquid
In recent years, several magnetic Mott insulators with strong spin-orbit coupling were suggested to be proximate to the Kitaev quantum spin liquid, whose one of the most exciting features is the fractionalization of spin excitations into itinerant Majorana fermions and static Z 2 fluxes. Unfortunately, the ground states of these systems cannot be easily captured by experiment, remaining featureless to conventional local probes. Here, we propose to study the signatures of fractionalized excitations by exploiting their coupling to the lattice vibrations, dubbed magnetoelastic coupling, which arises from the fact that the interaction between spins depends on the relative distance between them. We argue that the magnetoelastic coupling can lead to the distinct modification of the phonon dynamics, which can be observed by measuring renormalized phonon spectrum, the sound attenuation, and the phonon Hall viscosity. This makes the phonon dynamics a promising tool for the characterization and identification of quantum spin liquid phases. In this work, we focus on the magnetoelastic effects in the three-dimensional Kitaev model realized on the hyperhoneycomb lattice. Here, the hyperhoneycomb Kitaev spin liquid is particularly interesting since the strong Kitaev interaction was observed in the Kitaev magnet β-Li 2 IrO 3 , for which the spin-orbit entangled J eff = 1/2 moments of iridium ions form precisely the hyperhoneycomb lattice.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Parameter estimation in a structural acoustic system with fully nonlinear coupling conditions
A methodology for estimating physical parameters in a class of structural acoustic systems is presented. The general model under consideration consists of an interior cavity which is separated from an exterior noise source by an enclosing elastic structure. Piezoceramic patches are bonded to or embedded in the structure; these can be used both as actuators and sensors in applications ranging from the control of interior noise levels to the determination of structural flaws through nondestructive evaluation techniques. The presence and excitation of patches, however, changes the geometry and material properties of the structure as well as involves unknown patch parameters, thus necessitating the development of parameter estimation techniques which are applicable in this coupled setting. In developing a framework for approximation, parameter estimation and implementation, strong consideration is given to the fact that the input operator is unbonded due to the discrete nature of the patches. Moreover, the model is weakly nonlinear. As a result of the coupling mechanism between the structural vibrations and the interior acoustic dynamics. Within this context, an illustrating model is given, well-posedness and approximations results are discussed and an applicable parameter estimation methodology is presented. The scheme is then illustrated through several numerical examples with simulations modeling a variety of commonly used structural acoustic techniques for systems excitations and data collection.
Banks, H. T.↗
Conformationally Adaptable Extractant Flexes Strong Lanthanide Reverse-Size Selectivity
Chemical selectivity is traditionally understood in the context of rigid molecular scaffolds with precisely defined local coordination and chemical environments that ultimately facilitate a given transformation of interest. By contrast, nature leverages dynamic structures and strong coupling to enable specific interactions with target species in otherwise complex media. Taking inspiration from nature, we demonstrate unconventional selectivity in the solvent extraction of light over heavy lanthanides using a conformationally flexible ligand called octadecyl acyclopa (ODA). This novel ligand forms pseudocyclic molecular complexes with lanthanide ions at organic/aqueous interfaces, revealed by vibrational sum frequency generation spectroscopy. These complexes are extracted into the organic phase, where femtosecond structural dynamics are probed by two-dimensional infrared spectroscopy and ab initio molecular dynamics simulations to mechanistically frame the macroscopic selectivity trends. We find larger-than-expected structural fluctuations and bond lengths for heavy Ln–ODA complexes that arise from an inability of ODA to contort around the smaller ions to satisfy all would-be bonding interactions, despite forming some individually strong bonds. This finding contrasts with the binding of ODA with lighter lanthanides where, despite individually weaker bonds, collective interactions manifest that minimize structural fluctuations and give rise to enhanced thermodynamic stability. Furthermore, these results point to a new paradigm where conformational dynamics and cumulative bonding interactions can be used to facilitate unconventional chemical transformations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Analysis of the rotationally-resolved infrared spectrum of CD 3 79 Br and CD 3 81 Br between 900 and 1400 cm -1
We report the infrared spectrum of CD 3 79 Br and CD 3 81 Br between 900 cm -1 and 1400 cm -1 has been analyzed at high resolution. In this region, two fundamental vibrational states, v 2 = 1 and v 5 = 1, an overtone state, v 3 = 2, and a combination state, v 3 = v 6 = 1, have been analyzed for both isotopologues. As found in other halomethane molecules, strong Coriolis resonances couple the v 2 = 1 state to the v 5 = 1 state, and similar resonances were also used to describe the coupling found between the v 5 = 1 state to the v 3 = 2 state. A new determination of the K-dependent constant A 0 was performed for each isotopologue through the use of perturbation-allowed transitions. The values for A 0 determined from the analysis are 2.6001898(26) and 2.6001905(27) for CD 3 79 Br and CD 3 81 Br, respectively. Ab initio calculations were performed to examine the efficacy of high-level theoretical calculations to accurately predict spectroscopic constants. The ab initio calculations had variable success with the largest errors associated with the prediction of the ΔB rotational constants of the interacting states
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters
Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.
Water/chemistry↗
Time-dependent phenomena in correlated materials
Understanding time-dependent processes and light-matter interaction in strongly correlated materials, and the interplay between electronic, orbital, vibrational, and spin degrees of freedom, is a cornerstone of condensed matter. These mechanisms can be proven by measuring the response of the systems to time-dependent perturbations. The corresponding time scales are dictated by the way light couples to the different excitations, and how these excitations exchange energy and momentum. Our research advances our understanding of these processes, and the interpretation of different equilibrium and time-resolved spectroscopies. Our project encompasses two main themes: (i) developing and refining computational techniques to study non-equilibrium spectroscopies including non-perturbative effects and (ii) applications to non-equilibrium phenomena. We have developed a new computational approach that works directly in the time domain: by including all the degrees of freedom involved in the scattering process (e.g. electrons, photons, neutrons), we solve the time dependent problem: a faithful numerical simulation of the experiment. By measuring the energy and momentum of the outgoing particles, we can extract information about the energy and momentum absorbed by the system. Prior to our work, people attempting to model and calculate non-equilibrium spectral functions relied on a description of the scattering cross section based on a formulation in the frequency domain, a treatment that is extremely cumbersome and complex. Our technique works in and out of equilibrium and can reproduce spectra by several spectroscopic techniques, such as time-resolved photoemission, neutron scattering, Raman, X-ray spectroscopies (RIXS, Auger, XAS, XMCD), and, by not relying on analytical approximations, yields results that reveal novel overlooked transient mechanisms. These tools provide sorely needed intuition for understanding the phenomenology of strongly correlated materials and will help experimentalists in identifying signatures of relevant excitations in pump-probe experiments, such as those conducted in DOE supported facilities.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Ab initio multireference study of the BN molecule
The lowest 1Sigma(+) and 3Pi states of the BN molecule are studied using multireference configuration interaction (MRCI) and averaged coupled-pair functional (ACPF) methods and large atomic natural orbital (ANO) basis sets, as well as several coupled cluster methods. Our calculations strongly support a 3Pi ground state, but the a1Sigma(+) state lies only 381 +/- 100/cm higher. The a1Sigma(+) state wave function exhibits strong multireference character and, consequently, the predictions of the perturbationally-based single-reference CCSD(T) coupled cluster method are not as reliable in this case as the multireference results. The theoretical predictions for the spectroscopic constants of BN are in good agreement with experiment for the Chi3Pi state, but strongly suggest a misassignment of the fundamental vibrational frequency for the a1Sigma(+) state.
Martin, J. M. L.↗
Quiet Spike(TradeMark) Build-up Ground Vibration Testing Approach
Flight tests of Gulfstream Aerospace Corporation s Quiet Spike(TradeMark) hardware were recently completed on the NASA Dryden Flight Research Center F-15B airplane. NASA Dryden uses a modified F-15B airplane as a testbed aircraft to cost-effectively fly flight research experiments that are typically mounted underneath the F-15B airplane, along the fuselage centerline. For the Quiet Spike(TradeMark) experiment, however, instead of a centerline mounting, a relatively long forward-pointing boom was attached to the radar bulkhead of the F-15B airplane. The Quiet Spike(TradeMark) experiment is a stepping-stone to airframe structural morphing technologies designed to mitigate the sonic-boom strength of business jets over land. The Quiet Spike(TradeMark) boom is a concept in which an aircraft s noseboom would be extended prior to supersonic acceleration. This morphing effectively lengthens the aircraft, thus reducing the peak sonic-boom amplitude, but is also expected to partition the otherwise strong bow shock into a series of reduced-strength, noncoalescing shocklets. Prior to flying the Quiet Spike(TradeMark) experiment on the F-15B airplane several ground vibration tests were required to understand the Quiet Spike(TradeMark) modal characteristics and coupling effects with the F-15B airplane. However, due to the flight hardware availability and compressed schedule requirements, a "traditional" ground vibration test of the mated F-15B Quiet Spike(TradeMark) ready-for- flight configuration did not leave sufficient time available for the finite element model update and flutter analyses before flight testing. Therefore, a "nontraditional" ground vibration testing approach was taken. This paper provides an overview of each phase of the "nontraditional" ground vibration testing completed for the Quiet Spike(TradeMark) project which includes the test setup details, instrumentation layout, and modal results obtained in support of the structural dynamic modeling and flutter analyses.
Spivey, Natalie D.↗
The coupling of radiative transfer to quasi 1-D flows with thermochemical nonequilibrium
Quasi-one-dimensional nonequilibrium nozzle flows with coupled radiative transfer are considered. The strongly coupled formulation of radiation and flowfield leads to a governing set of integro-differential equations. A fully implicit numerical method using the full matrix inversion or block iteration methods is presented to solve these equations. The nonequilibrium gas model consists of two chemical species, molecular and atomic nitrogen. The thermodynamic state of the gas is described by two temperatures, translational-rotational and vibrational, and the thermal radiation is assumed to be governed by the vibrational temperature. In radiative transfer, gases are assumed to be absorbing and emitting, and a detailed spectral dependency of the absorption coefficient is prescribed for a non-gray gas. The numerical solutions of strongly radiating nonequilibrium flows are presented for both gray and non-gray gases.
Gokcen, Tahir↗
Quiet Spike Build-Up Ground Vibration Testing Approach
NASA's Dryden Flight Research Center uses a modified F-15B (836) aircraft as a testbed for a variety of flight research:experiments mounted underneath the aircraft fuselage. The F-15B was selected to fly Gulfstream Aerospace Corporation's (GAC)QuietSpike(TM)(QS) project; however, this experiment is very unique and unlike any of the previous testbed experiments flown on the F-15B. It involves the addition of a relatively long quiet spike boom attached to the radar bulkhead of the aircraft. This QS experiment is a stepping stone to airframe structural morphing technologies designed to mitigate sonic born strength of business jets over land. The QS boom is a concept in Which an aircraft's front-end would be extended prior to supersonic acceleration. This morphing would effectively lengthen the aircraft, reducing peak sonic boom amplitude, but is also expected to partition the otherwise strong bow shock into a series of reduced-strength, non-coalescing shocklets. Prior to flying the Quietspike(TM) experiment on the F-15B aircraft several ground vibration tests (GVT) were required in order to understand the QS modal characteristics and coupling effects with the F-15B. However, due to the project's late hardware delivery of the QS and the intense schedule, a "traditional" GVT of the mated F-1513 Quietspike(tm) ready-for-flight configuration would not have left sufficient time available for the finite element model update and flutter analyses before flight testing. Therefore, a "nontraditional" ground vibration testing approach was taken. The objective of the QuietSpike (TM) build-up ground testing approach was to ultimately obtain confidence in the F-15B Quietspike(TM) finite element model (FEM) to be used for the flutter analysis. In order to obtain the F15B QS FEM with reliable foundation stiffness between the QS and the F-15B radar bulkhead as well as QS modal characteristics, several different GVT configurations were performed. EAch of the four GVT's performed had a specific objective. The overall intent was to provide adequate data which would replicate a "traditional" F-15B QS GVT with actual ready-for-flight hardware. NASA Dryden was tasked with the conduct of the 1st, 2nd and 4th GVT and the 3rd GVT was GAC's responsibility. In order for this build-up GVT approach to be feasible, it was absolutely critical that each GVT configuration matched as closely as possible the connection interface configuration between the and aircraft bulkhead.
Spivey, Natalie D.↗
Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets
Lanthanide-based single-molecule magnets (SMMs) are promising building blocks for quantum memory and spintronic devices. Designing lanthanide-based SMMs with long spin relaxation time requires a detailed understanding of their electronic structure, including the crucial role of the spin-orbit coupling (SOC). While traditional calculations of SOC using the perturbation theory applied to a solution of the non-relativistic Schrödinger equation are valid for light atoms, this approach is questionable for systems containing heavy elements such as lanthanides. We investigate the accuracy of the perturbation estimates of SOC by variationally solving the Dirac equation for the [DyO] + molecule, a prototype of a lanthanide-based SMM. We show that the energy splittings between the M J states involved in spin relaxation depend on the interplay between strong SOC and dynamic electron correlations. Here, we demonstrate that this interplay affects the resonances between the spin and vibrational transitions, and, therefore, the spin relaxation time.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Vibration and flutter of mistuned bladed-disk assemblies
An analytical model for investigating vibration and flutter of mistuned bladed disk assemblies is presented. This model accounts for elastic, inertial and aerodynamic coupling between bending and torsional motions of each individual blade, elastic and inertial couplings between the blades and the disk, and aerodynamic coupling among the blades. The disk was modeled as a circular plate with constant thickness and each blade was represented by a twisted, slender, straight, nonuniform, elastic beam with a symmetric cross section. The elastic axis, inertia axis, and the tension axis were taken to be noncoincident and the structural warping of the section was explicitly considered. The blade aerodynamic loading in the subsonic and supersonic flow regimes was obtained from two-dimensional unsteady, cascade theories. All the possible standing wave modes of the disk and traveling wave modes of the blades were included. The equations of motion were derived by using the energy method in conjunction with the assumed mode shapes for the disk and the blades. Continuities of displacement and slope at the blade-disk junction were maintained. The equations were solved to investigate the effects of blade-disk coupling and blade frequency mistuning on vibration and flutter. Results showed that the flexibility of practical disks such as those used for current generation turbofans did not have a significant influence on either the tuned or mistuned flutter characteristics. However, the disk flexibility may have a strong influence on some of the system frequencies and on forced response.
Kaza, K. R. V.↗