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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Electrically tunable effective g-factor of a single hole in a lateral GaAs/AlGaAs quantum dot

Electrical tunability of the $g$-factor of a confined spin is a long-time goal of the spin qubit field. Here we utilize the electric dipole spin resonance (EDSR) to demonstrate it in a gated GaAs double-dot device confining a hole. This tunability is a consequence of the strong spin-orbit interaction (SOI) in the GaAs valence band. The SOI enables a spin-flip interdot tunneling, which, in combination with the simple spin-conserving charge transport leads to the formation of tunable hybrid spin-orbit molecular states. EDSR is used to demonstrate that the gap separating the two lowest energy states changes its character from a charge-like to a spin-like excitation as a function of interdot detuning or magnetic field. In the spin-like regime, the gap can be characterized by the effective $g$-factor, which differs from the bulk value owing to spin-charge hybridization, and can be tuned smoothly and sensitively by gate voltages.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Multimode two-dimensional vibronic spectroscopy. I. Orientational response and polarization-selectivity

Two-dimensional Electronic–Vibrational (2D EV) spectroscopy and two-dimensional Vibrational–Electronic (2D VE) spectroscopy are among the newest additions to the coherent multidimensional spectroscopy toolbox, and they are directly sensitive to vibronic couplings. In this first of two papers, the complete orientational response functions are developed for a model system consisting of two coupled anharmonic oscillators and two electronic states in order to simulate polarization-selective 2D EV and 2D VE spectra with arbitrary combinations of linearly polarized electric fields. Here, we propose analytical methods to isolate desired signals within complicated spectra and to extract the relative orientation between vibrational and vibronic dipole moments of the model system using combinations of polarization-selective 2D EV and 2D VE spectral features. Time-dependent peak amplitudes of coherence peaks are also discussed as means for isolating desired signals within the time-domain. This paper serves as a field guide for using polarization-selective 2D EV and 2D VE spectroscopies to map coupled vibronic coordinates on the molecular frame.

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

3,4‐Dicyanothiophene—a Versatile Building Block for Efficient Nonfullerene Polymer Solar Cells

Abstract In this contribution, a versatile building block, 3,4‐dicyanothiophene (DCT), which possesses structural simplicity and synthetic accessibility for constructing high‐performance, low‐cost, wide‐bandgap conjugated polymers for use as donors in polymer solar cells (PSCs), is reported. A prototype polymer, PB3TCN‐C66, and its cyano‐free analogue polymer PB3T‐C66, are synthesized to evaluate the potential of using DCT in nonfullerene PSCs. A stronger aggregation property in solution, higher thermal transition temperatures with higher enthalpies, a larger dipole moment, higher relative dielectric constant, and more linear conformation are exhibited by PB3TCN‐C66. Solar cells employing IT‐4F as the electron acceptor offer power conversion efficiencies (PCEs) of 11.2% and 2.3% for PB3TCN‐C66 and PB3T‐C66, respectively. Morphological characterizations reveal that the PB3TCN‐C66:IT‐4F blend exhibits better π–π paracrystallinity, a contracted domain size, and higher phase purity, consistent with its higher molecular interaction parameter, derived from thermodynamic calculations. Moreover, PB3TCN‐C66 offers a higher open‐circuit voltage and reduced energy loss than most state‐of‐the‐art wide‐bandgap polymers, without the need of additional electron‐withdrawing substituents. Two additional polymers derived from DCT also demonstrate promising performance with a higher PCE of 13.4% being achieved. Thus, DCT represents a versatile and promising building block for constructing high‐performance, low‐cost, conjugated polymers for application in PSCs.

Zhang, Bo↗
DOE OSTI2025

Thermal disorder and phonon softening in the ferroelectric phase transition of lead titanate

We report a molecular dynamics study of ab initio quality of the ferroelectric phase transition in crystalline PbTi⁢O3. We model anharmonicity accurately in terms of potential energy and polarization surfaces trained on density functional theory data with modern machine learning techniques. Our simulations demonstrate that the transition has a strong order-disorder character, in agreement with diffraction experiments, and provide fresh insight into the approach to equilibrium across the phase transition. We find that the emergence and disappearance of the macroscopic polarization is driven by dipolar switching at the nanometer scale. We also computed the infrared optical absorption spectra in both the ferroelectric and the paraelectric phases, finding good agreement with the experimental Raman frequencies. Often, the almost ideal displacive character of the soft mode detected by Raman scattering in the paraelectric phase has been contrasted with the order-disorder character of the transition suggested by diffraction experiments. We settle this issue by showing that the soft mode coexists with a strong Debye relaxation associated with thermal disordering of the dipoles. The Debye relaxation feature is centered at zero frequency and appears near the transition temperature in both the ferroelectric and the paraelectric phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1987

Theory of atomic additivity in molecular hyperpolizabilities

Hyperpolarizability is a function of frequency. This is called dispersion. Because of the Kramers-Kronig relations, researchers expect that a material that is dispersing light is also absorbing it. Where there is both dispersion and absorption, the molecular polarizabilities are complex functions of the frequency. This led researchers to consider atomic additivity in both the real and imaginary parts of the ordinary and hyperpolarizabilities. This effort is desirable not only from a theoretical point of view, but also because of the existence of a large body of complex refractive index data, which may be used to test the additivity principle with the complex valued ordinary dipole polarizability.

Baird, James K.↗
DOE OSTI2026

Cooperative effect of local active stresses on the macroscopic contractility of elastic fiber networks

The collective action of actively contractile units embedded in elastic biopolymer networks plays a crucial role in regulating the network's macroscopic mechanical response. Here, in this study, we investigate how the macroscopic boundary stress in model elastic fiber networks depends on the number and nature of embedded contractile units, each exerting an isotropic force dipole, as well as on the bending stiffness of fibers. We find that the macroscopic stress increases nonlinearly with the number of dipoles due to mutual stiffening of initially soft, bending-dominated networks. Using effective medium theory, we relate this enhanced contractility to an increase in the effective average network coordination number due to constraints imposed by the force dipoles. By comparing three distinct force dipole models that differ in their local structures, we demonstrate that the specific manner in which an active unit constrains the network strongly influences the onset and nature of the stiffening transition. Our results highlight that not only the quantity but also the local geometry of force-generating units critically determines the macroscopic mechanical behavior. This framework provides a physical basis for understanding how biological systems—such as molecular motors in the cytoskeleton, or adherent cells in the extracellular matrix—can modulate network-scale nonlinear elastic properties through local tuning of active force-generating units.

Biological and medical sciences↗
NASA NTRS1981

Effect of laser frequency on a collision-induced radiative process

A review is presented of the principles of collision induced radiative processes, followed by an examination of the effects of laser frequencies on these processes. A one-dimensional problem involving two electron states is considered, and it is found that the Hamiltonian of the radiation field is dominated by electric-dipole interaction which couples states of different parity. Transitions are noted to be dependent on collisions, and the complexities of three-dimensional systems are expressed as considerations of the angular momentum of the photon, the necessity of treating different states simultaneously, and the fact that a radiation field destroys rotational invariance. Changing the radiation frequency alters the crossing point and offers opportunities to study the interplay of potential surfaces with molecular dynamics. Experiments on Na+A systems are outlined for several collision energies and various laser frequencies. Multiple crossings were obtained, although the total cross-section, at all energies, decreased at 18,350/cm.

Devries, P. L.↗
NASA NTRS2018

Molecular Dynamics Simulations of Liquid and Polymer Electrolytes for Energy Storage Devices

Advancing beyond current lithium-ion technology is necessary in order to enable energy storage devices for electric airplanes. Electrolyte stability is a key limiting factor, yet the design of improved electrolytes remains a formidable challenge. Molecular dynamics (MD) simulations are a powerful tool for studying electrolytes, since they can be used to evaluate structural, thermodynamic, and transport properties, and can provide molecular-level detail often inaccessible to experimental techniques. Our computational materials groups at the NASA Ames Research Center has developed models and methods to accurately simulate both liquid and polymer electrolytes.We report the results from atomistic MD simulations of several electrolyte materials, with lithium salts dissolved in ionic liquids, dimethoxyethane (DME), and polyethylene oxide (PEO). For improved accuracy, we employ polarizable models, where each atom is given an environment-dependent atomic dipole. The simulations accurately predict bulk transport properties, including viscosity, diffusion, and ionic conductivity, in quantitative agreement with available experimental data. Moreover, the simulations provide important insights into the solvation structure of the lithium ions.We also report the results from coarse-grained MD simulations of polyanion electrolytes. In order to more efficiently capture the longer length- and time-scales of these systems, we employ a generic bead-spring model. These simulations provide important insight into how the polymer chain architecture and ionic interaction strengths affect the ionic aggregation behavior and cation dynamics. Despite the simplicity of the model, the simulations yield qualitative agreement with experimental data for similar systems.

Abbott, Lauren J.↗
NASA NTRS1990

New observations of interstellar organic molecules

Discussed here are new observations of 3-carbon-containing interstellar molecules which play an important role in the chemistry of dense molecular clouds: protonated carbon dioxide, formic acid, and propynal. In 1984 a new oxide of carbon, C3O, was discovered in the interstellar medium (Matthews et al. 1984; Brown et al. 1985). Theoretical models suggest that C3O is produced by dissociative electron recombination with the ion H3C3O+. Although no laboratory data for the branching ratios of such a recombination exist, it seemed to us likely that additional products would include H2C3O. This molecule has more than one isomeric form, but one stable species is propynal (HC2CHO), which had been suggested as a possible interstellar molecule by Winnewisser (1973). In observations at the National Radio Astronomy Observatory 43 m telescope in Green Bank earlier this year, researchers detected a line in the cold cloud TMC-1 which they assign to the 2(0,2)-1(0,1) transition of propynal. The observed line agrees with the laboratory frequency to well within the experimental uncertainty a few parts in 10 to the 7th power. Researchers sought and failed to detect the corresponding 2(1,1)-1(1,0) line, which is understandable given the presence of both a and b components of the electric dipole moment in propynal. The b type transitions will drain population from energy levels with K(sub p) does not equal 0 into the K(sub p) equal 0 stack. If the researchers' assignment is correct, this is the first interstellar detection of propynal. Assuming typical rotational temperatures for TMC-1 and that the line is optically thin, the column density determined is about 5 times 10 to the 12th power cm to the -2nd power, or about three times that for C3O. Formic acid (HCOOH) was the first organic acid to be observed in the interstellar medium, in the Galactic center source Sgr B2. The only other interstellar detection has been recently made in the giant molecular cloud in Orion. As part of the same project that led to the detection of propynal, researchers sought formic acid in the nearby, cold dark clouds TMC-1 and L134N. It is seen only in L134N. This difference between the two clouds appears to be consistent with a model in which the oxygen/carbon ratio is higher in L134N. This would be consistent with the higher abundances for SO and SO2, observed in that cloud, and the higher abundances of many carbon-rich species in TMC-1 (Irvine et al. 1985).

Irvine, W. M.↗
NASA NTRS1991

Theoretical studies of the extraterrestrial chemistry of biogenic elements and compounds

Organic compounds, molecules related to those in living systems, are found in many different extraterrestrial environments. The study of organic astrochemistry is important to exobiology both because it demonstrates the ubiquity of processes which led to life on Earth and because the dust clouds where molecules are found are analogs of the solar nebula from which the Earth formed. In the long chain of events leading from the Big Bang, and a universe composed of atomic hydrogen and helium, to the emergence of life on Earth, molecular interstellar clouds are an early link, the most primitive objects which display any significant organic chemistry. One such cloud was the direct precursor to the solar system and to all objects which it contains. Theoretical methods are ideally suited to studying interstellar cloud chemistry. They have been applied to determine spectroscopic constants of candidate interstellar molecules, mechanisms of ion-molecule reactions, and composition of dust grains. Accurate predictions of rotational constants and dipole moments of long-chain carbon molecules HC13N, HC15N, and C5O have been made to aid in determining the size limit of gas-phase interstellar molecules. Models of gas-phase interstellar chemistry use reaction rate constants measured at room temperature and extrapolated to interstellar temperatures. The temperature dependence of NH3(+)+H2 yields NH4(+)+H is anomalous, however, with a minimum rate at about 100K, casting doubt on the extrapolation procedures. The temperature dependence has now been explained.

Defrees, D. J.↗
DOE OSTI2023

Cations Control Lipid Bilayer Memcapacitance Associated with Long-Term Potentiation

Phospholipid bilayers can be described as capacitors whose capacitance per unit area (specific capacitance, C m ) is determined by their thickness and dielectric constant–independent of applied voltage. It is also widely assumed that the C m of membranes can be treated as a “biological constant”. Recently, using droplet interface bilayers (DIBs), it was shown that zwitterionic phosphatidylcholine (PC) lipid bilayers can act as voltage-dependent, nonlinear memory capacitors, or memcapacitors. When exposed to an electrical “training” stimulation protocol, capacitive energy storage in lipid membranes was enhanced in the form of long-term potentiation (LTP), which enables biological learning and long-term memory. LTP was the result of membrane restructuring and the progressive asymmetric distribution of ions across the lipid bilayer during training, which is analogous, for example, to exponential capacitive energy harvesting from self-powered nanogenerators. Here, we describe how LTP could be produced from a membrane that is continuously pumped into a nonequilibrium steady state, altering its dielectric properties. During this time, the membrane undergoes static and dynamic changes that are fed back to the system’s potential energy, ultimately resulting in a membrane whose modified molecular structure supports long-term memory storage and LTP. Here, we also show that LTP is very sensitive to different salts (KCl, NaCl, LiCl, and TmCl 3 ), with LiCl and TmCl 3 having the most profound effect in depressing LTP, relative to KCl. This effect is related to how the different cations interact with the bilayer zwitterionic PC lipid headgroups primarily through electric-field-induced changes to the statistically averaged orientations of water dipoles at the bilayer headgroup interface.

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

Relativistic Configuration-Interaction and Perturbation Theory Calculations for Heavy Atoms

Heavy atoms present challenges to atomic theory calculations due to the large number of electrons and their complicated interactions. Conventional approaches such as calculations based on Cowan’s code are limited and require a large number of parameters for energy agreement. One promising approach is relativistic configuration-interaction and many-body perturbation theory (CI-MBPT) methods. We present CI-MBPT results for various atomic systems where this approach can lead to reasonable agreement: La I, La II, Th I, Th II, U I, Pu II. Among atomic properties, energies, g-factors, electric dipole moments, lifetimes, hyperfine structure constants, and isotopic shifts are discussed. While in La I and La II accuracy for transitions is better than that obtained with other methods, more work is needed for actinides.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Silica nanocluster binding rate coefficients from molecular dynamics trajectory calculations

Oxide nanoparticle growth from vapor phase precursors occurs in high temperature aerosol reactors first via the formation of nanoclusters, which are nanometer-scale condensed-phase species composed of 10 1 -10 2 atoms. The binding rate for nanoclusters, defined as the rate at which two nanoclusters collide with and stick to one another, is hence of interest in predicting nanoparticle size distribution functions in an aerosol. We have utilized molecular dynamics (MD) trajectory calculations to determine the homogeneous (equal-sized) and heterogeneous (disparate-sized) binding rate coefficients of SiO2 (silica) nanoclusters composed of 18, 144, and 333 atoms. MD trajectory calculations incorporated all-atom models of nanoclusters using a combined Born–Huggins–Mayer-Lennard-Jones potential model, which accounts for both short range interactions and electrostatic interactions. MD calculations were utilized to determine the binding probability as a function of both initial relative velocity and impact parameter; integration of the binding probability across impact parameter and relative velocity space yields the binding rate coefficient. MD trajectory calculations reveal that the most common type of encounters between nanoclusters leading to binding are grazing collisions, i.e. instances where collision would not occur without induced dipole potential influences. The resulting binding rate coefficients are found to be extremely weakly dependent on system temperature, which is in contrast to the use of rate coefficient models which are the product of a hard-sphere collision rate coefficient and a constant enhancement factor (leading to a rate coefficient proportional to the square root of temperature). Enhancement factors defined from MD trajectory calculations fall in the range of 3–9 as system temperature decreases from 1500 K to 300 K. Furthermore, such large values suggest that potential interactions need to be considered when modeling oxide nanocluster growth in the gas phase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Chemistry, Structure, and Function of Lone Pairs in Extended Solids

The lone pair has been a known feature of the electronic structure of molecules for over 100 years. Beginning with the pioneering work of Lewis and others that was later developed into useful guidelines for predicting molecular structure, lone pairs and their steric consequences are now taught at the very earliest stages of a chemistry education. In the crystalline solid state, lone pairs have perhaps had a less visible yet equally consequential role, with a significant impact on a range of properties and functionalities. Important properties associated with s 2 electron-derived lone pairs include their role in creating conditions favorable for ion transport, in the formation and correlation of local dipoles and the resulting polar behavior leading to ferroics and multiferroics, in increasing the refractive index of glass, in reducing the thermal conductivity of thermoelectric materials, and in breaking local symmetry permitting second-harmonic light generation.. In recent years, the role of the lone pair in developing the electronic structure of some topological quantum materials has also been recognized. While structural distortions due to lone pairs have traditionally been characterized through their crystallography, recent advances in scattering and spectroscopy have revealed the presence of local lone pair-driven distortions that do not correlate over long length scales. The role of these crystallographically “hidden” lone pairs, their detection, and their impact on properties have become a growing body of work in the literature. Hidden lone pairs are an effective argument for considering a role for lone pairs that goes beyond their being objects that occupy space in the coordination polyhedra of cations. This Account introduces the chemistry of lone pairs in extended crystalline solids, including a discussion of when they are stereochemically active, how they manifest in the structure, and how their chemistry can be tuned by the chemical environment around them. Eventually, all of these factors work in unison to help develop and tune properties of interest. Certain specific examples of structure–property relationships in materials that are driven by lone pair behavior are described here, including the potential impact of lone pairs on the optical and electronic properties of hybrid halide perovskite compounds that are relevant to their photovoltaic applications. Here, we highlight the role of lone pairs in the dielectric behavior of geometrically frustrated pyrochlores, the temperature-dependent optoelectronic behavior of halide perovskites, the polar phase transitions in lead-free ferroelectric perovskites, and the compositional insulator-to-metal transition in ruthenium pyrochlores. The theme underpinning this Account is that the lone pair can be considered to be a powerful design element for a broad range of material function.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multimode two-dimensional vibronic spectroscopy. II. Simulating and extracting vibronic coupling parameters from polarization-selective spectra

We report experimental demonstrations of polarization-selection two-dimensional Vibrational-Electronic (2D VE) and 2D Electronic-Vibrational (2D EV) spectroscopies aim to map the magnitudes and spatial orientations of coupled electronic and vibrational coordinates in complex systems. The realization of that goal depends on our ability to connect spectroscopic observables with molecular structural parameters. In this paper, we use a model Hamiltonian consisting of two anharmonically coupled vibrational modes in electronic ground and excited states with linear and bilinear vibronic coupling terms to simulate polarization-selective 2D EV and 2D VE spectra. We discuss the relationships between the linear vibronic coupling and two-dimensional Huang–Rhys parameters and between the bilinear vibronic coupling term and Duschinsky mixing. We develop a description of the vibronic transition dipoles and explore how the Hamiltonian parameters and non-Condon effects impact their amplitudes and orientations. Using simulated polarization-selective 2D EV and 2D VE spectra, we show how 2D peak positions, amplitudes, and anisotropy can be used to measure parameters of the vibronic Hamiltonian and non-Condon effects. This paper, along with the first in the series, provides the reader with a detailed description of reading, simulating, and analyzing multimode, polarization-selective 2D EV and 2D VE spectra with an emphasis on extracting vibronic coupling parameters from complex spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Molecular processes in comets

A major effort was expended in developing procedures for calculating by quantum-mechanical methods the cross sections for the photodissociation of the hydroxyl radical OH. The molecule OH is the primary dissociation product of water and observations of OH when combined with a determination of the lifetime of OH in the solar radiation field can be used to calculate the rate of release of water from comets. There are many possible photodissociation channels whose efficiency depends upon the details of the spectrum of the radiation. We have calculated the potential energy curves of all the states of OH that can be reached by electric dipole absorption from the ground X(exp 2)(Pi) state by photons with energies up to about 12 eV.

Dalgarno, A.↗