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At least 55 records · Page 3

Progress towards subsurface spectroscopy inside heterogeneous materials using four wave mixing phase conjugation

Herein, we report preliminary results on subsurface spectroscopy inside heterogeneous materials using four wave mixing phase conjugation. For our test material we use an inert plastic bonded explosive simulant that contains fluorescent guidestar particles. Using phase conjugation, we are able to obtain spectral enhancements approximately equal to the phase conjugate reflectivity. Additionally, we discuss future directions to improve this technique to obtain greater signal enhancements.

47 OTHER INSTRUMENTATION↗

Rapid Conjugate Appearance of the Giant Ionospheric Lamb Wave Signatures in the Northern Hemisphere After Hunga-Tonga Volcano Eruptions

The explosive eruption of the Hunga-Tonga volcano in the southwest Pacific at 0415UT on 15 January 2022 triggered gigantic atmospheric disturbances with surface air pressure waves propagating around the globe in Lamb mode. In space, concentric traveling ionosphere disturbances (CTIDs) are also observed as a manifestation of air pressure waves in New Zealand ∼0500UT and Australia ∼0630UT. As soon as the air pressure waves reached central Australia ∼0800UT, conjugate CTIDs appeared almost simultaneously in the northern hemispheres through interhemispheric coupling, much earlier than the arrival of the surface air pressure waves to Japan after 1100UT. Combining observations over Australia and Japan between 0800 and 1000UT, both direct and conjugate CTIDs show similar horizontal phase velocities of 320–390 m/s, matching with the dispersion relation of Lamb mode. The arrival of atmospheric Lamb wave to Japan later created in situ CTIDs showing the same Lamb mode characteristics as the earlier conjugate CTIDs.

Concentric traveling ionospheric disturbances↗

Impact of Dihedral Angle in Conjugated Organic Cation on the Structures and Properties of Organic‐Inorganic Lead Iodides

Abstract Conjugated organic cations are intriguing for organic‐inorganic halide perovskites due to their direct participation in the optoelectronic properties of hybrid materials. In conjugated cations, the dihedral angle, or torsion angle, between adjacent aromatic rings is a critical secondary structural element. This angle influences not only the shape of the cations but also the overlap between the π‐orbitals on adjacent rings, thereby affecting their electronic properties. Understanding how variations in the dihedral angle impact the structure and properties of hybrid organic‐inorganic metal halides (HOIMHs) is fundamentally important. In this study, we utilized 2,2′‐dimethyl bipyridinium as the organic cation, reacting it with PbI₂ to form hybrid lead iodides. Remarkably, variations in the dihedral angle between the two pyridinium rings resulted in the formation of two distinct crystal structures with different band gaps. Our findings demonstrate that manipulating the dihedral angle offers a novel approach to controlling the structures and properties of hybrid metal halides with conjugated cations.

Chandra Patra, Bidhan [Department of Chemistry and↗

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Chemistry↗

Cyclically conjugated porphyrin trimers linked through benzo[4,5]imidazo[2,1- a ]isoindole bridges

Cyclically conjugated porphyrin trimers were prepared via a concise synthetic method. Zn-Trimer-1 displayed strong exciton coupling, suggesting the presence of effective electronic interactions. UV-Vis absorption and fluorescence spectra obtained through titration studies on the donor–acceptor adduct (Zn-Trimer-1–C60Im) indicate the occurrence of excited state photo-events. Inspired by nature's photosynthetic process of plants and bacteria, electronically interacting multiporphyrinic systems have long been investigated as synthetic models of natural photosynthetic systems. Remarkable successes have been achieved with cyclic porphyrin arrays, where porphyrins are arranged in a wheel-like structure or nanoring as photosynthetic antennae. Considerable efforts have also been devoted to constructing other porphyrin arrays such as molecular wires for potential applications in sensors, solar energy conversion, non-linear optical (NLO) materials, and more. Due to synthetic difficulties, cyclically conjugated porphyrin arrays in which porphyrins are arranged in planar geometry are very rare. Very recently, Anderson and coworkers have reported unprecedented β,β-directly linked porphyrin trimers and tetramers with different geometries, propeller and saddle, respectively, which result in distinct photophysical and electrochemical properties (Fig. 1a). In this paper, we present novel cyclically conjugated porphyrin trimers, which feature planar geometry with porphyrins assembled around the aromatic triphenylene at the center (Fig. 1b).

Han, Ting↗

Conjugation effect of amine molecules in non-aqueous Mg redox flow batteries

Nonaqueous magnesium redox flow batteries (Mg RFBs) are attractive for low-cost, high-energy-density and long-cycle-life stationary energy storage applications. However, state-of-the-art cathode redox-active molecules suffer from low solubility and low redox potential. Herein, we screened a range of cathode redox-active molecules and identified amine molecules as optimal to couple with the Mg anode. The properties of amine derivatives and their performances were collected to establish the correlation between molecular structures and electrochemical performances. The redox potential and solubility of these amine molecules were influenced by the π-conjugated and non-conjugated structures of amine derivatives. Density functional theory (DFT) simulations and the inverse aromatic fluctuation index (FLU −1 ) verified that conjugation had an important role in stabilizing the molecule and increasing its redox potential. Notably, tris[4-(diethylamino)phenyl]amine (TDPA) achieved the highest theoretical energy density (∼120 Wh L −1 ) due to its high solubility (∼0.9 M) and voltage (∼2.5 V vs. Mg/Mg 2+ ). We also demonstrated that ether solvents were crucial for stable, high-solubility catholytes, while bulk anions did not affect the redox potential of these p-type molecules. In a Mg-amine RFB configuration, the battery delivered 2.50 V, a specific discharge capacity of 106.5 mAh g −1 , an initial coulombic efficiency of 90.74%, and a capacity retention of 93.88% after 150 cycles.

Qin, Yunan [University of Utah, Salt Lake City, UT↗

Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Satellite observations of whistler-mode signals in the conjugate region of a 200-kilohertz station.

Study of the signals recorded by a narrow-band (about 200 Hz) receiver at a broadcast station operating at 200 kHz and in the conjugate region of Ashkhabad. The latitude of the station is nearly low enough for propagation of a 200-kHz signal in the ducted whistler mode to the conjugate hemisphere along field lines terminating at the station. In the dawn-dusk orbital plane signals are indeed relatively often observed in the conjugate region, but the source of the signals and their path of propagation is not completely clear. The pattern of observations is consistent with propagation over the long magnetospheric path in field-aligned ducts spread in longitude near 22 deg invariant latitude, but an interpretation involving nonducted propagation is preferred, in which the occasionally high electric-field intensities encountered (greater than 10 microvolts/m) result from focusing effects or from propagation near the resonance angle.

Laaspere, T.↗

Conjugate photoelectron fluxes observed on Atmosphere Explorer C

The results are presented of a number of observations made with the aid of the Atmosphere Explorer C spacecraft under conditions which provided an unambiguous opportunity to study photoelectrons entering the atmosphere after flowing along the geomagnetic field from the magnetic conjugate point. A graph is presented with energy spectra of electrons observed precipitating into the atmosphere when the magnetic conjugate point was illuminated. Another graph shows the average energy spectra of electrons observed at 263 km for a range of solar zenith angles when the zenith angles at the magnetic conjugate point varied from 100 to 81 deg.

Peterson, W. K.↗

Measurement of magnetic field aligned potential differences using high resolution conjugate photoelectron energy spectra

Simultaneous high-resolution observations of a distinctive feature in the energy spectrum of conjugate photoelectrons and spacecraft potential relative to the local ionosphere have allowed the net potential difference between magnetic conjugate points at latitudes below the region of low-energy (i.e., lower than 100 eV) auroral electron precipitation to be determined. Measurements made at 300 km from Atmosphere Explorer C show that there is normally no net potential difference between hemispheres in this region, which extended up to invariant latitudes as high as 74 deg. Two types of apparently related anomalous behavior were infrequently observed at high latitudes. During these periods the incident flux of conjugate photoelectrons was either decelerated by about 3 eV or was not detected.

Peterson, W. K.↗

Frequency translating phase conjugation circuit for active retrodirective antenna array

An active retrodirective antenna array which has central phasing from a reference antenna element through a "tree" structured network of transmission lines utilizes a number of phase conjugate circuits (PCCs) at each node and a phase reference regeneration circuit (PRR) at each node except the initial node. Each node virtually coincides with an element of the array. A PCC generates the exact conjugate phase of an incident signal using a phase locked loop which combines the phases in an up converter, divides the sum by 2 and mixes the result with the phase in a down converter for phase detection. The PRR extracts the phase from the conjugate phase. Both the PCC and the PRR are not only exact but also free from mixer degeneracy.

Chernoff, R.↗

Minimizing inner product data dependencies in conjugate gradient iteration

The amount of concurrency available in conjugate gradient iteration is limited by the summations required in the inner product computations. The inner product of two vectors of length N requires time c log(N), if N or more processors are available. This paper describes an algebraic restructuring of the conjugate gradient algorithm which minimizes data dependencies due to inner product calculations. After an initial start up, the new algorithm can perform a conjugate gradient iteration in time c*log(log(N)).

Vanrosendale, J.↗

Simultaneous conjugate observations of dynamic variations in high-latitude dayside convection due to changes in IMF By

Data from two conjugate HF radars currently operating at Goose Bay (Labrador) and the Halley Station (Antarctica), obtained for a single 45-min period about local noon on April 22, 1988, were used to study the near-instantaneous conjugate two-dimensional patterns of plasma convection in the vicinity of the cusp. In particular, the response of these plasma convection patterns to changes in the By component of the IMF was examined. Results indicate that, under quasi-stationary IMF conditions, the conjugate convection patterns are quite similar to the synthesized patterns of Heppner and Maynard (1987) and that the patterns respond rapidly to changes in the IMF By component. Results also show that transitions between convection states begin to occur within minutes of the time that an IMF state change is incident on the magnetospheric boundary, and that the convection reconfigurations expand poleward, completely filling the field of view of an HF radar within 6 min of the time of onset.

Greenwald, R. A.↗

Self-pumped and double phase conjugation in GaAs with applied dc electric field

Self-pumped and double phase conjugation are first demonstrated in undoped GaAs with applied dc electric field at 1.06 micron wavelength. Phase-conjugate reflectivities of up to 3 percent and 0.5 percent, respectively, are obtained and other dependences are reported. Reported values of the self-pumped phase-conjugate reflectivity are compared with those of InP.

Chua, P. L.↗

Phase conjugation by degenerate four wave mixing in disodium fluorescein solution in methanol

Organic dyes are known to show the resonant type of nonlinear optical properties, including phase conjugation. In the present work, disodium fluorescein in methanol is used as an organic nonlinear medium for degenerate four wave mixing at 532 nm to see the intensity dependence of the phase conjugate signal at different concentrations of the solution. It is observed that the maximum reflectivity of the signal occurs in a concentration range of 5 x 10(exp -3)/cu cm to 1.2 x 10(exp -2) g/cu cm. It is also observed that the intensity of the signal drops suddenly to less than half of its maximum outside the concentration range mentioned above. An investigation of the phase conjugate signal intensity by changing the delay time between probe signal and the forward pump is also examined. Briefly discussed is the possibility of population grating in dye liquids as a source of enhancing the third order susceptibility besides the other techniques mentioned in reference. The experiment is done by beam splitting the second harmonic (532 nm) of Nd:YAG laser, Q-switched at 20 pulses/sec (pulse width is approximately 8 and 200 mJ per pulse).

Abdeldayem, Hossin↗

Second and third order nonlinear optical properties of conjugated molecules and polymers

Second- and third-order nonlinear optical properties of some newly synthesized organic molecules and polymers are reported. Powder second-harmonic-generation efficiencies of up to 200 times urea have been realized for asymmetric donor-acceptor acetylenes. Third harmonic generation chi(3)s have been determined for a series of small conjugated molecules in solution. THG chi(3)s have also been determined for a series of soluble conjugated copolymers prepared using ring-opening metathesis polymerization. The results are discussed in terms of relevant molecular and/or macroscopic structural features of these conjugated organic materials.

Perry, Joseph W.↗

Experiments with conjugate gradient algorithms for homotopy curve tracking

There are algorithms for finding zeros or fixed points of nonlinear systems of equations that are globally convergent for almost all starting points, i.e., with probability one. The essence of all such algorithms is the construction of an appropriate homotopy map and then tracking some smooth curve in the zero set of this homotopy map. HOMPACK is a mathematical software package implementing globally convergent homotopy algorithms with three different techniques for tracking a homotopy zero curve, and has separate routines for dense and sparse Jacobian matrices. The HOMPACK algorithms for sparse Jacobian matrices use a preconditioned conjugate gradient algorithm for the computation of the kernel of the homotopy Jacobian matrix, a required linear algebra step for homotopy curve tracking. Here, variants of the conjugate gradient algorithm are implemented in the context of homotopy curve tracking and compared with Craig's preconditioned conjugate gradient method used in HOMPACK. The test problems used include actual large scale, sparse structural mechanics problems.

Irani, Kashmira M.↗

Squeezing in phase-conjugated resonance fluorescence

Emission of resonance fluorescence by an atom near the surface of a four-wave mixing phase conjugator is considered. The dipole radiation field, regarded as a Heisenberg-operator field, is decomposed into plane waves with the aid of Weyl's representation of the Green's function for the wave equation. Each plane-wave component which is incident on the surface of the nonlinear medium, is reflected as its phase-conjugate image. Summation of all reflected plane waves then yields the phase conjugate replica of the incident dipole radiation. This field adds to the radiation which is emitted by the atom into the direction away from the medium. The condition under which squeezing occurs in the emitted resonance fluorescence is investigated.

Arnoldus, Henk F.↗