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At least 1,099 records · Page 61

Non-Equilibrium in a Dust-Forming Low-Temperature Plasma: A CARS Study

Dust-forming low-temperature plasmas are versatile systems for the production of nanoparticles with tunable functionalities. While attractive from a materials processing point of view, these systems are inherently complex, with several plasma-induced phenomena determining the properties of the produced materials. Here, we characterize a carbon nanoparticle-forming plasma using coherent anti-Stokes Raman spectroscopy (CARS), with the primary goal of measuring gas temperature. While gas temperature is typically assumed to be at or slightly above room temperature in these reactors, we measure gas temperatures exceeding 1000 K under typical process conditions. We find a correlation between the gas temperature and the nanoparticle yield, suggesting that the particle nucleation and growth process releases energy within the reaction volume, leading to significant gas heating. In addition, we find that the relaxation of vibrationally excited species at the particle surfaces is a major contributor to their heating. In conclusion, these results underscore the complexity of these systems and the need for their more in-depth characterization using advanced techniques such as CARS.

Basic Plasma Phenomena and Gas Discharges↗

Spin–vibronic coherence drives singlet–triplet conversion

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet-triplet conversion in four structurally related dinuclear Pt(II) metal-metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt-Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin-vibronic mechanism. Further, we find that vectorial motion along the Pt-Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective incorporation of antimony into gallium nitride

Dilute concentrations of antimony (Sb) incorporation into GaN induce strong bandgap bowing and tunable room-temperature photoluminescence from the UV to the green spectral regions. However, the atomistic details of the incorporation of Sb into the GaN host remain unclear. In this work, we use first-principles calculations to understand the thermodynamics of Sb substitution into GaN and its effect on the optical and Raman spectra. Although it is empirically considered that Sb is preferentially incorporated as an anion (Sb3−) into the N sublattice, we demonstrate that Sb can also be incorporated as a cation (Sb3+, Sb5+) into the metal sublattice. Our thermodynamic analysis demonstrates that SbN0, SbGa2+, and SbGa0 can co-exist under Ga-rich conditions in n-type samples. We further confirm the dual incorporation of Sb by calculating the vibrational frequencies of different anionic and cationic substitutions to explain the origins of experimentally observed additional Raman peaks of Sb-doped GaN. Moreover, the calculated band structures of different Sb substitutions into GaN explain the experimental photoluminescence and optical absorption spectra. Overall, our analysis suggests that the coexistence of Sb3−, Sb3+, and Sb5+ substitutions into GaN explains the totality of experimental measurements. Our results demonstrate that the selective incorporation of Sb into GaN (and potentially other group-V elements such as As, P, or Bi) by tuning the growth conditions can drastically modify the electronic properties, for applications in visible light emitters and photocatalysis.

Physics↗

Atomic fluctuations in electronic materials revealed by dephasing

The microscopic origin and timescale of the fluctuations of the energies of electronic states has a significant impact on the properties of interest of electronic materials, with implication in fields ranging from photovoltaic devices to quantum information processing. Spectroscopic investigations of coherent dynamics provide a direct measurement of electronic fluctuations. Modern multidimensional spectroscopy techniques allow the mapping of coherent processes along multiple time or frequency axes and thus allow unprecedented discrimination between different sources of electronic dephasing. Exploiting modern abilities in coherence mapping in both amplitude and phase, we unravel dissipative processes of electronic coherences in the model system of CdSe quantum dots (QDs). The method allows the assignment of the nature of the observed coherence as vibrational or electronic. The expected coherence maps are obtained for the coherent longitudinal optical (LO) phonon, which serves as an internal standard and confirms the sensitivity of the technique. Fast dephasing is observed between the first two exciton states, despite their shared electron state and common environment. This result is contrary to predictions of the standard effective mass model for these materials, in which the exciton levels are strongly correlated through a common size dependence. In contrast, the experiment is in agreement with ab initio molecular dynamics of a single QD. Electronic dephasing in these materials is thus dominated by the realistic electronic structure arising from fluctuations at the atomic level rather than static size distribution. The analysis of electronic dephasing thereby uniquely enables the study of electronic fluctuations in complex materials.

36 MATERIALS SCIENCE↗

Piezoelectric Power Requirements for Active Vibration Control

This paper presents a method for predicting the power consumption of piezoelectric actuators utilized for active vibration control. Analytical developments and experimental tests show that the maximum power required to control a structure using surface-bonded piezoelectric actuators is independent of the dynamics between the piezoelectric actuator and the host structure. The results demonstrate that for a perfectly-controlled system, the power consumption is a function of the quantity and type of piezoelectric actuators and the voltage and frequency of the control law output signal. Furthermore, as control effectiveness decreases, the power consumption of the piezoelectric actuators decreases. In addition, experimental results revealed a non-linear behavior in the material properties of piezoelectric actuators. The material non- linearity displayed a significant increase in capacitance with an increase in excitation voltage. Tests show that if the non-linearity of the capacitance was accounted for, a conservative estimate of the power can easily be determined.

Brennan, Matthew C.↗

Estimating Shock Spectra: Extensions beyond GEVS

Shock response spectra (SRS) are the standard description of some vibration environments on spacecraft for equipment qualification. For shock events produced by pyrotechnic devices, SRS can have significant frequency content as high as 10 kHz. It is difficult to construct and analyze finite element models that can resolve dynamic behavior at such high frequencies. GEVS provides simple, empirically based methods for approximating the SRS for a wide variety of shock events. It begins with a base SRS according to the type of pyrotechnic device, and then provides attenuation relations to adjust this SRS according to distance from the shock source, the type of structural frame and the properties of any structural joints between the source and equipment. In our paper we extend GEVS to include more detailed information about the spacecraft structure. To retain the general framework of GEVS, we begin with a base SRS and adjust this SRS using attenuation relations. We use modal and traveling wave concepts to derive the attenuation relations for simple canonical structures. Then we show how these concepts can be used to analyze more complex structures using finite element mode shapes to explicitly calculate the attenuation factors. Since the low- to mid-frequency finite element modal information is extrapolated to obtain the low- to high-frequency attenuation relations, the resulting attenuated SRS is formulated as an upper bound rather than as mean predicted values. We illustrate the extended GEVS approach by analyzing the impact response of composite tubes and the shock response of the STEREO spacecraft.

Igusa, Takeru↗

InSight Aerothermal Environment Assessment

The InSight spacecraft was proposed to be a build-to-print copy of the Phoenix vehicle due to the knowledge that the lander payload would be similar and the trajectory would be similar. However, the InSight aerothermal analysts, based on tests performed in CO2 during the Mars Science Laboratory mission (MSL) and completion of Russian databases, considered radiative heat flux to the aftbody from the wake for the first time for a US Mars mission. The combined convective and radiative heat flux was used to determine if the as-flown Phoenix thermal protection system (TPS) design would be sufficient for InSight. All analyses showed that the design would be adequate. Once the InSight lander was successfully delivered to Mars on November 26, 2018, work began to reconstruct the atmosphere and trajectory in order to evaluate the aerothermal environments that were actually encountered by the spacecraft and to compare them to the design environments.The best estimated trajectory (BET) reconstructed for the InSight atmospheric entry fell between the two trajectories considered for the design, when looking at the velocity versus altitude values. The maximum heat rate design trajectory (MHR) flew at a higher velocity and the maximum heat load design trajectory (MHL) flew at a lower velocity than the BET. For TPS sizing, the MHL trajectory drove the design. Reconstruction has shown that the BET flew for a shorter time than either of the design environments, hence total heat load on the vehicle should have been less than used in design. Utilizing the BET, both DPLR and LAURA were first run to analyze the convective heating on the vehicle with no angle of attack. Both codes were run with axisymmetric, laminar flow in radiative equilibrium and vibrational non-equilibrium with a surface emissivity of 0.8. Eight species Mitcheltree chemistry was assumed with CO2, CO, N2, O2, NO, C, N, and O. Both codes agreed within 1% on the forebody and had the expected differences on the aftbody. The NEQAIR and HARA codes were used to analyze the radiative heating on the vehicle using full spherical ray-tracing. The codes agreed within 5% on most aftbody points of interest.The LAURA code was then used to evaluate the conditions at angle of attack at the peak heating and peak pressure times. Boundary layer properties were investigated to confirm that the flow over the forebody was laminar for the flight.Comparisons of the aerothermal heating determined for the reconstructed trajectory to the design trajectories showed that the as-flown conditions were less severe than design

Beck, Robin↗

InSight's Reconstructed Aerothermal Environments

The InSight spacecraft was proposed to be a build-to-print copy of the Phoenix vehicle due to the knowledge that the lander payload would be similar and the trajectory would be similar. However, the InSight aerothermal analysts, based on tests performed in CO2 during the Mars Science Laboratory mission (MSL) and completion of Russian databases, considered radiative heat flux to the aftbody from the wake for the first time for a US Mars mission. The combined convective and radiative heat flux was used to determine if the as-flown Phoenix thermal protection system (TPS) design would be sufficient for InSight. All analyses showed that the design would be adequate. Once the InSight lander was successfully delivered to Mars on November 26, 2018, work began to reconstruct the atmosphere and trajectory in order to evaluate the aerothermal environments that were actually encountered by the spacecraft and to compare them to the design environments.The best estimated trajectory (BET) reconstructed for the InSight atmospheric entry fell between the two trajectories considered for the design, when looking at the velocity versus altitude values. The maximum heat rate design trajectory (MHR) flew at a higher velocity and the maximum heat load design trajectory (MHL) flew at a lower velocity than the BET. For TPS sizing, the MHL trajectory drove the design. Reconstruction has shown that the BET flew for a shorter time than either of the design environments, hence total heat load on the vehicle should have been less than used in design. Utilizing the BET, both DPLR and LAURA were first run to analyze the convective heating on the vehicle with no angle of attack. Both codes were run with axisymmetric, laminar flow in radiative equilibrium and vibrational non-equilibrium with a surface emissivity of 0.8. Eight species Mitcheltree chemistry was assumed with CO2, CO, N2, O2, NO, C, N, and O. Both codes agreed within 1% on the forebody and had the expected differences on the aftbody. The NEQAIR and HARA codes were used to analyze the radiative heating on the vehicle using full spherical ray-tracing. The codes agreed within 5% on most aftbody points of interest.The LAURA code was then used to evaluate the conditions at angle of attack at the peak heating and peak pressure times. Boundary layer properties were investigated to confirm that the flow over the forebody was laminar for the flight.Comparisons of the aerothermal heating determined for the reconstructed trajectory to the design trajectories showed that the as-flown conditions were less severe than design

radiation↗

Crystalline Order Yet Glass-Like Heat Transport Driven by Hidden Local Distortions as the Structural Origin of Ultralow Thermal Conductivity in AgErTe 2

Given their rich chemical diversity and the interplay among the p-, d-, and f-orbitals of chalcogens, transition metals, and lanthanides, respectively, rare-earth transition-metal chalcogenides exhibit a wide variety of structural, magnetic, and transport phenomena. As a result, they form a particularly appealing platform for investigating structure–property relationships, emergent electronic and magnetic behaviors, and thermal transport. Here we investigate AgErTe 2 as a model system to understand phonon-glass behavior in ordered crystalline solids, which establishes the design principles for thermal barrier coatings and next-generation thermoelectrics. The local bonding asymmetry and lattice softness suppress the inherently low lattice thermal conductivity, resembling the characteristics of amorphous materials. This suppression is significantly influenced by local off-centering of Ag atoms, which breaks lattice periodicity while maintaining global crystallinity. The presence of antibonding states just below the Fermi level, arising from Ag 4d and Te 5p orbital interactions, leads to lattice softening and destabilizes ideal tetrahedral coordination, resulting in a pseudo Jahn–Teller distortion. Furthermore, the coexistence of weaker, more polarizable Ag–Te bonds and stronger Er–Te bonds creates a complex vibrational landscape enriched with low-frequency modes and enhanced phonon scattering. A pronounced disparity in interatomic force constants gives rise to highly localized, low-energy optical phonons linked to Ag rattling. These flat vibrational modes exhibit strong coupling with transverse acoustic phonons, resulting in ultrashort phonon lifetimes and mean free paths approaching interatomic distances. These features collectively enhance phonon scattering across a broad range of length and energy scales. This work offers a framework for engineering suppressed thermal conductivity in crystalline systems without the introduction of alloying elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the identification of continuous vibrating systems modelled by hyperbolic partial differential equations

This paper deals with the identification of spatially varying parameters in systems of finite spatial extent which can be described by second order hyperbolic differential equations. Two questions have been addressed. The first deals with 'partial identification' and inquires into the possibility of retrieving all the eigenvalues of the system from response data obtained at one location x-asterisk epsilon (0, 1). The second deals with the identification of the distributed coefficients rho(x), a(x) and b(x). Sufficient conditions for unique identification of all the eigenvalues of the system are obtained, and conditions under which the coefficients can be uniquely identified using suitable response data obtained at one point in the spatial domain are determined. Application of the results and their usefulness is demonstrated in the identification of the properties of tall building structural systems subjected to dynamic load environments.

Udwadia, F. E.↗

Theory and Simulation of A Novel Viscosity Measurement Method for High Temperature Semiconductor

The properties of molten semiconductors are good indicators for material structure transformation and hysteresis under temperature variations. Viscosity, as one of the most important properties, is difficult to measure because of high temperature, high pressure, and vapor toxicity of melts. Recently, a novel method was developed by applying a rotating magnetic field to the melt sealed in a suspended quartz ampoule, and measuring the transient torque exerted by rotating melt flow on the ampoule wall. The method was designed to measure viscosity in short time period, which is essential for evaluating temperature hysteresis. This paper compares the theoretical prediction of melt flow and ampoule oscillation with the experimental data. A theoretical model was established and the coupled fluid flow and ampoule torsional vibration equations were solved numerically. The simulation results showed a good agreement with experimental data. The results also showed that both electrical conductivity and viscosity could be calculated by fitting the theoretical results to the experimental data. The transient velocity of the melt caused by the rotating magnetic field was found reach equilibrium in about half a minute, and the viscosity of melt could be calculated from the altitude of oscillation. This would allow the measurement of viscosity in a minute or so, in contrast to the existing oscillation cup method, which requires about an hour for one measurement.

Lin, Bochuan↗

Microcanonical Kinetics of Water-Mediated Proton Transfer in 4ABAH + ·(H 2 O) n = 4–6 Clusters (ABA = Aminobenzoic Acid): A Model System for Size-Dependent Relaxation to Ergodic Behavior

Here, we leverage the unique properties of the 4ABAH + · (H 2 O) n clusters (ABA = 4-aminobenzoic acid, n = 4−6) to quantitatively address how a finite, isolated system evolves into an ergodic condition starting from localized arrangements in configuration space. This system adopts two distinct structural isomers in which water molecules cluster around the cationic centers of its two protomers with widely separated positive charge centers. These isomers arise from excess proton attachment to either the acid (O) or amino (N) group on opposite sides of the benzene ring. Both forms are captured and kinetically trapped using cryogenic ion methods and then selectively vibrationally excited through their mutually exclusive IR bands involving NH and OH stretching fundamentals. Because the IR excitation lies below the water binding energy, the system can evolve to explore slow, rare events that lead to the interconversion between the two isomers. The rates of these intracluster reactions are determined by using a pump−probe scheme involving ∼5 ns IR pump and UV probe lasers. The rates occur on the microsecond time scale, leading to steady state populations of the isomers, thus revealing the cluster size-dependent fractionation between the two species at microcanonical equilibrium. The steady state distributions are correlated with the expected trend in the cluster size-dependent reaction energetics, which are in turn consistent with changes in the relative densities of states of the two species. These results thus provide an unusually clear example in which complex, protic-solvent-mediated chemical transformations are captured within a finite system at a precisely determined internal energy.

Rana, Abhijit [Yale Univ., New Haven, CT (United S↗

Effect of joint damping and joint nonlinearity on the dynamics of space structures

Analyses of the effect of linear joint characteristics on the vibrations of a free-free, three-joint beam model show that increasing joint damping increases resonant frequencies and increases modal damping but only to the point where the joint gets 'locked up' by damping. This behavior is different from that predicted by modeling joint damping as proportional damping. Nonlinear analyses of the three-joint model with cubic springs at the joints show all the classical single DOF nonlinear response behavior at each resonance of the multiple DOF system: nondoubling of response for a doubling of forcing amplitude, multiple solutions, jump behavior, and resonant frequency shifts. These properties can be concisely quantified by characteristic backbone curves, which show the locus of resonant peaks for increasing forcing amplitude.

Bowden, Mary↗

Nanoparticle-Induced Disorder at Complex Liquid–Liquid Interfaces: Effects of Curvature and Compositional Synergy on Functional Surfaces

The self-assembly of surfactant monolayers at interfaces plays a sweeping role in tasks ranging from household cleaning to the regulation of the respiratory system. The synergy between different nanoscale species at an interface can yield assemblies with exceptional properties, which enhance or modulate their function. However, understanding the mechanisms underlying coassembly, as well as the effects of intermolecular interactions at an interface, remains an emerging and challenging field of study. Herein, we study the interactions of gold nanoparticles striped with hydrophobic and hydrophilic ligands with phospholipids at a liquid–liquid interface and the resulting surface-bound complexes. We show that these nanoparticles, which are themselves minimally surface active, have a direct concentration-dependent effect on the rapid reduction of tension for assembling phospholipids at the interface, implying molecular coassembly. Through the use of sum frequency generation vibrational spectroscopy, we reveal that nanoparticles impart structural disorder to the lipid molecular layers, which is related to the increased volumes that amphiphiles can sample at the curved surface of a particle. The results strongly suggest that hydrophobic and electrostatic attractions imparted by nanoparticle functionalization drive lipid–nanoparticle complex assembly at the interface, which synergistically aids lipid adsorption even when lipids and nanoparticles approach the interface from opposite phases. The use of tensiometric and spectroscopic analyses reveals a physical picture of the system at the nanoscale, allowing for a quantitative analysis of the intermolecular behavior that can be extended to other systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pole/zero cancellations in flexible space structures

A practical objective in the control of flexible space structures is to minimize the effects of vibrational dynamics at certain specified points on a structure. State feedback can be used to address this question by creating closed-loop modes which are unobservable at these points, and so do not contribute to the measured response. In the frequency domain, such modes correspond to pole/zero cancellations in the closed loop system. This paper analyzes the problem of pole/zero cancellation in flexible structures, making full use of the second-order form of such systems. An explicit expression is derived for the unique state feedback gain with minimum norm which cancels all open-loop zeros. Furthermore, the properties of the residual poles that remain observable in the closed-loop system are studied, and their stability proven for the case of colocated sensors and actuators.

Williams, Trevor↗

Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbon Cations: The Members - 3

In spite of the fact that the infrared spectroscopic properties of only a few isolated ionized polycyclic aromatic hydrocarbons (PAHs) are known, gaseous, ionized PAHs are thought to be responsible for a very common family of infrared interstellar emission bands. In order to provide a data base to test this hypothesis and, if borne out, to use this emission band family as a probe of many different interstellar environments, we are carrying out a thorough study of the infrared spectroscopic properties of neutral and ionized PAHs in argon matrices. Here we present the near and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo[ghilperylene, and coronene. The properties of naphthalene, the first member of the series, are given elsewhere. The spectra of perdeuterated phenanthrene and pyrene are also reported. For those molecules which have been previously studied (pyrene, d(10)-pyrene, and coronene), band positions and relative intensities are in agreement. In all cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeutero-phenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene,the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 5-20 times weaker than in the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Hudgins, D. M.↗

Revised Correlation between Odin/OSIRIS PMC Properties and Coincident TIMED/SABER Mesospheric Temperatures

The Optical Spectrograph and Infrared Imaging System (OSIRIS) instrument on board the Odin satellite detects Polar Mesospheric Clouds (PMCs) through the enhancement in the limb-scattered solar radiance. The Sounding of the Atmosphere using the Broadband Emission Radiometry (SABER) instrument on board the TIMED satellite is a limb scanning infrared radiometer that measures temperature and vertical profiles and energetic parameters for minor constituents in the mesosphere and lower thermosphere. The combination of OSIRIS and SABER data has been previously used to statistically derive thermal conditions for PMC existence [Petelina et al., 2005]. a, A.A. Kutepov, W.D. Pesnell, In this work, we employ the simultaneous common volume measurements of PMCs by OSIRIS and temperature profiles measured by SABER for the Northern Hemisphere summers of 2002-2005 and corrected in the polar region by accounting for the vibrational-vibrational energy exchange among the CO2 isotopes [Kutepov et al., 2006]. For each of 20 coincidences identified within plus or minus 1 degree latitude, plus or minus 2 degrees longitude and less than 1 hour time the frost point temperatures were calculated using the corresponding SABER temperature profile and water vapor densities of 1,3, and 10 ppmv. We found that the PMC presence and brightness correlated only with the temperature threshold that corresponds to the frost point. The absolute value of the temperature below the frost point, however, didn't play a significant role in the intensity of PMC signal for the majority of selected coincidences. The presence of several bright clouds at temperatures above the frost point is obviously related to the limitation of the limb geometry when some near- or far-field PMCs located at higher (and warmer) altitudes appear to be at lower altitudes.

Feofilov, A. G.↗

Exploring the Light-induced Dynamics in Solvated Metallogrid Complexes with Femtosecond Pulses Across the Electromagnetic Spectrum

Oligonuclear complexes of d 4 -d 7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to their mononuclear congeners is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2x2] iron(II) metallogrid complex are characterized by combining transient optical, infrared absorption and X-ray emission spectroscopic measurements on the femtosecond timescale. The analysis is supported by DFT calculations. The photocycle can be described in terms of intra-site transitions, where the Fe II in the low-spin (LS) state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally-hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picosecond to yield a metastable HS state living for several hundreds of nanoseconds. Additionally, systematic comparison with the closely related mononuclear complex [Fe(terpy) 2 ] 2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. Finally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗