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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Spin-dependent electron transport in zinc- and manganese-doped adenine molecules

The spin-dependent electron transport properties of zinc- and manganese-doped adenine molecules connected to zigzag graphene leads are studied in the zero bias regime using the non-equilibrium Green's function method. The conductance of the adenine molecule increased and became spin-dependent when a zinc or manganese atom was doped into the molecules. The effects of a transverse electric field on the spin-polarization of the transmitted electrons were investigated and the spin-polarization was controlled by changing the transverse electric field. Under the presence of a transverse electric field, both the zinc- and manganese-doped adenine molecules acted as spin-filters. The maximum spin-polarization of the manganese-doped adenine molecule was greater than the molecule doped with zinc.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Direct observation of adsorption geometry for the van der Waals adsorption of a single π-conjugated hydrocarbon molecule on Au(111)

Weak van der Waals adsorption of π-conjugated hydrocarbon molecules onto the gold surface, Au(111), is one of the essential processes in constructing organic-metal interfaces in organic electronics. Here we provide a first direct observation of adsorption geometry of a single π-conjugated hydrocarbon molecule on Au(111) using an atomically resolved scanning tunneling microscopy study combined with van der Waals density functional methodology. For the purpose, we utilized a highly symmetric π-conjugated hydrocarbon molecule, dehydrobenzo[12]annulene (DBA), which has a definite three-fold symmetry, the same as the Au(111) surface. Interestingly, our observations on an atomically resolved scale clearly indicate that the DBA molecule has only one adsorption configuration on Au(111) in spite of the weak van der Waals adsorption system. Based on the precisely determined adsorption geometry of DBA/Au(111), our calculation results imply that even a very small contribution of the interfacial orbital interaction at the organic-metal interface can play a decisive role in constraining the adsorption geometry even in the van der Waals adsorption system of a π-conjugated hydrocarbon molecule on the noblest Au(111) surface. Our observations provide not only deeper insight into the weak adsorption process, but also new perspectives to organic electronics using π-conjugated hydrocarbon molecules on the Au surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Inter-dot strain field effect on the optoelectronic properties of realistic InP lateral quantum-dot molecules

We report on numerical simulations of InP surface lateral quantum-dot molecules on In{sub 0.48}Ga{sub 0.52 }P buffer, using a model strictly derived by experimental results by extrapolation of the molecules shape from atomic force microscopy images. Our study has been inspired by the comparison of a photoluminescence spectrum of a high-density InP surface quantum dot sample with a numerical ensemble average given by a weighted sum of simulated single quantum-dot spectra. A lack of experimental optical response from the smaller dots of the sample is found to be due to strong inter-dot strain fields, which influence the optoelectronic properties of lateral quantum-dot molecules. Continuum electromechanical, k{sup →}·p{sup →} bandstructure, and optical calculations are presented for two different molecules, the first composed of two dots of nearly identical dimensions (homonuclear), the second of two dots with rather different sizes (heteronuclear). We show that in the homonuclear molecule the hydrostatic strain raises a potential barrier for the electrons in the connection zone between the dots, while conversely the holes do not experience any barrier, which considerably increases the coupling. Results for the heteronuclear molecule show instead that its dots do not appear as two separate and distinguishable structures, but as a single large dot, and no optical emission is observed in the range of higher energies where the smaller dot is supposed to emit. We believe that in samples of such a high density the smaller dots result as practically incorporated into bigger molecular structures, an effect strongly enforced by the inter-dot strain fields, and consequently it is not possible to experimentally obtain a separate optical emission from the smaller dots.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Alkali metal ion storage properties of sulphur and phosphorous molecules encapsulated in nanometer size carbon cylindrical pores

We investigated the physical and chemical stabilities of sulfur and phosphorus molecules encapsulated in a mesoporous carbon (MPC) and two kinds of single-walled carbon nanotubes (SWCNTs) having different cylindrical pore diameters. The sublimation temperatures of sulfur molecules encapsulated in MPC and the two kinds of SWCNTs were measured by thermo-gravimetric measurements. It was found that the sublimation temperature of sulfur molecules encapsulated in SWCNTs having mean tube diameter of 1.5 nm is much higher than any other molecules encapsulated in larger pores. It was also found that the capacity fading of lithium-sulfur battery can be diminished by encapsulation of sulfur molecules in SWCNTs. We also investigated the electrochemical properties of phosphorus molecules encapsulated in SWCNTs (P@SWCNTs). It was shown that P@SWCNT can adsorb and desorb both Li and Na ions reversibly.

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

Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes

Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for all water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 10{sup 8}–10{sup 9} V m{sup −1}, which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ∼1 V (∼2 ⋅ 10{sup 8} V m{sup −1}) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10{sup 8} V m{sup −1}) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred experimentally for 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) membranes but comparable to the number inferred for 1,2-dilauroyl-sn-glycero-3-phosphoethanolamine (DLPE) membranes. Some of the properties of the DMPG membrane are compared with those of the neutral zwitterionic DMPC bilayer membrane at 303 K and 1 atm, which is the same reduced temperature with respect to the gel-to-fluid transition temperature as 310 K is for the DMPG bilayer membrane.

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

Enhancement of Raman scattering signal of a few molecules using photonic nanojet mediated SERS technique

Now a days, single molecule surface enhanced Raman spectroscopy (SMSERS) has become a fascinating tool for studying the structural properties, static and dynamic events of single molecules (instead of ensemble average), with the help of efficient plasmonic nanostructures. This is extremely useful in the field of proteomics because the structural properties of protein molecules are heterogeneous. Even though, SMSERS provides wealthy information about single molecules, it demands high quality surface enhanced Raman scattering (SERS) substrates. So far, a very few researchers succeeded in demonstrating the single molecule Raman scattering using conventional SERS technique. However, the experimental S/N of the Raman signal has been found to be very poor. Recently, with the help of photonic nanojet of an optical microsphere, we were able to enhance the SERS signal of a few molecules adsorbed on the SERS substrates (gold symmetric and asymmetric nanodimers and trimers dispersed on a glass slide). Herein, we report a few details about photonic nanojet mediated SERS technique, a few experimental results and a detailed theoretical study on symmetric and asymmetric nanosphere dimers to understand the dependence of localised surface plasmon resonance (LSPR) wavelength of a nanodimer on the nanogap size and polarization of the excitation light.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Confinement of water molecule inside (2, 2) graphyne nanotube

Using density functional theory (DFT) calculations with generalized gradient approximation, the interaction between H{sub 2}O molecule and (2, 2) graphyne nanotube (GNT) has been investigated. The stable configuration due to the insertion of H{sub 2}O molecule inside (2, 2) GNT is determined on the basis of binding energy. The band gap of the GNT decreases due to the confinement of H{sub 2}O molecule. The charge analysis reveals that electrons are shifted from the H{sub 2}O molecule to the GNT. The electronic property of the GNT is highly influenced by the presence of H{sub 2}O molecule; thus, we may design a GNT based sensor for the detection of water molecule.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Tripartite entanglement dynamics of vibrations in triatomic molecules

In the present study, the dynamical behaviors of tripartite entanglement of vibrations in triatomic molecules are studied based on the Lie algebraic models of molecules. The dynamical behaviors of tripartite entanglement of the local mode molecule H{sub 2}O and normal mode molecule NO{sub 2} are comparatively studied for different initial states by employing the general concurrence. Our results show that the dynamics of tripartite entanglement are relied on the dynamics of intramolecular energy distribution. The local mode molecule is more suitable to construct the tripartite entangled states. Also, the greater degree of tripartite entanglement can be obtained if the stretching vibration is first excited. These results shed new light on the understanding of quantum multipartite entanglement of vibrations in the polyatomic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Excitation and dissociation of molecules by femtosecond IR laser radiation in the gas phase and on dielectric surfaces

This paper presents an overview of early studies and new experimental data on the effect of near-IR (0.8-1.8 {mu}m) and mid-IR (3.3-5.8 {mu}m) intense femtosecond (130-350 fs) laser pulses on polyatomic molecules in the gas phase and on the surface of substrates. We examine the vibrational dynamics of nine molecules containing a C=O chromophore group, which are initiated by resonance femtosecond IR laser radiation at a wavelength of {approx}5 {mu}m, and report measured characteristic times of intramolecular vibrational redistribution. The characteristic time of molecules containing a single C=O group lies in the range 2.4-20 ps and that of the Fe(CO){sub 5} and Cr(CO){sub 6} molecules lies in the nanosecond range ({approx}1.0 and {approx}1.5 ns, respectively). Carbon structures have been observed for the first time to result from the decomposition of (CF{sub 3}){sub 2}CCO molecules on the surface of metal fluorides under the effect of femtosecond IR laser radiation in the wavelength range 3.3-5.4 {mu}m with no gas-phase decomposition of the molecules. (extreme light fields and their applications)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Nonlocal state swapping of polar molecules in bilayers

The observation of significant dipolar effects in gases of ultracold polar molecules typically demands a strong external electric field to polarize the molecules. We show that, even in the absence of a significant polarization, dipolar effects may play a crucial role in the physics of polar molecules in bilayers, provided that the molecules in each layer are initially prepared in a different rotational state. Then, interlayer dipolar interactions result in a nonlocal swap of the rotational state between molecules in different layers, even for weak applied electric fields. The interlayer scattering due to the dipole-dipole interaction leads to a nontrivial dependence of the swapping rate on density, temperature, interlayer spacing, and population imbalance. For reactive molecules such as KRb, chemical recombination immediately follows a nonlocal swap and dominates the losses even for temperatures well above quantum degeneracy, and hence could be observed under current experimental conditions.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Attosecond probing and control of charge migration in carbon-chain molecule

In quantum mechanics, when an electron is quickly ripped off from a molecule, a superposition of new eigenstates of the cation creates an electron wave packet that governs the charge flow inside, which has been called charge migration (CM). Experimentally, extracting such dynamics at its natural (attosecond) timescale is quite difficult. We report the first such experiment in a linear carbon-chain molecule, butadiyne (C 4 H 2 ), via high-harmonic spectroscopy (HHS). By employing advanced theoretical and computational tools, we showed that the wave packet and the CM of a single molecule are reconstructed from the harmonic spectra for each fixed-in-space angle of the molecule. For this one-dimensional molecule, we calculate the center of charge $\langle$ x $\rangle$ ( t ) to obtain v cm , to quantify the migration speed and how it depends on the orientation angle. The findings also uncover how the electron dynamics at the first few tens to hundreds of attoseconds depends on molecular structure. The method can be extended to other molecules where the HHS technique can be employed.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2012

Vibrational excitation of a molecule by a resonance current

Correct expressions are obtained for calculating a tunnel-resonance current through molecules. The participation of molecular vibrations in the resonance charge transfer through a molecule and vibrational excitation of the molecule are determined by the reorganization energy E{sub r} of the vibrational system depending on the displacement of the equilibrium position of vibrational modes in passing from the neutral molecule to the resonance state of a molecular ion. The mean excitation energy of the molecule during the propagation of an elementary charge changes from E{sub r} at the voltage across electrodes close to the threshold up to 2E{sub r} at voltages considerably exceeding the threshold voltage. An expression is obtained for the stationary vibrational temperature of the molecule, which is proportional to the resonance current.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Simulation of Motion of H{sub 2} and D{sub 2} Molecules in Sextupole Magnets

We simulate the motion of hydrogen and deuterium molecules in the magnetic system of a setup intended for obtaining nuclear-spin-polarized molecules. Spatial separation of molecules with different magnetic moment projections by the spin filtration method in a nonuniform magnetic field is performed using superconducting sextupole magnets. Calculations are carried out for a magnetic field induction of 3.7 T at the poles and a nozzle temperature of 7 K. Simulation show that the ratio of polarized flux of hydrogen molecules to the detector to the total flux from the source nozzle is 2.3 × 10{sup –6}, nuclear polarization being close to 100%. Calculations performed for deuterium reveal that this ratio is 7 times smaller due to the smallness of the magnetic moment relative to hydrogen molecules. Trajectories of molecules in the magnetic system and their spatial distribution are represented graphically. Mathematical aspects of the algorithm of the computer program developed for this purpose are considered.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Spectroscopic Characterization of Key Aromatic and Heterocyclic Molecules: A Route toward the Origin of Life

To gain information on the abiotic synthesis of the building blocks of life from simple molecules, and their subsequent chemical evolution to biological systems, the starting point is the identification of target species in Titan-like planets; i.e., planets that resemble the primitive Earth, as well as in Earth-like planets in the habitable zone of their star, namely planets where life can be already originated. In this scenario, molecular spectroscopy plays a crucial role because spectroscopic signatures are at the basis of an unequivocal proof for the presence of these target molecules. Thanks to advances in many different techniques and NASA’s successful Kepler exoplanet transit mission, thousands of diverse planets outside of our solar system have been discovered. The James Webb Space Telescope (JWST), scheduled to be launched in 2018, will be very helpful in the identification of biosignature gases in Earth-like planets’ atmospheres and prebiotic molecule signatures in Titan-like atmospheres, by observing their absorption during transits. Although the search for key-target molecules in exoplanet atmospheres can be carried out by the JWST Transit Spectroscopy in the infrared (IR) region (0.6–29 μm wavelength range), opportunities for their detection in protostellar cores, protoplanetary disks, and on Titan are also offered by interferometric high spectral and spatial resolution observations using the Atacama Large Millimeter/submillimeter Array. In the present work, target molecules have been selected, and their spectroscopic characterization presented in view of supporting their infrared and complementary millimeter/submillimeter-wave spectral observations. In detail, the selected target molecules include: (1) the three-membered oxygen-containing heterocycles, oxirane and protonated oxirane; (2) the cyclopropenyl cation and its methyl derivative; (3) two examples of ortho- and peri-fused tri-cyclic aromatic rings, i.e., the phenalenyl cation (C{sub 13}H{sub 9}{sup +}) and anion (C{sub 13}H{sub 9}{sup -}); and (4) uracil, a specific RNA base.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Anisotropic Conductivity at the Single‐Molecule Scale

Abstract In most junctions built by wiring a single molecule between two electrodes, the electrons flow along only one axis: between the two anchoring groups. However, molecules can be anisotropic, and an orientation‐dependent conductance is expected. Here, we fabricated single‐molecule junctions by using the electrode potential to control the molecular orientation and access individual elements of the conductivity tensor. We measured the conductance in two directions, along the molecular plane as the benzene ring bridges two electrodes using anchoring groups (upright) and orthogonal to the molecular plane with the molecule lying flat on the substrate (planar). The perpendicular (planar) conductance is about 400 times higher than that along the molecular plane (upright). This offers a new method for designing a reversible room‐temperature single‐molecule electromechanical switch that controllably employs the electrode potential to orient the molecule in the junction in either “ON” or “OFF” conductance states.

Afsari, Sepideh↗
DOE OSTI2018

Efficiently Exploring Adsorption Space to Identify Privileged Adsorbents for Chemical Separations of a Diverse Set of Molecules

Although computational models have been used to predict adsorption of molecules in large libraries of porous adsorbents, previous work of this kind has focused on a small number of molecules as potential adsorbates. In this paper we use molecular simulations to consider the adsorption of a diverse range of molecules in a large collection of metal-organic framework (MOF) materials. Specifically, we obtain 11,304 isotherms from molecular simulations of 24 different adsorbates in 471 MOFs. This information allows us to explore several interesting questions that could not be addressed with previously available data. Here, we introduce highly computationally efficient methods that can predict isotherms for a wide range of adsorbing molecules with far less computation than traditional molecular simulations. By characterizing the 276 binary mixtures defined by the molecules we considered, we show that “privileged” adsorbents exist that are effective for separating many different molecular mixtures. Finally, we show that correlations that have been developed previously to predict molecular solubility in polymers are surprisingly effective in predicting the average properties of molecules adsorbing in MOFs.

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

Urban particulate matter induces the expression of receptors for early and late adhesion molecules on human monocytes

Highlights: • Inhalation of particles is related to local and systemic effects. • Activation of monocytes may play a role in the systemic effects induced by particles. • Monocytes may be activated by particles translocating from the lung into circulation, even at very low concentrations. • Expression of adhesion molecules receptors on monocytes increases the interaction between monocytes and endothelial cells. • Particles in concentration in the range of ng/mL are capable to induce the expression of receptors for adhesion molecules. Exposure to urban particulate matter (PM) is correlated with increases in the emergence of health services due to adverse events and deaths and is mainly related to cardiorespiratory complications. The translocation of particles from the lung into circulation has been proposed as a factor that may trigger systemic effects. Monocytes may be exposed to PM, and if the monocytes are activated, then they are likely to adhere to endothelial cells in a distant organ due to the expression of receptors for adhesion molecules. In the present study, we evaluated the expression of receptors for adhesion molecules (sLe{sup x}, PSGL-1, LFA-1, VLA-4 and α{sub V}β{sub 3}) in monocytes (U937 cells) exposed for 3 or 18 h to PM{sub 10} (0.001, 0.003, 0.010, 0.030, 0.300, 3 or 30 µg/mL). Exposed cells were co-cultured with human endothelial cells that were naive or previously exposed to the same particles. When U937 cells were exposed to PM{sub 10}, similar levels of expression for early and late receptors for adhesion molecules were observed from 30 ng/mL as those induced by TNF-α. Cells exposed to particles at concentrations above 30 ng/mL were more adhesive to naive or exposed human endothelial cells. Taken together, our results suggest that it is plausible that activated monocytes may play a role in systemic effects induced by PM{sub 10} due to the size distribution of the particles and the concentrations required to trigger the expression of receptors for adhesion molecules in monocytes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Evaluation of In Silico Multifeature Libraries for Providing Evidence for the Presence of Small Molecules in Synthetic Blinded Samples

The current gold standard for unambiguous molecular identification in metabolomics analysis is comparing two or more orthogonal properties from the analysis of authentic reference materials (standards) to experimental data acquired in the same laboratory with the same analytical methods. This represents a significant limitation for comprehensive chemical identification of small molecules in complex samples. The process is time-consuming and costly, and the majority of molecules are not yet represented by standards. Thus, there is a need to assemble evidence for the presence of small molecules in complex samples through the use of libraries containing calculated chemical properties. To address this need, we developed a Multi-Attribute Matching Engine (MAME) and a library derived in-part from our in silico Chemical Library Engine (ISiCLE). Here, we describe an initial evaluation of these methods in a blinded analysis of synthetic chemical mixtures as part of the U.S. Environmental Protection Agency’s (EPA) Non-Targeted Analysis Collaborative Trial (ENTACT, Phase 1). For molecules in all mixtures, the initial blinded false negative rate (FNR), false discovery rate (FDR), and accuracy were 57%, 77%, and 91%, respectively. For high evidence scores, the FDR was 35%. After unblinding of the sample compositions, we optimized the scoring parameters to better exploit the available evidence, and increased the accuracy for molecules suspected as present. The final FNR, FDR, and accuracy were 67%, 53%, and 96%, respectively. For high evidence scores, the FDR was 10%. This study demonstrates that multi-attribute matching methods in conjunction with in silico libraries may one day enable reduced reliance on experimentally-derived libraries for building evidence for the presence of molecules in complex samples.

Nunez, Jamie↗