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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane

We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Emission Control from Transition Metal Dichalcogenide Monolayers by Aggregation-Induced Molecular Rotors

Organic–inorganic (O–I) heterostructures, consisting of atomically thin inorganic semiconductors and organic molecules, present synergistic and enhanced optoelectronic properties with a high tunability. Here, we develop a class of air-stable vertical O–I heterostructures comprising a monolayer of transition-metal dichalcogenides (TMDs), including WS 2 , WSe 2 , and MoSe 2 , on top of tetraphenylethylene (TPE) core-based aggregation-induced emission (AIE) molecular rotors. The created O–I heterostructures yields a photoluminescence (PL) enhancement of up to ~950%, ~500%, and ~330% in the top monolayer WS 2 , MoSe 2 , and WSe 2 as compared to PL in their pristine monolayers, respectively. The strong PL enhancement is mainly attributed to the efficient photogenerated carrier process in the AIE luminogens (courtesy of their restricted intermolecular motions in the solid state) and the charge-transfer process in the created type I O–I heterostructures. Moreover, we observe an improvement in photovoltaic properties of the TMDs in the heterostructures including the quasi-Fermi level splitting, minority carrier lifetime, and light absorption. Overall, this work presents an inspiring example of combining stable, highly luminescent AIE-based molecules, with rich photochemistry and versatile applications, with atomically thin inorganic semiconductors for multifunctional and efficient optoelectronic devices.

14 SOLAR ENERGY↗
DOE OSTI2020

Optimal control of coupled quantum systems based on the first-order Magnus expansion: Application to multiple dipole-dipole-coupled molecular rotors

This paper presents a method for performing approximate optimal control simulations for quantum systems with multiple coupled degrees of freedom. In this work, the time evolution is simulated using the first-order Magnus expansion in the interaction picture, where the couplings between different degrees of freedom are treated as the perturbation. A numerical implementation procedure is presented that leverages upon pairwise couplings and the separability of the zeroth-order time evolution operator to achieve a reduced computational cost, which is analyzed with respect to the number of degrees of freedom. The formulation is compatible with gradient-free methods to optimize the control field, and a stochastic hill climbing algorithm is adopted for this purpose. As illustrations, optimal control simulations are performed for systems of two and three dipole-dipole-coupled molecular rotors under the influence of a control field. For the two-rotor system, the field is optimized to achieve either orientation or entanglement objectives. For the three-rotor system, the field is optimized either to orient all three rotors in the same direction or to orient one rotor in a particular direction while the other two rotors point in the opposite direction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Self‐Assembly Methods Induce Different Individual‐Polymer‐Block Solvation Responses

An understanding of block-specific responses to stimuli in self-assembled copolymers is essential for the effective design of responsive materials. Here, materials formed from different post-reaction processing methods of the same ROMP block copolymer exhibit different block-specific solvent responses, as characterized in situ by fluorescence lifetime imaging microscopy (FLIM). FLIM data were acquired by tagging the polar or nonpolar block separately with a covalently incorporated viscosity-sensitive fluorescent molecular rotor to measure the changing tightness or looseness of assembly upon changes in solvent composition. Rapid precipitation from an insoluble solvent to form a film results in tighter assembly and less difference in tightness/looseness between the two blocks. Further, it interrupts individual block-solvent response behavior. Both results indicate an apparent disruption of the core–shell assembly. This model from FLIM is further supported by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data from isolated solids, which show tighter long-range interactions and more long-range order in these kinetically trapped states. Here, the experiments develop FLIM as a method for pinpointing stimuli-responsive behaviors from different processing methods to individual blocks. Together these outcomes provide a future handle for tailoring solvent-triggered assembly/disassembly behavior.

López, Pía A. [University of California, Irvine, C↗
NASA NTRS1991

Theoretical molecular studies of astrophysical interest

When work under this grant began in 1974 there was a great need for state-to-state collisional excitation rates for interstellar molecules observed by radio astronomers. These were required to interpret observed line intensities in terms of local temperatures and densities, but, owing to lack of experimental or theoretical values, estimates then being used for this purpose ranged over several orders of magnitude. A problem of particular interest was collisional excitation of formaldehyde; Townes and Cheung had suggested that the relative size of different state-to-state rates (propensity rules) was responsible for the anomalous absorption observed for this species. We believed that numerical molecular scattering techniques (in particular the close coupling or coupled channel method) could be used to obtain accurate results, and that these would be computationally feasible since only a few molecular rotational levels are populated at the low temperatures thought to prevail in the observed regions. Such calculations also require detailed knowledge of the intermolecular forces, but we thought that those could also be obtained with sufficient accuracy by theoretical (quantum chemical) techniques. Others, notably Roy Gordon at Harvard, had made progress in solving the molecular scattering equations, generally using semi-empirical intermolecular potentials. Work done under this grant generalized Gordon's scattering code, and introduced the use of theoretical interaction potentials obtained by solving the molecular Schroedinger equation. Earlier work had considered only the excitation of a diatomic molecule by collisions with an atom, and we extended the formalism to include excitation of more general molecular rotors (e.g., H2CO, NH2, and H2O) and also collisions of two rotors (e.g., H2-H2).

Flynn, George↗
NASA NTRS1999

Pressure and Temperature Sensitive Paint Measurements on Rotors

Luminescent molecular probes imbedded in a polymer binder form a temperature or pressure paint. On excitation by light of the proper wavelength, the luminescence, which is quenched either thermally or by oxygen, is detected by a camera or photodetector. From the detected luminescent intensity, temperature and pressure can be determined. The basic photophysics, calibration, accuracy and time response of luminescent paints is described followed by applications in wind tunnels and in rotating machinery.

Sullivan, John↗
DOE OSTI2021

Rotational Dynamics of an Amphidynamic Zirconium Metal–Organic Framework Determined by Dielectric Spectroscopy

A zirconium metal–organic framework with a difluorophenylene rotator bearing a permanent electric dipole of ~3.2 D was synthesized, and its rotational motion was analyzed by temperature- and frequency-dependent broadband dielectric spectroscopy. While solid-state NMR confirms fast rotation qualitatively, the dissipation factors measured between 113 and 153 K suggested an activation energy E a = 2.6 kcal/mol, but deviations from a single Debye relaxation suggested a dynamic process that cannot be accounted for by a well-defined potential with a single activation barrier. The dynamic heterogeneity of the dipolar rotor was confirmed by analysis in terms of a Cole–Cole relaxation, which suggested a mean barrier of ~1.9 kcal/mol, with a heterogeneity that decreases as temperature increases. Based on the single-crystal structure, we propose that the kinetic heterogeneity results from a temperature-dependent potential where rotation motion is mediated by the escape of the rotator from an energy well created by a double Ph–H···F–Ph hydrogen bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Computational design of mechanically coupled axle-rotor protein assemblies

Natural molecular machines contain protein components that undergo motion relative to each other. Designing such mechanically constrained nanoscale protein architectures with internal degrees of freedom is an outstanding challenge for computational protein design. Here we explore the de novo construction of protein machinery from designed axle and rotor components with internal cyclic or dihedral symmetry. We find that the axle-rotor systems assemble in vitro and in vivo as designed. Using cryo–electron microscopy, we find that these systems populate conformationally variable relative orientations reflecting the symmetry of the coupled components and the computationally designed interface energy landscape. These mechanical systems with internal degrees of freedom are a step toward the design of genetically encodable nanomachines.

Science & Technology - Other Topics↗
NASA NTRS1971

Molecular collisions. XIV

Atom rigid rotor problem, applying generalized phase shift rotational excitation treatment in lowest approximation

Bernstein, R. B.↗
DOE OSTI2020

Hypothetical Efficiency of Electrical to Mechanical Energy Transfer during Individual Stochastic Molecular Switching Events

There are now many examples of single molecule rotors, motors and switches in the literature that, when driven by photons, electrons or chemical reactions, exhibit well defined motions. As a step towards using these single molecule devices to perform useful functions one must understand how they interact with their environment and quantify their ability to perform work on it. Using a single molecule rotary switch we examine the transfer of electrical energy, delivered via electron tunneling, to mechanical motion and measure the forces the switch experiences with a non-contact q-plus atomic force microscope. Action spectra reveal that the molecular switch has two stable states and can be excited resonantly between them at a bias of 100 mV via a one-electron inelastic tunneling process which corresponds to an energy input of 16 zepto Joules. Furthermore, while the electrically induced switching events are stochastic and no net work is to done on the cantilever, by measuring the forces between the molecular switch and the AFM cantilever we can derive the maximum hypothetical work the switch could perform during a single switching event which is ~55 meV, equal to 8.9 zepto Joules which translates to a hypothetical efficiency ~55% per individual inelastic tunneling electron induced switching event. When co considering the total electrical energy input this drops to 1x10 -7 % due to elastic tunneling events that dominate the tunneling current. However, this approach constitutes a general method for quantifying and comparing the energy input and output of molecularmechanical devices.

36 MATERIALS SCIENCE↗
NASA NTRS2013

Very-Low-Cost, Rugged Vacuum System

NASA, DoD, DHS, and commercial industry have a need for miniaturized, rugged, low-cost vacuum systems. Recent advances in sensor technology have led to the development of very small mass spectrometer detectors as well as other miniature analytical instruments. However, the vacuum systems to support these sensors remain large, heavy, and power-hungry. To meet this need, a miniaturized vacuum system was created based on a very small, rugged, and inexpensive- to-manufacture molecular drag pump (MDP). The MDP is enabled by the development of a miniature, veryhigh- speed, rugged, low-power, brushless DC motor optimized for wide temperature operation and long life. Such a pump represents an order-of-magnitude reduction in mass, volume, and cost over current, commercially available, state-ofthe- art vacuum pumps. The vacuum system consists of the MDP coupled to a ruggedized rough pump (for terrestrial applications or for planets with substantial atmospheres). The rotor in the MDP consists of a simple smooth cylinder of aluminum spinning at approximately 200,000 RPM inside an outer stator housing. The pump stator comprises a cylindrical aluminum housing with one or more specially designed grooves that serve as flow channels. To minimize the length of the pump, the gas is forced down the flow channels of the outer stator to the base of the pump. The gas is then turned and pulled toward the top through a second set of channels cut into an inner stator housing that surrounds the motor. The compressed gas then flows down channels in the motor housing to the exhaust port of the pump. The exhaust port of the pump is connected to a diaphragm or scroll pump. This pump delivers very high performance in a very small envelope. The design was simplified so that a smaller compression ratio, easier manufacturing process, and enhanced ruggedness can be achieved at the lowest possible cost. The machining of the rotor and stators is very simple compared to that necessary to fabricate TMP (turbo molecular pump) rotor and stator blades. Also, the symmetry of the rotor is such that dynamic balancing of the rotor is greatly simplified. Finally, because of the simplified design, the number of parts in the unit is cut by nearly a factor of three. In fact, there are only five parts, not counting the motor and off-the-shelf screws and O-rings. This reduces the amount of machining and also makes fit-up much simpler while allowing the maintenance of close tolerances.

Kline-Schoder, Robert↗
DOE OSTI2024

Bulk viscosity of the rigid rotor one-component plasma

Bulk viscosity of a plasma consisting of strongly coupled diatomic ions is computed using molecular dynamics simulations. The simulations are based on the rigid rotor one-component plasma, which is introduced as a model system that adds two degrees of molecular rotation to the traditional one-component plasma. It is characterized by two parameters: the Coulomb coupling parameter, Γ, and the bond length parameter, Ω. Results show that the long-range nature of the Coulomb potential can lead to long rotational relaxation times, which in turn yield large values for bulk viscosity. Here, the bulk-to-shear viscosity ratio is found to span from small to large values depending on the values of Γ and Ω. Although bulk viscosity is often neglected in plasma modeling, these results motivate that it can be large in molecular plasmas with rotational degrees of freedom.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Hydrodynamic spin-orbit coupling in asynchronous optically driven micro-rotors

Abstract Vortical flows of rotating particles describe interactions ranging from molecular machines to atmospheric dynamics. Yet to date, direct observation of the hydrodynamic coupling between artificial micro-rotors has been restricted by the details of the chosen drive, either through synchronization (using external magnetic fields) or confinement (using optical tweezers). Here we present a new active system that illuminates the interplay of rotation and translation in free rotors. We develop a non-tweezing circularly polarized beam that simultaneously rotates hundreds of silica-coated birefringent colloids. The particles rotate asynchronously in the optical torque field while freely diffusing in the plane. We observe that neighboring particles orbit each other with an angular velocity that depends on their spins. We derive an analytical model in the Stokes limit for pairs of spheres that quantitatively explains the observed dynamics. We then find that the geometrical nature of the low Reynolds fluid flow results in a universal hydrodynamic spin-orbit coupling. Our findings are of significance for the understanding and development of far-from-equilibrium materials.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Direct observation of coherence transfer and rotational-to-vibrational energy exchange in optically centrifuged CO2 super-rotors

Abstract Optical centrifuges are laser-based molecular traps that can rotationally accelerate molecules to energies rivalling or exceeding molecular bond energies. Here we report time and frequency-resolved ultrafast coherent Raman measurements of optically centrifuged CO 2 at 380 Torr spun to energies beyond its bond dissociation energy of 5.5 eV ( J max = 364, E rot = 6.14 eV, E rot / k B = 71, 200 K). The entire rotational ladder from J = 24 to J = 364 was resolved simultaneously which enabled a more accurate measurement of the centrifugal distortion constants for CO 2 . Remarkably, coherence transfer was directly observed, and time-resolved, during the field-free relaxation of the trap as rotational energy flowed into bending-mode vibrational excitation. Vibrationally excited CO 2 ( ν 2 > 3) was observed in the time-resolved spectra to populate after 3 mean collision times as a result of rotational-to-vibrational (R-V) energy transfer. Trajectory simulations show an optimal range of J for R-V energy transfer. Dephasing rates for molecules rotating up to 5.5 times during one collision were quantified. Very slow decays of the vibrational hot band rotational coherences suggest that they are sustained by coherence transfer and line mixing.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1978

Effect of molecular anisotropy on beam scattering measurements

Within the energy sudden approximation, the total integral and total differential scattering cross sections are given by the angle average of scattering cross sections computed at fixed rotor orientations. Using this formalism the effect of molecular anisotropy on scattering of He by HCl and by CO is examined. Comparisons with accurate close coupling calculations indicate that this approximation is quite reliable, even at very low collision energies, for both of these systems. Comparisons are also made with predictions based on the spherical average of the interaction. For HCl the anisotropy is rather weak and its main effect is a slight quenching of the oscillations in the differential cross sections relative to predictions of the spherical averaged potential. For CO the anisotropy is much stronger, so that the oscillatory pattern is strongly quenched and somewhat shifted. It appears that the sudden approximation provides a simple yet accurate method for describing the effect of molecular anisotropy on scattering measurements.

Goldflam, R.↗