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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electronic Structure of Molecular Cobalt Catalysts for H 2 Production Revealed by Multifrequency EPR

Improving the design of hydrogen evolution reaction (HER) catalysts requires a detailed understanding of the catalyst's structure and environment. Here wwe have used multifrequency electron paramagnetic resonance (EPR) spectroscopy (X-band, Q-band, and D-band) in combination with density functional theory (DFT) modeling to elucidate the electronic structure of three Co(II) molecular catalysts for H 2 evolution to determine correlations of electronic structure parameters with catalytic activity and stability. The Co(II) coordination complexes investigated here are representative of two types of H 2 -evolving molecular catalysts: cobaloximes, formed from cobalt coordination to two glyoxime ligands, and cobalt poly(pyridyl) complexes, which commonly have either four or five pyridyl ligands coordinating a single Co(II) ion. These Co(II) complexes were studied in a variety of solvents with a range of polarities and stoichiometric amounts of potential ligands to the cobalt ion to assess the strength and nature of ligand- cobalt interactions. Using magnetic resonance parameters obtained by EPR spectroscopy as reference data, we reconstructed the electronic structure of the Co(II) complexes with the help of DFT modeling. For all three catalysts, we uncovered a linear correlation between the Co(II) A z value and the g x value that is dependent on the strength of the axial ligands. The correlations that we have established between the electronic structure and metal coordination environment provide insight into the structural and electronic factors underpinning the observed trends in HER catalysis activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Modifying the Optical Emission of Vanadyl Phthalocyanine via Molecular Self-Assembly on van der Waals Materials

Vanadyl phthalocyanine (VOPc) is a promising organic molecule for applications in quantum information because of its thermal stability, efficient processing, and potential as a spin qubit. The deposition of VOPc in different molecular orientations allows the properties to be customized for integration into various devices. However, such customization has yet to be fully leveraged to alter its intrinsic properties, particularly optical emission. Normally, VOPc films on dielectric substrates emit a broad photoluminescence peak in the near-infrared range, attributed to transitions in the Pc ring from its π orbital structure. Here, in this work, we demonstrate that the dominant optical transition of VOPc can be shifted by ∼250 meV through the controlled deposition of thin films on van der Waals material substrates. The weak interactions with van der Waals materials allow the molecules to uniquely self-assemble, resulting in modified optical behavior modulated by the molecular phase and thickness. This work connects the self-assembling properties of molecules to their altered electronic structures and the resulting optical emission.

anions↗
DOE OSTI2020

Organic-Inorganic Reaction of Li-Containing thin film: Structure of Lithium Propane Dioxide via MLD

In combining organometallic with organic precursors, molecular layer deposition (MLD) offers not only an expanded portfolio of molecular combinations but specifically the possibility of tuning mechanical properties for more robust functionality. This is appealing for applications in energy storage, where ion transport in and out of electrodes causes significant stress/strain cycling. It is particularly opportune for Li-ion solid state batteries (LISSBs), where electrode and solid electrolyte structures are usually arranged densely for high power and energy. Despite diverse MLD applications to date, little prior research has been aimed at Li-containing MLD materials and processes. Here, we report the MLD growth and process for a lithium-containing organic thin film using lithium tert-butoxide (LiO t Bu) and 1,3-propanediol, leading to an MLD film of lithium propane dioxide, Li 2 O 2 C 3 H 6 (LPDO), identified through X-ray photoelectron spectroscopy (XPS) and ab initio calculations. The growth showed self-limiting behavior for both precursors, with significant nucleation delay before linear growth at 0.23 Å/cycle at 150 °C, and 0.15 Å/cycle at 200 °C. XPS-determined stoichiometry was Li 1.6 O 2.2 C 3 H 6 at both 150 and 200 °C, while additional species, presumably from incomplete reaction, were found at 100 °C, leading to a notably higher (0.84 Å/cycle) growth rate. The LPDO film showed crystallinity and high surface roughness when grown on the crystalline substrate, while on the amorphous substrate, an amorphous LPDO film with low surface roughness was observed. In addition, high air sensitivity of LPDO film was observed, with Li propyl carbonate and Li carbonate formation under air exposure. Further modification strategies were proposed in order to achieve a MLD or atomic layer deposition-/MLD-based solid electrolyte material.

25 ENERGY STORAGE↗
DOE OSTI2020

Machine Learning-Based Upscaling of Finite-Size Molecular Dynamics Diffusion Simulations for Binary Fluids

Molecular diffusion coefficients calculated using molecular dynamics (MD) simulations suffer from finite-size (i.e., finite box size and finite particle number) effects. Results from finite-sized MD simulations can be upscaled to infinite simulation size by applying a correction factor. For self-diffusion of single-component fluids, this correction has been well-studied by many researchers including Yeh and Hummer (YH); for binary fluid mixtures, a modified YH correction was recently proposed for correcting MD-predicted Maxwell–Stephan (MS) diffusion rates. In this study we use both empirical and machine learning methods to identify improvements to the finite-size correction factors for both self-diffusion and MS diffusion of binary Lennard-Jones (LJ) fluid mixtures. Using artificial neural networks (ANNs), the error in the corrected LJ fluid diffusion is reduced by an order of magnitude versus existing YH corrections, and the ANN models perform well for mixtures with large dissimilarities in size and interaction energies where the YH correction proves insufficient.

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

A Hotspot’s Better Half: Non-Equilibrium Intra-Molecular Strain in Shock Physics

Shockwave interactions with a material’s microstructure localizes energy into hotspots, which act as nucleation sites for complex processes such as phase transformations and chemical reactions. To date, hotspots have been described via their temperature fields. Nonreactive, all-atom molecular dynamics simulations of shock-induced pore collapse in a molecular crystal show that more energy is localized as potential energy (PE) than can be inferred from the temperature field and that PE localization persists beyond thermal diffusion. Furthermore, the origin of the PE hotspot is traced to large intramolecular strains, storing energy in modes readily available for chemical decomposition.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence

Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum–classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.

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

Charge-Transfer Luminescence in a Molecular Donor–Acceptor Complex: Computational Insights

Donor–acceptor molecular complexes are a popular class of materials utilizing charge-transfer states for practical applications. A recent class of donor–acceptor dyads based on the fluorescent BODIPY functionalized with triphenylamine (TPA) shows the peculiar property of dual fluorescence. It is hypothesized that instead of the sensitized charge-transfer state being optically dark, it provides an additional bright radiative pathway. In this study, we use time-dependent density functional theory to characterize the energetic alignment of excitonic and charge-transfer states in a BODIPY-TPA molecular complex. We observe that using a long-range exchange corrected functional in combination with state-specific solvation scheme gives a qualitatively correct alignment of the exciton and charge-transfer states and an enhancement in oscillator strength for the equilibrium solvated charge-transfer state, in agreement with experiment. Furthermore, this work provides rationalization of charge-transfer state emission and provides a foundation to explore charge-transfer using ab initio excited-state nonadiabatic dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Direct Observation of Twin van der Waals Molecular Chains

The van der Waals (vdW) assemblies are the most common structures of materials. However, directly mapping intermolecular electron clouds of a vdW assembly has never been obtained, even though the intramolecular electron clouds were visualized by atomic-resolution techniques. In this report, we unprecedently mapped the intermolecular electron cloud of the assembles of ethanol molecules via ethyl groups with noncontact atomic force microscopy at 5 K, leading to the first visualization of vdW molecular chains, in which ethanol molecules assemble into twin vdW molecular chains in a reverse parallel configuration on Ag(111) plane. Furthermore, spontaneous order-disorder transitions in the chain were dynamically observed, suggesting its unusual properties different from 2D vdW materials. In conclusion, these findings provide an "eye" to see the atomic world of vdW materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Utilizing Quantum Cascade Lasers for Ultranarrow Velocity Resolution and Quantum-State Selectivity in Molecular Beam Scattering and Spectroscopy

Here, we demonstrate the capability of a narrow linewidth quantum cascade laser (QCL) to selectively excite a very narrow velocity range of nitric oxide (σ ≤ 7(3) m/s) with a pure ro-vibrational quantum state. By implementing a counter-propagating geometry, the molecules are selectively excited according to the Doppler shift of the ro-vibrational transition frequency such that the velocity width associated with the excited molecules depends only on the QCL linewidth. We demonstrate a velocity distribution limited by the effective linewidth of our free-running QCL (Γ = 3.2 MHz). Our development provides a cost-effective, flexible approach to resolve quantum-state selective chemical dynamics with excellent velocity resolution in a wide variety of molecules with infrared-active transitions. This technique has been formulated to provide ultrahigh collisional energy resolution in molecular beams to delineate final quantum-state product pairs in studies of molecular collisions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Long-Range Dispersion Governs the Behavior of Near-Critical Fluids: Universal Scaling and Implications for Accurate Molecular Simulation

Computer simulations of near-critical and supercritical fluids often deviate from experimental results, a discrepancy commonly attributed to force-field resolutions and inaccuracies. We demonstrate that these errors primarily stem from using finite cutoff schemes for dispersion interactions, which become effectively long-range as the correlation length grows near the critical point. By employing the smooth particle-mesh Ewald method to account for full long-range dispersion, we show that coarse-grained models can also achieve high quantitative accuracy for n-undecane and propylbenzene. This approach enables the precise determination of density fluctuations and correlation lengths, which exhibit universal critical scaling and depend on the molecular size and shape. Our findings resolve a longstanding debate in molecular simulations of near-critical fluids, establishing that capturing long-wavelength fluctuations is essential for bridging the gap between the microscopic behavior and macroscopic critical phenomena.

Chen, Guang↗
DOE OSTI2020

Influences of Hydrogen Bonding-Based Stabilization of Bolaamphiphile Layers on Molecular Diffusion within Organic Nanotubes Having Inner Carboxyl Groups

This paper reports molecular diffusion behavior in two bolaamphiphile-based organic nanotubes having inner carboxyl groups with different inner dimeters (10 and 20 nm) and wall structures, COOH-ONT 10nm and COOH-ONT 20nm , using imaging fluorescence correlation spectroscopy (imaging FCS). Here, the results were compared to those previously obtained in a similar nanotube with inner amine groups (NH 2 -ONT 10nm ). COOH-ONT 10nm , as with NH 2 -ONT 10nm , were formed from a rolled bolaamphiphile layer incorporating triglycine moieties, whereas COOH-ONT 20nm consisted of four stacks of triglycine-free bolaamphiphile layers. Imaging FCS measurements were carried out for anionic sulforhodamine B (SRB), zwitterionic/cationic rhodamine B (RB) and cationic rhodamine-123 (R123) diffusing within ONTs (1–9 µm long) at different pH (3.4–8.4) and ionic strengths (1.6–500 mM). Diffusion coefficients (D) of these dyes in the ONTs were very small (0.01–0.1 µm 2 /s), reflecting the significant contributions of molecule-nanotube interactions to diffusion. The D of SRB was larger at higher pH and ionic strength, indicating the essential role of electrostatic repulsion that was enhanced by the deprotonation of the inner carboxyl groups. Importantly, the D of SRB was virtually independent of nanotube inner diameter and wall structure, indicating the diffusion of the hydrophilic molecule was controlled by short timescale adsorption/desorption processes onto the inner surface. In contrast, pH effects on D were less clear for relatively hydrophobic R123 and RB, suggesting the significant contributions of non-Coulombic interactions. Interestingly, the diffusion of these molecules in COOH-ONT 20nm was slower than in COOH-ONT 10nm . Slower diffusion in COOH-ONT20nm was attributable to relatively efficient partitioning of the hydrophobic dyes into the bolaamphiphile layers, which was reduced in COOH-ONT 10nm due to the stabilization of its layer by polyglycine-II-type hydrogen bonding networks. These results show that, by tuning the bolaamphiphile structures and their intermolecular interactions, unique environments can be created within the nanospaces for enhanced molecular separations and reactions.

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

Orientation and Conformation of Proteins at the Air–Water Interface Determined from Integrative Molecular Dynamics Simulations and Sum Frequency Generation Spectroscopy

Understanding the assembly of proteins at the air-water interface (AWI) informs the formation of protein films, emulsion properties, and protein aggregation. Determination of protein conformation and orientation at an interface is difficult to resolve with a single experimental or simulation technique alone. To date, the interfacial structure of even one of the most widely studied proteins, lysozyme, at the AWI remains unresolved. Here in this study, molecular dynamics (MD) simulations are used to determine if the protein adopts a side-on, head-on, or axial orientation at the AWI with two different forcefields, GROMOS-53a6 + SPC/E and a99SB-disp + TIP4P-D. Vibrational sum frequency generation (SFG) spectroscopy experiments and spectral SFG calculations validate consistency between the structure determined from MD and experiments. Overall, we show with strong agreement that lysozyme adopts an axial conformation at pH 7. Further, we provide molecular-level insight as to how pH influences the binding domains of lysozyme resulting in side-on adsorption near the isoelectric point of the lysozyme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Tuning the Solvation and Solubility Properties of Molecularly Heterogeneous Nonionic Deep Eutectic Solvents via Interface Organization

Common separation techniques, such as liquid− liquid extraction, are usually used for extractions and purifications due to their industrial scalability and affordability. However, these well-established practices are hindered by low selectivity and challenges in recovering solutes and solvents. Deep eutectic solvents (DES), a fairly new type of solvent, have the potential to overcome these issues. DESs are binary mixtures whose physical properties can be tuned by selecting the appropriate precursors to facilitate and/or enhance processes such as extraction. A promising DES for selective separations is formed when lauric acid (LA) is mixed with N-methylacetamide (NMA). This LA-NMA DES has a heterogeneous microscopic structure that can solvate compounds with completely different polarities. This study explores how forming an organized structure on the mesoscale affects the solubility of nonpolar solutes in nonionic DESs. To this end, the molecular and mesoscale structures and their effect on the solubility and solvation properties are evaluated for the LA-NMA DES and two new DESs with slight chemical variations in their precursors. It is observed that the organization of the nonpolar DES domains and, consequently, of their interfaces directly relates to the solubility of nonpolar compounds. Specifically, correctly selecting the DES precursors that form organized nonpolar domains leads to an organized interface in which the nonpolar solutes are solvated, thereby increasing the solubility. Additionally, enhanced dissolution power was observed in a completely different DES with mesoscale order in its molecular structure and composed of menthol and lauric acid. The latter result further validates the proposed tunability of the DES dissolution power through organized interfaces, extending it beyond a specific DES family and opening the possibility of new extraction-tailored designer solvents.

Extraction↗
DOE OSTI2020

Electrodeposition of Zinc in Aqueous Electrolytes Containing High Molecular Weight Polymers

Strong polarization of the ion distribution in liquid electrolytes subjected to potential differences exceeding the thermal voltage, V T = kT/e, produces a hydrodynamic instability termed electroconvection at ion-selective interfaces. Electroconvection is desirable in some situations (e.g., electrodialysis) because it promotes mixing in a stagnant electrolyte layer, enhancing the ion flux at a fixed potential difference. It is undesirable in others (e.g., electrodeposition of metals) where early experiments show that convective fluid rolls associated with hydrodynamic instability in bounded electrolytes produce preferential metal deposition at localized regions on an electrode. Such localized deposition drives the family of morphological instabilities loosely termed dendritic electrodeposition. We experimentally investigate the effect of ultrahigh molecular weight polymer additives on the onset conditions and physical characteristics of both instabilities. Direct observations of electrodeposit morphology and tracer particle motions used in tandem with indirect electrokinetic measurements reveal that even at moderate concentrations, the polymer additives have a large beneficial effect in extending the range of electric potentials where stable electrodeposition is observed. Additionally, we report that at polymer concentrations above the entanglement threshold, high molecular weight polymers impart elasticity to liquid electrolytes which dampen electroconvective flow at a cation-selective interface but have at most a minimal effect on the bulk ionic conductivity of the liquid.

25 ENERGY STORAGE↗
DOE OSTI2022

How Cooperatively Folding Are Homopolymer Molecular Knots?

Detailed thermodynamic analysis of complex systems with multiple stable configurational states allows for insight into the cooperativity of each individual transition. In this work, we derive a heat capacity decomposition comprising contributions from each individual configurational state, which together sum to a baseline heat capacity, and contributions from each state-to-state transition. We apply this analysis framework to a series of replica exchange molecular dynamics simulations of linear and 1-1 coarse-grained homo-oligomer models, which fold into stable, configurationally well-defined molecular knots, in order to better understand the parameters leading to stable and cooperative folding of these knots. We find that a stiff harmonic backbone bending angle potential is key to achieving knots with specific 3D structures. Tuning the backbone equilibrium angle in small increments yields a variety of knot topologies. Populations of different knotted states as a function of temperature can also be manipulated by tuning the backbone torsion stiffness or by adding side-chain beads. We find that sharp total heat capacity peaks for the homo-oligomer knots are largely due to a coil-to-globule transition rather than a cooperative knotting step. Furthermore, in some cases, the cooperativity of globule-to-knot and coil-to-globule transitions is comparable, suggesting that highly cooperative folding to knotted structures can be achieved by refining the model parameters or adding sequence specificity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Isolating Chemical Reaction Mechanism as a Variable with Reactive Coarse-Grained Molecular Dynamics: Step-Growth versus Chain-Growth Polymerization

Here we present a general approach to isolate chemical reaction mechanism as an independently controllable variable across chemically distinct systems. Modern approaches to reduce the computational expense of molecular dynamics simulations often group multiple atoms into a single “coarse-grained” interaction site, which leads to a loss of chemical resolution. In this work we convert this shortcoming into a feature and use identical coarse-grained models to represent molecules that share nonreactive characteristics but react by different mechanisms. As a proof of concept, we use this approach to simulate and investigate distinct, yet similar, trifunctional isocyanurate resin formulations that polymerize by either chain- or step-growth. Because the underlying molecular mechanics of these models are identical, all emergent differences are a function of the reaction mechanism only. We find that the microscopic morphologies resemble related all-atom simulations and that simulated mechanical testing reasonably agrees with experiment.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermodynamic Trends for Reduction of CO by Molecular Complexes

Selective reduction of CO 2 into fuels and chemical feedstocks is highly desirable to reduce our dependence on fossil fuels. Most molecular catalysts afford 2e – reduction products, such as CO or HCO 2 – , as opposed to more reduced products. Here we present an analysis of the thermodynamic limitations for reduction of the CO ligand in the form of a series of isostructural group 6 carbonyl complexes, Cp*M(CO) 3 (P(OMe) 3 ) + (M = Cr, Mo, and W). Additionally, the free energy for stepwise transfer of a hydride (H – ) and a proton (H + ) to the CO ligand, resulting in a hydroxycarbene (CHOH) complex, was measured by equilibration with H – /H + donors and acceptors with known hydricity or acidity. Together, these two reaction steps are equivalent to a net addition of H 2 across the CO ligand. A large and unfavorable free energy for H 2 addition (Δ G ° H2 ) was measured for all three complexes and decreases in the order Cr > Mo > W. The trend for these complexes is opposite to the trend previously reported for group 7 carbonyl complexes, for which Δ G ° H2 decreases moving up the group, Re > Mn. Computational analysis indicates the trends can be described in terms of electrostatic effects, where a low Δ G ° H2 is obtained in complexes that balance the atomic charges of the M–C≡O fragment of the complex. These findings can be used to design metal carbonyl complexes with a more energetically accessible H 2 addition, which will facilitate the development of molecular catalysts for reduction of CO.

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

Ion Pairing Mediates Molecular Organization Across Liquid/Liquid Interfaces

Liquid/liquid interfaces play a central role in scientific fields ranging from nanomaterial synthesis and soft matter electronics to nuclear waste remediation and chemical separations. This diversity of functions arises from an interface’s ability to respond to changing conditions in its neighboring bulk phases. Understanding what drives this interfacial flexibility can provide novel avenues for designing new functional interfaces. However, limiting this progress is an inadequate understanding of the subtle intermolecular and interphase interactions taking place at the molecular level. Here, we use surface-specific vibrational sum frequency generation spectroscopy combined with atomistic molecular dynamics simulations to investigate the self-assembly and structure of model ionic oligomers consisting of an oligodimethylsiloxane (ODMS) tail covalently attached to a positively charged methyl imidazolium (MIM + ) head group at buried oil/aqueous interfaces. We show how the presence of seemingly innocuous salts can impart dramatic changes to the ODMS tail conformations in the oil phase via specific ion effects and ion-pairing interactions taking place in the aqueous phase. These specific ion interactions are shown to drive enhanced amphiphile adsorption, induce morphological changes, and disrupt emergent hydrogen-bonding structures at the interface. Tuning these interactions allows for independent control over the oligomer structure in the oil phase versus interfacial population changes and represents key mechanistic insight that is needed to control chemical reactions at liquid/liquid interfaces.

36 MATERIALS SCIENCE↗