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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Modular Assembly of FTO|Chromophore-Catalyst Hierarchical Films Based on Strong Dipole Interactions

Here, we have designed and characterized modular self-assembled hierarchical films containing a molecular catalyst tethered to an anchoring molecule by means of dipole-induced dipole interactions. In order to do so, two new Co III -based molecular catalyst candidates were designed, namely, [Co III L 1 (pyrr) 2 ]ClO 4 (Co1) and [Co III L 2 (pyrr) 2 ]ClO 4 (Co2), where L 1 and L 2 are the respective deprotonated forms of N,N′-[4,5-bis(dodecyloxy)-1,2-phenylene]dipicolinamide and N,N′-[4,5-bis(methoxyethoxy)-1,2-phenylene]dipicolinamide and were characterized by electrochemical, electronic, and film formation properties. Species Co1 and Co2 were deposited onto an anchor molecule such as octylphosphonic acid (OPA) or the chromophoric [Ru II (bpy PO3H ) 2 (bpy C7 )]Cl 2 (Ru) previously attached onto conductive fluorine-doped tin oxide (FTO). Four hierarchical films of the form substrate|anchor-catalyst were obtained, namely, FTO|OPA-Co1, FTO|OPA-Co2, FTO|Ru-Co1, and FTO|Ru-Co2, and the role of dipole-dipole interactions between anchor and catalyst modules was assessed. These newly synthesized hierarchical films were characterized by a host of surface-specific methods that include X-ray photoelectron spectroscopy, ellipsometry, X-ray fluorescence, and water contact angle, thus enabling an unprecedented level of analysis. Compared to the weak C-H van der Waals interactions exhibited by Co1, the presence of alkoxy chains in Co2 ensures stronger dipole-dipole interactions with the alkyl chain of the anchors due to O···H formation. The persistence of their redox properties, which include metal oxidation, and directionality of electron transport were probed suggesting direct relevance to catalytic processes such as water oxidation.

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

Electric field sensitivity of molecular color centers

Molecular color centers with S=1 ground states are promising candidates for quantum sensing of electric fields. These molecules have an electronic structure similar to solid state color centers, but they allow for processing modalities that permit direct interfacing with an analyte. Currently, it is unknown how sensitive these molecules are to electric fields and what molecular properties affect their sensitivity. We perform density functional theory calculations to understand the impact of electric fields on the electronic structure of five nominally tetrahedral molecular color centers exhibiting variable transition metal chemistry and ligand densities. We then extract the Stark parameters from each of these molecules and compare them to molecular properties such as the dipole moment and inner shell stiffness and find that the dipole moment of the molecule largely governs sensitivity. We predict that polar heteroleptic molecules may have electric field sensitivities comparable to solid state color centers such as nitrogen-vacancy centers in diamond.

Physics↗
DOE OSTI2020

Trapping of lithium atoms in a large hollow optical dipole trap

We describe the trapping of lithium atoms in an optical dipole trap about 1 mm in size, with a nearly rectangular potential. The trap has the shape of a cylinder with flat bases. The confinement region is bounded by thin walls produced by light with a frequency blue-detuned from an atomic transition (resonance) frequency by 19 GHz. Before trapping, the gas is collected and cooled in a magneto-optical trap whose centre nearly coincides with the centre of the dipole trap. After switching off the magneto-optical trap, we have photographed the atoms remaining in the dipole trap. (paper)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Molecular Heterogeneous Multiferroics (DOE BES Final Technical Report)

This project aims to explore a new class of molecular heterogeneous multiferroics towards room temperature stimuli-responsive magnetoelectricity by untangling the complex interplay between molecular magnetism and molecular ferroelectricity, and their stimuli-responsiveness. The research hypothesis is to examine if the rational design and molecular engineering of hydrogen bonded molecular heterogeneous multiferroics will enable rapid proton-transfer between molecular ferroelectric and magnetic building blocks to control its magnetism and intramolecular spin and dipole interactions, a promising pathway toward a new mechanism of room temperature ME coupling effect in molecular materials. With arbitrary choice and precise organization of molecular building blocks underlying tunable spin and dipole interactions, driven by external stimuli (electrical, magnetic and optical), a variety of multifunctional molecular multiferroics will be created and characterized, which could provide the understanding for the design of next-generation stimuli-responsive molecular magnetoelectronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Molecular-Level Insights into the NMR Relaxivity of Gadobutrol Using Quantum and Classical Molecular Simulations

MRI is an indispensable diagnostic tool in modern medicine; however, understanding the molecular-level processes governing NMR relaxation of water in the presence of MRI contrast agents remains a challenge, hindering the molecular-guided development of more effective contrast agents. By using quantum-based polarizable force fields, the first-of-its-kind molecular dynamics (MD) simulations of Gadobutrol are reported where the 1 H NMR longitudinal relaxivity r 1 of the aqueous phase is determined without any adjustable parameters. The MD simulations of r 1 dispersion (i.e., frequency dependence) show good agreement with measurements at frequencies of interest in clinical MRI. Importantly, the simulations reveal key insights into the molecular level processes leading to r 1 dispersion by decomposing the NMR dipole–dipole autocorrelation function G(t) into a discrete set of molecular modes, analogous to the eigenmodes of a quantum harmonic oscillator. The molecular modes reveal important aspects of the underlying mechanisms governing r 1 , such as its multiexponential nature and the importance of the second eigenmodal decay. By simply analyzing the MD trajectories on a parameter-free approach, the Gadobutrol simulations show that the outer-shell water contributes ∼50% of the total relaxivity r 1 compared to the inner-shell water, in contrast to simulations of (nonchelated) gadolinium-aqua where the outer shell contributes only ∼15% of r 1 . The deviation between simulations and measurements of r 1 below clinical MRI frequencies is used to determine the low-frequency electron-spin relaxation time for Gadobutrol, in good agreement with independent studies.

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

Tuning the melting point of selected ionic liquids through adjustment of the cation’s dipole moment.

In prior research with thermally robust salts [Cassity et al., PCCP, 2017, 19, 31560] it was noted that an increase in the dipole moment of the cation generally led to a decrease in the melting point. Molecular dynamics simulations of the liquid state revealed that an increased dipole moment reduces cation-cation repulsions through dipole-dipole alignment. This was believed to reduce the liquid phase enthalpy, which would tend to lower the melting point of the IL. Here, we also test this principle by replacing hydrogen atoms with fluorine atoms at selected positions within the cation. This allows us to alter the electrostatics of the cation without substantially affecting the sterics. Furthermore, the strength of the dipole moment can be controlled by choosing different positions within the cation for replacement. We studied variants of four different parent cations paired with bistriflimide and determined their melting points, and enthalpies and entropies of fusion through DSC experiments. The decreases in the melting point were determined to be enthalpically driven. We found that the dipole moment of the cation, as determined by quantum chemical calculations, is inversely correlated with the melting point of the given compound. Molecular dynamics simulations of the crystalline and solid states of two isomers showed differences in their enthalpies of fusion that closely matched those seen experimentally. Moreover, this reduction in the enthalpy of fusion was determined to be caused by an increase in the enthalpy of the crystalline state. We provide evidence that dipole-dipole interactions between cations leads to the formation of cationic domains in the crystalline state. These cationic associations partially block favourable cation–anion interactions, which are recovered upon melting. If, however, the dipole- dipole interactions between cations is too strong they have a tendency to form glasses. This study provides a design rule for lowering the melting point of structurally similar ILs by altering their dipole moment.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Amphiphile conformation impacts aggregate morphology and solution structure across multiple lengthscales

Although the self-assembly of amphiphiles is well-studied in aqueous solutions, much less is understood about the fundamental driving forces and structure property relationships in non-polar media. In recent work [Journal of Physical Chemistry B, 2020, 124, 10822.] the authors have studied a series of malonomide-based amphiphiles that are relevant to liquid-liquid extraction. That work demonstrated that aggregation is largely driven by local dipole-dipole interactions between molecules. Here, we build upon this observation to develop a more detailed understanding of how the balance of dipole-dipole interactions (controlled by conformation) and molecular architecture influences the morphology of the aggregates across lengthscales. Using constrained molecular dynamics about key degrees of freedom, we demonstrate that the conformation of N,N-dimethyl,N,N-dioctylhexylethoxy malonamide (DMDOHEMA) and N,N-dimethyl,N,N-dibutyltetradecyl malonamide (DMDBTDMA) has a significant impact upon self-association - where appropriate conformational sampling is essential. To quantify the aggregate morphology, several graph theoretic and persistent homology based properties are determined. The former examines the patterns of intermolecular interactions within clusters, while the latter examines the 3-dimensional spatial distribution. Based upon these analyses, we find that the morphology of aggregates, particularly at higher malonamide concentration, depends on a balance of dipole alignment and alkyl tail sterics. Dipole alignment encourages linear patterns of the intermolecular interactions within aggregates, while the alkyl tail steric interactions between the malonamide result in noticeably less linear aggregates for DMDOHEMA than DMDBTDMA. This is reflected in the spatial distribution, where more holes or voids exist between extractants within the DMDOHEMA that distribute within the solution in more of a "swiss cheese" arrangement as opposed to the more filamentous distribution of DMBDTDMA. This study links conformation and molecular structure to the morphology of amphiphile assemblies, and serves as a basis for ongoing study of multicomponent amphiphile solutions with polar and other solutes, and how these impact aggregation phenomena.

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

Computing molecular excited states on a D-Wave quantum annealer

Abstract The possibility of using quantum computers for electronic structure calculations has opened up a promising avenue for computational chemistry. Towards this direction, numerous algorithmic advances have been made in the last five years. The potential of quantum annealers, which are the prototypes of adiabatic quantum computers, is yet to be fully explored. In this work, we demonstrate the use of a D-Wave quantum annealer for the calculation of excited electronic states of molecular systems. These simulations play an important role in a number of areas, such as photovoltaics, semiconductor technology and nanoscience. The excited states are treated using two methods, time-dependent Hartree–Fock (TDHF) and time-dependent density-functional theory (TDDFT), both within a commonly used Tamm–Dancoff approximation (TDA). The resulting TDA eigenvalue equations are solved on a D-Wave quantum annealer using the Quantum Annealer Eigensolver (QAE), developed previously. The method is shown to reproduce a typical basis set convergence on the example $$\hbox {H}_2$$ H 2 molecule and is also applied to several other molecular species. Characteristic properties such as transition dipole moments and oscillator strengths are computed as well. Three potential energy profiles for excited states are computed for $$\hbox {NH}_3$$ NH 3 as a function of the molecular geometry. Similar to previous studies, the accuracy of the method is dependent on the accuracy of the intermediate meta-heuristic software called qbsolv.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Bond order predictions using deep neural networks

Machine learning is an extremely powerful tool for the modern theoretical chemist since it provides a method for bypassing costly algorithms for solving the Schrödinger equation. Already, it has proven able to infer molecular and atomic properties such as charges, enthalpies, dipoles, excited state energies, and others. Most of these machine learning algorithms proceed by inferring properties of individual atoms, even breaking down total molecular energy into individual atomic contributions. In this paper, we introduce a modified version of the Hierarchically Interacting Particle Neural Network (HIP-NN) capable of making predictions on the bonds between atoms rather than on the atoms themselves. We train the modified HIP-NN to infer bond orders for a large number of small organic molecules as computed via the Natural Bond Orbital package. We demonstrate that the trained model is extensible to molecules much larger than those in the training set by studying its performance on the COMP6 dataset. This method has applications in cheminformatics and force field parameterization and opens a promising future for machine learning models to predict other quantities that are defined between atoms such as density matrix elements, Hamiltonian parameters, and molecular reactivities.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures

In this work, the role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n-dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N,N'-dimethyl-N,N'-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid-q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups, with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.

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

Deep-Learning Interatomic Potential Connects Molecular Structural Ordering to the Macroscale Properties of Polyacrylonitrile

Polyacrylonitrile (PAN) is an important commercial polymer, bearing atactic stereochemistry resulting from nonselective radical polymerization. As such, an accurate, fundamental understanding of governing interactions among PAN molecular units is indispensable for advancing the design principles of final products at reduced processability costs. While ab initio molecular dynamics (AIMD) simulations can provide the necessary accuracy for treating key interactions in polar polymers, such as dipole–dipole interactions and hydrogen bonding, and analyzing their influence on the molecular orientation, their implementation is limited to small molecules only. Herein, we show that the neural network interatomic potentials (NNIPs) that are trained on the small-scale AIMD data (acquired for oligomers) can be efficiently employed to examine the structures and properties at large scales (polymers). NNIP provides critical insight into intra- and interchain hydrogen-bonding and dipolar correlations and accurately predicts the amorphous bulk PAN structure validated by modeling the experimental X-ray structure factor. Furthermore, the NNIP-predicted PAN properties, such as density and elastic modulus, are in good agreement with their experimental values. Overall, the trend in the elastic modulus is found to correlate strongly with the PAN structural orientations encoded in the Hermans orientation factor. In conclusion, this study enables the ability to predict the structure–property relations for PAN and analogues with sustainable ab initio accuracy across scales.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantifying Species Populations in Multivalent Borohydride Electrolytes

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH 4 ) 2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg 2+ and Ca 2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Additionally, concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg 2+ and Ca 2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH 4 ) 2 /tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.

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

Range and strength of mechanical interactions of force dipoles in elastic fiber networks

Mechanical forces generated by myosin II molecular motors drive diverse cellular processes, most notably shape change, division and locomotion. These forces may be transmitted over long range through the cytoskeletal medium – a disordered, viscoelastic network of biopolymers. The resulting cell size scale force chains can in principle mediate mechanical interactions between distant actomyosin units, leading to self-organized structural order in the cell cytoskeleton. Inspired by such force transmission through elastic structures in the cytoskeleton, we consider a percolated fiber lattice network, where fibers are represented as linear elastic elements that can both bend and stretch, and the contractile activity of myosin motors is represented by force dipoles. Then, by using a variety of metrics, we show how two such contractile force dipoles interact with each other through their mutual mechanical deformations of the elastic fiber network. As a prelude to two-dipole interactions, we quantify how forces propagate through the network from a single anisotropic force dipole by analyzing clusters of nodes connected by highly strained bonds, as well as through the decay rate of strain energy with distance from a force dipole. We show that predominant fiber bending screens out force propagation, resulting in reduced and strongly network configuration-dependent dipole interactions. On the other hand, stretching-dominated networks support longer-ranged inter-dipole interactions that recapitulate the predictions of linear elasticity theory. By characterizing the differences between tensile and compressive force propagation in the fiber network, we show how inter-dipole interaction depends on the dipoles’ mutual separation and orientation. The resulting elastic interaction energy may mediate a force between multiple distant dipoles, leading to their self-organization into ordered configurations. In conclusion, this provides a potential pathway for active mechanical force-driven structural order in elastic biopolymer networks.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Molecular polarizabilities as fingerprints of perturbations to water by ions and confinement

Perturbations to water, both by ions and confining media, have been the focus of numerous experimental and theoretical studies. Yet, several open questions remain, including the extent to which such perturbations modify the structural and dielectric properties of the liquid. Here, we present a first-principles molecular dynamics study of alkali cations in water (Li + , Na + , and K + ) as well as of water and LiCl and KCl solutions under confinement within carbon nanotubes (CNTs) of small diameter (1.1-1.5 nm). Our simulations support the view that the water structure is only modified locally in the presence of cations. We found that molecular polarizabilities are fingerprints of hydrogen bonding modifications, which occur at most up to the second solvation shell for all cations in bulk water. Under confinement, we found that the overall value of the molecular polarizability of water molecules near the surface is determined by the balance of two effects, which are quantitatively different in CNTs of different radii: the presence of broken hydrogen bonds at the surface leads to a decrease in the polarizabilities of water molecules, while the interaction with the CNT enhances polarizabilities. Interestingly, the reduction in dipole moments of interfacial water molecules under confinement is instead driven only by changes in the water structure and not by interfacial interactions. As expected, confinement effects on water molecular polarizabilities and dipole moments are more pronounced in the case of the 1.1 nm CNT.

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

Spectroscopy of atoms in an optical dipole trap using spectrally selective heating by a probe laser field

Spectral properties of atoms localised in an optical dipole trap are studied using the method of spectrally selective heating by a probe field. The method is based on measuring the number of atoms in a trap after they interact with a probe field. The dependence of the number of atoms on the frequency of the probe field fully characterises the shift and width of the spectral absorption line of trapped atoms. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Widespread Negative Longitudinal Piezoelectric Responses in Ferroelectric Crystals with Layered Structures

In this study, we investigate the underlying mechanisms of the universal negative piezoelectricity in low-dimensional layered materials by carrying out first-principles calculations. Two-dimensional layered ferroelectric CuInP 2 S 6 is analyzed in detail as a typical example, but the theory can be applied to any other low-dimensional layered piezoelectrics. Consistent with the theory proposed in [Phys. Rev. Lett. 119, 207601 (2017), the anomalous negative piezoelectricity in CuInP 2 S 6 also results from its negative clamped-ion term, which cannot be compensated by the positive internal-strain part. Here, we focus on a more general rule by proposing that having a negative clamped-ion term should be universal among piezoelectric materials, which is attributed to the “lag of Wannier center” effect. The internal-strain term, which is the change in polarization due to structural relaxation in response to strain, is mostly determined by the spatial structure and chemical bonding of the material. In a low-dimensional layered piezoelectric material such as CuInP 2 S 6 , the internal-strain term is approximately zero. This is because the internal structure of the molecular layers, which are bonded by the weak van der Waals interaction, responds little to the strain. As a result, the magnitude of the dipole, which depends strongly on the dimension and structure of the molecular layer, also has a small response with respect to strain. An equation bridging the internal strain responses in low-dimensional and three-dimensional piezoelectrics is also derived to analytically express this point. This work aims to deepen our understanding about this anomalous piezoelectric effect, especially in low-dimensional layered materials, and provide strategies for discovering materials with novel electromechanical properties.

2-dimensional systems↗