Synthesis of vibration dampers
A method which uses a mathematical accelerometer is proposed for determining the 3rd derivative of the displacement in shock absorbers.
Kamayev, V. A.↗
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Synthesis of parameters of a machine set, according to amplitudes of vibration, in the case of coaxial misalignment of shafts
Dynamic synthesis of the coupling parameters permits the building of coaxially aligned connected machines with very small disturbing forces. Considered is the case of two machines connected by a flexible coupling; one machine is installed on shock absorbers with four degrees of freedom. A movement leveling synthesis considers the coaxial nonalignment parameters for the shaft arrangement and determines the optimum coupling rigidity at which the vibration amplitude is at a minimum.
Rondomanskas, M. S.↗
Automated Construction of Potential Energy Surfaces Suitable to Describe van der Waals Complexes with Highly Excited Nascent Molecules: The Rotational Spectra of Ar–CS( v ) and Ar–SiS( v )
Some reactions produce extremely hot nascent products which nevertheless can form sufficiently long-lived van der Waals (vdW) complexes—with atoms or molecules from a bath gas—as to be observed via microwave spectroscopy. Theoretical calculations of such unbound resonance states can be much more challenging than ordinary bound-state calculations depending on the approach employed. One encounters not just the floppy, and perhaps multiwelled potential energy surface (PES) characteristic of vdWs complexes, but in addition, one must contend with excitation of the intramolecular modes and its corresponding influence on the PES. Straightforward computation of the (resonance) rovibrational levels of interest, involves the added complication of the unbound nature of the wave function, often treated with techniques such as introducing a complex absorbing potential. Here, we have demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates—one for each reaction product vibrational quantum number of interest—can produce vdW levels for the complex with spectroscopic accuracy. This requires constructing a series of appropriately weighted lower-dimensional PESs for which we use our freely available PES-fitting code AUTOSURF. The applications of this study are the Ar–CS and Ar–SiS complexes, which are isovalent to Ar–CO and Ar–SiO, the latter of which we considered in a previously reported study. Using a series of vibrationally effective PESs, rovibrational levels and predicted microwave transition frequencies for both complexes were computed variationally. A series of shifting rotational transition frequencies were also computed as a function of the diatom vibrational quantum number. The predicted transitions were used to guide and inform an experimental effort to make complementary observations. Comparisons are given for the transitions that are within the range of the spectrometer and were successfully recorded. Calculations of the rovibrational level pattern agree to within 0.2% with experimental measurements.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electron energy deposition in N2 gas
The processes by which energetic electrons lose energy in a weakly ionized gas of molecular nitrogen are analyzed and calculations are carried out taking into account the discrete nature of the excitation processes. The excitation, ionization, dissociation and heating efficiencies are computed for energies up to 200 eV absorbed in a gas with fractional ionizations varying from 10(-6) to 10(-2). Individual vibrational excitations up to the seventh vibrational level are presented.
Fox, J. L.↗
Potential uses of vacuum bubbles in noise and vibration control
Vacuum bubbles are new acoustic elements which are dynamically more compliant than the gas volume they replace, but which are statically robust. They are made of a thin metallic shell with vacuum in their cavity. Consequently, they pose no danger in terms of contamination or fire hazard. The potential of the vacuum bubble concept for noise and vibration control was assessed with special emphases on spacecraft and aircraft applications. The following potential uses were identified: (1) as a cladding, to reduce sound radiation of vibrating surfaces and the sound excitation of structures, (2) as a screen, to reflect or absorb an incident sound wave, and (3) as a liner, to increase low frequency sound transmission loss of double walls and to increase the low frequency sound attenuation of muffler baffles. It was found that geometric and material parameters must be controlled to a very high accuracy to obtain optimal performance and that performance is highly sensitive to variations in static pressure. Consequently, it was concluded that vacuum bubbles have more potential in spacecraft applications where static pressure is controlled more than in aircraft applications where large fluctuations in static pressure are common.
Ver, Istvan L.↗
Density functional study of relaxation of adsorbate vibration modes: Dominance of anharmonic interaction
Formulation and density functional workflow for calculating the lifetime of vibrational modes of molecular adsorbates on solid surfaces due to vibration–phonon coupling are presented. The anharmonic coupling is invoked to give the correct description of the origin of temperature dependence. Using pyrrolidine (C 4 H 9 N) absorbed on the Cu(001) surface as a concrete example, here we show that the anharmonic coupling can be one to two orders more significant than the harmonic interaction for the broadening of vibrational spectra, especially as temperature increases. These results challenge the common assumption that the anharmonic interaction is weak and call for attention of considering its effect in quantum relaxation and related problems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Study of noise reduction characteristics of composite fiber-reinforced panels, interior panel configurations, and the application of the tuned damper concept
The application of fiber reinforced composite materials, such as graphite epoxy and Kevlar, for secondary or primary structures developing in the commercial airplane industry was investigated. A composite panel program was initiated to study the effects of some of the parameters that affect noise reduction of these panels. The fiber materials and the ply orientation were chosen to be variables in the test program. It was found that increasing the damping characteristics of a structural panel will reduce the vibration amplitudes at resonant frequencies with attendant reductions in sound reduction. Test results for a dynamic absorber, a tuned damper, are presented and evaluated.
Lameris, J.↗
Computerized Design and Generation of Low-Noise Gears with Localized Bearing Contact
The results of research projects directed at the reduction of noise caused by misalignment of the following gear drives: double-circular arc helical gears, modified involute helical gears, face-milled spiral bevel gears, and face-milled formate cut hypoid gears are presented. Misalignment in these types of gear drives causes periodic, almost linear discontinuous functions of transmission errors. The period of such functions is the cycle of meshing when one pair of teeth is changed for the next. Due to the discontinuity of such functions of transmission errors high vibration and noise are inevitable. A predesigned parabolic function of transmission errors that is able to absorb linear discontinuous functions of transmission errors and change the resulting function of transmission errors into a continuous one is proposed. The proposed idea was successfully tested using spiral bevel gears and the noise was reduced a substantial amount in comparison with the existing design. The idea of a predesigned parabolic function is applied for the reduction of noise of helical and hypoid gears. The effectiveness of the proposed approach has been investigated by developed TCA (tooth contact analysis) programs. The bearing contact for the mentioned gears is localized. Conditions that avoid edge contact for the gear drives have been determined. Manufacturing of helical gears with new topology by hobs and grinding worms has been investigated.
Litvin, Faydor L.↗
CH4 nonlocal thermodynamic equilibrium in the atmospheres of the giant planets
The present consideration of methane's vibrational relaxation in the Giant Planets' upper stratospheres employs a model for the thermalization of solar energy absorbed under non-LTE conditions, at the 1.7, 2.3. and 3.3 micron-centered CH4 band groups. On this basis, a range of model atmospheres was produced, reflecting current uncertainties concerning CH4 collisional excitation rates. At 0.1 mbar, all of the non-LTE models are within 2 K of the LTE reference models; the extreme non-LTE models steadily depart from reference LTE ones, however, and reach about + or - 20 K at 0,1 mbar.
Appleby, John F.↗
Computerized Design and Generation of Low-noise Helical Gears with Modified Surface Topology
An approach for design and generation of low-noise helical gears with localized bearing contact is proposed. The approach is applied to double circular arc helical gears and modified involute helical gears. The reduction of noise and vibration is achieved by application of a predesigned parabolic function of transmission errors that is able to absorb a discontinuous linear function of transmission errors caused by misalignment. The localization of the bearing contact is achieved by the mismatch of pinion-gear tooth surfaces. Computerized simulation of meshing and contact of the designed gears demonstrated that the proposed approach will produce a pair of gears that has a parabolic transmission error function even when misalignment is present. Numerical examples for illustration of the developed approach are given.
Litvin, F. L.↗
Generation and Computerized Simulation of Meshing and Contact of Modified Involute Helical Gears
The design and generation of modified involute helical gears that have a localized and stable bearing contact, and reduced noise and vibration characteristics are described. The localization of the bearing contact is achieved by the mismatch of the two generating surfaces that are used for generation of the pinion and the gear. The reduction of noise and vibration will be achieved by application of a parabolic function of transmission errors that is able to absorb the almost linear function of transmission errors caused by gear misalignment. The meshing and contact of misaligned gear drives can be analyzed by application of computer programs that have been developed. The computations confirmed the effectiveness of the proposed modification of the gear geometry. A numerical example that illustrates the developed theory is provided.
Litvin, Faydor L.↗
Resonance sound absorber with yielding wall
A single-sheet resonance system for normal incidence of sound was investigated to study in detail the effect of sympathetic vibration of the resonator front wall on sound absorption.
INSTRUMENTS - RESONATORS↗
Thermodynamic Analysis of Boundary Layer Species During Ablation
The focus of this work is on carbon clusters, hydrocarbons and other carbonaceous species which are constituents of pyrolysis gases injected into the boundary layer. Some of these molecules are observed to have absorption spectra in the VUV and UV region that match the emission spectra of atomic nitrogen and oxygen. Hence, they can potentially absorb the radiation impinging on the heat shield. Accurate thermodynamic data is not available for many of these species over the relevant temperature range for reentry. The objective of this work is to determine the thermochemical properties of potential radiation absorbing molecules using accurate ab initio quantum chemistry calculations. We have compiled a database of formation enthalpies, anharmonic vibrational frequencies and rotational constants for the ground and low-lying excited electronic states of these carbonaceous species. Using these thermochemical properties, we compute equilibrium mole fractions and observe that the mole fractions of some species of interest are significant, thus they could affect the radiative heat flux. Furthermore, comparisons of the formation enthalpies and mole fractions are made with data from literature.
heatshields↗
Biomimetic Light Harvesting Complexes Based on Self-Assembled Dye-DNA Nanostructures (Final Technical Report)
A fundamental limitation in the development of artificial molecular light harvesting structures is that generally if one places pigment molecules close enough to achieve very high energy transfer efficiency and absorbance cross section, the dyes interact in such a way that self-quenching occurs. This limits both the optical cross section and the overall efficiency of light capture in such systems. Nature overcomes this problem and achieves efficient energy transfer without self-quenching by controlling the environment, vibration characteristics, orientation and dynamics of the pigments involved in light harvesting. Natural light harvesting systems have evolved highly intricate chromophore architectures of protein-bound organic molecules that absorb and funnel solar energy with high efficiency and fast transfer rates using elegant excitonic circuitries. Nature achieves this precise control over the properties of pigment complexes by using specific proteins as templates to guide the formation of very well-defined pigment aggregates, groups of pigment molecules that are in close enough contact to undergo excitonic interactions resulting in new electronic properties that were not present in the monomer. In synthetic systems, pigment aggregates are well known, and J-aggregates and H-aggregates have been long studied for their unique properties. In Nature, the chlorosomes of green bacteria form what appear to be classical J-aggregates and the light harvesting complexes of purple nonsulfur bacteria form ring structures that have many of the properties of J-aggregates such as a red-shifted absorbance spectrum and excited states that are delocalized over multiple pigment molecules. These photosynthetic systems leverage the spectral and enhanced transport properties of J-like aggregates to achieve fast exciton transport within the antenna and thus high light-harvesting efficiency. The close interaction of the pigments results in substantial electronic coupling that lifts the degeneracy of excitonic states and therefore modifies the absorption and emission spectra of the monomer. In the case of J-aggregation, lower energy excitonic states acquire significant oscillator strength, resulting in a characteristic bathochromic shift of the absorption and fluorescence and often superradiant delocalized exciton states.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Analytical testing
Analytical methods for combining flight acceleration and strain data with shake test mobility data to predict the effects of structural changes on flight vibrations and strains are presented. This integration of structural dynamic analysis with flight performance is referred to as analytical testing. The objective of this methodology is to analytically estimate the results of flight testing contemplated structural changes with minimum flying and change trials. The category of changes to the aircraft includes mass, stiffness, absorbers, isolators, and active suppressors. Examples of applying the analytical testing methodology using flight test and shake test data measured on an AH-1G helicopter are included. The techniques and procedures for vibration testing and modal analysis are also described.
Flannelly, W. G.↗
Fundamental Studies of the Vibrational, Electronic, and Photophysical Properties of Tetrapyrrolic Architectures
The ability to capture and utilize light in the near-ultraviolet (NUV), visible and near-infrared (NIR-I and NIR-II) spectral regions (i.e., 320–400, 400–700, 700–1000, 1000–1700 nm) is essential for any solar-energy conversion scheme. Nature employs chlorophylls and bacteriochlorophylls in light-harvesting architectures to absorb light in the blue and red/NIR regions. Accessory pigments (carotenoids, bilins) augment absorption of the (bacterio)chlorophylls in the green region. The harvested energy is funneled to a reaction center protein, where charge separation occurs. Subsequent migration of the electron and the hole stabilizes and stores the energy from light via redox chemistry. The long-term objective of the Bocian/Holten&Kirmaier/Lindsey research program under this DOE grant has been to develop tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy and separate charge with high efficiency. Integral to the program has been iterative cycles of design, synthesis and characterization that provided deep insights into the relationships between chemical composition, electronic structure, and key static and dynamic properties (vibrational, redox, photophysical, energy/charge transfer) of tetrapyrrolic systems. Such architectures included monomers, dyads, larger arrays, and complexes with accessory components. The objective was to develop molecular designs and guiding principles to enhance current and future energy-conversion schemes. Molecular arrays targeted to address one or more fundamental questions concerning light harvesting and energy/charge transfer were constructed from analogues of the naturally occurring hemes, chlorophylls and bacteriochlorophylls. Diverse, tunable synthetic building blocks were prepared that spanned the three respective tetrapyrrole families, which are the porphyrins, chlorins and bacteriochlorins. Thus, the research focused on porphyrins as well as synthetic surrogates for chlorophylls (chlorins, 13 1 -oxophorbines and chlorin-imides) and bacteriochlorophylls (bacteriochlorins, bacterio-13 1 -oxophorbines and bacteriochlorin-imides), generically termed hydroporphyrins. Although the three tetrapyrrole classes (porphyrins, chlorins and bacteriochlorins) absorb light strongly in the violet-blue spectral region, the long-wavelength absorption band typically lies in the green-orange, red, and NIR regions, respectively, with increasing intensity. Understanding the spectra, electronic structure, and energy/charge-transfer properties of such tetrapyrrolic macrocycles is of central importance for the rational design of molecular architectures for solar-energy conversion. Our integrated program of molecular design and synthesis coupled with a variety of spectroscopic, electrochemical, and computational studies have probed from first principles how structural and electronic properties of tetrapyrrolic macrocycles dictate spectral properties as well as the rates of ground-state hole/electron transfer and excited-state energy flow in multicomponent architectures. Individual molecules and multicomponent architectures were designed to test ideas of fundamental importance, often requiring the development of new synthetic methodology. The members of the collaborative team had almost daily discussions by phone and/or e-mail concerning design of molecules, flow of compounds between the labs, planning of physical characterization studies, discussing results and analysis and integrating into design of next generation architectures, and the preparation of manuscripts. Furthermore, students and postdocs in the different labs routinely communicated with one another to facilitate the advancement of the research activities. In short, a highly integrated and collaborative research program was well established among the groups. The research effort involved molecular design and synthesis of synthetic molecular architectures by the Lindsey group integrated with physicochemical and photophysical characterization by the Bocian group and the Holten&Kirmaier group (Figure 2). The Bocian group carried out electrochemical, electron paramagnetic resonance (EPR), resonance Raman (RR), and Fourier-transform infrared (FT-IR) studies, as well as density functional theory (DFT) calculations and the time-dependent extension (TDDFT) to gain insight into excited-state properties. The Holten&Kirmaier group carried out static and time-resolved absorption and fluorescence spectroscopy studies and simulated absorption spectra using molecular orbital (MO) energies from DFT as input to the four-orbital model to complement the TDDFT calculations. The combined measurements provided understanding of the vibrational/electronic properties of the individual molecules and the changes that occur upon incorporation into multicomponent architectures. This information underpinned elucidating the mechanisms and timescales of ground-state hole/electron transfer and excited-state energy and charge transfer.
14 SOLAR ENERGY↗
Vapor Phase Installation of CpCo(CO) 2 in MOF‐808
Metal-organic frameworks (MOFs), including MOF-808 present an opportunity for vapor phase installation of reactive centers that may serve as uniform sites for precision catalysis. The mechanism of cobalt installation in MOF-808 through atomic layer deposition (ALD) upon CpCo(CO )2 exposure is investigated through in situ FTIR spectroscopy complemented by density functional theory modeling. The role of subsequent H 2 O exposure in the hydrolysis of carbonyl and cyclopentadienyl ligands to complete the installation is also investigated. In situ FTIR study reveals that upon exposure of CpCo(CO) 2 to MOF-808 at 115 °C, a long-lived, stable intermediate is formed that presents carbonyl stretching vibrations similar to the undissociated precursor that are attributed to multiple chemisorbed carbonyl complexes. In MOF-808, cobalt species are initially absorbed near the BTC linker rather than directly on the nodes, revealing the importance of non-covalent interactions in the installation process. DFT suggests that H 2 O exposure promotes carbonyl elimination but leaves a cyclopentadienyl-capped cobalt that is more stable than the complete hydrolysis product. The simulations are consistent with cobalt installation in MOF-808 using CpCo(CO) 2 and H 2 O at 115 °C and further consistent with the lack of ALD thin film deposition of cobalt oxide thin films on planar supports.
36 MATERIALS SCIENCE↗
The promise of multicyclic control
Several types of rotors which employ multicyclic control are reviewed and compared. Their differences are high-lighted and their potential advantages and disadvantages are discussed. The flow field these rotors must operate in is discussed, and it is shown that simultaneous elimination of vibration and oscillatory blade loads is not an inherent solution to the roughness problem. The use of rotor blades as energy absorbers is proposed. Input-output relations are considered and a gain control for ROMULAN, a multicyclic controlling computer program, is introduced. Implications of the introduction of multicyclic systems into helicopters are discussed.
Mccloud, J. L., III↗