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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Magneto-Dielectric Effects Induced by Optically-Generated Intermolecular Charge-Transfer States in Organic Semiconducting Materials

Traditionally, magneto-dielectric effects have been developed by combining ferroelectric and magnetic materials. Here, we show a magneto-dielectric effect from optically-generated intermolecular charge-transfer states in an organic semiconducting donor:acceptor (PVK:TCNB) system. We observe in magnetic field effects of photoluminescence that a magnetic field can change singlet/triplet population ratio in intermolecular charge-transfer states. Furthermore, our theoretical analysis and experimental evidence indicate that the singlets and triplets in charge-transfer states have stronger and weaker electrical polarizations, respectively. Therefore, the observed magneto-dielectric effect can be attributed to magnetically-dependent singlet/triplet ratio in intermolecular charge-transfer states. In principle, a magneto-dielectric effect can be generated through two different channels based on magneto-polarization and magneto-current effects when the singlet/triplet ratio in intermolecular charge-transfer states is changed by a magnetic field. We find, from the simulation of dielectric effects, that magneto-polarization and magneto-current effects play primary and secondary roles in the generation of magneto-dielectric effect.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI - ˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 V vs. SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI - ˙*) oxidation potential of -2.1 V vs. SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO 2 reduction catalysts. However, once an electron is transferred from NDI - ˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we have designed a molecular triad system comprising an NDI - ˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO) 3 carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI - ˙ to NDI - ˙* is followed by ultrafast reduction of DPA to DPA - ˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI - ˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.

bio-inspired↗
DOE OSTI2018

Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites

The bimolecular rate coefficients ($k_q^{obs}$) for quenching the metal-to-ligand charge transfer excited states of two Ru polypyridine complexes containing H-bond accepting sites by six p-substituted phenols exhibit abrupt deviations from the expected linear correlations of log$k_q^{obs}$ with phenol’s Hammett σ p constant. This pattern is attributed to a transition of the quenching mechanism from a concerted electron-proton transfer (EPT) to a proton transfer (PT); the latter becomes predominant for the most acidic phenols in MeCN, but not in CH 2 Cl 2 . This assertion is supported by a detailed thermochemical analysis, which also excludes the quenching pathways involving electron transfer from phenols with or without deprotonation of phenols to the solvent, either concerted or sequential. The transition from EPT to PT upon the σ p increase is consistent/supported by the magnitudes of the measured and computed PhOH/OD kinetic isotope effects and by the observed reduction of the EPT product yields upon replacing the low σ p methoxyphenol by the high σ p nitrophenol. In addition to modulating the relative contribution of the EPT and PT quenching pathways, the solvent strongly affects the bimolecular rate coefficients for the EPT quenching proper. Unlike with H-atom transfer reactions, this kinetic solvent effect could not be quantitatively accounted for by the phenol-solvent H-bonding alone, which suggests a solvent effect on the H-bonding constants in the phenol-Ru complex precursor exciplexes and/or on the unimolecular EPT rate coefficients within these exciplexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

Here, photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies. Both n -BA and iso-BA perovskites consist of mixed-phase 2D quantum wells with various layer thicknesses, where the photo-generated charges undergo inter-phase charge transfer from thinner quantum wells to thicker ones. By shortening the spacer from n -BA to iso-BA, the transfer rates are significantly increased, which can also diminish the charge accumulation in thin quantum wells induced by the unbalanced electron and hole charge transfer rates. Under high excitation intensity, the shorter spacing cation is found to further facilitate the energy transfer, which can compete with fast high-order carrier recombination and consequently improve the charge transfer efficiency. Intriguingly, we observe the existence of extra bulk 3D phases embedded within iso-BA perovskites, which can efficiently collect the confined charges within 2D phases and then transport them with faster carrier mobility and slower recombination rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Colloidal semiconductor nanocrystals in energy transfer reactions

Excitonic energy transfer is a versatile mechanism by which colloidal semiconductor nanocrystals can interact with a variety of nanoscale species. While this process is analogous to dipole–dipole coupling in molecular systems, the corresponding energy transfer dynamics can deviate from that of molecular assemblies due to manifestations of bulk-like features in semiconductor colloids. In particular, weak exciton binding, small singlet–triplet exciton splitting, and the energy disorder across nanocrystal ensembles can all play distinctive roles in the ensuing energy conversion processes. To characterize the variety of energy transfer schemes involving nanocrystals, this feature article will discuss the latest research by both our group and other groups on the key scenarios under which nanocrystals can engage in energy transfer with other nanoparticles, organic fluorophores, and plasmonic nanostructures, highlighting potential technological benefits to be gained from such processes. We will also shed light on experimental strategies for probing the energy transfer in nanocrystal-based assemblies, with a particular emphasis on novel characterization techniques.

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

Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers

Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN) 4 (2,2'-bipyridine)] 2- (1), [Fe(CN) 4 (2,3-bis(2-pyridyl)pyrazine)] 2- (2) and [Fe(CN) 4 (2,2'-bipyrimidine)] 2- (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the 1 MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the 3 MLCT lifetime to range from 180 fs to 67 ps. The 3 MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred ( 3 MC) excited state, as established by the Tanabe–Sugano analysis of the Fe 2p3d RIXS data. In contrast, the 3 MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing 3 MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The 3 MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm -1 ), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the 3 MLCT and the 3 MC states and suppression of the intramolecular distortion of the acceptor ligand in the 3 MLCT excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Voltage-dependent excitation dynamics in UV-absorbing organic photovoltaics with efficient charge transfer exciton emission

Intermolecular charge-transfer excitons play a central role in determining the performance of organic solar cells as their voltage-dependent formation, dissociation, and recombination dynamics contribute to photocurrent generation, radiative/nonradiative voltage losses, and photovoltaic fill factor. Here, we explore the properties of brightly-emitting wide energy gap (>2 eV) charge transfer excitons by measuring the voltage-dependent photoluminescence, photocurrent, and ultrafast pump–probe transient absorption spectra of organic solar cells employing five UV-absorbing donor molecules that differ only by the length of the oligophenylene or acene group at their core. We find that organic solar cells with a strong correlation between their voltage-dependent photocurrent and charge-transfer exciton photoluminescence have low photovoltaic fill factors as they require voltage to facilitate efficient charge-transfer exciton dissociation. In contrast, solar cells that are efficient can readily generate charges without an applied field and have a separate population of tightly-bound charge-transfer excitons that are responsible for emission. Furthermore, considering that the sum of all excitation loss rates (i.e., recombination and charge extraction) must be equal to the excitation generation rate in the steady state, these voltage-dependent data allow us to solve for the voltage-dependent fate of all excitations in the solar cells and estimate upper and lower bounds for geminate and non-geminate recombination, respectively.

14 SOLAR ENERGY↗
DOE OSTI2012

Controlling the column spacing in isothermal magnetic advection to enable tunable heat and mass transfer

Isothermal magnetic advection (IMA) is a recently discovered method of inducing highly organized, non-contact flow lattices in suspensions of magnetic particles, using only uniform ac magnetic fields of modest strength. The initiation of these vigorous flows requires neither a thermal gradient nor a gravitational field, and so can be used to transfer heat and mass in circumstances where natural convection does not occur. These advection lattices are comprised of a square lattice of antiparallel flow columns. If the column spacing is sufficiently large compared to the column length and the flow rate within the columns is sufficiently large, then one would expect efficient transfer of both heat and mass. Otherwise, the flow lattice could act as a countercurrent heat exchanger and only mass will be efficiently transferred. Although this latter case might be useful for feeding a reaction front without extracting heat, it is likely that most interest will be focused on using IMA for heat transfer. In this paper, we explore the various experimental parameters of IMA to determine which of these can be used to control the column spacing. These parameters include the field frequency, strength, and phase relation between the two field components, the liquid viscosity, and particle volume fraction. Finally, we find that the column spacing can easily be tuned over a wide range to enable the careful control of heat and mass transfer.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Coherent transfer of nuclear spin polarization in field-cycling NMR experiments

Coherent polarization transfer effects in a coupled spin network have been studied over a wide field range. The transfer mechanism is based on exciting zero-quantum coherences between the nuclear spin states by means of non-adiabatic field jump from high to low magnetic field. Subsequent evolution of these coherences enables conversion of spin order in the system, which is monitored after field jump back to high field. Such processes are most efficient when the spin system passes through an avoided level crossing during the field variation. The polarization transfer effects have been demonstrated for N-acetyl histidine, which has five scalar coupled protons; the initial spin order has been prepared by applying RF-pulses at high magnetic field. The observed oscillatory transfer kinetics is taken as a clear indication of a coherent mechanism; level crossing effects have also been demonstrated. The experimental data are in very good agreement with the theoretical model of coherent polarization transfer. The method suggested is also valid for other types of initial polarization in the spin system, most notably, for spin hyperpolarization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Direct comparison of graphene devices before and after transfer to different substrates

The entire graphene field-effect-transistor devices first fabricated on SiO{sub 2}/Si are peeled from the surface and placed on a different wafer. Both longitudinal and transverse resistivity measurements of the devices before and after the transfer are measured to calculate the mobility for a direct comparison. After transferred to different SiO{sub 2}/Si wafers, the mobility, generally, is comparable, and the defect density does not show any significant increase, which indicates the degradation due to the transfer process itself is minimal. The same method can be applied to transfer graphene devices to any arbitrary substrates (e.g., SrTiO{sub 3} or STO). The transfer method developed here not only eliminates the need to locate single-layer graphene on non-SiO{sub 2}/Si substrates for patterning but also provides a convenient way to study the effects of various substrates on graphene electronic properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Design of the transfer line from booster to storage ring at 3 GeV

The Synchrotron Booster Ring accelerates the e-beam up to 3 GeV and particles are transported from booster to storage ring by transfer line. In this study, two options are considered, the first one is a long booster which shares the same tunnel with storage ring and the second one is a compact booster. As a result, two transfer line are designed based on booster options. The optical design is constrained by the e-beam Twiss parameters entering and leaving the transfer line. Twiss parameters in the extraction point of booster are used for the entrance of transfer line and are matched in the exit of transfer line to the injection point of the storage ring.

43 PARTICLE ACCELERATORS↗
DOE OSTI2016

Geometric and energetic considerations of surface fluctuations during ion transfer across the water-immiscible organic liquid interface

Molecular dynamics simulations and umbrella sampling free energy calculations are used to examine the thermodynamics, energetics, and structural fluctuations that accompany the transfer of a small hydrophilic ion (Cl{sup −}) across the water/nitrobenzene interface. By examining several constrained interface structures, we isolate the energetic costs of interfacial deformation and co-transfer of hydration waters during the ion transfer. The process is monitored using both energy-based solvation coordinates and a geometric coordinate recently introduced by Morita and co-workers to describe surface fluctuations. Our simulations show that these coordinates provide a complimentary description of the water surface fluctuations during the transfer and are necessary for elucidating the mechanism of the ion transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Near-field radiative heat transfer between doped-Si parallel plates separated by a spacing down to 200 nm

Heat transfer between two objects separated by a nanoscale vacuum gap holds great promise especially in energy harvesting applications such as near-field thermophotovoltaic systems. However, experimental validation of nanoscale radiative heat transfer has been largely limited to tip-plate configurations due to challenges of maintaining small gap spacing over a relatively large area. Here in this paper, we report measurements of heat transfer near room temperature between two 1 cm by 1 cm doped-Si parallel plates, separated by a vacuum gap from about 200 nm to 780 nm. The measured strong near-field radiative transfer is in quantitative agreement with the theoretical prediction based on fluctuational electrodynamics. The largest measured radiative heat flux is 11 times as high as the blackbody limit for the same hot and cold surface temperatures. Our experiments have produced the highest radiative heat transfer rate observed to date across submicron distances between objects near room temperature.

42 ENGINEERING↗
DOE OSTI2018

Bio-inspired self-agitator for convective heat transfer enhancement

Convective heat transfer plays an important role in both the fundamental research and the development of high-performance heat exchangers. Inspired by blades of grass vibrating in the wind, we developed a self-agitator for convective heat transfer enhancement. Because of fluid-structure interactions, the agitator, with self-sustained vibration, can generate strong vortices to significantly break the thermal boundary layer and improve fluid mixing for enhanced convective heat transfer. In particular, we establish a methodology to link the vorticity field at a preferred frequency to the optimal improvement in the convective heat transfer. To identify the self-agitator preferred frequency, mode analysis is performed with simulation results using dynamic mode decomposition. Experimental results are also obtained to further validate the proposed approach. These results show that the proposed self-agitator design can improve the convective heat transfer by 120% in a conventional heat exchanger without additional pumping power requirements and can achieve a Nusselt number of up to 30 within the laminar flow region, which is improved by 200% with the same Reynolds number compared to the clean channel.

Li, Zheng↗
DOE OSTI2018

Charge transfer-tuned magnetism in Nd-substituted Gd 5 Si 4

We report a charge-transfer mechanism in tuning of magnetism of Nd-substituted Gd 5-x Nd x Si 4 (x = 1 and 2.5) compounds. The X-ray absorption near edge structure measurements demonstrated that Nd substitutions for Gd induce charge transfer of 5 d electrons from Gd to Nd. The charge transfer weakens spin-orbital coupling of Gd but strengthens that of Nd. Consequently, the magnetization responses of the substituted compounds to low magnetic fields are increased while their saturation magnetization is reduced. Electronic structure calculations showed that the charge transfer stabilizes a ferromagnetic and a ferrimagnetic structure in the compounds with x = 1 and 2.5, respectively, but that it does not change the 5 d –3 p hybridization significantly. It is suggested that the charge transfer of 5d electrons may occur in other rare earth-substituted Gd 5 Si 4 compounds allowing for tuning of their magnetism.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Vibrational coherence transfer illuminates dark modes in models of the FeFe hydrogenase active site

Within the conceptual framework of Redfield theory, the optical response function arises from the dynamical evolution of the system’s density operator, where nonunitary relaxation is encoded in the Redfield relaxation superoperator. In the conventional approach, the so-called secular approximation neglects terms that induce transitions between distinct coherences and among coherences and populations. The rationale is that these nonsecular terms are small in comparison to the far more dominant population relaxation and coherence dephasing contributions. Since two-dimensional infrared (2D-IR) spectroscopy has significant contributions arising from population relaxation and transfer pathways, it can be challenging to isolate signatures of the nonsecular relaxation. We report om this paper that in three diiron dithiolate hexacarbonyl complexes that serve as small-molecule models of the [FeFe] hydrogenase H-cluster subsite, a fortuitous vibrational energy structure enables direct and clear signatures of vibrational coherence transfer in alkane solution. This finding holds promise towards developing a molecularly detailed understanding of the mechanism of vibrational coherence transfer processes, thanks to the ease of synthesizing derivatives based on the chemical modularity of these well studied diiron compounds. In addition to the fundamental need to characterize coherence transfer in molecular spectroscopy, we find in this set of molecules a practical utility for the nonsecular dynamics: the ability to determine the frequency of an IR-inactive mode. A coherence generated during the waiting time of the 2D-IR measurement transfers to a coherence involving the single dark CO stretching mode, which modulates some peak amplitudes in the 2D spectrum, revealing its transient excitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Three-state harmonic models for photoinduced charge transfer

A widely used strategy for simulating the charge transfer between donor and acceptor electronic states in an all-atom anharmonic condensedphase system is based on invoking linear response theory to describe the system in terms of an effective spin-boson model Hamiltonian. Extending this strategy to photoinduced charge transfer processes requires also taking into consideration the ground electronic state in addition to the excited donor and acceptor electronic states. In this paper, we revisit the problem of describing such nonequilibrium processes in terms of an effective three-state harmonic model. We do so within the framework of nonequilibrium Fermi’s golden rule (NE-FGR) in the context of photoinduced charge transfer in the carotenoid–porphyrin–C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran (THF). To this end, we consider different ways for obtaining a three-state harmonic model from the equilibrium autocorrelation functions of the donor–acceptor, donor–ground, and acceptor–ground energy gaps, as obtained from all-atom molecular dynamics simulations of the CPC 60 /THF system. The quantum-mechanically exact time-dependent NE-FGR rate coefficients for two different charge transfer processes in two different triad conformations are then calculated using the effective three-state model Hamiltonians as well as a hierarchy of more approximate expressions that lead to the instantaneous Marcus theory limit. Our results show that the photoinduced charge transfer in CPC 60 /THF can be described accurately by the effective harmonic three-state models and that nuclear quantum effects are small in this system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗