In Situ Analysis of Martian Regolith with the SAM Experiment During the First Mars Year of the MSL Mission: Identification of Organic Molecules by Gas Chromatography from Laboratory Measurements

NASA Technical Reports Server (NTRS)

Millan, M.; Szopa, C.; Buch, A.; Coll, P.; Glavin, D. P.; Freissinet, C.; Navarro-Gonzalez, R.; Francois, P.; Coscia, D.; Bonnet, J. Y.;

Interaction between phases in the liquid–gas system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, R. S., E-mail: bmsmirnov@gmail.com; Smirnov, B. M.

This work analyzes the equilibrium between a liquid and a gas over this liquid separated by an interface. Various gas forms exist inside the liquid: dissolved gas molecules attached to solvent molecules, free gas molecules, and gaseous bubbles. Thermodynamic equilibrium is maintained between two phases; the first phase is the liquid containing dissolved and free molecules, and the second phase is the gas over the liquid and bubbles inside it. Kinetics of gas transition between the internal and external gas proceeds through bubbles and includes the processes of bubbles floating up and bubble growth as a result of association duemore » to the Smoluchowski mechanism. Evolution of a gas in the liquid is considered using the example of oxygen in water, and numerical parameters of this system are given. In the regime under consideration for an oxygen–water system, transport of oxygen into the surrounding air proceeds through micron-size bubbles with lifetimes of hours. This regime is realized if the total number of oxygen molecules in water is small compared with the numbers of solvated and free molecules in the liquid.« less

Sympathetic Cooling of Molecular Ions in Selected Rotational and Vibrational States Produced by Threshold Photoionization

NASA Astrophysics Data System (ADS)

Tong, Xin; Winney, Alexander H.; Willitsch, Stefan

2010-10-01

We present a new method for the generation of rotationally and vibrationally state-selected, translationally cold molecular ions in ion traps. Our technique is based on the state-selective threshold photoionization of neutral molecules followed by sympathetic cooling of the resulting ions with laser-cooled calcium ions. Using N2+ ions as a test system, we achieve >90% selectivity in the preparation of the ground rovibrational level and state lifetimes on the order of 15 minutes limited by collisions with background-gas molecules. The technique can be employed to produce a wide range of apolar and polar molecular ions in the ground and excited rovibrational states. Our approach opens up new perspectives for cold quantum-controlled ion-molecule-collision studies, frequency-metrology experiments with state-selected molecular ions and molecular-ion qubits.

Adsorption of gas molecules on Cu impurities embedded monolayer MoS2: A first- principles study

NASA Astrophysics Data System (ADS)

Zhao, B.; Li, C. Y.; Liu, L. L.; Zhou, B.; Zhang, Q. K.; Chen, Z. Q.; Tang, Z.

2016-09-01

Adsorption of small gas molecules (O2, NO, NO2 and NH3) on transition-metal Cu atom embedded monolayer MoS2 was investigated by first-principles calculations based on the density-functional theory (DFT). The embedded Cu atom is strongly constrained on the sulfur vacancy of monolayer MoS2 with a high diffusion barrier. The stable adsorption geometry, charge transfer and electronic structures of these gas molecules on monolayer MoS2 embedded with transition-metal Cu atom are discussed in detail. It is found that the monolayer MoS2 with embedded Cu atom can effectively capture these gas molecules with high adsorption energy. The NH3 molecule acts as electron donor after adsorption, which is different from the other gas molecules (O2, NO, and NO2). The results suggest that MoS2-Cu system may be promising for future applications in gas molecules sensing and catalysis, which is similar to those of the transition-metal embedded graphene.

Stimulated Raman scattering holography for time-resolved imaging of methane gas.

PubMed

Amer, Eynas; Gren, Per; Edenharder, Stefan; Sjödahl, Mikael

2016-05-01

In this paper, pulsed digital holographic detection is coupled to the stimulated Raman scattering (SRS) process for imaging gases. A Q-switched Nd-YAG laser (532 nm) has been used to pump methane gas (CH₄) at pressures up to 12 bars. The frequency-tripled (355 nm) beam from the same laser was used to pump an optical parametric oscillator (OPO). The Stokes beam (from the OPO) has been tuned to 629.93 nm so that the frequency difference between the pump (532 nm) and the Stokes beams fits a Raman active vibrational mode of the methane molecule (2922  cm^-1). The pump beam has been spatially modulated with fringes produced in a Michelson interferometer. The pump and the Stokes beams were overlapped in time, space, and polarization on the gas molecules, resulting in a stimulated Raman gain of the Stokes beam and a corresponding loss of the pump beam through the SRS process. The resulting gain of the Stokes beam has been detected using pulsed digital holography by blending it with a reference beam on the detector. Two holograms of the Stokes beam, without and with the pump beam fringes present, were recorded. Intensity maps calculated from the recorded digital holograms showed amplification of the Stokes beam at the position of overlap with the pump beam fringes and the gas molecules. The gain of the Stokes beam has been separated from the background in the Fourier domain. A gain of about 4.5% at a pump beam average intensity of 4  MW/cm² and a Stokes beam intensity of 0.16  MW/cm² have been recorded at a gas pressure of 12 bars. The gain decreased linearly with decreasing gas pressure. The results show that SRS holography is a promising technique to pinpoint a specific species and record its spatial and temporal distribution.

Adsorption of CO and O2 molecules on Li metal adsorbed graphene: Search for graphene based gas sensors

NASA Astrophysics Data System (ADS)

Kaur, Gagandeep; Gupta, Shuchi; Sachdeva, Ritika; Dharamvir, Keya

2018-05-01

Adsorption of small gas molecules (such as CO and O2) on pristine graphene (PG) and Li-adsorbed graphene (PG-Li) have been investigated using first principles methods within density functional theory (DFT). We also notice that PG-Li has a higher chemical reactivity towards the gas molecules as compared to PG and these molecules have higher adsorption energy on this surface. Moreover, the strong interactions between PG-Li and the adsorbed molecules (as compared to PG and gas molecules) induce dramatic changes to the electronic properties of PG adsorbed with Li and make PG-Li a promising candidate as sensing material for CO and O2 gases.

Detection of gas molecules on single Mn adatom adsorbed graphyne: a DFT-D study

NASA Astrophysics Data System (ADS)

Lu, Zhansheng; Lv, Peng; Ma, Dongwei; Yang, Xinwei; Li, Shuo; Yang, Zongxian

2018-02-01

As one of the prominent applications in intelligent systems, gas sensing technology has attracted great interest in both industry and academia. In the current study, the pristine graphyne (GY) without and with a single Mn atom is investigated to detect the gas molecules (CO, CH4, CO2, NH3, NO and O2). The pristine GY is promising to detect O2 molecules because of its chemical adsorption on GY with large electron transfer. The great stability of the Mn/GY is found, and the Mn atom prefers to anchor at the alkyne ring as a single atom. Upon single Mn atom anchoring, the sensitivity and selectivity of GY based gas sensors is significantly improved for various molecules, except CH4. The recovery time of the Mn/GY after detecting the gas molecules may help to appraise the detection efficiency for the Mn/GY. The current study will help to understand the mechanism of detecting the gas molecules, and extend the potentially fascinating applications of GY-based materials.

Magnetic trapping of cold bromine atoms.

PubMed

Rennick, C J; Lam, J; Doherty, W G; Softley, T P

2014-01-17

Magnetic trapping of bromine atoms at temperatures in the millikelvin regime is demonstrated for the first time. The atoms are produced by photodissociation of Br2 molecules in a molecular beam. The lab-frame velocity of Br atoms is controlled by the wavelength and polarization of the photodissociation laser. Careful selection of the wavelength results in one of the pair of atoms having sufficient velocity to exactly cancel that of the parent molecule, and it remains stationary in the lab frame. A trap is formed at the null point between two opposing neodymium permanent magnets. Dissociation of molecules at the field minimum results in the slowest fraction of photofragments remaining trapped. After the ballistic escape of the fastest atoms, the trapped slow atoms are lost only by elastic collisions with the chamber background gas. The measured loss rate is consistent with estimates of the total cross section for only those collisions transferring sufficient kinetic energy to overcome the trapping potential.

First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

NASA Astrophysics Data System (ADS)

Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

2018-06-01

Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

Quartz-enhanced photo-acoustic spectroscopy for breath analyses

NASA Astrophysics Data System (ADS)

Petersen, Jan C.; Lamard, Laurent; Feng, Yuyang; Focant, Jeff-F.; Peremans, Andre; Lassen, Mikael

2017-03-01

An innovative and novel quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for highly sensitive and selective breath gas analysis is introduced. The QEPAS sensor consists of two acoustically coupled micro- resonators (mR) with an off-axis 20 kHz quartz tuning fork (QTF). The complete acoustically coupled mR system is optimized based on finite element simulations and experimentally verified. Due to the very low fabrication costs the QEPAS sensor presents a clear breakthrough in the field of photoacoustic spectroscopy by introducing novel disposable gas chambers in order to avoid cleaning after each test. The QEPAS sensor is pumped resonantly by a nanosecond pulsed single-mode mid-infrared optical parametric oscillator (MIR OPO). Spectroscopic measurements of methane and methanol in the 3.1 μm to 3.7 μm wavelength region is conducted. Demonstrating a resolution bandwidth of 1 cm-1. An Allan deviation analysis shows that the detection limit at optimum integration time for the QEPAS sensor is 32 ppbv@190s for methane and that the background noise is solely due to the thermal noise of the QTF. Spectra of both individual molecules as well as mixtures of molecules were measured and analyzed. The molecules are representative of exhaled breath gasses that are bio-markers for medical diagnostics.

Exploration of bulk and interface behavior of gas molecules and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid using equilibrium and nonequilibrium molecular dynamics simulation and quantum chemical calculation.

PubMed

Yang, Quan; Achenie, Luke E K

2018-04-18

Ionic liquids (ILs) show brilliant performance in separating gas impurities, but few researchers have performed an in-depth exploration of the bulk and interface behavior of penetrants and ILs thoroughly. In this research, we have performed a study on both molecular dynamics (MD) simulation and quantum chemical (QC) calculation to explore the transport of acetylene and ethylene in the bulk and interface regions of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]-[BF4]). The diffusivity, solubility and permeability of gas molecules in the bulk were researched with MD simulation first. The subdiffusion behavior of gas molecules is induced by coupling between the motion of gas molecules and the ions, and the relaxation processes of the ions after the disturbance caused by gas molecules. Then, QC calculation was performed to explore the optical geometry of ions, ion pairs and complexes of ions and penetrants, and interaction potential for pairs and complexes. Finally, nonequilibrium MD simulation was performed to explore the interface structure and properties of the IL-gas system and gas molecule behavior in the interface region. The research results may be used in the design of IL separation media.

Millimeter-wave Absorption Studies of Molecules in Diffuse Clouds

NASA Astrophysics Data System (ADS)

Lucas, Robert; Liszt, Harvey S.

1999-10-01

With IRAM instruments in the last few years, we have been using compact extragalactic millimeter wave radio sources as background objects to study the absorption spectrum of diffuse interstellar gas at millimeter wavelengths. The molecular content of interstellar gas has turned out to be unexpectedly rich. Simple polyatomic molecules such as HCO+, C2H are quite ubiquitous near the Galactic plane (beta < 15o), and many species are detected in some directions (CO, HCO+, H2CO, HCN, HNC, CN, C2H, C3H2, H2S, CS, HCS+, SO, SiO). Remarkable proportionality relations are found between related species such as HCO+ and OH, or CN, HCN and HNC. The high abundance of some species is still a challenge for current models of diffuse cloud chemistry. A factor of 10 increase in the sensitivity will make such studies achievable in denser clouds, where the chemistry is still more active and where abundances are nowadays only available by emission measurements, and thus subject to uncertainties due to sometimes poorly understood line formation and excitation conditions.

Where is OH and Does It Trace the Dark Molecular Gas (DMG)?

NASA Astrophysics Data System (ADS)

Li, Di; Tang, Ningyu; Nguyen, Hiep; Dawson, J. R.; Heiles, Carl; Xu, Duo; Pan, Zhichen; Goldsmith, Paul F.; Gibson, Steven J.; Murray, Claire E.; Robishaw, Tim; McClure-Griffiths, N. M.; Dickey, John; Pineda, Jorge; Stanimirović, Snežana; Bronfman, L.; Troland, Thomas; PRIMO Collaboration

2018-03-01

Hydroxyl (OH) is expected to be abundant in diffuse interstellar molecular gas because it forms along with H2 under similar conditions and forms within a similar extinction range. We have analyzed absorption measurements of OH at 1665 MHz and 1667 MHz toward 44 extragalactic continuum sources, together with the J = 1–0 transitions of 12CO, 13CO, and C18O, and the J = 2–1 transition of 12CO. The excitation temperatures of OH were found to follow a modified lognormal distribution f({T}ex})\\propto \\tfrac{1}{\\sqrt{2π }σ }\\exp ≤ft[-\\tfrac{{[{ln}({T}ex})-{ln}(3.4{{K}})]}2}{2{σ }2}\\right], the peak of which is close to the temperature of the Galactic emission background (CMB+synchrotron). In fact, 90% of the OH has excitation temperatures within 2 K of the Galactic background at the same location, providing a plausible explanation for the apparent difficulty of mapping this abundant molecule in emission. The opacities of OH were found to be small and to peak around 0.01. For gas at intermediate extinctions (AV ∼ 0.05–2 mag), the detection rate of OH with a detection limit N(OH) ≃ 1012 cm‑2 is approximately independent of AV. We conclude that OH is abundant in the diffuse molecular gas and OH absorption is a good tracer of “dark molecular gas (DMG).” The measured fraction of DMG depends on the assumed detection threshold of the CO data set. The next generation of highly sensitive low-frequency radio telescopes, such as FAST and SKA, will make feasible the systematic inventory of diffuse molecular gas through decomposing, in velocity, the molecular (e.g., OH and CH) absorption profiles toward background continuum sources with numbers exceeding what is currently available by orders of magnitude.

Selective gas adsorption and I-V response of monolayer boron phosphide introduced by dopants: A first-principle study

NASA Astrophysics Data System (ADS)

Cheng, Yongfa; Meng, Ruishen; Tan, Chunjian; Chen, Xianping; Xiao, Jing

2018-01-01

Two-dimensional (2D) materials have gained tremendous research interests for gas sensing applications because of their ultrahigh theoretical specific surface areas and unique electronic properties. Here, we investigate the adsorption of CO, SO2, NH3, O2, NO and NO2 gas molecules on pure and doped boron phosphide (BP) systems using first-principles calculations to exploit their potential in gas sensing. Our results predict that all six gas molecules show stronger adsorption interactions on impurities-doped BP over the pristine monolayer BP. Al-doped BP shows the highest sensitivity to all gas molecules, but N-doped BP is more suitable as a sensing material for SO2, NO and NO2 due to the feasibility of desorption. We further calculated the current-voltage (I-V) relation by mean of nonequilibrium Green's function (NEGF) formalism. The I-V curves indicate that the electronic properties of the doping systems change significantly with gas adsorption by studying the nonparamagnetic molecules NH3 and the paramagnetic molecules NO, which can be more likely to be measured experimentally compared to graphene and phosphorene. This work explores the possibility of BP as a superior sensor through introducing the appropriate dopants.

Highly Enhanced Gas Adsorption Properties in Vertically Aligned MoS2 Layers.

PubMed

Cho, Soo-Yeon; Kim, Seon Joon; Lee, Youhan; Kim, Jong-Seon; Jung, Woo-Bin; Yoo, Hae-Wook; Kim, Jihan; Jung, Hee-Tae

2015-09-22

In this work, we demonstrate that gas adsorption is significantly higher in edge sites of vertically aligned MoS2 compared to that of the conventional basal plane exposed MoS2 films. To compare the effect of the alignment of MoS2 on the gas adsorption properties, we synthesized three distinct MoS2 films with different alignment directions ((1) horizontally aligned MoS2 (basal plane exposed), (2) mixture of horizontally aligned MoS2 and vertically aligned layers (basal and edge exposed), and (3) vertically aligned MoS2 (edge exposed)) by using rapid sulfurization method of CVD process. Vertically aligned MoS2 film shows about 5-fold enhanced sensitivity to NO2 gas molecules compared to horizontally aligned MoS2 film. Vertically aligned MoS2 has superior resistance variation compared to horizontally aligned MoS2 even with same surface area exposed to identical concentration of gas molecules. We found that electrical response to target gas molecules correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. Density functional theory (DFT) calculations corroborate the experimental results as stronger NO2 binding energies are computed for multiple configurations near the edge sites of MoS2, which verifies that electrical response to target gas molecules (NO2) correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. We believe that this observation extends to other 2D TMD materials as well as MoS2 and can be applied to significantly enhance the gas sensor performance in these materials.

Detection of the barium daughter in 136Xe -->136Ba + 2e- by in situ single-molecule fluorescence imaging

NASA Astrophysics Data System (ADS)

Nygren, David

2015-10-01

To proceed toward effective ``discovery class'' ton-scale detectors in the search for neutrino-less double beta decay, a robust technique for rejection of all radioactivity-induced backgrounds is urgently needed. An efficient technique for detection of the barium daughter in the decay 136Xe -->136Ba + 2e- would provide a long-sought pathway toward this goal. Single-molecule fluorescent imaging appears to offer a new way to detect the barium daughter atom, which emerges naturally in an ionized state in pure xenon. A doubly charged barium ion can initiate a chelation process with a non-fluorescent precursor molecule, leading to a highly fluorescent complex. Repeated photo-excitation of the complex can reveal both presence and location of a single ionized atom with high precision and selectivity. Detection within the active volume of a xenon gas Time Projection Chamber operating at high pressure would be automatic, and with a capability for redundant confirmation.

The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry

NASA Astrophysics Data System (ADS)

Ellis, Wade C.; Lewis, Charlotte R.; Openshaw, Anna P.; Farnsworth, Paul B.

2016-09-01

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

High-resolution mid-infrared spectroscopy of buffer-gas-cooled methyltrioxorhenium molecules

NASA Astrophysics Data System (ADS)

Tokunaga, S. K.; Hendricks, R. J.; Tarbutt, M. R.; Darquié, B.

2017-05-01

We demonstrate cryogenic buffer-gas cooling of gas-phase methyltrioxorhenium (MTO). This molecule is closely related to chiral organometallic molecules where the parity-violating energy differences between enantiomers is measurable. The molecules are produced with a rotational temperature of approximately 6 K by laser ablation of an MTO pellet inside a cryogenic helium buffer gas cell. Facilitated by the low temperature, we demonstrate absorption spectroscopy of the 10.2 μm antisymmetric Re=O stretching mode of MTO with a resolution of 8 MHz and a frequency accuracy of 30 MHz. We partially resolve the hyperfine structure and measure the nuclear quadrupole coupling of the excited vibrational state. Our ability to produce dense samples of complex molecules of this type at low temperatures represents a key step towards a precision measurement of parity violation in a chiral species.

SENSITIVE PRESSURE GAUGE

DOEpatents

Ball, W.P.

1961-01-01

An electron multiplier device is described. It has a plurality of dynodes between an anode and cathode arranged to measure pressure, temperature, or other environmental physical conditions that proportionately iinfuences the quantity of gas molecules between the dynodes. The output current of the device is influenced by the reduction in electron multiplication at the dynodes due to energy reducing collisions of the electrons with the gas molecules between the dynodes. More particularly, the current is inversely proportional to the quantity of gas molecules, viz., the gas pressure. The device is, hence, extremely sensitive to low pressures.

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

Doping and defect-induced germanene: A superior media for sensing H2S, SO2, and CO2 gas molecules

NASA Astrophysics Data System (ADS)

Monshi, M. M.; Aghaei, S. M.; Calizo, I.

2017-11-01

First-principles calculations based on density functional theory (DFT) have been employed to investigate the structural, electronic, and gas-sensing properties of pure, defected, and doped germanene nanosheets. Our calculations have revealed that while a pristine germanene nanosheet adsorbs CO2 weakly, H2S moderately, and SO2 strongly, the introduction of vacancy defects increases the sensitivity significantly which is promising for future gas-sensing applications. Mulliken population analysis imparts that an appreciable amount of charge transfer occurs between gas molecules and a germanene nanosheet which supports our results for adsorption energies of the systems. The enhancement of the interactions between gas molecules and the germanene nanosheet has been further investigated by density of states. Projected density of states provides detailed insight of the gas molecule's contribution in the gas-sensing system. Additionally, the influences of substituted dopant atoms such as B, N, and Al in the germanene nanosheet have also been considered to study the impact on its gas sensing ability. There was no significant improvement found in the doped gas sensing capability of germanene over the vacancy defects, except for CO2 upon adsorption on N-doped germanene.

Method of monitoring photoactive organic molecules in-situ during gas-phase deposition of the photoactive organic molecules

DOEpatents

Forrest, Stephen R.; Vartanian, Garen; Rolin, Cedric

2015-06-23

A method for in-situ monitoring of gas-phase photoactive organic molecules in real time while depositing a film of the photoactive organic molecules on a substrate in a processing chamber for depositing the film includes irradiating the gas-phase photoactive organic molecules in the processing chamber with a radiation from a radiation source in-situ while depositing the film of the one or more organic materials and measuring the intensity of the resulting photoluminescence emission from the organic material. One or more processing parameters associated with the deposition process can be determined from the photoluminescence intensity data in real time providing useful feedback on the deposition process.

Exploring the dynamic behaviors and transport properties of gas molecules in a transmembrane cyclic peptide nanotube.

PubMed

Li, Rui; Fan, Jianfen; Li, Hui; Yan, Xiliang; Yu, Yi

2013-12-05

The dynamic behaviors and transport properties of O2, CO2, and NH3 molecules through a transmembrane cyclic peptide nanotube (CPNT) of 8×cyclo-(WL)4/POPE have been investigated by steered molecular dynamics (SMD) simulations and adaptive biasing force (ABF) samplings. Different external forces are needed for three gas molecules to enter the channel. The periodic change of the pulling force curve for a gas traveling through the channel mainly arises from the regular and periodic arrangement of the composed CP subunits of the CPNT. Radial distribution functions (RDFs) between gas and water disclose the density decrease of channel water, which strongly aggravates the discontinuity of H-bond formation between a gas molecule and the neighboring water. Compared to hardly any H-bond formation between CO2 (or O2) and the framework of the CPNT, NH3 can form abundant H-bonds with the carbonyl/amide groups of the CPNT, leading to a fierce competition to NH3-water H-bonded interactions. In addition to direct H-bonded interactions, all three gases can form water bridges with the tube. The potential profile of mean force coincides with the occurring probability of a gas molecule along the tube axis. The energy barriers at two mouths of the CPNT elucidate the phenomenon that CO2 and O2 are thoroughly confined in the narrow lumen while NH3 can easily go outside the tube. Intermolecular interactions of each gas with channel water and the CPNT framework and the formation of H-bonds and water bridges illuminate the different gas translocation behaviors. The results uncover interesting and comprehensive mechanisms underlying the permeation characteristics of three gas molecules traveling through a transmembrane CPNT.

Brome isotope selective control of CF3Br molecule clustering by IR laser radiation in gas-dynamic expansion of CF3Br - Ar mixture

NASA Astrophysics Data System (ADS)

Apatin, V. M.; Lokhman, V. N.; Makarov, G. N.; Ogurok, N.-D. D.; Ryabov, E. A.

2018-02-01

We report the results of research on the experimental control of CF3Br molecule clustering under gas-dynamic expansion of the CF3Br - Ar mixture at a nozzle exit by using IR laser radiation. A cw CO2 laser is used for exciting molecules and clusters in the beam and a time-of-flight mass-spectrometer with laser UV ionisation of particles for their detection. The parameters of the gas above the nozzle are determined (compositions and pressure) at which intensive molecule clustering occurs. It is found that in the case of the CF3Br gas without carrier when the pressure P0 above the nozzle does not exceed 4 atm, molecular clusters actually are not generated in the beam. If the gas mixture of CF3Br with argon is used at a pressure ratio 1 : N, where N >= 3, and the total pressure above the nozzle is P0 >= 2 atm, then there occurs molecule clustering. We study the dependences of the efficiency of suppressing the molecule clustering on parameters of the exciting pulse, gas parameters above the nozzle, and on a distance of the molecule irradiation zone from the nozzle exit section. It is shown that in the case of resonant vibrational excitation of gas-dynamically cooled CF3Br molecules at the nozzle exit one can realise isotope-selective suppression of molecule clustering with respect to bromine isotopes. With the CF3Br - Ar mixtures having the pressure ratio 1 : 3 and 1 : 15, the enrichment factors obtained with respect to bromine isotopes are kenr ≈ 1.05 ± 0.005 and kenr ≈ 1.06 ± 0.007, respectively, under jet irradiation by laser emission in the 9R(30) line (1084.635 cm-1). The results obtained let us assume that this method can be used to control clustering of molecules comprising heavy element isotopes, which have a small isotopic shift in IR absorption spectra.

How Properties of Solid Surfaces Modulate the Nucleation of Gas Hydrate

PubMed Central

Bai, Dongsheng; Chen, Guangjin; Zhang, Xianren; Sum, Amadeu K.; Wang, Wenchuan

2015-01-01

Molecular dynamics simulations were performed for CO2 dissolved in water near silica surfaces to investigate how the hydrophilicity and crystallinity of solid surfaces modulate the local structure of adjacent molecules and the nucleation of CO2 hydrates. Our simulations reveal that the hydrophilicity of solid surfaces can change the local structure of water molecules and gas distribution near liquid-solid interfaces, and thus alter the mechanism and dynamics of gas hydrate nucleation. Interestingly, we find that hydrate nucleation tends to occur more easily on relatively less hydrophilic surfaces. Different from surface hydrophilicity, surface crystallinity shows a weak effect on the local structure of adjacent water molecules and on gas hydrate nucleation. At the initial stage of gas hydrate growth, however, the structuring of molecules induced by crystalline surfaces are more ordered than that induced by amorphous solid surfaces. PMID:26227239

How Does Dense Molecular Gas Contribute to Star Formation in the Starburst Galaxy NGC 2146?

NASA Astrophysics Data System (ADS)

Wofford, Alia

2017-01-01

The starburst galaxy NGC 2146 is believed to have been formed approximately 800 Myr ago, when two galaxies collided with each other possibly leading to a burst of star formation. NGC 2146 is known as a starburst galaxy for the high frequency of star formation going on in its molecular clouds. These clouds serve as nurseries for star formation to occur. Hydrogen Cyanide (HCN) and Carbon monoxide (CO) are molecules found in molecular gas clouds. HCN molecules are tracers for high density star forming gas. Whereas, CO molecules are tracers for low density star forming gas. In this project, we are observing these two molecules and their proximity to where the stars are forming in the galaxy to determine if the star formation is occurring in the same area as the high and low density molecular gas areas in starburst galaxy NGC 2146.

Exploration of sensing of nitrogen dioxide and ozone molecules using novel TiO2/Stanene heterostructures employing DFT calculations

NASA Astrophysics Data System (ADS)

Abbasi, Amirali; Sardroodi, Jaber Jahanbin

2018-06-01

Based on the density functional theory (DFT) calculations, we explored the sensing capabilities and electronic structures of TiO2/Stanene heterostructures as novel and highly efficient materials for detection of toxic NO2 and O3 molecules in the environment. Studied gas molecules were positioned at different sites and orientations towards the nanocomposite, and the adsorption process was examined based on the most stable structures. We found that both of these molecules are chemically adsorbed on the TiO2/Stanene heterostructures. The calculations of the adsorption energy indicate that the fivefold coordinated titanium sites of the TiO2/Stanene are the most stable sites for the adsorption of NO2 and O3 molecules. The side oxygen atoms of the gas molecules were found to be chemically bonded to these titanium atoms. The adsorption of gas molecules is an exothermic process, and the adsorption on the pristine nanocomposite is more favorable in energy than that on the nitrogen-doped nanocomposite. The effects of van der Waals interactions were taken into account, which indicate the adsorption energies were increased for the most sable configurations. The gas sensing response and charge transfers were analyzed in detail. The pristine nanocomposites have better sensing response than the doped ones. The spin density distribution plots indicate that the magnetization was mainly located over the adsorbed gas molecules. Mulliken charge analysis reveals that both NO2 and O3 molecules behave as charge acceptors, as evidenced by the accumulation of electronic charges on the adsorbed molecules predicted by charge density difference calculations. Our DFT results provide a theoretical basis for an innovative gas sensor system designed from a sensitive TiO2/Stanene heterostructures for efficient detection of harmful air pollutants such as NO2 and O3.

Computation of Hypersonic Shock Wave Flows of Multi-Component Reactive Gas Mixtures Using the Generalized Boltzmann Equation

DTIC Science & Technology

2009-03-27

ones like the Lennard - Jones potential with established parameters for each gas (e.g. N2 and 02), and for inelastic collisions DSMC method employs...solution of the collision integral. Lennard - Jones potential with two free parameters is used to obtain the elastic cross-section of the gas molecules...and the so called "combinatory relations" are used to obtain parameters of Lennard - Jones potential for an interaction of molecule A with molecule B

Probing Buffer-Gas Cooled Molecules with Direct Frequency Comb Spectroscopy in the Mid-Infrrared

NASA Astrophysics Data System (ADS)

Spaun, Ben; Changala, Bryan; Bjork, Bryce J.; Heckl, Oliver H.; Patterson, David; Doyle, John M.; Ye, Jun

2015-06-01

We present the first demonstration of cavity-enhanced direct frequency comb spectroscopy on buffer-gas cooled molecules.By coupling a mid-infrared frequency comb to a high-finesse cavity surrounding a helium buffer-gas chamber, we can gather rotationally resolved absorption spectra with high sensitivity over a broad wavelength region. The measured ˜10 K rotational and translational temperatures of buffer-gas cooled molecules drastically simplify the observed spectra, compared to those of room temperature molecules, and allow for high spectral resolution limited only by Doppler broadening (10-100 MHz). Our system allows for the extension of high-resolution spectroscopy to larger molecules, enabling detailed analysis of molecular structure and dynamics, while taking full advantage of the powerful optical properties of frequency combs. A. Foltynowicz et al. Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide. Applied Physics B, vol. 110, pp. 163-175, 2013. {D. Patterson and J. M. Doyle. Cooling molecules in a cell for FTMW spectroscopy. Molecular Physics 110, 1757-1766, 2012

Slow approach to steady motion of a concave body in a free-molecular gas

NASA Astrophysics Data System (ADS)

Tsuji, Tetsuro; Arai, Junichi; Kawano, Satoyuki

2015-07-01

A body in a free-molecular gas accelerated by a constant external force is considered on the basis of kinetic theory. The body is an infinitely long rectangular hollow column with one face removed, and thus it has a squarish U -shaped cross section. The concave part of the body points toward the direction of motion, and thus the gas molecules may be trapped in the concavity. Gas molecules undergo diffuse reflection on a base part, whereas specular reflection on two lateral parts. It is numerically shown that the velocity of the body approaches a terminal velocity, for which a drag force exerted by the gas counterbalances the external force, in such a way that their difference decreases in proportion to the inverse square of time for a large time. This rate of approach is slower than the known rate proportional to the inverse cube of time in the case of a body without concavity [Aoki et al., Phys. Rev. E 80, 016309 (2009), 10.1103/PhysRevE.80.016309]. Based on the detailed investigation on the velocity distribution function of gas molecules impinging on the body, it is clarified that the concavity prevents some molecules from escaping to infinity. This trapping enhances the effect of recollision between the body and the gas molecules, which is the cause of the inverse power laws, and thus leads to the slower approach.

Organic-inorganic nano-composite films for photonic applications made by multi-beam multi-target pulsed laser deposition with remote control of the plume directions

NASA Astrophysics Data System (ADS)

Darwish, Abdalla M.; Moore, Shaelynn; Mohammed, Aziz; Alexander, Deonte'; Bastian, Tyler; Dorlus, Wydglif; Sarkisov, Sergey S.; Patel, Darayas N.; Mele, Paolo; Koplitz, Brent

2016-09-01

There has been an explosive interest in the technique of laser assisted deposition of polymer nano-composite films exploiting the matrix assisted pulsed laser evaporation (MAPLE) with regard to the polymer host as can be judged form recent publications.1-4 In MAPLE, a frozen solution of a polymer in a relatively volatile solvent is used as a laser target. The solvent and concentration are selected so that first, the polymer of interest can dissolve to form a dilute, particulate free solution, second, the majority of the laser energy is initially absorbed by the solvent molecules and not by the solute molecules, and third, there is no photochemical reaction between the solvent and the solute. The light-material interaction in MAPLE can be described as a photothermal process. The photon energy absorbed by the solvent is converted to thermal energy that causes the polymer to be heated but the solvent to vaporize. As the surface solvent molecules are evaporated into the gas phase, polymer molecules are exposed at the gas-target matrix interface. The polymer molecules attain sufficient kinetic energy through collective collisions with the evaporating solvent molecules, to be transferred into the gas phase. By careful optimization of the MAPLE deposition conditions (laser wavelength, repetition rate, solvent type, concentration, temperature, and background gas and gas pressure), this process can occur without any significant polymer decomposition. The MAPLE process proceeds layer-by-layer, depleting the target of solvent and polymer in the same concentration as the starting matrix. When a substrate is positioned directly in the path of the plume, a coating starts to form from the evaporated polymer molecules, while the volatile solvent molecules are evacuated by the pump from the deposition chamber. In case of fabrication of polymer nanocomposites, MAPLE targets are usually prepared as nano-colloids of the additives of interest in the initial polymer solutions. Mixing the components of different nature, organic polymers and inorganic dopants, in the same target at a certain proportion and exposing them to the same laser beam not necessarily brings good quality nano-composite films. The laser pulse energy and wavelength cannot be optimized for each component individually. Also, the mixing proportion in the composite film is dictated by the initial proportion of the target and thus cannot be changed in the process. These limitations were removed in the recently proposed method of multi-beam and multi-target deposition (in its doublebeam/ dual-target variation) using a MAPLE polymer target and one inorganic target, each being concurrently exposed to laser beams of different wavelengths.5-14 Using the method, nano-composite films of polymer poly(methyl methacrylate) known as PMMA doped with a rare earth (RE) inorganic upconversion phosphor compounds were prepared. Also, a nano-composite film of thermoelectric film of inorganic aluminum-doped ZnO known as AZO was impregnated with PMMA nano-fillers with the purpose of improving electrical conductivity and thermoelectric performance.10, 14 The polymer target was a frozen (to a temperature of liquid nitrogen) PMMA solution in chlorobenzene exposed to a 1064- nm laser beam from a Q-switched Nd:YAG pulsed laser. The inorganic targets were the pellets made of the compressed micro-powders of highly efficient RE-doped NaYF4 or the sintered powder of AZO concurrently ablated with the

Characterization and calibration of a combined laser Raman, fluorescence and coherent Raman spectrometer

NASA Astrophysics Data System (ADS)

Lawhead, Carlos; Cooper, Nathan; Anderson, Josiah; Shiver, Tegan; Ujj, Laszlo

2014-03-01

Electronic and vibrational spectroscopy is extremely important tools used in material characterization; therefore a table-top laser spectrometer system was built in the spectroscopy lab at the UWF physics department. The system is based upon an injection seeded nanosecond Nd:YAG Laser. The second and the third harmonics of the fundamental 1064 nm radiation are used to generate Raman and fluorescence spectra measured with MS260i imaging spectrograph occupied with a CCD detector and cooled to -85 °C, in order to minimize the dark background noise. The wavelength calibration was performed with the emission spectra of standard gas-discharge lamps. Spectral sensitivity calibration is needed before any spectra are recorded, because of the table-top nature of the instrument. A variety of intensity standards were investigated to find standards suitable for our table top setup that do not change the geometry of the system. High quality measurement of Raman standards where analyzed to test spectral corrections. Background fluorescence removal methods were used to improve Raman signal intensity reading on highly fluorescent molecules. This instrument will be used to measure vibrational and electronic spectra of biological molecules.

Investigation of molecule-adsorption kinetics by a pulsed laser desorption technique

NASA Astrophysics Data System (ADS)

Varakin, V. N.; Lozovskii, A. D.; Panesh, A. M.; Simonov, A. P.

1987-02-01

The laser thermal desorption technique is used to measure the adsorption kinetics of SO2 and CO molecules on stainless steel with the aim of investigating the initial stage of oxidation of the steel by adsorbed CO molecules. Attention is given to the dependence of the rate of establishment of the equilibrium concentration of adsorbed molecules on SO2-gas pressure; CO adsorption kinetics on stainless steel at a gas pressure of 9 x 10 to the -8th torr; and the dependence of the concentration of adsorbed CO molecules on exposure in the gas at a pressure of 9 x 10 to the -8th torr under irradiation by laser pulses with repetition periods of 1-2, 2-4, 3-6, and 4-8 min.

Genetic interactions between the hedgehog co-receptors Gas1 and Boc regulate cell proliferation during murine palatogenesis

PubMed Central

Xavier, Guilherme M.; Seppala, Maisa; Papageorgiou, Spyridon N.; Fan, Chen-Ming; Cobourne, Martyn T.

2016-01-01

Abnormal regulation of Sonic hedgehog (Shh) signaling has been described in a variety of human cancers and developmental anomalies, which highlights the essential role of this signaling molecule in cell cycle regulation and embryonic development. Gas1 and Boc are membrane co-receptors for Shh, which demonstrate overlapping domains of expression in the early face. This study aims to investigate potential interactions between these co-receptors during formation of the secondary palate. Mice with targeted mutation in Gas1 and Boc were used to generate Gas1; Boc compound mutants. The expression of key Hedgehog signaling family members was examined in detail during palatogenesis via radioactive in situ hybridization. Morphometric analysis involved computational quantification of BrdU-labeling and cell packing; whilst TUNEL staining was used to assay cell death. Ablation of Boc in a Gas1 mutant background leads to reduced Shh activity in the palatal shelves and an increase in the penetrance and severity of cleft palate, associated with failed elevation, increased proliferation and reduced cell death. Our findings suggest a dual requirement for Boc and Gas1 during early development of the palate, mediating cell cycle regulation during growth and subsequent fusion of the palatal shelves. PMID:27811357

Superdiffusive gas recovery from nanopores

NASA Astrophysics Data System (ADS)

Wu, Haiyi; He, Yadong; Qiao, Rui

2016-11-01

Understanding the recovery of gas from reservoirs featuring pervasive nanopores is essential for effective shale gas extraction. Classical theories cannot accurately predict such gas recovery and many experimental observations are not well understood. Here we report molecular simulations of the recovery of gas from single nanopores, explicitly taking into account molecular gas-wall interactions. We show that, in very narrow pores, the strong gas-wall interactions are essential in determining the gas recovery behavior both quantitatively and qualitatively. These interactions cause the total diffusion coefficients of the gas molecules in nanopores to be smaller than those predicted by kinetic theories, hence slowing down the rate of gas recovery. These interactions also lead to significant adsorption of gas molecules on the pore walls. Because of the desorption of these gas molecules during gas recovery, the gas recovery from the nanopore does not exhibit the usual diffusive scaling law (i.e., the accumulative recovery scales as R ˜t1 /2 ) but follows a superdiffusive scaling law R ˜tn (n >0.5 ), which is similar to that observed in some field experiments. For the system studied here, the superdiffusive gas recovery scaling law can be captured well by continuum models in which the gas adsorption and desorption from pore walls are taken into account using the Langmuir model.

A permanent magnet trap for buffer gas cooled atoms and molecules

NASA Astrophysics Data System (ADS)

Nohlmans, D.; Skoff, S. M.; Hendricks, R. J.; Segal, D. M.; Sauer, B. E.; Hinds, E. A.; Tarbutt, M. R.

2013-05-01

Cold molecules are set to provide a wealth of new science compared to their atomic counterparts. Here we want to present preliminary results for cooling and trapping atoms/molecules in a permanent magnetic trap. By replacing the conventional buffer gas cell with an arrangement of permanent magnets, we will be able to trap a fraction of the molecules right where they are cooled. For this purpose we have designed a quadrupole trap using NdFeB magnets, which has a trap depth of 0.4 K for molecules with a magnetic moment of 1 μB. Cold helium gas is pulsed into the trap region by a solenoid valve and the atoms/molecules are subsequently ablated into this and cooled via elastic collisions, leaving a fraction of them trapped. This new set-up is currently being tested with lithium atoms as they are easier to make. After having optimised the trapping and detection processes, we will use the same trap for YbF molecules.

Explaining the differential solubility of flue gas components in ionic liquids from first-principle calculations.

PubMed

Prasad, B Ram; Senapati, Sanjib

2009-04-09

Flue gas is greatly responsible for acid rain formation and global warming. New generation ionic liquids (ILs) have potential in controlling the flue gas emissions, as they acquire high absorptivity for the component gases SO(2), CO(2), etc. The association of the IL-gas interactions to the absorptivity of gas molecules in ILs is, however, poorly understood. In this paper, we present a molecular level description of the interactions of ILs with SO(2), CO(2), and N(2) and show its implications to the differential gas solubility. Our results indicate that the IL anion-gas interactions play a key role in deciding the gas solubility in ILs, particularly for polar gases such as SO(2). On the other hand, regular solution assumption applies to N(2) solubility. In accordance with the previous theoretical and experimental findings, our results also imply that the IL anions dominate the interactions with gas molecules while the cations play a secondary role and the underlying fluid structures of the ILs remain unperturbed by the addition of gas molecules.

Natural gas hydrates; vast resource, uncertain future

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Gas hydrates are naturally occurring icelike solids in which water molecules trap gas molecules in a cagelike structure known as a clathrate. Although many gases form hydrates in nature, methane hydrate is by far the most common; methane is the most abundant natural gas. The volume of carbon contained in methane hydrates worldwide is estimated to be twice the amount contained in all fossil fuels on Earth, including coal.

Fast, high temperature and thermolabile GC--MS in supersonic molecular beams

NASA Astrophysics Data System (ADS)

Dagan, Shai; Amirav, Aviv

1994-05-01

This work describes and evaluates the coupling of a fast gas chromatograph (GC) based on a short column and high carrier gas flow rate to a supersonic molecular beam mass spectrometer (MS). A 50 cm long megabore column serves for fast GC separation and connects the injector to the supersonic nozzle source. Sampling is achieved with a conventional syringe based splitless sample injection. The injector contains no septum and is open to the atmosphere. The linear velocity of the carrier gas is controlled by a by-pass (make-up) gas flow introduced after the column and prior to the supersonic nozzle. The supersonic expansion serves as a jet separator and the skimmed supersonic molecular beam (SMB) is highly enriched with the heavier organic molecules. The supersonic molecular beam constituents are ionized either by electron impact (EI) or hyperthermal surface ionization (HSI) and mass analyzed. A 1 s fast GC--MS of four aromatic molecules in methanol is demonstrated and some fundamental aspects of fast GC--MS with time limit constraints are outlined. The flow control (programming) of the speed of analysis is shown and the analysis of thermolabile and relatively non-volatile molecules is demonstrated and discussed. The tail-free, fast GC--MS of several mixtures is shown and peak tailing of caffeine is compared with that of conventional GC--MS. The improvement of the peak shapes with the SMB--MS is analyzed with the respect to the elimination of thermal vacuum chamber background. The extrapolated minimum detected amount was about 400 ag of anthracence-d10, with an elution time which was shorter than 2s. Repetitive injections could be performed within less than 10 s. The fast GC--MS in SMB seems to be ideal for fast target compound analysis even in real world, complex mixtures. The few seconds GC--MS separation and quantification of lead (as tetraethyllead) in gasoline, caffeine in coffee, and codeine in a drug is demonstrated. Controlled HSI selectivity is demonstrated in the range of 101 to 104 anthracene/decane which helped to simplify the selective analysis of aromatic molecules in gasoline. The contribution of SMB to the operation of the fast GC--MS is summarized and the compatibility with conventional GC having a megabore column is shown. Splitless injections of 100 [mu]L sample solutions for trace level concentration detection is also presented (with a conventional GC).

Seeing Stars in Serpens

NASA Technical Reports Server (NTRS)

2006-01-01

Infant stars are glowing gloriously in this infrared image of the Serpens star-forming region, captured by NASA's Spitzer Space Telescope.

The reddish-pink dots are baby stars deeply embedded in the cosmic cloud of gas and dust that collapsed to create it. A dusty disk of cosmic debris, or 'protoplanetary disk,' that may eventually form planets, surrounds the infant stars.

Wisps of green throughout the image indicate the presence of carbon rich molecules called polycyclic aromatic hydrocarbons. On Earth, these molecules can be found on charred barbecue grills and in automobile exhaust. Blue specks sprinkled throughout the image are background stars in our Milky Way galaxy.

The Serpens star-forming region is located approximately 848 light-years away in the Serpens constellation.

The image is a three-channel, false-color composite, where emission at 4.5 microns is blue, emission at 8.0 microns is green, and 24 micron emission is red.

Optimal Background Estimators in Single-Molecule FRET Microscopy.

PubMed

Preus, Søren; Hildebrandt, Lasse L; Birkedal, Victoria

2016-09-20

Single-molecule total internal reflection fluorescence (TIRF) microscopy constitutes an umbrella of powerful tools that facilitate direct observation of the biophysical properties, population heterogeneities, and interactions of single biomolecules without the need for ensemble synchronization. Due to the low signal/noise ratio in single-molecule TIRF microscopy experiments, it is important to determine the local background intensity, especially when the fluorescence intensity of the molecule is used quantitatively. Here we compare and evaluate the performance of different aperture-based background estimators used particularly in single-molecule Förster resonance energy transfer. We introduce the general concept of multiaperture signatures and use this technique to demonstrate how the choice of background can affect the measured fluorescence signal considerably. A new, to our knowledge, and simple background estimator is proposed, called the local statistical percentile (LSP). We show that the LSP background estimator performs as well as current background estimators at low molecular densities and significantly better in regions of high molecular densities. The LSP background estimator is thus suited for single-particle TIRF microscopy of dense biological samples in which the intensity itself is an observable of the technique. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Small molecule inhibitors block Gas6-inducible TAM activation and tumorigenicity.

PubMed

Kimani, Stanley G; Kumar, Sushil; Bansal, Nitu; Singh, Kamalendra; Kholodovych, Vladyslav; Comollo, Thomas; Peng, Youyi; Kotenko, Sergei V; Sarafianos, Stefan G; Bertino, Joseph R; Welsh, William J; Birge, Raymond B

2017-03-08

TAM receptors (Tyro-3, Axl, and Mertk) are a family of three homologous type I receptor tyrosine kinases that are implicated in several human malignancies. Overexpression of TAMs and their major ligand Growth arrest-specific factor 6 (Gas6) is associated with more aggressive staging of cancers, poorer predicted patient survival, acquired drug resistance and metastasis. Here we describe small molecule inhibitors (RU-301 and RU-302) that target the extracellular domain of Axl at the interface of the Ig-1 ectodomain of Axl and the Lg-1 of Gas6. These inhibitors effectively block Gas6-inducible Axl receptor activation with low micromolar IC 50s in cell-based reporter assays, inhibit Gas6-inducible motility in Axl-expressing cell lines, and suppress H1299 lung cancer tumor growth in a mouse xenograft NOD-SCIDγ model. Furthermore, using homology models and biochemical verifications, we show that RU301 and 302 also inhibit Gas6 inducible activation of Mertk and Tyro3 suggesting they can act as pan-TAM inhibitors that block the interface between the TAM Ig1 ectodomain and the Gas6 Lg domain. Together, these observations establish that small molecules that bind to the interface between TAM Ig1 domain and Gas6 Lg1 domain can inhibit TAM activation, and support the further development of small molecule Gas6-TAM interaction inhibitors as a novel class of cancer therapeutics.

Molecules, magic and forgetful fruit flies: the supernatural science of medical gas research.

PubMed

Mychaskiw, George

2011-09-06

Medical gas research often involves the study of molecules under extraphysiologic conditions, that is, conditions that do not exist in nature. This "supernatural" nature of medical gas research sometimes produces results that appear to be almost "magic" to those schooled in traditional physiology"Any sufficiently advanced technology is indistinguishable from magic".-Arthur C. Clarke.

Potential interstellar noble gas molecules: ArOH+ and NeOH+ rovibrational analysis from quantum chemical quartic force fields

NASA Astrophysics Data System (ADS)

Theis, Riley A.; Fortenberry, Ryan C.

2016-03-01

The discovery of ArH+ in the interstellar medium has shown that noble gas chemistry may be of more chemical significance than previously believed. The present work extends the known chemistry of small noble gas molecules to NeOH+ and ArOH+. Besides their respective neonium and argonium diatomic cation cousins, these hydroxyl cation molecules are the most stable small noble gas molecules analyzed of late. ArOH+ is once again more stable than the neon cation, but both are well-behaved enough for a complete quartic force field analysis of their rovibrational properties. The Ar-O bond in ArOH+ , for instance, is roughly three-quarters of the strength of the Ar-H bond in ArH+ highlighting the rigidity of this system. The rotational constants, geometries, and vibrational frequencies for both molecules and their various isotopologues are computed from ab initio quantum chemical theory at high-level, and it is shown that these cations may form in regions where peroxy or weakly-bound alcohols may be present. The resulting data should be of significant assistance for the laboratory or observational analysis of these potential interstellar molecules.

Sensitivity and resolution in frequency comb spectroscopy of buffer gas cooled polyatomic molecules

NASA Astrophysics Data System (ADS)

Changala, P. Bryan; Spaun, Ben; Patterson, David; Doyle, John M.; Ye, Jun

2016-12-01

We discuss the use of cavity-enhanced direct frequency comb spectroscopy in the mid-infrared region with buffer gas cooling of polyatomic molecules for high-precision rovibrational absorption spectroscopy. A frequency comb coupled to an optical enhancement cavity allows us to collect high-resolution, broad-bandwidth infrared spectra of translationally and rotationally cold (10-20 K) gas-phase molecules with high absorption sensitivity and fast acquisition times. The design and performance of the combined apparatus are discussed in detail. Recorded rovibrational spectra in the CH stretching region of several organic molecules, including vinyl bromide (CH_2CHBr), adamantane (C_{10}H_{16}), and diamantane (C_{14}H_{20}) demonstrate the resolution and sensitivity of this technique, as well as the intrinsic challenges faced in extending the frontier of high-resolution spectroscopy to large complex molecules.

Guest Molecule Exchange Kinetics for the 2012 Ignik Sikumi Gas Hydrate Field Trial

DOE Office of Scientific and Technical Information (OSTI.GOV)

White, Mark D.; Lee, Won Suk

A commercially viable technology for producing methane from natural gas hydrate reservoirs remains elusive. Short-term depressurization field tests have demonstrated the potential for producing natural gas via dissociation of the clathrate structure, but the long-term performance of the depressurization technology ultimately requires a heat source to sustain the dissociation. A decade of laboratory experiments and theoretical studies have demonstrated the exchange of pure CO2 and N2-CO2 mixtures with CH4 in sI gas hydrates, yielding critical information about molecular mechanisms, recoveries, and exchange kinetics. Findings indicated the potential for producing natural gas with little to no production of water and rapidmore » exchange kinetics, generating sufficient interest in the guest-molecule exchange technology for a field test. In 2012 the U.S. DOE/NETL, ConocoPhillips Company, and Japan Oil, Gas and Metals National Corporation jointly sponsored the first field trial of injecting a mixture of N2-CO2 into a CH4-hydrate bearing formation beneath the permafrost on the Alaska North Slope. Known as the Ignik Sikumi #1 Gas Hydrate Field Trial, this experiment involved three stages: 1) the injection of a N2-CO2 mixture into a targeted hydrate-bearing layer, 2) a 4-day pressurized soaking period, and 3) a sustained depressurization and fluid production period. Data collected during the three stages of the field trial were made available after an extensive quality check. These data included continuous temperature and pressure logs, injected and recovered fluid compositions and volumes. The Ignik Sikumi #1 data set is extensive, but contains no direct evidence of the guest-molecule exchange process. This investigation is directed at using numerical simulation to provide an interpretation of the collected data. A numerical simulator, STOMP-HYDT-KE, was recently completed that solves conservation equations for energy, water, mobile fluid guest molecules, and hydrate guest molecules, for up to three gas hydrate guest molecules: CH4, CO2, and N2. The independent tracking of mobile fluid and hydrate guest molecules allows for the kinetic exchange of guest molecules between the mobile fluids and hydrate. The particular interest of this numerical investigation is to determine whether kinetic exchange parameters, determined from laboratory-scale experiments, are directly applicable to interpreting the Ignik Sikumi #1 data.« less

Ion mobility sensor

DOEpatents

Koo, Jackson C.; Yu, Conrad M.

2005-08-23

An ion mobility sensor which can detect both ion and molecules simultaneously. Thus, one can measure the relative arrival times between various ions and molecules. Different ions have different mobility in air, and the ion sensor enables measurement of ion mobility, from which one can identify the various ions and molecules. The ion mobility sensor which utilizes a pair of glow discharge devices may be designed for coupling with an existing gas chromatograph, where various gas molecules are already separated, but numbers of each kind of molecules are relatively small, and in such cases a conventional ion mobility sensor cannot be utilized.

Molecules, magic and forgetful fruit flies: the supernatural science of medical gas research

PubMed Central

2011-01-01

Medical gas research often involves the study of molecules under extraphysiologic conditions, that is, conditions that do not exist in nature. This "supernatural" nature of medical gas research sometimes produces results that appear to be almost "magic" to those schooled in traditional physiology "Any sufficiently advanced technology is indistinguishable from magic". -Arthur C. Clarke PMID:22146602

DFT study of adsorption behavior of NO, CO, NO2, and NH3 molecules on graphene-like BC3: A search for highly sensitive molecular sensor

NASA Astrophysics Data System (ADS)

Mehdi Aghaei, Sadegh; Monshi, M. M.; Torres, I.; Zeidi, S. M. J.; Calizo, I.

2018-01-01

The adsorption behaviors of toxic gas molecules (NO, CO, NO2, and NH3) on the graphene-like boron carbide (BC3) are investigated using first-principle density functional theory. The graphene-like BC3 monolayer is a semiconductor with a band gap of 0.733 eV. It is discovered that all the above gas molecules are chemisorbed on the BC3 sheet while they retain their molecular forms. It is also revealed that the NO2 gas molecule could be dissociated into NO and O species through the adsorption process. The amounts of charge transfer upon adsorption of CO and NH3 gas molecules on the BC3 are found to be small. The band gap changes in BC3 as a result of interactions with CO and NH3 are only 4.63% and 16.7%, indicating that the BC3-based sensor has a low and moderate sensitivity to CO and NH3, respectively. Contrariwise, upon adsorption of NO or NO2 on the BC3, significant charges are transferred from the molecules to the BC3 sheet, causing a semiconductor-metal and semiconductor-p type semiconductor transition. Our study suggests that the BC3-based sensor has a high potential for NO and NO2 detection due to the significant conductance changes, moderate adsorption energy, and short recovery time. More excitingly, the BC3 is a likely catalyst for dissociation of the NO2 gas molecule.

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Ehrenfreund, P.; Kuan, Y. J.

2001-01-01

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Adsorption of HCN molecules on Ni, Pd and Pt-doped (7, 0) boron nitride nanotube: a DFT study

NASA Astrophysics Data System (ADS)

Habibi-Yangjeh, Aziz; Basharnavaz, Hadi

2018-05-01

We studied affinity of pure and Ni, Pd and Pt-doped (7, 0) boron nitride nanotubes (BNNTs) to toxic HCN molecules using density functional theory calculations. The results indicated that the pure (7, 0) BNNTs can weakly adsorb HCN molecules with adsorption energy of -0.2474 eV. Upon adsorption of HCN molecules on this nanotube, the band gap energy was decreased from 3.320 to 2.960 eV. The more negative adsorption energy between these transition metal-doped (7, 0) BNNTs and HCN molecules indicated that doping of (7, 0) BNNTs with Ni, Pd and Pt elements can significantly improve the affinity of BNNTs toward this gas. Additionally, it was found that the interaction energy between HCN molecules and Pt-doped BNNTs is more negative than those of the Ni and Pd-doped BNNTs. These observations suggested that the Pt-doped (7, 0) BNNTs are strongly sensitive to HCN molecules and therefore it may be used in gas sensor devices for detecting this toxic gas.

Room temperature CO and H2 sensing with carbon nanoparticles.

PubMed

Kim, Daegyu; Pikhitsa, Peter V; Yang, Hongjoo; Choi, Mansoo

2011-12-02

We report on a shell-shaped carbon nanoparticle (SCNP)-based gas sensor that reversibly detects reducing gas molecules such as CO and H(2) at room temperature both in air and inert atmosphere. Crystalline SCNPs were synthesized by laser-assisted reactions in pure acetylene gas flow, chemically treated to obtain well-dispersed SCNPs and then patterned on a substrate by the ion-induced focusing method. Our chemically functionalized SCNP-based gas sensor works for low concentrations of CO and H(2) at room temperature even without Pd or Pt catalysts commonly used for splitting H(2) molecules into reactive H atoms, while metal oxide gas sensors and bare carbon-nanotube-based gas sensors for sensing CO and H(2) molecules can operate only at elevated temperatures. A pristine SCNP-based gas sensor was also examined to prove the role of functional groups formed on the surface of functionalized SCNPs. A pristine SCNP gas sensor showed no response to reducing gases at room temperature but a significant response at elevated temperature, indicating a different sensing mechanism from a chemically functionalized SCNP sensor.

High-resolution submillimeter-wave radiometry of supersonic flow

NASA Technical Reports Server (NTRS)

Dionne, G. F.; Weiss, J. A.; Fitzgerald, J. F.; Fetterman, H. R.; Litvak, M. M.

1983-01-01

The recent development of a high-resolution submillimeter-wave heterodyne radiometer has made possible the first measurements of H2O molecule rotational line excitation temperatures and detailed profiles in supersonic flow. Absorption signals were measured across the flow for the 2/11/ from 2//02/ (752 GHz) para-H2O rotational transition against a hot background. These signals decrease downstream owing to the volume expansion of the gas away from the sonic nozle exit in the high-vacuum chamber. Radiative transfer calculations based on the large-velocity-gradient approximation and multilevel statistical equilibrium agree with these results and with the measured spectral line shapes. The data reveal nearly isentropic gas expansion and cooling. These studies have shown that submillimeter-wave heterodyne radiometry can be useful for remote sensing of supersonic flow with low mass flux, provided the signal transmission is through a dry or thin atmosphere.

A mechanistic model for the superglue fuming of latent fingerprints.

PubMed

Czekanski, Patrick; Fasola, Michael; Allison, John

2006-11-01

The use of superglue vapors to detect latent fingerprints, known as superglue fuming, is a chemical process that has not been fully described. The role of the fingerprint material in the process, leading to formation of methyl cyanoacrylate polymer at the site of the fingerprint, remains to be established. Films of liquid alkanes respond similarly to actual fingerprints in the fuming experiment. Their responses depended on the hydrocarbon used, viscosity, and film thickness. Aspects such as film thickness appear to be relevant for actual fingerprints as well. A model was proposed in light of these observations. The model compares the process with gas chromatography, in which molecules partition between the gas phase and a stationary phase. Aspects such as accumulation of superglue monomers by partitioning into a thin film (or wax) are consistent with the preferential response of fingerprints on surfaces relative to the background.

Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution

NASA Technical Reports Server (NTRS)

Brown, Paul D.; Charnley, S. B.

1991-01-01

The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.

Magnetic trapping of buffer-gas-cooled chromium atoms and prospects for the extension to paramagnetic molecules

NASA Astrophysics Data System (ADS)

Bakker, Joost M.; Stoll, Michael; Weise, Dennis R.; Vogelsang, Oliver; Meijer, Gerard; Peters, Achim

2006-10-01

We report the successful buffer-gas cooling and magnetic trapping of chromium atoms with densities exceeding 1012 atoms per cm3 at a temperature of 350 mK for the trapped sample. The possibilities of extending the method to buffer-gas cool and magnetically trap molecules are discussed. To minimize the most important loss mechanism in magnetic trapping, molecules with a small spin spin interaction and a large rotational constant are preferred. Both the CrH (6Σ+ ground state) and MnH (7Σ+) radicals appear to be suitable systems for future experiments.

Gas-phase geometry optimization of biological molecules as a reasonable alternative to a continuum environment description: fact, myth, or fiction?

PubMed

Sousa, Sérgio Filipe; Fernandes, Pedro Alexandrino; Ramos, Maria João

2009-12-31

Gas-phase optimization of single biological molecules and of small active-site biological models has become a standard approach in first principles computational enzymology. The important role played by the surrounding environment (solvent, enzyme, both) is normally only accounted for through higher-level single point energy calculations performed using a polarizable continuum model (PCM) and an appropriate dielectric constant with the gas-phase-optimized geometries. In this study we analyze this widely used approximation, by comparing gas-phase-optimized geometries with geometries optimized with different PCM approaches (and considering different dielectric constants) for a representative data set of 20 very important biological molecules--the 20 natural amino acids. A total of 323 chemical bonds and 469 angles present in standard amino acid residues were evaluated. The results show that the use of gas-phase-optimized geometries can in fact be quite a reasonable alternative to the use of the more computationally intensive continuum optimizations, providing a good description of bond lengths and angles for typical biological molecules, even for charged amino acids, such as Asp, Glu, Lys, and Arg. This approximation is particularly successful if the protonation state of the biological molecule could be reasonably described in vacuum, a requirement that was already necessary in first principles computational enzymology.

The sensing mechanism of N-doped SWCNTs toward SF6 decomposition products: A first-principle study

NASA Astrophysics Data System (ADS)

Gui, Yingang; Tang, Chao; Zhou, Qu; Xu, Lingna; Zhao, Zhongyong; Zhang, Xiaoxing

2018-05-01

In order to monitor the insulation status of SF6-insulated equipment on-line, SOF2 and SO2F2, two typical decomposition products of SF6 under electric discharge condition, are chosen as the target gases to evaluate the type and severity of discharge. In this work, single N atom doping method is adopted to improve the gas sensitivity of single wall carbon nanotubes to SOF2 and SO2F2. Single and double gas molecules adsorptions are considered to completely analyze the adsorption properties of N-doped single wall carbon nanotubes. Calculation results show that N atom doping enhances the surface activity of carbon nanotubes. When gas molecules physically adsorbed on N-doped single wall carbon nanotubes, the weak interaction between gas molecules and N-doped single wall carbon nanotubes nearly not changes the electrical property according to analysis of the density of states and molecular orbitals. While the chemisorption between gas molecules and N-doped single wall carbon nanotubes distinctly decreases the conductivity of adsorption system.

DFT study of adsorption of picric acid molecule on the surface of single-walled ZnO nanotube; as potential new chemical sensor

NASA Astrophysics Data System (ADS)

Farmanzadeh, Davood; Tabari, Leila

2015-01-01

Using density functional theory (DFT), we have investigated the adsorption of picric acid (PA) molecule on the surface of (8,0) single-walled ZnO nanotube (ZnONT). The results show that the PA molecule can be chemisorbed on the surface of ZnONT with adsorption energies of -82.01 and -75.26 kJ/mol in gas and aqueous phase, respectively. Frontier molecular orbital analysis show that HOMO/LUMO gap of ZnONT reduces from 1.66 and 1.75 eV in the pristine nanotube to 0.83 and 0.72 eV in PA-adsorbed form in gas and aqueous phase, respectively. It suggests that the process can affect the electronic properties of the studied nanotube which would lead to its conductance change upon the adsorption of PA molecule. The modifying effect on the electrical conductance of ZnONT underlies the working mechanism of gas sensors for detecting the PA molecules. Analyses of the adsorption behavior of the electrically charged ZnONT toward PA molecule in the gas phase show that the PA molecule can be strongly adsorbed on the negatively charged ZnONT surface with significant adsorption energy (-135.1 kJ/mol). However, from the HOMO/LUMO gap changes, it can be concluded that the positive ZnONT might sensitively detect the PA molecule in comparison to the negative tube. These results can provide helpful information for experimental investigation to develop novel nanotube-based sensors.

Cryogenic buffer-gas loading and magnetic trapping of CrH and MnH molecules

NASA Astrophysics Data System (ADS)

Stoll, Michael; Bakker, Joost M.; Steimle, Timothy C.; Meijer, Gerard; Peters, Achim

2008-09-01

We report on the buffer-gas cooling and trapping of CrH and MnH molecules in a magnetic quadrupole trap with densities on the order of 106cm-3 at a temperature of 650mK . Storage times of up to 180ms have been observed, corresponding to a 20-fold lifetime enhancement with respect to the field-free diffusion through the He3 buffer-gas. Using Monte Carlo trajectory simulations, inelastic molecule- He3 collision cross sections of 1.6×10-18 and 3.1×10-17cm2 are extracted for CrH and MnH, respectively. Furthermore, elastic molecule- He3 collision cross sections of 1.4(±0.5)×10-14cm2 are determined for both species. We conclude that the confinement time of these molecules in a magnetic trapping field is limited by inelastic collisions with the helium atoms leading to Zeeman relaxation.

Stochastic algorithm for simulating gas transport coefficients

NASA Astrophysics Data System (ADS)

Rudyak, V. Ya.; Lezhnev, E. V.

2018-02-01

The aim of this paper is to create a molecular algorithm for modeling the transport processes in gases that will be more efficient than molecular dynamics method. To this end, the dynamics of molecules are modeled stochastically. In a rarefied gas, it is sufficient to consider the evolution of molecules only in the velocity space, whereas for a dense gas it is necessary to model the dynamics of molecules also in the physical space. Adequate integral characteristics of the studied system are obtained by averaging over a sufficiently large number of independent phase trajectories. The efficiency of the proposed algorithm was demonstrated by modeling the coefficients of self-diffusion and the viscosity of several gases. It was shown that the accuracy comparable to the experimental one can be obtained on a relatively small number of molecules. The modeling accuracy increases with the growth of used number of molecules and phase trajectories.

Time dependent chemistry in dense molecular clouds. I - Grain surface reactions, gas/grain interactions and infrared spectroscopy

NASA Technical Reports Server (NTRS)

Dhendecourt, L. B.; Allamandola, L. J.; Greenberg, J. M.

1985-01-01

For the fist time, a time-dependent model is described which includes the role of grains in the production of molecules in dense clouds including ion-molecule gas phase chemistry. The approach provides information regarding the coupling between the two phases. Although the coupling between the two chemistries is extremely strong, the two domains maintain their own identities. While H2O, CH4, and NH3 are made efficiently, with a high production rate on grains and released back to the gas phase, the gas phase is essentially responsible for the formation of CO, a very stable molecule which may or may not react on grains with atomic oxygen and may or may not form CO2.

Background of the Hammett equation as observed for isolated molecules: meta- and para-substituted benzoic acids.

PubMed

Exner, Otto; Böhm, Stanislav

2002-09-06

Fundamental model compounds for the Hammett equation, meta- and para-substituted benzoic acids, were investigated by the density functional theory at the B3LYP/6-311+G(d,p) level. Energies of 25 acids and of their anions were calculated in all possible conformations and from them the energies of the assumed mixture of conformers. Relative acidities correlated with the experimental gas-phase acidities almost within the experimental uncertainty, much more precisely than in the case of previous calculations at lower levels. Dissection of the substituent effects into those operating in the acid molecule and in the anion was carried out by means of isodesmic reactions starting from monosubstituted benzenes. Both effects are cooperating in the resulting effect on the acidity; those in the acid molecule are smaller but not negligible. They are also responsible for some deviations from the Hammett equation (through-resonance of para donor substituents) and for the weaker resonance in the acid molecule in meta derivatives; in the anions the inductive and resonance effects are almost equal. On the other hand, the cooperation of effects in the acid and in the anion makes the relative acidity more sensitive to electron withdrawing and is probably one of the reasons why the Hammett equation is so generally valid.

Interference-free coherence dynamics of gas-phase molecules using spectral focusing.

PubMed

Wrzesinski, Paul J; Roy, Sukesh; Gord, James R

2012-10-08

Spectral focusing using broadband femtosecond pulses to achieve highly selective measurements has been employed for numerous applications in spectroscopy and microspectroscopy. In this work we highlight the use of spectral focusing for selective excitation and detection of gas-phase species. Furthermore, we demonstrate that spectral focusing, coupled with time-resolved measurements based upon probe delay, allows the observation of interference-free coherence dynamics of multiple molecules and gas-phase temperature making this technique ideal for gas-phase measurements of reacting flows and combustion processes.

Mid infrared emission spectroscopy of carbon plasma.

PubMed

Nemes, Laszlo; Brown, Ei Ei; S-C Yang, Clayton; Hommerich, Uwe

2017-01-05

Mid infrared time-resolved emission spectra were recorded from laser-induced carbon plasma. These spectra constitute the first study of carbon materials LIB spectroscopy in the mid infrared range. The carbon plasma was induced using a Q-switched Nd: YAG laser. The laser beam was focused to high purity graphite pellets mounted on a translation stage. Mid infrared emission from the plasma in an atmospheric pressure background gas was detected by a cooled HgCdTe detector in the range 4.4-11.6μm, using long-pass filters. LIB spectra were taken in argon, helium and also in air. Despite a gate delay of 10μs was used there were strong backgrounds in the spectra. Superimposed on this background broad and noisy emission bands were observed, the form and position of which depended somewhat on the ambient gas. The spectra were digitally smoothed and background corrected. In argon, for instance, strong bands were observed around 4.8, 6.0 and 7.5μm. Using atomic spectral data by NIST it could be concluded that carbon, argon, helium and nitrogen lines from neutral and ionized atoms are very weak in this spectral region. The width of the infrared bands supports molecular origin. The infrared emission bands were thus compared to vibrational features of carbon molecules (excluding C2) of various sizes on the basis of previous carbon cluster infrared absorption and emission spectroscopic analyses in the literature and quantum chemical calculations. Some general considerations are given about the present results. Copyright © 2016 Elsevier B.V. All rights reserved.

Persistent Infrared Spectral Hole-Burning for Impurity Vibrational Modes in Solids.

DTIC Science & Technology

1986-09-30

infrared vibrational transitions of impurity molecules in solids. Examples include 1,2- difluoroethane in rare gas matrices, perrhenate ions in alkali...observed consists of infrared vibrational transitions of impurity molecules in solids. Examples include 1,2- difluoroethane in rare gas matrices...solids. Examples include 1,2- difluoroethane in rare gas matrices, perrhenate ions in alkali halide crystals, and most recently, cyanide and nitrite

Tunable electronic and optical properties of gas molecules adsorbed monolayer graphitic ZnO: Implications for gas sensor and environment monitoring

NASA Astrophysics Data System (ADS)

Zhang, Wei; Du, Qikui; Zhang, Lifa

2017-12-01

Due to the large surface area and the peculiar electronic characters, great attention has been paid to 2D materials for the gas sensing applications. Here, using the hybrid density functional calculations, we systematically study the adsorptions of gas molecules on the monolayer graphitic ZnO (g-ZnO), including CO, H2, H2O, H2S, NH3, NO, NO2, O2, and SO2. For most of the molecules, g-ZnO shows superior sensing performance to the well-known MoS2, black phosphorus, blue phosphorus, antimonene, and germanene. H2S, NO, NO2, and SO2 act as charge acceptors, and CO, H2, H2O, and NH3 serve as charge donors. These molecules also induce distinct modifications to the electronic structures, work functions, and optical adsorptions. NO, NO2, and O2 form flat bands in the bandgaps of the spin-up or spin-down states, whereas other molecules mainly tune the bandgaps and the orbital couplings. In particular, g-ZnO is most likely to adsorb the atmospheric pollutant SO2, which has the strongest interaction through hybridizing its widely broadened 2p orbitals with the 3d orbitals of g-ZnO. Moreover, the improved visible light absorption is demonstrated in the NO2 adsorbed g-ZnO. Our results not only confirm that the electronic and optical properties of g-ZnO can be effectively tuned by the selective adsorption of gas molecules but also provide insightful guidance for the potential application of g-ZnO in the field of gas sensors.

Ergodic properties of the multidimensional rayleigh gas with a semipermeable barrier

NASA Astrophysics Data System (ADS)

Erdős, L.; Tuyen, D. Q.

1990-06-01

We consider a multidimensional system consisting of a particle of mass M and radius r (molecule), surrounded by an infinite ideal gas of point particles of mass m (atoms). The molecule is confined to the unit ball and interacts with its boundary ( barrier) via elastic collision, while the atoms are not affected by the boundary. We obtain convergence to equilibrium for the molecule from almost every initial distribution on its position and velocity. Furthermore, we prove that the infinite composite system of the molecule and the atoms is Bernoulli.

Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

2016-09-01

Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

Advances in structure elucidation of small molecules using mass spectrometry

PubMed Central

Fiehn, Oliver

2010-01-01

The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules. Electronic supplementary material The online version of this article (doi:10.1007/s12566-010-0015-9) contains supplementary material, which is available to authorized users. PMID:21289855

Study on the Characteristics of Gas Molecular Mean Free Path in Nanopores by Molecular Dynamics Simulations

PubMed Central

Liu, Qixin; Cai, Zhiyong

2014-01-01

This paper presents studies on the characteristics of gas molecular mean free path in nanopores by molecular dynamics simulation. Our study results indicate that the mean free path of all molecules in nanopores depend on both the radius of the nanopore and the gas-solid interaction strength. Besides mean free path of all molecules in the nanopore, this paper highlights the gas molecular mean free path at different positions of the nanopore and the anisotropy of the gas molecular mean free path at nanopores. The molecular mean free path varies with the molecule’s distance from the center of the nanopore. The least value of the mean free path occurs at the wall surface of the nanopore. The present paper found that the gas molecular mean free path is anisotropic when gas is confined in nanopores. The radial gas molecular mean free path is much smaller than the mean free path including all molecular collisions occuring in three directions. Our study results also indicate that when gas is confined in nanopores the gas molecule number density does not affect the gas molecular mean free path in the same way as it does for the gas in unbounded space. These study results may bring new insights into understanding the gas flow’s characteristic at nanoscale. PMID:25046745

Three new defined proton affinities for polybasic molecules in the gas-phase: Proton microaffinity, proton macroaffinity and proton overallaffinity

NASA Astrophysics Data System (ADS)

Salehzadeh, Sadegh; Bayat, Mehdi

2006-08-01

A theoretical study on complete protonation of a series of tetrabasic molecules with general formula N[(CH 2) nNH 2][(CH 2) mNH 2][(CH 2) pNH 2] (tren, pee, ppe, tpt, epb and ppb) is reported. For first time, three kinds of gas-phase proton affinities for each polybasic molecule are defined as: 'proton microaffinity (PA n, i)', 'proton macroaffinity (PA)' and 'proton overall affinity ( PA)'. The variations of calculated logPA in the series of these molecules is very similar to that of their measured log Kn. There is also a good correlation between the calculated gas-phase proton macroaffinities and proton overallaffinities with corresponding equilibrium macroconstants and overall protonation constants in solution.

Observing Organic Molecules in Interstellar Gases: Non Equilibrium Excitation.

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent; Faure, Alexandre; Remijan, Anthony; Szalewicz, Krzysztof

2014-06-01

In order to observe quantitatively organic molecules in interstellar gas, it is necessary to understand the relative importance of photonic and collisional excitations. In order to do so, collisional excitation transfer rates have to be computed. We undertook several such studies, in particular for H_2CO and HCOOCH_3. Both species are observed in many astrochemical environments, including star-forming regions. We found that those two molecules behave in their low-lying rotational levels in an opposite way. For cis methyl-formate, a non-equilibrium radiative transfer treatment of rotational lines is performed, using a new set of theoretical collisional rate coefficients. These coefficients have been computed in the temperature range 5 to 30 K by combining coupled-channel scattering calculations with a high accuracy potential energy surface for HCOOCH_3 -- He. The results are compared to observations toward the Sagittarius B2(N) molecular cloud. A total of 2080 low-lying transitions of methyl formate, with upper levels below 25 K, were treated. These lines are found to probe a cold (30 K), moderately dense (n ˜ 104 cm-3) interstellar gas. In addition, our calculations indicate that all detected emission lines with a frequency below 30 GHz are collisionally pumped weak masers amplifying the background of Sgr B2(N). This result demonstrates the generality of the inversion mechanism for the low-lying transitions of methyl formate. For formaldehyde, we performed a similar non-equilibrium treatment, with H_2 as the collisional partner, thanks to the accurate H_2CO - H_2 potential energy surface . We found very different energy transfer rates for collisions with para-H_2 (J=0) and ortho-H_2 (J=1). The well-known absorption against the cosmological background of the 111→ 101 line is shown to depend critically on the difference of behaviour between para and ortho-H_2, for a wide range of H_2 density. We thank the CNRS-PCMI French national program for continuous support and the CHESS Herschel KP program for travel supports. Discussions with C. Ceccarelli, P. Hily-Blant and S. Maret are acknowledged.

Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

PubMed

Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

2016-08-08

Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Calculation of the Electron Transport Parameters and Energy Distribution Function for CF3I with noble gases mixtures using Monte Carlo simulation program

NASA Astrophysics Data System (ADS)

Jawad, Enas A.

2018-05-01

In this paper, The Monte Carlo simulation program has been used to calculation the electron energy distribution function (EEDF) and electric transport parameters for the gas mixtures of The trif leoroiodo methane (CF3I) ‘environment friendly’ with a noble gases (Argon, Helium, kryptos, Neon and Xenon). The electron transport parameters are assessed in the range of E/N (E is the electric field and N is the gas number density of background gas molecules) between 100 to 2000Td (1 Townsend = 10-17 V cm2) at room temperature. These parameters, namely are electron mean energy (ε), the density –normalized longitudinal diffusion coefficient (NDL) and the density –normalized mobility (μN). In contrast, the impact of CF3I in the noble gases mixture is strongly apparent in the values for the electron mean energy, the density –normalized longitudinal diffusion coefficient and the density –normalized mobility. Note in the results of the calculation agreed well with the experimental results.

Ion mobilities in diatomic gases: measurement versus prediction with non-specular scattering models.

PubMed

Larriba, Carlos; Hogan, Christopher J

2013-05-16

Ion/electrical mobility measurements of nanoparticles and polyatomic ions are typically linked to particle/ion physical properties through either application of the Stokes-Millikan relationship or comparison to mobilities predicted from polyatomic models, which assume that gas molecules scatter specularly and elastically from rigid structural models. However, there is a discrepancy between these approaches; when specular, elastic scattering models (i.e., elastic-hard-sphere scattering, EHSS) are applied to polyatomic models of nanometer-scale ions with finite-sized impinging gas molecules, predictions are in substantial disagreement with the Stokes-Millikan equation. To rectify this discrepancy, we developed and tested a new approach for mobility calculations using polyatomic models in which non-specular (diffuse) and inelastic gas-molecule scattering is considered. Two distinct semiempirical models of gas-molecule scattering from particle surfaces were considered. In the first, which has been traditionally invoked in the study of aerosol nanoparticles, 91% of collisions are diffuse and thermally accommodating, and 9% are specular and elastic. In the second, all collisions are considered to be diffuse and accommodating, but the average speed of the gas molecules reemitted from a particle surface is 8% lower than the mean thermal speed at the particle temperature. Both scattering models attempt to mimic exchange between translational, vibrational, and rotational modes of energy during collision, as would be expected during collision between a nonmonoatomic gas molecule and a nonfrozen particle surface. The mobility calculation procedure was applied considering both hard-sphere potentials between gas molecules and the atoms within a particle and the long-range ion-induced dipole (polarization) potential. Predictions were compared to previous measurements in air near room temperature of multiply charged poly(ethylene glycol) (PEG) ions, which range in morphology from compact to highly linear, and singly charged tetraalkylammonium cations. It was found that both non-specular, inelastic scattering rules lead to excellent agreement between predictions and experimental mobility measurements (within 5% of each other) and that polarization potentials must be considered to make correct predictions for high-mobility particles/ions. Conversely, traditional specular, elastic scattering models were found to substantially overestimate the mobilities of both types of ions.

Phoretic Force Measurement for Microparticles Under Microgravity Conditions

NASA Technical Reports Server (NTRS)

Davis, E. J.; Zheng, R.

1999-01-01

This theoretical and experimental investigation of the collisional interactions between gas molecules and solid and liquid surfaces of microparticles involves fundamental studies of the transfer of energy, mass and momentum between gas molecules and surfaces. The numerous applications include particle deposition on semiconductor surfaces and on surfaces in combustion processes, containerless processing, the production of nanophase materials, pigments and ceramic precursors, and pollution abatement technologies such as desulfurization of gaseous effluents from combustion processes. Of particular emphasis are the forces exerted on microparticles present in a nonuniform gas, that is, in gaseous surroundings involving temperature and concentration gradients. These so-called phoretic forces become the dominant forces when the gravitational force is diminished, and they are strongly dependent on the momentum transfer between gas molecules and the surface. The momentum transfer, in turn, depends on the gas and particle properties and the mean free path and kinetic energy of the gas molecules. The experimental program involves the particle levitation system shown. A micrometer size particle is held between two heat exchangers enclosed in a vacuum chamber by means of ac and dc electric fields. The ac field keeps the particle centered on the vertical axis of the chamber, and the dc field balances the gravitational force and the thermophoretic force. Some measurements of the thermophoretic force are presented in this paper.

Gas Hydrates of Coal Layers as a Methane Source in the Atmosphere and Mine Working

NASA Astrophysics Data System (ADS)

Dyrdin, Valery; Shepeleva, Sofya; Kim, Tatiana

2017-11-01

Living conditions of gas hydrates of a methane in a coal matrix as one of possible forms of finding of molecules of a methane in coal layers are considered. However, gas hydrates are formed not in all mineral coals even under the thermobaric conditions corresponding to their equilibrium state as the minimum humidity and the corresponding pore width are necessary for each brand of coal for formation of gas hydrate. It is shown that it depends on electric electrical dipole moment of a macromolecule of coal. Coals of brands K, D, Zh were considered. The electric field created by the surface of coal does not allow molecules of water to carry out threedimensional driving, and they keep on an internal surface of a time. By means of theoretical model operation a dipole - dipole interaction of molecules of water with the steam surface of coal values of energy of fiber interaction for various functional groups located in coal "fringe" which size for the first and second layers does not allow molecules of water to participate in formation of gas hydrates are received. For coals of brands K, Zh, D, considering distribution of a time on radiuses, the percent of moisture, which cannot share in education solid coal of gas solutions, is calculated.

The study of electronic structure and properties of silicene for gas sensor application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wella, Sasfan A.; Syaputra, Marhamni; Wungu, Triati D. K., E-mail: triati@fi.itb.ac.id

2016-03-11

In this study, we investigated the adsorption of gas molecules (H{sub 2}S, CO) on pristine silicene using first principles calculation. The structure, electronic properties, and adsorption energy of H{sub 2}S,CO/silicene are discussed thoroughly. We found that the pristine silicenewith low buckling structure is the most stable as compared with planar and high buckling structures. Silicene was able to detect a gas molecule which can be observed according tothe density of states analysis. Though a gas molecule adsorbed weakly, the electronic properties of the low buckling pristine silicene changed from semi-metal (zero band gap) to semiconductor. The adsorption energy of H{submore » 2}S and CO on silicene is 0.075 eV and 0.06 eV, respectively.« less

Unifying diffusion and seepage for nonlinear gas transport in multiscale porous media

NASA Astrophysics Data System (ADS)

Song, Hongqing; Wang, Yuhe; Wang, Jiulong; Li, Zhengyi

2016-09-01

We unify the diffusion and seepage process for nonlinear gas transport in multiscale porous media via a proposed new general transport equation. A coherent theoretical derivation indicates the wall-molecule and molecule-molecule collisions drive the Knudsen and collective diffusive fluxes, and constitute the system pressure across the porous media. A new terminology, nominal diffusion coefficient can summarize Knudsen and collective diffusion coefficients. Physical and numerical experiments show the support of the new formulation and provide approaches to obtain the diffusion coefficient and permeability simultaneously. This work has important implication for natural gas extraction and greenhouse gases sequestration in geological formations.

Gas separation device based on electrical swing adsorption

DOEpatents

Judkins, Roddie R.; Burchell, Timothy D.

1999-10-26

A method and apparatus for separating one constituent, especially carbon dioxide, from a fluid mixture, such as natural gas. The fluid mixture flows through an adsorbent member having an affinity for molecules of the one constituent, the molecules being adsorbed on the adsorbent member. A voltage is applied to the adsorbent member, the voltage imparting a current flow which causes the molecules of the one constituent to be desorbed from the adsorbent member.

Electrochemistry of single nanobubbles. Estimating the critical size of bubble-forming nuclei for gas-evolving electrode reactions.

PubMed

German, Sean R; Edwards, Martin A; Chen, Qianjin; Liu, Yuwen; Luo, Long; White, Henry S

2016-12-12

In this article, we address the fundamental question: "What is the critical size of a single cluster of gas molecules that grows and becomes a stable (or continuously growing) gas bubble during gas evolving reactions?" Electrochemical reactions that produce dissolved gas molecules are ubiquitous in electrochemical technologies, e.g., water electrolysis, photoelectrochemistry, chlorine production, corrosion, and often lead to the formation of gaseous bubbles. Herein, we demonstrate that electrochemical measurements of the dissolved gas concentration, at the instant prior to nucleation of an individual nanobubble of H 2 , N 2 , or O 2 at a Pt nanodisk electrode, can be analyzed using classical thermodynamic relationships (Henry's law and the Young-Laplace equation - including non-ideal corrections) to provide an estimate of the size of the gas bubble nucleus that grows into a stable bubble. We further demonstrate that this critical nucleus size is independent of the radius of the Pt nanodisk employed (<100 nm radius), and weakly dependent on the nature of the gas. For example, the measured critical surface concentration of H 2 of ∼0.23 M at the instant of bubble formation corresponds to a critical H 2 nucleus that has a radius of ∼3.6 nm, an internal pressure of ∼350 atm, and contains ∼1700 H 2 molecules. The data are consistent with stochastic fluctuations in the density of dissolved gas, at or near the Pt/solution interface, controlling the rate of bubble nucleation. We discuss the growth of the nucleus as a diffusion-limited process and how that process is affected by proximity to an electrode producing ∼10 11 gas molecules per second. Our study demonstrates the advantages of studying a single-entity, i.e., an individual nanobubble, in understanding and quantifying complex physicochemical phenomena.

Laboratory Studies of Stabilities of Heterocyclic Aromatic Molecules: Suggested Gas Phase Ion-Molecule Routes to Production in Interstellar Gas Clouds

NASA Technical Reports Server (NTRS)

Adams, Nigel G.; Fondren, L. Dalila; McLain, Jason L.; Jackson, Doug M.

2006-01-01

Several ring compounds have been detected in interstellar gas clouds, ISC, including the aromatic, benzene. Polycyclic aromatic hydrocarbons, PAHs, have been implicated as carriers of diffuse interstellar bands (DIBs) and unidentified infrared (UIR) bands. Heterocyclic aromatic rings of intermediate size containing nitrogen, possibly PreLife molecules, were included in early searches but were not detected and a recent search for Pyrimidine was unsuccessful. Our laboratory investigations of routes to such molecules could establish their existence in ISC and suggest conditions under which their concentrations would be maximized thus aiding the searches. The stability of such ring compounds (C5H5N, C4H4N2, C5H11N and C4H8O2) has been tested in the laboratory using charge transfer excitation in ion-molecule reactions. The fragmentation paths, including production of C4H4(+), C3H3N(+) and HCN, suggest reverse routes to the parent molecules, which are presently under laboratory investigation as production sources.

A Proposed Dynamic Pressure and Temperature Primary Standard

PubMed Central

Rosasco, Gregory J.; Bean, Vern E.; Hurst, Wilbur S.

1990-01-01

Diatomic gas molecules have a fundamental vibrational motion whose frequency is affected by pressure in a simple way. In addition, these molecules have well defined rotational energy levels whose populations provide a reliable measure of the thermodynamic temperature. Since information concerning the frequency of vibration and the relative populations can be determined by laser spectroscopy, the gas molecules themselves can serve as sensors of pressure and temperature. Through measurements under static conditions, the pressure and temperature dependence of the spectra of selected molecules is now understood. As the time required for the spectroscopic measurement can be reduced to nanoseconds, the diatomic gas molecule is an excellent candidate for a dynamic pressure/temperature primary standard. The temporal response in this case will be limited by the equilibration time for the molecules to respond to changes in local thermodynamic variables. Preliminary feasibility studies suggest that by using coherent anti-Stokes Raman spectroscopy we will be able to measure dynamic pressure up to 108 Pa and dynamic temperature up to 1500 K with an uncertainty of 5%. PMID:28179756

SPECIAL ISSUE DEVOTED TO THE 80TH BIRTHDAY OF S.A. AKHMANOV: Transient coherent anti-Stokes Raman scattering spectroscopy as a tool for measuring the diffusion coefficient and size of gas molecules

NASA Astrophysics Data System (ADS)

Nikitin, Sergei Yu

2009-07-01

Formulas are derived for evaluating the diffusion coefficient and size of gas molecules from transient coherent anti-Stokes Raman scattering measurements. Numerical estimates are presented for hydrogen.

Measurement of the orientation of buffer-gas-cooled, electrostatically-guided ammonia molecules

NASA Astrophysics Data System (ADS)

Steer, Edward W.; Petralia, Lorenzo S.; Western, Colin M.; Heazlewood, Brianna R.; Softley, Timothy P.

2017-02-01

The extent to which the spatial orientation of internally and translationally cold ammonia molecules can be controlled as molecules pass out of a quadrupole guide and through different electric field regions is examined. Ammonia molecules are collisionally cooled in a buffer gas cell, and are subsequently guided by a three-bend electrostatic quadrupole into a detection chamber. The orientation of ammonia molecules is probed using (2 + 1) resonance-enhanced multiphoton ionisation (REMPI), with the laser polarisation axis aligned both parallel and perpendicular to the time-of-flight axis. Even with the presence of a near-zero field region, the ammonia REMPI spectra indicate some retention of orientation. Monte Carlo simulations propagating the time-dependent Schrödinger equation in a full basis set including the hyperfine interaction enable the orientation of ammonia molecules to be calculated - with respect to both the local field direction and a space-fixed axis - as the molecules pass through different electric field regions. The simulations indicate that the orientation of ∼95% of ammonia molecules in JK =11 could be achieved with the application of a small bias voltage (17 V) to the mesh separating the quadrupole and detection regions. Following the recent combination of the buffer gas cell and quadrupole guide apparatus with a linear Paul ion trap, this result could enable one to examine the influence of molecular orientation on ion-molecule reaction dynamics and kinetics.

Study the Formation of H2, HD and D2 under Various Interstellar Conditions

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Chakrabarti, Sandip Kumar; Das, Ankan

2016-07-01

Hydrogen is the most abundant molecule in the Interstellar medium (ISM). Formation of gas phase hydrogen molecule is inefficient; perhaps grain surface acts as a necessary ingredients for the formation of H_2 molecule. H atoms accrete on the grain surface, recombine there and desorb in the gas phase. Similarly, deuterium accretion on grain surfaces can produce simple dueterated molecules (HD and D_2) on the ISM. Unlike gas phase reactions, rate equations can not yield accurate result for grain surface reactions due to inherent randomness of surface species. We use Monte-Carlo method to follow this surface chemistry which effectively take care of this randomness. We use square grids and impose periodic boundary condition on them to mimic the spherical nature of grains. Various types of rough surfaces are considered to study the impact on effective production rates. We found that these simple but most important molecules are produced in low temperature (physisorption sites) as well as in high temperature (chemisorption sites) regions.

Difficulties in Laboratory Studies and Astronomical Observations of Organic Molecules: Hydroxyacetone and Lactic Acid

NASA Technical Reports Server (NTRS)

Apponi, A. J.; Brewster, M. A.; Hoy, J.; Ziurys, L. M.

2006-01-01

For the past 35 years, radio astronomy has revealed a rich organic chemistry in the interstellar gas, which is exceptionally complex towards active star-forming regions. New solar systems condense out of this gas and may influence the evolution of life on newly formed planets. Much of the biologically important functionality is present among the some 130 gas-phase molecules found to date, including alcohols, aldehydes, ketones, acids, amines, amides and even the simplest sugar - glycolaldehyde. Still, many unidentified interstellar radio signals remain, and their identification relies on further laboratory study. The molecules hydroxyacetone and lactic acid are relatively small organic molecules, but possess rather complex rotational spectra owing to their high asymmetry. Hydroxyacetone is particularly problematic because it possess a very low barrier to internal rotation, and exhibits strong coupling of the free-rotor states with the overall rotation of the molecule. As in the case of acetamide, a full decomposition method was employed to order the resultant eigenstates onto normal asymmetric top eigenvectors.

Composition and method for hydrogen storage

NASA Technical Reports Server (NTRS)

Mao, Wendy L. (Inventor); Mao, Ho-Kwang (Inventor)

2004-01-01

A method for hydrogen storage includes providing water and hydrogen gas to a containment volume, reducing the temperature of the water and hydrogen gas to form a hydrogen clathrate at a first cryogenic temperature and a first pressure and maintaining the hydrogen clathrate at second cryogenic temperature within a temperature range of up to 250 K to effect hydrogen storage. The low-pressure hydrogen hydrate includes H.sub.2 O molecules, H.sub.2 molecules and a unit cell including polyhedron cages of hydrogen-bonded frameworks of the H.sub.2 O molecules built around the H.sub.2 molecules.

Effects of the surroundings and conformerisation of n-dodecane molecules on evaporation/condensation processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gun’ko, Vladimir M.; Sir Harry Ricardo Laboratories, School of Computing, Engineering and Mathematics, University of Brighton, Cockcroft Building, Lewes Road, Brighton BN2 4GJ; Nasiri, Rasoul

2015-01-21

The evaporation/condensation coefficient (β) and the evaporation rate (γ) for n-dodecane vs. temperature, gas pressure, gas and liquid density, and solvation effects at a droplet surface are analysed using quantum chemical density functional theory calculations of several ensembles of conformers of n-dodecane molecules in the gas phase (hybrid functional ωB97X-D with the cc-pVTZ and cc-pVDZ basis sets) and in liquid phase (solvation method: SMD/ωB97X-D). It is shown that β depends more strongly on a number of neighbouring molecules interacting with an evaporating molecule at a droplet surface (this number is estimated through changes in the surface Gibbs free energy ofmore » solvation) than on pressure in the gas phase or conformerisation and cross-conformerisation of molecules in both phases. Thus, temperature and the surrounding effects at droplet surfaces are the dominant factors affecting the values of β for n-dodecane molecules. These values are shown to be similar (at reduced temperatures T/T{sub c} < 0.8) or slightly larger (at T/T{sub c} > 0.8) than the values of β calculated by the molecular dynamics force fields (MD FF) methods. This endorses the reliability of the previously developed classical approach to estimation of β by the MD FF methods, except at temperatures close to the critical temperature.« less

Theoretical contamination of cryogenic satellite telescopes

NASA Technical Reports Server (NTRS)

Murakami, M.

1978-01-01

The state of contaminant molecules, the deposition rate on key surfaces, and the heat transfer rate were estimated by the use of a zeroth-order approximation. Optical surfaces of infrared telescopes cooled to about 20 K should be considered to be covered with at least several deposition layers of condensible molecules without any contamination controls. The effectiveness of the purge gas method of contamination controls was discussed. This method attempts to drive condensible molecules from the telescope tube by impacts with a purge gas in the telescope tube. For this technique to be sufficiently effective, the pressure of the purge gas must be more than 2 x .000001 torr. The influence caused by interactions of the purged gas with the particulate contaminants was found to slightly increase the resident times of the particulate contaminants within the telescope field of view.

Anti-site defected MoS2 sheet-based single electron transistor as a gas sensor

NASA Astrophysics Data System (ADS)

Sharma, Archana; Husain, Mushahid; Srivastava, Anurag; Khan, Mohd. Shahid

2018-05-01

To prevent harmful and poisonous CO gas molecules, catalysts are needed for converting them into benign substances. Density functional theory (DFT) calculations have been used to study the adsorption of CO and CO2 gas molecules on the surface of MoS2 monolayer with Mo atom embedded at S-vacancy site (MoS). The strong interaction between Mo metal with pristine MoS2 sheet suggests its strong binding nature. Doping Mo into MoS2 sheet enhances CO and CO2 adsorption strength. The sensing response of MoS-doped MoS2 system to CO and CO2 gas molecules is obtained in the single electron transistor (SET) environment by varying bias voltage. Doping reduces charging energy of the device which results in fast switching of the device from OFF to ON state.

Photoinduced nucleation: a novel tool for detecting molecules in air at ultra-low concentrations

DOEpatents

Katz, Joseph L.; Lihavainen, Heikki; Rudek, Markus M.; Salter, Brian C.

2002-01-01

A method and apparatus for determining the presence of molecules in a gas at concentrations of less than about 100 ppb. Light having wavelengths in the range from about 200 nm to about 350 nm is used to illuminate a flowing sample of the gas causing the molecules if present to form clusters. A mixture of the illuminated gas and a vapor is cooled until the vapor is supersaturated so that there is a small rate of homogeneous nucleation. The supersaturated vapor condenses on the clusters thus causing the clusters to grow to a size sufficient to be counted by light scattering and then the clusters are counted.

Method and source for producing a high concentration of positively charged molecular hydrogen or deuterium ions

DOEpatents

Ehlers, K.W.; Leung, K.N.

1983-07-26

One principal object of the present invention is to provide a novel method and apparatus for generating a high concentration of H/sub 2//sup +/ or D/sub 2//sup +/ ions by using a new and improved multicusp ion source. The basic principle in achieving a high percentage of H/sub 2//sup +/ or D/sub 2//sup +/ ions is to extract them from the source as soon as they are produced. Otherwise they will react with background gas molecules to form tri-atomic ions H/sub 3//sup +/ or D/sub 3//sup +/ or be dissociated by electrons. The former reaction H/sub 2//sup +/ + H/sub 2/ ..-->.. H/sub 3//sup +/ + H can have a very short mean free path length lambda. Assuming a background neutral gas density of approximately 3.3 x 10/sup 13/ cm/sup -3/ and a cross-section sigma of approximately 6 x 10/sup -15/ cm/sup 2/, lambda = (n/sub 0/ sigma)/sup -1/ is estimated to be about 5 cm. Thus the distance traversed by the H/sub 2//sup +/ ion before it arrives at the extractor electrode cannot exceed this value. This in turn sets a limit on the length of the source chamber.

Electronic properties and gas adsorption behaviour of pristine, silicon-, and boron-doped (8, 0) single-walled carbon nanotube: A first principles study.

PubMed

Azam, Mohd Asyadi; Alias, Farizul Muiz; Tack, Liew Weng; Seman, Raja Noor Amalina Raja; Taib, Mohamad Fariz Mohamad

2017-08-01

Carbon nanotubes (CNTs) have received enormous attention due to their fascinating properties to be used in various applications including electronics, sensing, energy storage and conversion. The first principles calculations within density functional theory (DFT) have been carried out in order to investigate the structural, electronic and optical properties of un-doped and doped CNT nanostructures. O 2 , CO 2 , and CH 3 OH have been chosen as gas molecules to study the adsorption properties based on zigzag (8,0) SWCNTs. The results demonstrate that the adsorption of O 2 , CO 2, and CH 3 OH gas molecules on pristine, Si-doped and B-doped SWCNTs are either physisorption or chemisorption. Moreover, the electronic properties indicating SWCNT shows significant improvement toward gas adsorption which provides the impact of selecting the best gas sensor materials towards detecting gas molecule. Therefore, these pristine, Si-, and B-doped SWCNTs can be considered to be very good potential candidates for sensing application. Copyright © 2017 Elsevier Inc. All rights reserved.

Measurements of water molecule density by tunable diode laser absorption spectroscopy in dielectric barrier discharges with gas-water interface

NASA Astrophysics Data System (ADS)

Tachibana, Kunihide; Nakamura, Toshihiro; Kawasaki, Mitsuo; Morita, Tatsuo; Umekawa, Toyofumi; Kawasaki, Masahiro

2018-01-01

We measured water molecule (H2O) density by tunable diode-laser absorption spectroscopy (TDLAS) for applications in dielectric barrier discharges (DBDs) with a gas-water interface. First, the effects of water temperature and presence of gas flow were tested using a Petri dish filled with water and a gas injection nozzle. Second, the TDLAS system was applied to the measurements of H2O density in two types of DBDs; one was a normal (non-inverted) type with a dielectric-covered electrode above a water-filled counter electrode and the other was an inverted type with a water-suspending mesh electrode above a dielectric-covered counter electrode. The H2O density in the normal DBD was close to the density estimated from the saturated vapor pressure, whereas the density in the inverted DBD was about half of that in the former type. The difference is attributed to the upward gas flow in the latter type, that pushes the water molecules up towards the gas-water interface.

Theory of gas hydrates: effect of the approximation of rigid water lattice.

PubMed

Pimpalgaonkar, Hrushikesh; Veesam, Shivanand K; Punnathanam, Sudeep N

2011-08-25

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed. © 2011 American Chemical Society

Liquid and gas phase NMR spectra of 13CH313CHO acetaldehyde

NASA Astrophysics Data System (ADS)

Makulski, Włodzimierz; Wikieł, Agata J.

2018-01-01

The gas phase NMR experiments perform a vital role in establishing the magnetic shielding and spin-spin coupling constants which are free from intermolecular interactions, equivalent to the parameter of isolated molecules. This work is concerned with an acetaldehyde molecule. Small amounts of acetaldehyde 13CH313CHO in gaseous matrices of CO2 and Xe were studied using high-precision 1H and 13C NMR measurements. Results were extrapolated to the zero-density limit permitting the determinations of the 1H and 13C absolute nuclear magnetic shielding of an isolated acetaldehyde molecule. The difference between the experimental and recent theoretical DFT results is discussed. Several samples of 13CH313CHO dissolved in popular organic and inorganic solvents were also investigated. Gas-to-solution shifts show the influence of the association process when acetaldehyde is transferred from gas to liquid state. Several spin-spin coupling constants in the gas phase and in different solvents were precisely measured.

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

NASA Technical Reports Server (NTRS)

Millan, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Glavin, D. P.; Freissinet, C.; Eigenbrode, J. L.; Archer, P. D., Jr,; Sutter, B.; Mahaffy, P.

2017-01-01

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Simulations of Propane and Butane Gas Sensor Based on Pristine Armchair Graphene Nanoribbon

NASA Astrophysics Data System (ADS)

Rashid, Haroon; Koel, Ants; Rang, Toomas

2018-05-01

Over the last decade graphene and its derivatives have gained a remarkable place in research field. As silicon technology is approaching to its geometrical limits so there is a need of alternate that can replace it. Graphene has emerged as a potential candidate for future nano-electronics applications due to its exceptional and extraordinary chemical, optical, electrical and mechanical properties. Graphene based sensors have gained significance for a wide range of sensing applications like detection of biomolecules, chemicals and gas molecules. It can be easily used to make electrical contacts and manipulate them according to the requirements as compared to the other nanomaterials. The intention of the work presented in this article is to contribute in this field by simulating a novel and cheap graphene nanoribbon sensor for the household gas leakage detection. QuantumWise Atomistix (ATK) software is used for the simulations of propane and butane gas sensor. Projected device density of the states (PDDOS) and the transmission spectrum of the device in the proximity of gas molecules are calculated and discussed. The change in the electric current through the device in the presence of the gas molecules is used as a gas detection mechanism for the simulated sensor.

Analytical vacuum force, atmospheric pressure dispute

NASA Astrophysics Data System (ADS)

Yongquan, Han

Typically, the gap gas molecules is 10-9 m, since the center speed of the tornado is over 100 m / sec, it divided by the speed of a tornado, the gap of the gas molecules becomes 10-11m. Equivalent to the gap when there is no tornado that the gas molecules allow radiation to pass through, equivalent to the gap is reduced gas molecules 100 times by a tornado. There is no change in the Earth's radiate, the Earth's radiation is reduced to one percent of the original intensity by the radiation through the tornado periphery into the center of the tornado. According to the APS Division of Nuclear Physics in APS -2013 Fall Meeting - Event - Gravitational radiation theory http://meetings.aps.org/Meeting/DNP13/Session/FB.8, which I published, the gravity will br reduced to the original gravity percentage one. Waterspout by the Earth's gravity to become the original one percent. Cause the external of the tornadoes atmospheric pressure is constant, the height waterspout should support column height atmospheric pressure is 100 times,that height waterspout may reach nearly kilometers.

Receptors useful for gas phase chemical sensing

DOEpatents

Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A

2015-02-17

The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

A theoretical study on metal atom-modified BC3 sheets for effects of gas molecule adsorptions

NASA Astrophysics Data System (ADS)

Tang, Yanan; Cui, Xiao; Chen, Weiguang; Zhu, Dalei; Chai, Huaduo; Dai, Xianqi

2018-06-01

Based on the first-principle calculations, the chemical reactivity of transition metal (Fe, Co, Ni, and Cu) dopants within BC3 sheets toward toxic gas molecules (CO, NO, NO2, SO2, and HCN) is comparably investigated. First, the adsorbed gases on metal-modified BC3 sheets exhibit the different stability. Compared with other gases, the metal-modified BC3 substrates exhibit the stronger affinity toward the NO and NO2 molecules (> 1.0 eV), while the adsorbed HCN has the smallest adsorption energy, illustrating that the NO and NO2 as specific toxic gas molecule can be easily detected. Second, the adsorbed gas molecules can effectively regulate the electronic structure and magnetic property of BC3 systems. Fox example, the strong adsorption of NO and NO2 on Fe-modified BC3 systems exhibits non-magnetic property, yet these gases on Co modified BC3 systems exhibit the magnetic character. In addition, the adsorbed NO and SO2 can induce and turn the degree of magnetic moments of Ni- and Cu-modified BC3 systems. Therefore, the different kinds of adsorbed gases on metal-modified BC3 sheets can be distinguished through investigating the changed magnetic moments of system, which would provide important information for designing the functional BC3-based materials.

Interactions of gaseous molecules with X-ray photons and photoelectrons in AP-XPS study of solid surface in gas phase.

PubMed

Tao, Franklin Feng; Nguyen, Luan

2018-04-18

Studies of the surface of a catalyst in the gas phase via photoelectron spectroscopy is an important approach to establish a correlation between the surface of a catalyst under reaction conditions or during catalysis and its corresponding catalytic performance. Unlike the well understood interactions between photoelectrons and the atomic layers of a surface in ultrahigh vacuum (UHV) and the well-developed method of quantitative analysis of a solid surface in UHV, a fundamental understanding of the interactions between X-ray photons and gaseous molecules and between photoelectrons and molecules of the gas phase in ambient pressure X-ray photoelectron spectroscopy (AP-XPS) is lacking. Through well designed experiments, here the impact of the interactions between photoelectrons and gaseous molecules and interactions between X-ray photons and gaseous molecules on the intensity of the collected photoelectrons have been explored. How the changes in photoelectron intensity resulting from these interactions influence measurement of the authentic atomic ratio of element M to A of a solid surface has been discussed herein, and methods to correct the measured nominal atomic ratio of two elements of a solid surface upon travelling through a gas phase to its authentic atomic ratio have been developed.

Light-powered micromotor driven by geometry-assisted, asymmetric photon-heating and subsequent gas convection

NASA Astrophysics Data System (ADS)

Han, Li-Hsin; Wu, Shaomin; Condit, J. Christopher; Kemp, Nate J.; Milner, Thomas E.; Feldman, Marc D.; Chen, Shaochen

2010-05-01

We report on the design, fabrication, and analysis of a light-driven micromotor. The micromotor was created from a nanoporous polymer with close-packed gold nanoparticles which generate heat by absorbing light. The blades of the micromotor were curved, forming convex and concave sides. Upon lateral irradiation, by geometric effect the convex side transfers more photon-generated heat to the surrounding gas molecules, causing a convective motion of gas and leading to the rotation of the micromotor. The light-driven motions of gas molecules were analyzed using molecular dynamics modeling.

Exchange and correlation in positronium-molecule scattering

NASA Astrophysics Data System (ADS)

Fabrikant, I. I.; Wilde, R. S.

2018-05-01

Exchange and correlations play a particularly important role in positronium (Ps) collisions with atoms and molecules, since the static potential for Ps interaction with a neutral system is zero. Theoretical description of both effects is a very challenging task. In the present work we use the free-electron-gas model to describe exchange and correlations in Ps collisions with molecules similar to the approach widely used in the theory of electron-molecule collisions. The results for exchange and correlation energies are presented as functions of the Fermi momentum of the electron gas and the Ps incident energy. Using the Thomas-Fermi model, these functions can be converted into exchange and correlation potentials for Ps interaction with molecules as functions of the distance between the projectile and the target.

Natural Gas Evolution in a Gas Hydrate Melt: Effect of Thermodynamic Hydrate Inhibitors.

PubMed

Sujith, K S; Ramachandran, C N

2017-01-12

Natural gas extraction from gas hydrate sediments by injection of hydrate inhibitors involves the decomposition of hydrates. The evolution of dissolved gas from the hydrate melt is an important step in the extraction process. Using classical molecular dynamics simulations, we study the evolution of dissolved methane from its hydrate melt in the presence of two thermodynamic hydrate inhibitors, NaCl and CH 3 OH. An increase in the concentration of hydrate inhibitors is found to promote the nucleation of methane nanobubbles in the hydrate melt. Whereas NaCl promotes bubble formation by enhancing the hydrophobic interaction between aqueous CH 4 molecules, CH 3 OH molecules assist bubble formation by stabilizing CH 4 bubble nuclei formed in the solution. The CH 3 OH molecules accumulate around the nuclei leading to a decrease in the surface tension at their interface with water. The nanobubbles formed are found to be highly dynamic with frequent exchange of CH 4 molecules between the bubble and the surrounding liquid. A quantitative analysis of the dynamic behavior of the bubble is performed by introducing a unit step function whose value depends on the location of CH 4 molecules with respect to the bubble. It is observed that an increase in the concentration of thermodynamic hydrate inhibitors reduces the exchange process, making the bubble less dynamic. It is also found that for a given concentration of the inhibitor, larger bubbles are less dynamic compared to smaller ones. The dependence of the dynamic nature of nanobubbles on bubble size and inhibitor concentration is correlated with the solubility of CH 4 and the Laplace pressure within the bubble. The effect of CO 2 on the formation of nanobubble in the CH 4 -CO 2 mixed gas hydrate melt in the presence of inhibitors is also examined. The simulations show that the presence of CO 2 molecules significantly reduces the induction time for methane nanobubble nucleation. The role of CO 2 in the early nucleation of bubble is explained based on the interaction between the bubble and the dissolved CO 2 molecules.

BN-C Hybrid Nanoribbons as Gas Sensors

NASA Astrophysics Data System (ADS)

Darvishi Gilan, Mahdi; Chegel, Raad

2018-02-01

The effects of carbon monoxide (CO) and ammonia (NH3) molecules adsorption on the various composites of boron nitride and graphene BN-C hybrid nanoribbons are investigated using the non-equilibrium Green's function (NEGF) technique based on density functional theory (DFT). The effects of adsorption with possible random configurations on the average of the density of states (DOS), transmission coefficient, and the current-voltage ( I- V) characteristics are calculated. The results indicate that, by embedding armchair graphene nanoribbon (AGNR) with boron nitride nanoribbon (BNNR), the various electronic properties can be observed after gas molecule adsorption. The electronic structure and gap of hybrids system is modified due to gas adsorption, and the systems act like the n-type semiconductor by NH3 molecule adsorption. The hybrid structures due to their tunable band gap are better candidates for gas detecting compared to the pristine BNNRs and AGNRs.

The Chemistry and Excitation of Water in Molecular Clouds

NASA Technical Reports Server (NTRS)

Hollenbach, David

2003-01-01

We model the chemistry and thermal balance of opaque molecular clouds exposed to an external flux of ultraviolet photons. We include the processes of gas phase and grain surface chemical reactions; in particular we examine closely the freezing of atoms and molecules onto grain surfaces and the desorption of molecules from grain surfaces as a function of depth into a molecular cloud. We find that on the surface of a molecular cloud the gas phase water abundances are low because of photodissociation, and the grain phase water (ice) abundance is low because of photodesorption of water from the grain surfaces. Deeper into the cloud, at A(sub v) less than or approximately 2-8 depending on the strength of the external ultraviolet flux, the gas phase water abundance increases with depth as the photodissociation rates decline due to dust attenuation of the ultraviolet field. However, beyond A(sub v) less than or approximately 2-8 the gas phase water abundance declines because the water freezes as water ice on the grains, and photodesorption is no longer effective in clearing the ice. A peak water abundance of about 10(exp -6) to 10(exp -7) occurs at about A(sub v) approximately 2-8, relatively independent of the gas density and the ultraviolet field. We show that such a model matches very closely the observations of the Submillimeter Wave Astronomical Satellite (SWAS), a NASA Small Explorer Mission. The model elucidates several mechanisms that have been recently invoked to understand gas phase chemistry in clouds, including-the freeze-out of molecules onto grain surface, the desorption of these molecules from the surfaces, and the abundance gradients of molecules as functions of depth into molecular clouds.

Applying Alkyl-Chain Surface Functionalizations in Mesoporous Inorganic Structures: Their Impact on Gas Flow and Selectivity Depending on Temperature.

PubMed

Besser, Benjamin; Ahmed, Atiq; Baune, Michael; Kroll, Stephen; Thöming, Jorg; Rezwan, Kurosch

2016-10-12

Porous inorganic capillary membranes are prepared to serve as model structures for the experimental investigation of the gas transport in functionalized mesopores. The porous structures possess a mean pore diameter of 23 nm which is slightly reduced to 20 nm after immobilizing C 16 -alkyl chains on the surface. Gas permeation measurements are performed at temperatures ranging from 0 to 80 °C using Ar, N 2 , and CO 2 . Nonfunctionalized structures feature a gas transport according to Knudsen diffusion with regard to gas flow and selectivity. After C 16 -functionalization, the gas flow is reduced by a factor of 10, and the ideal selectivities deviate from the Knudsen theory. CO 2 adsorption measurements show a decrease in total amount of adsorbed gas and isosteric heat of adsorption. It is hypothesized that the immobilized C 16 -chains sterically influence the gas transport behavior without a contribution from adsorption effects. The reduced gas flow derives from an additional surface resistance caused by the C 16 -chains spacially limiting the adsorption and desorption directions for gas molecules propagating through the structure, resulting in longer diffusion paths. In agreement, the gas flow is found to correlate with the molecular diameter of the gas species (CO 2 < Ar < N 2 ) increasing the resistance for larger molecules. This affects the ideal selectivities with the relation [Formula: see text]. The influence on selectivity increases with increasing temperature which leads to the conclusion that the temperature induced movement of the C 16 -chains is responsible for the stronger interaction between gas molecules and surface functional groups.

Shielding concepts for low-background proportional counter arrays in surface laboratories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aalseth, Craig E.; Humble, Paul H.; Mace, Emily K.

2016-02-01

Development of ultra low background gas proportional counters has made the contribution from naturally occurring radioactive isotopes – primarily and activity in the uranium and thorium decay chains – inconsequential to instrumental sensitivity levels when measurements are performed in above ground surface laboratories. Simple lead shielding is enough to mitigate against gamma rays as gas proportional counters are already relatively insensitive to naturally occurring gamma radiation. The dominant background in these surface laboratory measurements using ultra low background gas proportional counters is due to cosmic ray generated muons, neutrons, and protons. Studies of measurements with ultra low background gas proportionalmore » counters in surface and underground laboratories as well as radiation transport Monte Carlo simulations suggest a preferred conceptual design to achieve the highest possible sensitivity from an array of low background gas proportional counters when operated in a surface laboratory. The basis for a low background gas proportional counter array and the preferred shielding configuration is reported, especially in relation to measurements of radioactive gases having low energy decays such as 37Ar.« less

Alternative Fuels Data Center: Filling CNG Fuel Tanks

Science.gov Websites

, therefore containing less energy by volume when the fuel system reaches the rated pressure. For this reason because when gas molecules are compressed, they create heat. The faster they are compressed, the more they heat up and expand. So when the gas is compressed rapidly through a fast-fill process, the molecules

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

Mapping of local argon impingement on a virtual surface: an insight for gas injection during FEBID

NASA Astrophysics Data System (ADS)

Wanzenboeck, H. D.; Hochleitner, G.; Mika, J.; Shawrav, M. M.; Gavagnin, M.; Bertagnolli, E.

2014-12-01

During the last decades, focused electron beam induced deposition (FEBID) has become a successful approach for direct-write fabrication of nanodevices. Such a deposition technique relies on the precursor supply to the sample surface which is typically accomplished by a gas injection system using a tube-shaped injector nozzle. This precursor injection strategy implies a position-dependent concentration gradient on the surface, which affects the geometry and chemistry of the final nanodeposit. Although simulations already proposed the local distribution of nozzle-borne gas molecules impinging on the surface, this isolated step in the FEBID process has never been experimentally measured yet. This work experimentally investigates the local distribution of impinging gas molecules on the sample plane, isolating the direct impingement component from surface diffusion or precursor depletion by deposition. The experimental setup used in this work maps and quantifies the local impinging rate of argon gas over the sample plane. This setup simulates the identical conditions for a precursor molecule during FEBID. Argon gas was locally collected with a sniffer tube, which is directly connected to a residual gas analyzer for quantification. The measured distribution of impinging gas molecules showed a strong position dependence. Indeed, a 300-µm shift of the deposition area to a position further away from the impingement center spot resulted in a 50 % decrease in the precursor impinging rate on the surface area. With the same parameters, the precursor distribution was also simulated by a Monte Carlo software by Friedli and Utke and showed a good correlation between the empirical and the simulated precursor distribution. The results hereby presented underline the importance of controlling the local precursor flux conditions in order to obtain reproducible and comparable deposition results in FEBID.

Fe-doped graphene nanosheet as an adsorption platform of harmful gas molecules (CO, CO2, SO2 and H2S), and the co-adsorption in O2 environments

NASA Astrophysics Data System (ADS)

Cortés-Arriagada, Diego; Villegas-Escobar, Nery; Ortega, Daniela E.

2018-01-01

The adsorption of pollutant gases (CO, CO2, SO2 and H2S) onto Fe-doped graphene nanosheets (FeG) is studied on the basis of density functional theory calculations at the PBE/Def2-SVP level of theory. The most stable adsorption configurations, binding characteristics, electronic properties and stability at room temperature of the FeG-Gas interactions is fully analyzed. The gas molecules are chemisorbed onto FeG with adsorption energies in the range of 0.54-1.8 eV, with an enhanced adsorption strength compared to intrinsic graphene. The stability of the FeG-Gas interactions is dominated by Lewis-acid-base interactions, and its strength is sorted as SO2 > CO > H2S > CO2. The adsorption stability is also retained at room temperature (300 K). Due to the strong interaction of SO2, CO, and H2S, FeG could catalyze or activate these gas molecules, suggesting the possibility of FeG as a catalyst substrate. The electron acceptor/donor character of CO, CO2, SO2 and H2S molecules when adsorbed onto FeG causes charge transfer processes that are responsible for the change in conductance of FeG; thus, the response of the HOMO-LUMO gap of FeG under gas adsorption could be useful for sensing applications. Furthermore, the analysis of the co-adsorption in O2 environments shows that the CO2 interaction turns unstable onto FeG, while the sensing response towards H2S is suppressed. Finally, these results give new insights into the emerging applications of Fe-doped graphene in gas capture/filtration devices, solid-state gas sensors or as a catalyst substrate.

Characterization of Vacuum Facility Background Gas Through Simulation and Considerations for Electric Propulsion Ground Testing

NASA Technical Reports Server (NTRS)

Yim, John T.; Burt, Jonathan M.

2015-01-01

The background gas in a vacuum facility for electric propulsion ground testing is examined in detail through a series of cold flow simulations using a direct simulation Monte Carlo (DSMC) code. The focus here is on the background gas itself, its structure and characteristics, rather than assessing its interaction and impact on thruster operation. The background gas, which is often incorrectly characterized as uniform, is found to have a notable velocity within a test facility. The gas velocity has an impact on the proper measurement of pressure and the calculation of ingestion flux to a thruster. There are also considerations for best practices for tests that involve the introduction of supplemental gas flows to artificially increase the background pressure. All of these effects need to be accounted for to properly characterize the operation of electric propulsion thrusters across different ground test vacuum facilities.

Fluorescence spectroscopy of trapped molecular ions

NASA Astrophysics Data System (ADS)

Wright, Kenneth Charles

This thesis describes the development of a unique instrument capable of detecting fluorescence emission from large gas phase molecular ions trapped in a three-dimensional quadrupole ion trap. The hypothesis that has formed the basis of this work is the belief that fluorescence spectroscopy can be combined with ion trap mass spectrometry to probe the structure of gas phase molecular ions. The ion trap provides a rarefied environment where fluorescence experiments can be conducted without interference from solvent molecules or impurities. Although fluorescence was not detected during preliminary experiments, two significant experimental challenges associated with detecting the gas phase fluorescence of ions were discovered. First, gas phase ions were vulnerable to photodissociation and low laser powers were necessary to avoid photodissociation. Since fluorescence emission is directly proportional to laser intensity, a lower laser power limits the fluorescence signal. Second, the fluorescence emission was not significantly Stokes shifted from the excitation. The lack of Stokes shift meant the small fluorescence signal must be detected in the presence of a large amount of background scatter generated by the excitation. Initially, this background was seven orders of magnitude higher than the analytical signal ultimately detected. A specially designed fiber optic probe was inserted between the electrodes of the ion trap to stop light scattered off the outside surfaces of the trap from reaching the detector. The inside surfaces of the ion trap were coated black to further reduce the amount of scattered light collected. These innovations helped reduced the background by six orders of magnitude and fluorescence emission from rhodamine-6G was detected. Pulse counting experiments were used to optimize fluorescence detection. The effects of trapping level, laser power, and irradiation time were investigated and optimized. The instrument developed in this work not only allows for the detection of fluorescent photons, but the sensitivity is high enough for the light to be dispersed and an emission spectrum recorded. The emission spectra of rhodamine-6G and 5-carboxyrhodamine-6G ions reported in this thesis represent the first spectra recorded from large molecular ions confined in a quadrupole ion trap. Finally, anti-Stokes fluorescence from rhodamine-6G was also detected.

Infrared monitoring of the Space Station environment

NASA Technical Reports Server (NTRS)

Kostiuk, Theodor; Jennings, Donald E.; Mumma, Michael J.

1988-01-01

The measurement and monitoring of infrared emission in the environment of the Space Station has a twofold importance - for the study of the phenomena itself and as an aid in planning and interpreting Station based infrared experiments. Spectral measurements of the infrared component of the spacecraft glow will, along with measurements in other spectral regions, provide data necessary to fully understand and model the physical and chemical processes producing these emissions. The monitoring of the intensity of these emissions will provide background limits for Space Station based infrared experiments and permit the determination of optimum instrument placement and pointing direction. Continuous monitoring of temporal changes in the background radiation (glow) will also permit better interpretation of Station-based infrared earth sensing and astronomical observations. The primary processes producing infrared emissions in the Space Station environment are: (1) Gas phase excitations of Station generated molecules ( e.g., CO2, H2O, organics...) by collisions with the ambient flux of mainly O and N2. Molecular excitations and generation of new species by collisions of ambient molecules with Station surfaces. They provide a list of resulting species, transition energies, excitation cross sections and relevant time constants. The modeled spectrum of the excited species occurs primarily at wavelengths shorter than 8 micrometer. Emissions at longer wavelengths may become important during rocket firing or in the presence of dust.

Physics of Molecules

NASA Astrophysics Data System (ADS)

Williams, D.; Murdin, P.

2000-11-01

Many varieties of molecule have been detected in the Milky Way and in other galaxies. The processes by which these molecules are formed and destroyed are now broadly understood (see INTERSTELLAR CHEMISTRY). These molecules are important components of galaxies in two ways. Firstly, radiation emitted by molecules enables us to trace the presence of diffuse gas, to infer its physical properties and ...

Physics with Cold Molecules Using Buffer Gas Cooling: Precision Measurement, Collisions, and Laser Cooling

NASA Astrophysics Data System (ADS)

Hutzler, Nicholas R.; Doyle, John M.

2014-06-01

Cryogenic buffer gas cooled beams and cells can be used to study many species, from atoms and polar molecules to biomolecules. We report on recent applications of this technique to improve the limit on the electron electric dipole moment [1], load polar molecules into a magnetic trap through optical pumping [2], perform chirally sensitive microwave spectroscopy on polyatomic molecules [3], progress towards magneto-optical trapping of polar molecules [4], and studies of atom-molecule sticking [5]. [1] The ACME Collaboration: J. Baron et al., Science 343, p. 269 (2014) [2] B. Hemmerling et al., arXiv:1310.2669, to appear in Phys. Rev. Lett. [3] D. Patterson, M. Schnell, & J. M. Doyle, Nature 497, p. 475 (2013) [4] H. Lu et al., arXiv:1310.3239, to appear in New. J. Phys. [5] J. Piskorski et al., under preparation

Rotational relaxation of fluoromethane molecules in low-temperature collisions with buffer-gas helium

NASA Astrophysics Data System (ADS)

Li, Xingjia; Xu, Liang; Yin, Yanning; Xu, Supeng; Xia, Yong; Yin, Jianping

2016-06-01

We propose a method to study the rotational relaxation of polar molecules [here taking fluoromethane (CH3F ) as an example] in collisions with 3.5 K buffer-gas helium (He) atoms by using an electrostatic guiding technique. The dependence of the guiding signal of CH3F on the injected He flux and the dependence of the guiding efficiency of CH3F on its rotational temperature are investigated both theoretically and experimentally. By comparing the experimental and simulated results, we find that the translational and rotational temperatures of the buffer-gas cooled CH3F molecules can reach to about 5.48 and 0.60 K, respectively, and the ratio between the translational and average rotational collisional cross sections of CH3F -He is γ =σt/σr=36.49 ±6.15 . In addition, the slowing, cooling, and boosting effects of the molecular beam with different injected He fluxes are also observed and their forming conditions are investigated in some detail. Our study shows that our proposed method can not only be used to measure the translational and rotational temperatures of the buffer-gas cooled molecules, but also to measure the ratio of the translational collisional cross section to the average rotational collisional cross section, and even to measure the average rotational collisional cross section when the translational collisional cross section is measured by fitting the lifetime of molecule signal to get a numerical solution from the diffusion equation of buffer-gas He atoms in the cell.

Effect of Electric Field on Gas Hydrate Nucleation Kinetics: Evidence for the Enhanced Kinetics of Hydrate Nucleation by Negatively Charged Clay Surfaces.

PubMed

Park, Taehyung; Kwon, Tae-Hyuk

2018-03-06

Natural gas hydrates are found widely in oceanic clay-rich sediments, where clay-water interactions have a profound effect on the formation behavior of gas hydrates. However, it remains unclear why and how natural gas hydrates are formed in clay-rich sediments in spite of factors that limit gas hydrate formation, such as small pore size and high salinity. Herein, we show that polarized water molecules on clay surfaces clearly promote gas hydrate nucleation kinetics. When water molecules were polarized with an electric field of 10 4 V/m, gas hydrate nucleation occurred significantly faster with an induction time reduced by 5.8 times. Further, the presence of strongly polarized water layers at the water-gas interface hindered gas uptake and thus hydrate formation, when the electric field was applied prior to gas dissolution. Our findings expand our understanding of the formation habits of naturally occurring gas hydrates in clay-rich sedimentary deposits and provide insights into gas production from natural hydrate deposits.

Interactions between nitrogen and oxygen molecules studied by gas-phase NMR spectroscopy

NASA Astrophysics Data System (ADS)

Garbacz, Piotr; Misiak, Maria; Jackowski, Karol

2018-05-01

Gas-phase 14N and 15N NMR studies of nitrogen and synthetic air pressurized up to 300 bar were performed. It was found that the magnetic shielding of an isolated N2 molecule, σ0(N) = -63.4(2) ppm, is in good agreement with the results of ab initio calculations. The binary N2-O2 interactions contribute to shielding an order of the magnitude larger than the N2-N2 pairs. For nitrogen the three body collisions become observable by NMR for pressure higher than 200 bar and the appropriate coefficient can be practically assigned to the interaction between one molecule of N2 and a pair of O2 molecules.

Molecule formation and infrared emission in fast interstellar shocks. I Physical processes

NASA Technical Reports Server (NTRS)

Hollenbach, D.; Mckee, C. F.

1979-01-01

The paper analyzes the structure of fast shocks incident upon interstellar gas of ambient density from 10 to the 7th per cu cm, while focusing on the problems of formation and destruction of molecules and infrared emission in the cooling, neutral post shock gas. It is noted that such fast shocks initially dissociate almost all preexisting molecules. Discussion covers the physical processes which determine the post shock structure between 10 to the 4 and 10 to the 2 K. It is shown that the chemistry of important molecular coolants H2, CO, OH, and H2O, as well as HD and CH, is reduced to a relatively small set of gas phase and grain surface reactions. Also, the chemistry follows the slow conversion of atomic hydrogen into H2, which primarily occurs on grain surfaces. The dependence of this H2 formation rate on grain and gas temperatures is examined and the survival of grains behind fast shocks is discussed. Post shock heating and cooling rates are calculated and an appropriate, analytic, universal cooling function is developed for molecules other than hydrogen which includes opacities from both the dust and the lines.

Boltzmann equations for a binary one-dimensional ideal gas.

PubMed

Boozer, A D

2011-09-01

We consider a time-reversal invariant dynamical model of a binary ideal gas of N molecules in one spatial dimension. By making time-asymmetric assumptions about the behavior of the gas, we derive Boltzmann and anti-Boltzmann equations that describe the evolution of the single-molecule velocity distribution functions for an ensemble of such systems. We show that for a special class of initial states of the ensemble one can obtain an exact expression for the N-molecule velocity distribution function, and we use this expression to rigorously prove that the time-asymmetric assumptions needed to derive the Boltzmann and anti-Boltzmann equations hold in the limit of large N. Our results clarify some subtle issues regarding the origin of the time asymmetry of Boltzmann's H theorem.

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

NASA Astrophysics Data System (ADS)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the analysis of the data from the upcoming remote and in-situ observations on Mars, as those to be performed by instruments on the ESA's ExoMars Trace Gas Orbiter and ExoMars rover.

[Raman Characterization of Hydrate Crystal Structure Influenced by Mine Gas Concentration].

PubMed

Zhang, Bao-yong; Zhou, Hong-ji; Wu, Qiang; Gao, Xia

2016-01-01

CH4 /C2H6/N2 mixed hydrate formation experiments were performed at 2 degrees C and 5 MPa for three different mine gas concentrations (CH4/C2H6/N2, G1 = 54 : 36 : 10, G2 = 67.5 : 22.5 : 10, G3 = 81 : 9 : 10). Raman spectra for hydration products were obtained by using Microscopic Raman Spectrometer. Hydrate structure is determined by the Raman shift of symmetric C-C stretching vibration mode of C2H6 in the hydrate phase. This work is focused on the cage occupancies and hydration numbers, calculated by the fitting methods of Raman peaks. The results show that structure I (s I) hydrate forms in the G1 and G2 gas systems, while structure II (s II) hydrate forms in the G3 gas system, concentration variation of C2H6 in the gas samples leads to a change in hydrate structure from s I to s II; the percentages of CH4 and C2H6 in s I hydrate phase are less affected by the concentration of gas samples, the percentages of CH4 are respectively 34.4% and 35.7%, C2H6 are respectively 64.6% and 63.9% for gas systems of G1 and G2, the percentages of CH4 and 2 H6 are respectively 73.5% and 22.8% for gas systems of G3, the proportions of object molecules largely depend on the hydrate structure; CH4 and C2H6 molecules occupy 98%, 98% and 92% of the large cages and CH4 molecules occupy 80%, 60% and 84% of the small cages for gas systems of G1, G2 and G3, respectively; additionally, N2 molecules occupy less than 5% of the small cages is due to its weak adsorption ability and the lower partial pressure.

A flexible metal–organic framework: Guest molecules controlled dynamic gas adsorption

DOE PAGES

Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; ...

2015-04-13

A flexible metal–organic framework (MOF) of [Zn 3(btca) 2(OH) 2]·(guest) n (H 2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N 2, He, and Ar induce a structural transition with a corresponding appearance of additional steps in the isotherms. Physical insights into the dynamic adsorption behaviors of flexible compound 1 were detected by gas adsorption at different temperatures and different pressures and confirmed by Fourier transform infrared spectroscopy and molecular simulations. Interestingly, by taking advantage of the flexible nature inherent to the framework, this MOF material enables highlymore » selective adsorption of CO 2/N 2, CO 2/Ar, and CO 2/He of 36.3, 32.6, and 35.9, respectively, at 298 K. Furthermore, this class of flexible MOFs has potential applications for controlled release, molecular sensing, noble gas separation, smart membranes, and nanotechnological devices.« less

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minitti, Michael

2015-06-22

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

ScienceCinema

Minitti, Michael

2018-02-14

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

Random-hole optical fiber evanescent-wave gas sensing.

PubMed

Pickrell, G; Peng, W; Wang, A

2004-07-01

Research on development of optical gas sensors based on evanescent-wave absorption in random-hole optical fibers is described. A process to produce random-hole optical fibers was recently developed that uses a novel in situ bubble formation technique. Gas molecules that exhibit characteristic vibrational absorption lines in the near-IR region that correspond to the transmission window for silica optical fiber have been detected through the evanescent field of the guided mode in the pore region. The presence of the gas molecules in the holes of the fiber appears as a loss at wavelengths that are characteristic of the particular gas species present in the holes. An experimental setup was constructed with these holey fibers for detection of acetylene gas. The results clearly demonstrate the characteristic absorptions in the optical spectra that correspond to the narrow-line absorptions of the acetylene gas, and this represents what is to our knowledge the first report of random-hole fiber gas sensing in the literature.

Influence of an O2 background gas on the composition and kinetic energies of species in laser induced La0.4Ca0.6MnO3 plasmas

NASA Astrophysics Data System (ADS)

Chen, Jikun; Stender, Dieter; Bator, Matthias; Schneider, Christof W.; Lippert, Thomas; Wokaun, Alexander

2013-08-01

Oxygen is one of the most commonly used background gases for pulsed laser deposition of oxide thin films. In this work the properties of a 308 nm laser-induced La0.4Ca0.6MnO3 plasma were analyzed using a quadrupole mass spectrometer combined with an energy analyzer, to investigate the interaction between the various plasma species and the background gas. The composition and kinetic energies of the plasma species were compared in vacuum and an O2 background gas at different pressures. It has been observed that the O2 background gas decreases the kinetic energy of the positively charged atomic plasma species. In addition, the interaction with the O2 background gas causes the generation of positive diatomic oxide species of LaO+, CaO+ and MnO+. The amount of negatively charged diatomic or tri-atomic oxide species decreases in the O2 background compared to vacuum, while the amount of O2- increases strongly.

Apparatus for reducing solvent luminescence background emissions

DOEpatents

Affleck, Rhett L.; Ambrose, W. Patrick; Demas, James N.; Goodwin, Peter M.; Johnson, Mitchell E.; Keller, Richard A.; Petty, Jeffrey T.; Schecker, Jay A.; Wu, Ming

1998-01-01

The detectability of luminescent molecules in solution is enhanced by reducing the background luminescence due to impurity species also present in the solution. A light source that illuminates the solution acts to photolyze the impurities so that the impurities do not luminesce in the fluorescence band of the molecule of interest. Molecules of interest may be carried through the photolysis region in the solution or may be introduced into the solution after the photolysis region.

Three milieux for interstellar chemistry: gas, dust, and ice

NASA Astrophysics Data System (ADS)

Herbst, Eric

The interdisciplinary science of astrochemistry is 45 years of age, if we pinpoint its origin to have occurred when the first polyatomic molecules were detected in the interstellar gas. Since that time, the field has grown remarkably from an esoteric area of research to one that unites scientists around the globe. Almost 200 different molecules have been detected in the gas-phase of interstellar clouds, mainly by rotational spectroscopy, while dust particles and their icy mantles in colder regions can be probed by vibrational spectroscopy. Astrochemistry is exciting to scientists in a number of different fields. Astronomers are interested in molecular spectra from the heavens because such spectra are excellent probes of the physical conditions where molecules exist, while chemists are interested in the exotic molecules, their spectra, and the unusual chemical processes that produce and destroy them under conditions often very different from those on our home planet. Chemical simulations involving thousands of reactions are now used to calculate concentrations and spectra of interstellar molecules as functions of time. Even biologists share an interest in the subject, because the interstellar clouds of gas and dust, portions of which collapse to form stars and planetary systems, contain organic molecules that may become part of the initial inventory of new planets and may indeed be the precursors of life. An irresistible subject to its practitioners, astrochemistry is proving to be exciting to a much wider audience. In this perspective article, the field is first introduced, and the emphasis is then placed on the three environments in which chemistry occurs in the interstellar medium: the gas phase, the surfaces of bare dust particles, and the ice mantles that cover bare grains in cold dense interstellar clouds. What we do know and what we do not know is distinguished. The status of chemical simulations for a variety of interstellar sources having to do with stellar and planetary evolution is surveyed. An optimistic view of the future of astrochemistry ends the article.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Munish, E-mail: munishsharmahpu@live.com; Jamdagni, Pooja; Ahluwalia, P. K.

We present a first principle study of interaction of toxic gas molecules (NO, NO{sub 2} and SO{sub 2}) with monolayer MoSe{sub 2}. The predicted order of sensitivity of gas molecule is NO{sub 2} > SO{sub 2} > NO. Adsorbed molecules strongly influence the electronic behaviour of monolayer MoSe{sub 2} by inducing impurity levels in the vicinity of Fermi energy. NO and SO{sub 2} is found to induce p-type doping effect while semiconductor to metallic transitions occur on NO{sub 2} adsorption. Our findings may guide the experimentalist for fabricating sensor devices based on MoSe{sub 2} monolayer.

Homebuilt single-molecule scanning confocal fluorescence microscope studies of single DNA/protein interactions.

PubMed

Zheng, Haocheng; Goldner, Lori S; Leuba, Sanford H

2007-03-01

Many technical improvements in fluorescence microscopy over the years have focused on decreasing background and increasing the signal to noise ratio (SNR). The scanning confocal fluorescence microscope (SCFM) represented a major improvement in these efforts. The SCFM acquires signal from a thin layer of a thick sample, rejecting light whose origin is not in the focal plane thereby dramatically decreasing the background signal. A second major innovation was the advent of high quantum-yield, low noise, single-photon counting detectors. The superior background rejection of SCFM combined with low-noise, high-yield detectors makes it possible to detect the fluorescence from single-dye molecules. By labeling a DNA molecule or a DNA/protein complex with a donor/acceptor dye pair, fluorescence resonance energy transfer (FRET) can be used to track conformational changes in the molecule/complex itself, on a single molecule/complex basis. In this methods paper, we describe the core concepts of SCFM in the context of a study that uses FRET to reveal conformational fluctuations in individual Holliday junction DNA molecules and nucleosomal particles. We also discuss data processing methods for SCFM.

Radon induced background processes in the KATRIN pre-spectrometer

NASA Astrophysics Data System (ADS)

Fränkle, F. M.; Bornschein, L.; Drexlin, G.; Glück, F.; Görhardt, S.; Käfer, W.; Mertens, S.; Wandkowsky, N.; Wolf, J.

2011-10-01

The KArlsruhe TRItium Neutrino (KATRIN) experiment is a next generation, model independent, large scale tritium β-decay experiment to determine the effective electron anti-neutrino mass by investigating the kinematics of tritium β-decay with a sensitivity of 200 meV/c 2 using the MAC-E filter technique. In order to reach this sensitivity, a low background level of 10 -2 counts per second (cps) is required. This paper describes how the decay of radon in a MAC-E filter generates background events, based on measurements performed at the KATRIN pre-spectrometer test setup. Radon (Rn) atoms, which emanate from materials inside the vacuum region of the KATRIN spectrometers, are able to penetrate deep into the magnetic flux tube so that the α-decay of Rn contributes to the background. Of particular importance are electrons emitted in processes accompanying the Rn α-decay, such as shake-off, internal conversion of excited levels in the Rn daughter atoms and Auger electrons. While low-energy electrons (<100 eV) directly contribute to the background in the signal region, higher energy electrons can be stored magnetically inside the volume of the spectrometer. Depending on their initial energy, they are able to create thousands of secondary electrons via subsequent ionization processes with residual gas molecules and, since the detector is not able to distinguish these secondary electrons from the signal electrons, an increased background rate over an extended period of time is generated.

Sympathetic cooling of polyatomic molecules with S-state atoms in a magnetic trap.

PubMed

Tscherbul, T V; Yu, H-G; Dalgarno, A

2011-02-18

We present a rigorous theoretical study of low-temperature collisions of polyatomic molecular radicals with (1)S(0) atoms in the presence of an external magnetic field. Accurate quantum scattering calculations based on ab initio and scaled interaction potentials show that collision-induced spin relaxation of the prototypical organic molecule CH(2)(X(3)B(1)) (methylene) and nine other triatomic radicals in cold (3)He gas occurs at a slow rate, demonstrating that cryogenic buffer-gas cooling and magnetic trapping of these molecules is feasible with current technology. Our calculations further suggest that it may be possible to create ultracold gases of polyatomic molecules by sympathetic cooling with alkaline-earth atoms in a magnetic trap.

Factors controlling precision and accuracy in isotope-ratio-monitoring mass spectrometry

NASA Technical Reports Server (NTRS)

Merritt, D. A.; Hayes, J. M.

1994-01-01

The performance of systems in which picomole quantities of sample are mixed with a carrier gas and passed through an isotope-ratio mass spectrometer system was examined experimentally and theoretically. Two different mass spectrometers were used, both having electron-impact ion sources and Faraday cup collector systems. One had an accelerating potential of 10kV and accepted 0.2 mL of He/min, producing, under those conditions, a maximum efficiency of 1 CO2 molecular ion collected per 700 molecules introduced. Comparable figures for the second instrument were 3 kV, 0.5 mL of He/min, and 14000 molecules/ion. Signal pathways were adjusted so that response times were <200 ms. Sample-related ion currents appeared as peaks with widths of 3-30 s. Isotope ratios were determined by comparison to signals produced by standard gases. In spite of rapid variations in signals, observed levels of performance were within a factor of 2 of shot-noise limits. For the 10-kV instrument, sample requirements for standard deviations of 0.1 and 0.5% were 45 and 1.7 pmol, respectively. Comparable requirements for the 3-kV instrument were 900 and 36 pmol. Drifts in instrumental characteristics were adequately neutralized when standards were observed at 20-min intervals. For the 10-kV instrument, computed isotopic compositions were independent of sample size and signal strength over the ranges examined. Nonlinearities of <0.04%/V were observed for the 3-kV system. Procedures for observation and subtraction of background ion currents were examined experimentally and theoretically. For sample/ background ratios varying from >10 to 0.3, precision is expected and observed to decrease approximately 2-fold and to depend only weakly on the precision with which background ion currents have been measured.

The gas phase origin of complex organic molecules precursors in prestellar cores

NASA Astrophysics Data System (ADS)

Bacmann, A.; Faure, A.

2015-05-01

Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

Loosely-Bound Diatomic Molecules.

ERIC Educational Resources Information Center

Balfour, W. J.

1979-01-01

Discusses concept of covalent bonding as related to homonuclear diatomic molecules. Article draws attention to the existence of bound rare gas and alkaline earth diatomic molecules. Summarizes their molecular parameters and offers spectroscopic data. Strength and variation with distance of interatomic attractive forces is given. (Author/SA)

Dynamic terahertz spectroscopy of gas molecules mixed with unwanted aerosol under atmospheric pressure using fibre-based asynchronous-optical-sampling terahertz time-domain spectroscopy

PubMed Central

Hsieh, Yi-Da; Nakamura, Shota; Abdelsalam, Dahi Ghareab; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Hindle, Francis; Yasui, Takeshi

2016-01-01

Terahertz (THz) spectroscopy is a promising method for analysing polar gas molecules mixed with unwanted aerosols due to its ability to obtain spectral fingerprints of rotational transition and immunity to aerosol scattering. In this article, dynamic THz spectroscopy of acetonitrile (CH3CN) gas was performed in the presence of smoke under the atmospheric pressure using a fibre-based, asynchronous-optical-sampling THz time-domain spectrometer. To match THz spectral signatures of gas molecules at atmospheric pressure, the spectral resolution was optimized to 1 GHz with a measurement rate of 1 Hz. The spectral overlapping of closely packed absorption lines significantly boosted the detection limit to 200 ppm when considering all the spectral contributions of the numerous absorption lines from 0.2 THz to 1 THz. Temporal changes of the CH3CN gas concentration were monitored under the smoky condition at the atmospheric pressure during volatilization of CH3CN droplets and the following diffusion of the volatilized CH3CN gas without the influence of scattering or absorption by the smoke. This system will be a powerful tool for real-time monitoring of target gases in practical applications of gas analysis in the atmospheric pressure, such as combustion processes or fire accident. PMID:27301319

Production of cold beams of ND{sub 3} with variable rotational state distributions by electrostatic extraction of He and Ne buffer-gas-cooled beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Twyman, Kathryn S.; Bell, Martin T.; Heazlewood, Brianna R.

2014-07-14

The measurement of the rotational state distribution of a velocity-selected, buffer-gas-cooled beam of ND{sub 3} is described. In an apparatus recently constructed to study cold ion-molecule collisions, the ND{sub 3} beam is extracted from a cryogenically cooled buffer-gas cell using a 2.15 m long electrostatic quadrupole guide with three 90° bends. (2+1) resonance enhanced multiphoton ionization spectra of molecules exiting the guide show that beams of ND{sub 3} can be produced with rotational state populations corresponding to approximately T{sub rot} = 9–18 K, achieved through manipulation of the temperature of the buffer-gas cell (operated at 6 K or 17 K),more » the identity of the buffer gas (He or Ne), or the relative densities of the buffer gas and ND{sub 3}. The translational temperature of the guided ND{sub 3} is found to be similar in a 6 K helium and 17 K neon buffer-gas cell (peak kinetic energies of 6.92(0.13) K and 5.90(0.01) K, respectively). The characterization of this cold-molecule source provides an opportunity for the first experimental investigations into the rotational dependence of reaction cross sections in low temperature collisions.« less

Dynamic terahertz spectroscopy of gas molecules mixed with unwanted aerosol under atmospheric pressure using fibre-based asynchronous-optical-sampling terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Hsieh, Yi-Da; Nakamura, Shota; Abdelsalam, Dahi Ghareab; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Hindle, Francis; Yasui, Takeshi

2016-06-01

Terahertz (THz) spectroscopy is a promising method for analysing polar gas molecules mixed with unwanted aerosols due to its ability to obtain spectral fingerprints of rotational transition and immunity to aerosol scattering. In this article, dynamic THz spectroscopy of acetonitrile (CH3CN) gas was performed in the presence of smoke under the atmospheric pressure using a fibre-based, asynchronous-optical-sampling THz time-domain spectrometer. To match THz spectral signatures of gas molecules at atmospheric pressure, the spectral resolution was optimized to 1 GHz with a measurement rate of 1 Hz. The spectral overlapping of closely packed absorption lines significantly boosted the detection limit to 200 ppm when considering all the spectral contributions of the numerous absorption lines from 0.2 THz to 1 THz. Temporal changes of the CH3CN gas concentration were monitored under the smoky condition at the atmospheric pressure during volatilization of CH3CN droplets and the following diffusion of the volatilized CH3CN gas without the influence of scattering or absorption by the smoke. This system will be a powerful tool for real-time monitoring of target gases in practical applications of gas analysis in the atmospheric pressure, such as combustion processes or fire accident.

Dynamic terahertz spectroscopy of gas molecules mixed with unwanted aerosol under atmospheric pressure using fibre-based asynchronous-optical-sampling terahertz time-domain spectroscopy.

PubMed

Hsieh, Yi-Da; Nakamura, Shota; Abdelsalam, Dahi Ghareab; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Hindle, Francis; Yasui, Takeshi

2016-06-15

Terahertz (THz) spectroscopy is a promising method for analysing polar gas molecules mixed with unwanted aerosols due to its ability to obtain spectral fingerprints of rotational transition and immunity to aerosol scattering. In this article, dynamic THz spectroscopy of acetonitrile (CH3CN) gas was performed in the presence of smoke under the atmospheric pressure using a fibre-based, asynchronous-optical-sampling THz time-domain spectrometer. To match THz spectral signatures of gas molecules at atmospheric pressure, the spectral resolution was optimized to 1 GHz with a measurement rate of 1 Hz. The spectral overlapping of closely packed absorption lines significantly boosted the detection limit to 200 ppm when considering all the spectral contributions of the numerous absorption lines from 0.2 THz to 1 THz. Temporal changes of the CH3CN gas concentration were monitored under the smoky condition at the atmospheric pressure during volatilization of CH3CN droplets and the following diffusion of the volatilized CH3CN gas without the influence of scattering or absorption by the smoke. This system will be a powerful tool for real-time monitoring of target gases in practical applications of gas analysis in the atmospheric pressure, such as combustion processes or fire accident.

Continuous diffraction of molecules and disordered molecular crystals

PubMed Central

Yefanov, Oleksandr M.; Ayyer, Kartik; White, Thomas A.; Barty, Anton; Morgan, Andrew; Mariani, Valerio; Oberthuer, Dominik; Pande, Kanupriya

2017-01-01

The intensities of far-field diffraction patterns of orientationally aligned molecules obey Wilson statistics, whether those molecules are in isolation (giving rise to a continuous diffraction pattern) or arranged in a crystal (giving rise to Bragg peaks). Ensembles of molecules in several orientations, but uncorrelated in position, give rise to the incoherent sum of the diffraction from those objects, modifying the statistics in a similar way as crystal twinning modifies the distribution of Bragg intensities. This situation arises in the continuous diffraction of laser-aligned molecules or translationally disordered molecular crystals. This paper develops the analysis of the intensity statistics of such continuous diffraction to obtain parameters such as scaling, beam coherence and the number of contributing independent object orientations. When measured, continuous molecular diffraction is generally weak and accompanied by a background that far exceeds the strength of the signal. Instead of just relying upon the smallest measured intensities or their mean value to guide the subtraction of the background, it is shown how all measured values can be utilized to estimate the background, noise and signal, by employing a modified ‘noisy Wilson’ distribution that explicitly includes the background. Parameters relating to the background and signal quantities can be estimated from the moments of the measured intensities. The analysis method is demonstrated on previously published continuous diffraction data measured from crystals of photosystem II [Ayyer et al. (2016 ▸), Nature, 530, 202–206]. PMID:28808434

Matrix-isolation and ab initio study of HKrCCCl and HXeCCCl

NASA Astrophysics Data System (ADS)

Zhu, Cheng; Räsänen, Markku; Khriachtchev, Leonid

2015-12-01

We report on two new noble-gas molecules, HKrCCCl and HXeCCCl, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of HCCCl in the matrices and subsequent thermal annealing. The HCCCl precursor is produced by microwave discharge of a mixture of a matrix gas with trichloroethylene (HClC=CCl2). The assignments of the new noble-gas molecules are supported by deuteration experiments and quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory with the def2-TZVPPD basis set. No evidence of ClXeCCH, which is computationally reliably stable, is found in the experiments. ClKrCCH as well as the Ar compounds HArCCCl and ClArCCH are not observed either, which is in agreement with the calculations.

Measurements of stratospheric odd nitrogen at Arrival Heights, Antarctica, in 1991

NASA Technical Reports Server (NTRS)

Keys, J. Gordon; Johnston, Paul V.; Blatherwick, R. D.; Murcray, Frank J.

1994-01-01

An FTIR spectrometer was installed at Arrival Heights, Antarctica (78 deg S, 167 deg E) in February 1991 to measure the evolution of stratospheric HNO3 during the year. In particular, it was the intention to make the first observations of HNO3 trends during autumn, concurrently with ongoing measurements of column NO2 made with a grating spectrometer. The time-series of NO2 in the Antarctic shows a rapid decline in the column amount during autumn, and a slow recovery in spring, as the photochemical conditions move the species to and from higher storage reservoirs. The new nitric acid data show for the first time that during autumn the vertical column increases from approximately 1.9 x 10(exp 16) molecule cm(exp -2) at day 30 to approximately 3.1 x 10(exp 16) molecule cm(exp -2) by day 100. When the sun returns in spring, it is found that the column amount has fallen to about half the value at the end of autumn. Spring amounts are variable, but as found in the data from previous years remain low inside the vortex. The autumn increase is attributed to the heterogeneous conversion of N2O5 to gas-phase HNO3 on background aerosols. Low nitric acid column amounts at the start of spring suggest that the HNO3 has moved from the gas to the condensed phase on polar stratospheric clouds with the advent of low temperatures during the polar night.

Preservation of organic matter on Mars by sulfur

NASA Astrophysics Data System (ADS)

Eigenbrode, J. L.; Steele, A.; Summons, R. E.; McAdam, A.; Sutter, B.; Franz, H. B.; Freissinet, C.; Millan, M.; Glavin, D. P.; Szopa, C.; Conrad, P. G.; Mahaffy, P. R.

2016-12-01

Deltaic-lacustrine mudstones at Pahrump Hills, Gale Crater, Mars yielded a variety of sulfur-containing volatiles upon heating to 500-860°C, as detected by the Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover. The detection of organosulfur compounds comprising thiophenes, dimethylsulfide and thiols by gas chromatography-mass spectrometry and evolved gas analyses, together with aromatic and other hydrocarbon molecules with distributions specific to the sample (i.e., not from the SAM background) indicate that some or all of these organic fragments released at high temperatures are indigenous to the mudstones. The organosulfur compounds are most likely derived from sulfur organics in the sediments. However, there is a possibility that sulfurization of some organic fragments occurred in the oven. On Earth, sulfurization of organic matter is a key process that aids preservation over geological time-scales. This is because it reduces reactive functional groups and adds cross links between small unstable molecules thereby converting them into recalcitrant macromolecules. Sulfurization of organic materials prior to deposition and during early diagenesis may have been a key mechanism responsible for organic matter preservation in the Murray formation mudstones. Sulfur-bearing organics have also been observed in carbonaceous meteorites and there is indication of their presence in the Tissint martian meteorite. A quantitative assessment of organosulfur compounds relative to their non-organic counterparts will be presented for the Murray formation mudstones analyzed by SAM and meteorites analyzed in the laboratory under similar analytical conditions.

Novel Semi-Parametric Algorithm for Interference-Immune Tunable Absorption Spectroscopy Gas Sensing

PubMed Central

Michelucci, Umberto; Venturini, Francesca

2017-01-01

One of the most common limits to gas sensor performance is the presence of unwanted interference fringes arising, for example, from multiple reflections between surfaces in the optical path. Additionally, since the amplitude and the frequency of these interferences depend on the distance and alignment of the optical elements, they are affected by temperature changes and mechanical disturbances, giving rise to a drift of the signal. In this work, we present a novel semi-parametric algorithm that allows the extraction of a signal, like the spectroscopic absorption line of a gas molecule, from a background containing arbitrary disturbances, without having to make any assumption on the functional form of these disturbances. The algorithm is applied first to simulated data and then to oxygen absorption measurements in the presence of strong fringes.To the best of the authors’ knowledge, the algorithm enables an unprecedented accuracy particularly if the fringes have a free spectral range and amplitude comparable to those of the signal to be detected. The described method presents the advantage of being based purely on post processing, and to be of extremely straightforward implementation if the functional form of the Fourier transform of the signal is known. Therefore, it has the potential to enable interference-immune absorption spectroscopy. Finally, its relevance goes beyond absorption spectroscopy for gas sensing, since it can be applied to any kind of spectroscopic data. PMID:28991161

Conceptual Design of Electron-Beam Generated Plasma Tools

NASA Astrophysics Data System (ADS)

Agarwal, Ankur; Rauf, Shahid; Dorf, Leonid; Collins, Ken; Boris, David; Walton, Scott

2015-09-01

Realization of the next generation of high-density nanostructured devices is predicated on etching features with atomic layer resolution, no damage and high selectivity. High energy electron beams generate plasmas with unique features that make them attractive for applications requiring monolayer precision. In these plasmas, high energy beam electrons ionize the background gas and the resultant daughter electrons cool to low temperatures via collisions with gas molecules and lack of any accelerating fields. For example, an electron temperature of <0.6 eV with densities comparable to conventional plasma sources can be obtained in molecular gases. The chemistry in such plasmas can significantly differ from RF plasmas as the ions/radicals are produced primarily by beam electrons rather than those in the tail of a low energy distribution. In this work, we will discuss the conceptual design of an electron beam based plasma processing system. Plasma properties will be discussed for Ar, Ar/N2, and O2 plasmas using a computational plasma model, and comparisons made to experiments. The fluid plasma model is coupled to a Monte Carlo kinetic model for beam electrons which considers gas phase collisions and the effect of electric and magnetic fields on electron motion. The impact of critical operating parameters such as magnetic field, beam energy, and gas pressure on plasma characteristics in electron-beam plasma processing systems will be discussed. Partially supported by the NRL base program.

CO2 capture from simulated fuel gas mixtures using semiclathrate hydrates formed by quaternary ammonium salts.

PubMed

Park, Sungwon; Lee, Seungmin; Lee, Youngjun; Seo, Yongwon

2013-07-02

In order to investigate the feasibility of semiclathrate hydrate-based precombustion CO2 capture, thermodynamic, kinetic, and spectroscopic studies were undertaken on the semiclathrate hydrates formed from a fuel gas mixture of H2 (60%) + CO2 (40%) in the presence of quaternary ammonium salts (QASs) such as tetra-n-butylammonium bromide (TBAB) and fluoride (TBAF). The inclusion of QASs demonstrated significantly stabilized hydrate dissociation conditions. This effect was greater for TBAF than TBAB. However, due to the presence of dodecahedral cages that are partially filled with water molecules, TBAF showed a relatively lower gas uptake than TBAB. From the stability condition measurements and compositional analyses, it was found that with only one step of semiclathrate hydrate formation with the fuel gas mixture from the IGCC plants, 95% CO2 can be enriched in the semiclathrate hydrate phase at room temperature. The enclathration of both CO2 and H2 in the cages of the QAS semiclathrate hydrates and the structural transition that results from the inclusion of QASs were confirmed through Raman and (1)H NMR measurements. The experimental results obtained in this study provide the physicochemical background required for understanding selective partitioning and distributions of guest gases in the QAS semiclathrate hydrates and for investigating the feasibility of a semiclathrate hydrate-based precombustion CO2 capture process.

Non-equilibrium kinetics of plasma-assisted combustion: the role of electronically excited atoms and molecules

NASA Astrophysics Data System (ADS)

Popov, Nikolay

2016-09-01

A review of experimental and theoretical investigations of the effect of electronically excited atoms and molecules on the induction delay time and on the shift of the ignition temperature threshold of combustible mixtures is presented. At relatively low initial gas temperature, the effect of excited O(1D) atoms on the oxidation and reforming of combustible mixtures is quite significant due to the high rates of reactions of O(1D) atoms with hydrogen and hydrocarbon molecules. The singlet oxygen molecules, O2(a1Δg) , participate both in chain initiation and chain branching reactions, but the effect of O2(a1Δg) in the ignition processes is generally less important compared to the oxygen atoms. To reduce the ignition delay time and decrease the temperature threshold of fuel-air mixtures, the use of gas discharges with relatively high E/N values is recommended. In this case the reactions of electronically excited N2(A3Σu+ , B3πg , C3πu , a'1Σu-) molecules, and atomic particles in ground and electronically excited states are extremely important. The energy stored in electronic excitation of atoms and molecules is spent on the additional dissociation of oxygen and fuel molecules, on the fast gas heating, and finally to the triggering of chain branching reactions. This work was partially supported by AOARD AFOSR, FA2386-13-1-4064 grant and Linked International Laboratory LIA KaPPA (France-Russia).

Update on the direct n-n scattering experiment at the reactor YAGUAR

NASA Astrophysics Data System (ADS)

Stephenson, S. L.; Crawford, B. E.; Furman, W. I.; Lychagin, E. V.; Muzichka, A. Yu.; Nekhaev, G. V.; Sharapov, E. I.; Shvetsov, V. N.; Strelkov, A. V.; Levakov, B. G.; Lyzhin, A. E.; Chernukhin, Yu. I.; Howell, C. R.; Mitchell, G. E.; Tornow, W.; Showalter-Bucher, R. A.

2013-10-01

The first direct measurement of the 1S0 neutron-neutron scattering experiment using the YAGUAR aperiodic reactor at the Russian Federal Nuclear Center - All Russian Research Institute of Technical Physics has preliminary results. Thermal neutrons are scattered from a thermal neutron ``gas'' within the scattering chamber of the reactor and measured via time-of-flight. These initial results show an unexpectedly large thermal neutron background now understood to be from radiation-induced desorption within the scattering chamber. Analysis of the neutron time-of-flight spectra suggests neutron scattering from H2 and possibly H2O molecules. An experimental value for the desorption yield ηγ of 0.02 molecules/gamma agrees with modeled results. Techniques to reduce the effect of the nonthermal desorption will be presented. This work was supported in part by ISTC project No. 2286, Russia Found. Grant 01-02-17181, the US DOE grants Nos. DE-FG02-97-ER41042 and DE-FG02-97-ER41033, and by the US NSF through Award Nos. 0107263 and 0555652.

Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

USGS Publications Warehouse

Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

2007-01-01

The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

Method and apparatus for reducing solvent luminescence background emissions

DOEpatents

Affleck, R.L.; Ambrose, W.P.; Demas, J.N.; Goodwin, P.M.; Johnson, M.E.; Keller, R.A.; Petty, J.T.; Schecker, J.A.; Wu, M.

1998-10-27

The detectability of luminescent molecules in solution is enhanced by reducing the background luminescence due to impurity species also present in the solution. A light source that illuminates the solution acts to photolyze the impurities so that the impurities do not luminesce in the fluorescence band of the molecule of interest. Molecules of interest may be carried through the photolysis region in the solution or may be introduced into the solution after the photolysis region. 6 figs.

Apparatus for reducing solvent luminescence background emissions

DOEpatents

Affleck, R.L.; Ambrose, W.P.; Demas, J.N.; Goodwin, P.M.; Johnson, M.E.; Keller, R.A.; Petty, J.T.; Schecker, J.A.; Wu, M.

1998-11-10

The detectability of luminescent molecules in solution is enhanced by reducing the background luminescence due to impurity species also present in the solution. A light source that illuminates the solution acts to photolyze the impurities so that the impurities do not luminesce in the fluorescence band of the molecule of interest. Molecules of interest may be carried through the photolysis region in the solution or may be introduced into the solution after the photolysis region. 6 figs.

Method and apparatus for reducing solvent luminescence background emissions

DOEpatents

Affleck, Rhett L.; Ambrose, W. Patrick; Demas, James N.; Goodwin, Peter M.; Johnson, Mitchell E.; Keller, Richard A.; Petty, Jeffrey T.; Schecker, Jay A.; Wu, Ming

1998-01-01

The detectability of luminescent molecules in solution is enhanced by reducing the background luminescence due to impurity species also present in the solution. A light source that illuminates the solution acts to photolyze the impurities so that the impurities do not luminesce in the fluorescence band of the molecule of interest. Molecules of interest may be carried through the photolysis region in the solution or may be introduced into the solution after the photolysis region.

Emission characteristics of Xe-RbBr plasma

NASA Astrophysics Data System (ADS)

Heneral, A. A.; Avtaeva, S. V.

2017-12-01

The luminescence spectra of the longitudinal pulsed-periodic discharge in Xe-RbBr gas-vapour mixtures at low pressures are experimentally studied. Conditions for obtaining strong UV radiation of XeBr* exiplex molecules in the spectral range of 200-425 nm are found. The greatest output of the XeBr* UV radiation is provided at temperature of the gas-discharge tube walls of ~1000 K. The maximum UV emission power of the whole plasma volume is 4.8 W. Formation of XeBr* exciplex molecules in the pulsed-periodic discharge in Xe-RbBr gas-vapour mixtures at low pressures is discussed.

Gas temperature measurements in deuterium hollow cathode glow discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majstorović, Gordana, E-mail: gordana.majstorovic@va.mod.gov.rs; Šišović, Nikola, E-mail: nikolas@ff.bg.ac.rs

2016-03-25

We report results of optical emission spectroscopy measurements of rotational T{sub rot} and translational (gas) temperature of deuterium molecules in a hollow cathode (HC) glow discharge. The rotational temperature of excited electronic state of D{sub 2} was determined from the intensity distribution in the rotational structure of Q branch of the two Fulcher-α diagonal bands: (ν’=ν”=2) and (ν’=ν”=3). The population of excited energy levels, determined from relative line intensities, was used to derive radial rotational temperature distributions as well as gas temperature distribution of deuterium molecule.

Interstellar hydrogen bonding

NASA Astrophysics Data System (ADS)

Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

2018-06-01

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

Monolayer Cu2Si as a potential gas sensor for NOx and COx (x = 1, 2): A first-principles study

NASA Astrophysics Data System (ADS)

Zhu, Hao-Hao; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

2018-02-01

Although the metal-decoration can enhance the sensing properties of two-dimensional (2D) materials, the cyclic utilization of materials is hindered by the clustering tendency of metal atoms. Furthermore, there exists a risk of explosion of combustible gases with the electrical measure. Based on first-principles calculations, we investigate the adsorption of various gas molecules (O2, NO, NO2, NH3, N2, CO, CH4 and CO2) on the 2D Cu-Si extended system (Cu2Si). The NOx molecules are chemisorbed on the Cu2Si monolayer, while other gas molecules (except CH4 and N2) are held by an interaction intermediating between the physisorbed and chemisorbed states. The strong hybridizations between N 2p and Si 3p (Cu 4p) orbitals lead to the large adsorption energies. Interestingly, the adsorption of NOx (1 μB) and CO2 (2 μB) can induce magnetic moments on the intrinsically nonmagnetic Cu2Si monolayer. The magnetic moment of NO-Cu2Si mainly arises from the molecule, while the magnetic moments for the NO2 and CO2 adsorption almost origin from the monolayer. In addition, an antiferromagnetic coupling is found in CO-Cu2Si. The changes in magnetization upon the gas adsorption may be detected sensitively and safely, suggesting the Cu2Si monolayer is potential for gas sensing.

UV Photodesorption of Methanol in Pure and CO-rich Ices: Desorption Rates of the Intact Molecule and of the Photofragments

NASA Astrophysics Data System (ADS)

Bertin, Mathieu; Romanzin, Claire; Doronin, Mikhail; Philippe, Laurent; Jeseck, Pascal; Ligterink, Niels; Linnartz, Harold; Michaut, Xavier; Fillion, Jean-Hugues

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7-14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10-5 molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10-6 molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH3OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH3, OH, H2CO, and CH3O/CH2OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH3O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS2.

PubMed

Zhou, Changjie; Yang, Weihuang; Zhu, Huili

2015-06-07

Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS2 upon adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO). The most stable configuration of the adsorbed molecules, the adsorption energy, and the degree of charge transfer between adsorbate and substrate were determined. All evaluated molecules were physisorbed on monolayer WS2 with a low degree of charge transfer and accept charge from the monolayer, except for NH3, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS2 are not significantly altered upon adsorption of H2, H2O, NH3, and CO, whereas the lowest unoccupied molecular orbitals of O2, NO, and NO2 are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS2. The phenomenon of Fermi-level pinning was discussed in light of the traditional and orbital mixing charge transfer theories. The impacts of the charge transfer mechanism on Fermi-level pinning were confirmed for the gas molecules adsorbed on monolayer WS2. The proposed mechanism governing Fermi-level pinning is applicable to the systems of adsorbates on recently developed two-dimensional materials, such as graphene and transition metal dichalcogenides.

Resonance bonding in XNgY (X = F, Cl, Br, I; Ng = Kr or Xe; Y = CN or NC) molecules: an NBO/NRT investigation.

PubMed

Song, Junjie; Su, Yue; Jia, Yanping; Chen, Lusheng; Zhang, Guiqiu

2018-05-07

Several noble-gas-containing molecules XNgY were observed experimentally. However, the bonding in such systems is still not understood. Using natural bond orbital and natural resonance theory (NBO/NRT) methods, the present work investigated bonding of the title molecules. The results show that each of the studied XNgY molecules should be better described as a resonance hybrid of ω-bonding and [Formula: see text]-type long-bonding structures: X: - Ng +  - Y, X - Ng + : Y - , and X ^ Y. The ω-bonding and long-bonding make competing contributions to the composite resonance hybrid due to the accurately preserved bond order conservation principle. We find that the resonance bonding is highly tunable for these noble-gas-containing molecules due to its dependence on the nature of the halogen X or the central noble-gas atoms Ng. When the molecule XNgY consists of a relatively lighter Ng atom, a relatively low-electronegative X atom, and the CN fragment rather than NC, the long-bonding structure X ^ Y tends to be highlighted. In contrast, the heavy Ng atom and high-electronegative X atom will enhance the ω-bonding structure. Overall, the present work provides electronic principles and chemical insights that help understand the bonding in these XNgY species.

Calculation of ground state rotational populations for kinetic gas homonuclear diatomic molecules including electron-impact excitation and wall collisions.

PubMed

Farley, David R

2010-09-07

A model has been developed to calculate the ground state rotational populations of homonuclear diatomic molecules in kinetic gases, including the effects of electron-impact excitation, wall collisions, and gas feed rate. The equations are exact within the accuracy of the cross sections used and of the assumed equilibrating effect of wall collisions. It is found that the inflow of feed gas and equilibrating wall collisions can significantly affect the rotational distribution in competition with nonequilibrating electron-impact effects. The resulting steady-state rotational distributions are generally Boltzmann for N≥3, with a rotational temperature between the wall and feed gas temperatures. The N=0,1,2 rotational level populations depend sensitively on the relative rates of electron-impact excitation versus wall collision and gas feed rates.

Electronic properties of NH{sub 4}-adsorbed graphene nanoribbon as a promising candidate for a gas sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harada, Naoki, E-mail: harada.naoki@jp.fujitsu.com; Sato, Shintaro

2016-05-15

The electronic properties of NH{sub 4}-adsorbed N = 7 armchair graphene nanoribbons (AGNRs) were theoretically investigated using self-consistent atomistic simulations to explore the feasibility of AGNRs as a gas sensing material. Whereas a pristine AGNR has a finite band gap and is an intrinsic semiconductor, an NH{sub 4}-adsorbed AGNR exhibits heavily doped n-type properties similar to a graphene sheet with the molecules adsorbed. The electric characteristics of a back-gated AGNR gas sensor were also simulated and the drain current changed exponentially with increasing number of adsorbed molecules. We may conclude that an AGNR is promising as a highly sensitive gas-sensingmore » material with large outputs.« less

Effect of lattice-gas atoms on the adsorption behaviour of thioether molecules.

PubMed

Pan, Yi; Yang, Bing; Hulot, Catherine; Blechert, Siegfried; Nilius, Niklas; Freund, Hans-Joachim

2012-08-21

Using STM topographic imaging and spectroscopy, we have investigated the adsorption of two thioether molecules, 1,2-bis(phenylthio)benzene and (bis(3-phenylthio)-phenyl)sulfane, on noble and transition metal surfaces. The two substrates show nearly antipodal behaviour. Whereas complexes with one or two protruding centres are observed on Au(111), only flat and uniform ad-structures are found on NiAl(110). The difference is ascribed to the possibility of the thioethers to form metal-organic complexes by coordinating lattice-gas atoms on the Au(111), while only the pristine molecules adsorb on the alloy surface. The metal coordination in the first case is driven by the formation of strong Au-S bonds and enables the formation of characteristic monomer, dimer and chain-like structures of the thioethers, using the Au atoms as linkers. A similar mechanism is not available on the NiAl, because no lattice gas develops at this surface at room temperature. Our work demonstrates how surface properties, i.e. the availability of mobile ad-species, determine the interaction of organic molecules with metallic substrates.

Liquid crystal-on-organic field-effect transistor sensory devices for perceptive sensing of ultralow intensity gas flow touch.

PubMed

Seo, Jooyeok; Park, Soohyeong; Nam, Sungho; Kim, Hwajeong; Kim, Youngkyoo

2013-01-01

We demonstrate liquid crystal-on-organic field-effect transistor (LC-on-OFET) sensory devices that can perceptively sense ultralow level gas flows. The LC-on-OFET devices were fabricated by mounting LC molecules (4-cyano-4'-pentylbiphenyl - 5CB) on the polymer channel layer of OFET. Results showed that the presence of LC molecules on the channel layer resulted in enhanced drain currents due to a strong dipole effect of LC molecules. Upon applying low intensity nitrogen gas flows, the drain current was sensitively increased depending on the intensity and time of nitrogen flows. The present LC-on-OFET devices could detect extremely low level nitrogen flows (0.7 sccm-11 μl/s), which could not be felt by human skins, thanks to a synergy effect between collective behavior of LC molecules and charge-sensitive channel layer of OFET. The similar sensation was also achieved using the LC-on-OFET devices with a polymer film skin, suggesting viable practical applications of the present LC-on-OFET sensory devices.

Analyzing adsorption characteristics of CO2, N2 and H2O in MCM-41 silica by molecular simulation

NASA Astrophysics Data System (ADS)

Chang, Shing-Cheng; Chien, Shih-Yao; Chen, Chieh-Li; Chen, Cha'o.-Kuang

2015-03-01

The adsorption characteristics of carbon dioxide, nitrogen and water molecules in MCM-41 mesoporous molecular sieve have been investigated by the molecular simulation. We evaluate the pressure-adsorption isotherms and adsorption density profiles under variant gas pressure, operating temperature and mesopore radius of MCM-41 by the grand canonical Monte Carlo simulation. According to the calculated adsorption energy distributions, the adsorption mechanisms of gas in MCM-41 are mainly divided into three types, namely "surface adsorption" on the pore wall, "multilayer adsorption" on the adsorbed gas molecules and "molecular self-aggregation" near the pore center. In addition, the adsorption characteristics of water molecules in MCM-41 are found to be quite different from those of carbon dioxide and nitrogen due to the hydrogen bonds effect. The results indicate that the MCM-41 is practicable in engineering application for the capture, storage, and re-use of water molecules, since it is temperature-sensitive and can achieve significant adsorption loadings within a small range of pressure values via the capillary condensation phenomena.

Pulse gas chromatographic study of adsorption of substituted aromatics and heterocyclic molecules on MIL-47 at zero coverage.

PubMed

Duerinck, Tim; Couck, Sarah; Vermoortele, Frederik; De Vos, Dirk E; Baron, Gino V; Denayer, Joeri F M

2012-10-02

The low coverage adsorptive properties of the MIL-47 metal organic framework toward aromatic and heterocyclic molecules are reported in this paper. The effect of molecular functionality and size on Henry adsorption constants and adsorption enthalpies of alkyl and heteroatom functionalized benzene derivates and heterocyclic molecules was studied using pulse gas chromatography. By means of statistical analysis, experimental data was analyzed and modeled using principal component analysis and partial least-squares regression. Structure-property relationships were established, revealing and confirming several trends. Among the molecular properties governing the adsorption process, vapor pressure, mean polarizability, and dipole moment play a determining role.

Lowering the Spectral Detection Threshold for Molecular Impurities in Gas Mixtures by Interference Multiplexing

NASA Astrophysics Data System (ADS)

Ivanov, M. P.; Tolmachev, Yu. A.

2018-05-01

We consider the most feasible ways to significantly improve the sensitivity of spectroscopic methods for detection and measurement of trace concentrations of greenhouse gas molecules in the atmosphere. The proposed methods are based on combining light fluxes from a number of spectral components of the specified molecule on the same photodetector, taking into account the characteristic features of the transmission spectrum of devices utilizing multipath interference effects.

Two dimensional laser induced fluorescence in the gas phase: a spectroscopic tool for studying molecular spectroscopy and dynamics

NASA Astrophysics Data System (ADS)

Gascooke, Jason R.; Lawrance, Warren D.

2017-11-01

Two dimensional laser induced fluorescence (2D-LIF) extends the usual laser induced fluorescence technique by adding a second dimension, the wavelength at which excited states emit, thereby significantly enhancing the information that can be extracted. It allows overlapping absorption features, whether they arise from within the same molecule or from different molecules in a mixture, to be associated with their appropriate "parent" state and/or molecule. While the first gas phase version of the technique was published a decade ago, the technique is in its infancy, having been exploited by only a few groups to date. However, its potential in gas phase spectroscopy and dynamics is significant. In this article we provide an overview of the technique and illustrate its potential with examples, with a focus on those utilising high resolution in the dispersed fluorescence dimension.

The G value in plasma and radiation chemistry

NASA Technical Reports Server (NTRS)

Baird, James K.; Miller, George P.; Li, Ning

1990-01-01

The application of the G-value concept to plasma chemistry is considered. A general formula which expresses the G value for a general reaction in terms of experimentally controllable parameters is derived by applying simple gas-dynamic theory to a plasma reactor with straight walls. The formula expresses the G value as a function of the electrical power absorbed, the fraction of molecules transformed, and the flow rate of the gas entering the reactor. The formula was applied to the ammonia plasma radio-frequency discharge data of d'Agostino et al. (1981); the results showed that the G(-NH3) value lies in the range of 6.0-20 molecules/100 eV, depending on the conditions. This similarity of the G(-NH3) value with Peterson's (1974) range 2.7-10 found for the gas-phase radiolysis of ammonia, suggests that there might be a common reaction mechanism initiated by inelastic electron-molecule collisions.

Matrix-isolation and ab initio study of HKrCCCl and HXeCCCl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Cheng; Räsänen, Markku; Khriachtchev, Leonid, E-mail: leonid.khriachtchev@helsinki.fi

2015-12-28

We report on two new noble-gas molecules, HKrCCCl and HXeCCCl, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of HCCCl in the matrices and subsequent thermal annealing. The HCCCl precursor is produced by microwave discharge of a mixture of a matrix gas with trichloroethylene (HClC=CCl{sub 2}). The assignments of the new noble-gas molecules are supported by deuteration experiments and quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory with the def2-TZVPPD basis set. No evidence of ClXeCCH, which is computationally reliably stable, is found in the experiments. ClKrCCH as well as themore » Ar compounds HArCCCl and ClArCCH are not observed either, which is in agreement with the calculations.« less

Conversion of fullerenes to diamond

DOEpatents

Gruen, Dieter M.

1994-01-01

A method of forming synthetic hydrogen defect free diamond or diamond like films on a substrate. The method involves providing vapor containing fullerene molecules with or without an inert gas, providing a device to impart energy to the fullerene molecules, fragmenting at least in part some of the fullerene molecules in the vapor or energizing the molecules to incipient fragmentation, ionizing the fullerene molecules, impinging ionized fullerene molecules on the substrate to assist in causing fullerene fragmentation to obtain a thickness of diamond on the substrate.

Role of phosphatidylserine receptors in enveloped virus infection.

PubMed

Morizono, Kouki; Chen, Irvin S Y

2014-04-01

We recently demonstrated that a soluble protein, Gas6, can facilitate viral entry by bridging viral envelope phosphatidylserine to Axl, a receptor tyrosine kinase expressed on target cells. The interaction between phosphatidylserine, Gas6, and Axl was originally shown to be a molecular mechanism through which phagocytes recognize phosphatidylserine exposed on dead cells. Since our initial report, several groups have confirmed that Axl/Gas6, as well as other phosphatidylserine receptors, facilitate entry of dengue, West Nile, and Ebola viruses. Virus binding by viral envelope phosphatidylserine is now a viral entry mechanism generalized to many families of viruses. In addition to Axl/Gas6, various molecules are known to recognize phosphatidylserine; however, the effects of these molecules on virus binding and entry have not been comprehensively evaluated and compared. In this study, we examined most of the known human phosphatidylserine-recognizing molecules, including MFG-E8, TIM-1, -3, and -4, CD300a, BAI1, and stabilin-1 and -2, for their abilities to facilitate virus binding and infection. Using pseudotyped lentiviral vectors, we found that a soluble phosphatidylserine-binding protein, MFG-E8, enhances transduction. Cell surface receptors TIM-1 and -4 also enhance virus binding/transduction. The extent of enhancement by these molecules varies, depending on the type of pseudotyping envelope proteins. Mutated MFG-E8, which binds viral envelope phosphatidylserine without bridging virus to cells, but, surprisingly, not annexin V, which has been used to block phagocytosis of dead cells by concealing phosphatidylserine, efficiently blocks these phosphatidylserine-dependent viral entry mechanisms. These results provide insight into understanding the role of viral envelope phosphatidylserine in viral infection. Envelope phosphatidylserine has previously been shown to be important for replication of various envelope viruses, but details of this mechanism(s) were unclear. We were the first to report that a bifunctional serum protein, Gas6, bridges envelope phosphatidylserine to a cell surface receptor, Axl. Recent studies demonstrated that many envelope viruses, including vaccinia, dengue, West Nile, and Ebola viruses, utilize Axl/Gas6 to facilitate their entry, suggesting that the phosphatidylserine-mediated viral entry mechanism can be shared by various enveloped viruses. In addition to Axl/Gas6, various molecules are known to recognize phosphatidylserine; however, the effects of these molecules on virus binding and entry have not been comprehensively evaluated and compared. In this study, we examined most human phosphatidylserine-recognizing molecules for their abilities to facilitate viral infection. The results provide insights into the role(s) of envelope phosphatidylserine in viral infection, which can be applicable to the development of novel antiviral reagents that block phosphatidylserine-mediated viral entry.

Quenching methods for background reduction in luminescence-based probe-target binding assays

DOEpatents

Cai, Hong [Los Alamos, NM; Goodwin, Peter M [Los Alamos, NM; Keller, Richard A [Los Alamos, NM; Nolan, Rhiannon L [Santa Fe, NM

2007-04-10

Background luminescence is reduced from a solution containing unbound luminescent probes, each having a first molecule that attaches to a target molecule and having an attached luminescent moiety, and luminescent probe/target adducts. Quenching capture reagent molecules are formed that are capable of forming an adduct with the unbound luminescent probes and having an attached quencher material effective to quench luminescence of the luminescent moiety. The quencher material of the capture reagent molecules is added to a solution of the luminescent probe/target adducts and binds in a proximity to the luminescent moiety of the unbound luminescent probes to quench luminescence from the luminescent moiety when the luminescent moiety is exposed to exciting illumination. The quencher capture reagent does not bind to probe molecules that are bound to target molecules and the probe/target adduct emission is not quenched.

Conversion of fullerenes to diamonds

DOEpatents

Gruen, Dieter M.

1995-01-01

A method of forming synthetic diamond or diamond-like films on a substrate surface. The method involves the steps of providing a vapor selected from the group of fullerene molecules or an inert gas/fullerene molecule mixture, providing energy to the fullerene molecules consisting of carbon-carbon bonds, the energized fullerene molecules breaking down to form fragments of fullerene molecules including C.sub.2 molecules and depositing the energized fullerene molecules with C.sub.2 fragments onto the substrate with farther fragmentation occurring and forming a thickness of diamond or diamond-like films on the substrate surface.

Momentum-resolved radio-frequency spectroscopy of a spin-orbit-coupled atomic Fermi gas near a Feshbach resonance in harmonic traps

NASA Astrophysics Data System (ADS)

Peng, Shi-Guo; Liu, Xia-Ji; Hu, Hui; Jiang, Kaijun

2012-12-01

We theoretically investigate the momentum-resolved radio-frequency spectroscopy of a harmonically trapped atomic Fermi gas near a Feshbach resonance in the presence of equal Rashba and Dresselhaus spin-orbit coupling. The system is qualitatively modeled as an ideal gas mixture of atoms and molecules, in which the properties of molecules, such as the wave function, binding energy, and effective mass, are determined from the two-particle solution of two interacting atoms. We calculate separately the radio-frequency response from atoms and molecules at finite temperatures by using the standard Fermi golden rule and take into account the effect of harmonic traps within local density approximation. The total radio-frequency spectroscopy is discussed as functions of temperature and spin-orbit coupling strength. Our results give a qualitative picture of radio-frequency spectroscopy of a resonantly interacting spin-orbit-coupled Fermi gas and can be directly tested in atomic Fermi gases of 40K atoms at Shanxi University and 6Li atoms at the Massachusetts Institute of Technology.

Qatar: Background and U.S. Relations

DTIC Science & Technology

2010-05-05

pending completion of the long-planned expansion of liquefied natural gas (LNG) output to 78 million tones per year is expected to buoy public revenue...study the effects of completed projects on the country’s gas reserves and to plan for efficient management of gas resources for the future. Many...45 Meeting with Qatar Petroleum , Qatar Gas , and Ras Gas executives, Ras Laffan, Qatar, January 2005. . Qatar: Background and U.S. Relations

Method for mapping a natural gas leak

DOEpatents

Reichardt, Thomas A [Livermore, CA; Luong, Amy Khai [Dublin, CA; Kulp, Thomas J [Livermore, CA; Devdas, Sanjay [Albany, CA

2009-02-03

A system is described that is suitable for use in determining the location of leaks of gases having a background concentration. The system is a point-wise backscatter absorption gas measurement system that measures absorption and distance to each point of an image. The absorption measurement provides an indication of the total amount of a gas of interest, and the distance provides an estimate of the background concentration of gas. The distance is measured from the time-of-flight of laser pulse that is generated along with the absorption measurement light. The measurements are formatted into an image of the presence of gas in excess of the background. Alternatively, an image of the scene is superimposed on the image of the gas to aid in locating leaks. By further modeling excess gas as a plume having a known concentration profile, the present system provides an estimate of the maximum concentration of the gas of interest.

Natural gas leak mapper

DOEpatents

Reichardt, Thomas A [Livermore, CA; Luong, Amy Khai [Dublin, CA; Kulp, Thomas J [Livermore, CA; Devdas, Sanjay [Albany, CA

2008-05-20

A system is described that is suitable for use in determining the location of leaks of gases having a background concentration. The system is a point-wise backscatter absorption gas measurement system that measures absorption and distance to each point of an image. The absorption measurement provides an indication of the total amount of a gas of interest, and the distance provides an estimate of the background concentration of gas. The distance is measured from the time-of-flight of laser pulse that is generated along with the absorption measurement light. The measurements are formated into an image of the presence of gas in excess of the background. Alternatively, an image of the scene is superimosed on the image of the gas to aid in locating leaks. By further modeling excess gas as a plume having a known concentration profile, the present system provides an estimate of the maximum concentration of the gas of interest.

Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

PubMed

Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

2012-11-01

A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

Understanding and modulating the high-energy properties of noble-gas hydrides from their long-bonding: an NBO/NRT investigation on HNgCO+/CS+/OSi+ and HNgCN/NC (Ng = He, Ar, Kr, Xe, Rn) molecules.

PubMed

Zhang, Guiqiu; Song, Junjie; Fu, Lei; Tang, Kongshuang; Su, Yue; Chen, Dezhan

2018-04-18

The noble-gas hydrides, HNgX (X is an electronegative atom or fragment), represent potential high-energy materials because their two-body decomposition process, HNgX → Ng + HX, is strongly exoergic. Our previous studies have shown that each member of the HNgX (X = halogen atom or CN/NC fragment) molecules is composed of three leading resonance structures: two ω-bonding structures (H-Ng+ :X- and H:- Ng+-X) and one long-bonding structure (H∧X). The last one paints a novel [small sigma, Greek, circumflex]-type long-bonding picture. The present study focuses on the relationship between this novel bonding motif and the unusual energetic properties. We chose HNgCO+/CS+/OSi+/CN/NC, with the formula HNgAB (Ng = He, Ar, Kr, Xe, Rn; AB = CO+/CS+/OSi+/CN/NC) as the research system. We first investigated the bonding of HNgCO+ and its analogous HNgCS+/OSi+ species using NBO/NRT methods, and quantitatively compared the bonding with that in HNgCN/NC molecules. NBO/NRT results showed that each of the HNgCO+/CS+/OSi+ molecules could be better represented as a resonance hybrid of ω-bonding and long-bonding structures, but the long-bonding is much weaker than that in HNgCN/NC molecules. Furthermore, we introduced the long-bonding concept into the rationalization of the high-energy properties, and found a good correlation between the highly exothermic two-body dissociation channel and the long-bond order, bH-A. We also found that the long-bond order is highly tunable for these noble-gas hydrides due to its dependence on the nature of the electronegative AB fragments or the central noble-gas atoms, Ng. On the basis of these results, we could optimize the energetic properties by changing the long-bonding motif of our studied molecules. Overall, this study shows that the long-bonding model provides an easy way to rationalize and modulate the unusual energy properties of noble-gas hydrides, and that it is helpful to predict some noble-gas hydrides as potential energetic materials.

Detection of hydrogen dissolved in acrylonitrile butadiene rubber by 1H nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Nishimura, Shin; Fujiwara, Hirotada

2012-01-01

Rubber materials, which are used for hydrogen gas seal, can dissolve hydrogen during exposure in high-pressure hydrogen gas. Dissolved hydrogen molecules were detected by solid state 1H NMR of the unfilled vulcanized acrylonitrile butadiene rubber. Two signals were observed at 4.5 ppm and 4.8 ppm, which were assignable to dissolved hydrogen, in the 1H NMR spectrum of NBR after being exposed 100 MPa hydrogen gas for 24 h at room temperature. These signals were shifted from that of gaseous hydrogen molecules. Assignment of the signals was confirmed by quantitative estimation of dissolved hydrogen and peak area of the signals.

Chemical evolution of the gas in C-type shocks in dark clouds

NASA Astrophysics Data System (ADS)

Nesterenok, A. V.

2018-07-01

A magnetohydrodynamic model of a steady, transverse C-type shock in a dense molecular cloud is presented. A complete gas-grain chemical network is taken into account: the gas-phase chemistry, the adsorption of gas species on dust grains, various desorption mechanisms, the grain surface chemistry, the ion neutralization on dust grains, the sputtering of grain mantles. The population densities of energy levels of ions CI, CII and OI and molecules H2, CO, H2O are computed in parallel with the dynamical and chemical rate equations. The large velocity gradient approximation is used in the line radiative transfer calculations. The simulations consist of two steps: (i) modelling of the chemical and thermal evolution of a static molecular cloud and (ii) shock simulations. A comparison is made with the results of publicly available models of similar physical systems. The focus of the paper is on the chemical processing of gas material and ice mantles of dust grains by the shock. Sputtering of ice mantles takes place in the shock region close to the temperature peak of the neutral gas. At high shock speeds, molecules ejected from ice mantles are effectively destroyed in hot gas, and their survival time is low—of the order of dozens of years. After a passage of high-speed C-type shock, a zone of high abundance of atomic hydrogen appears in the cooling postshock gas that triggers formation of complex organic species such as methanol. It is shown that abundances of some complex organic molecules (COMs) in the postshock region can be much higher than in the preshock gas. These results are important for interpretation of observations of COMs in protostellar outflows.

Gas Sensing Analysis of Ag-Decorated Graphene for Sulfur Hexafluoride Decomposition Products Based on the Density Functional Theory

PubMed Central

Zhang, Xiaoxing; Huang, Rong; Gui, Yingang; Zeng, Hong

2016-01-01

Detection of decomposition products of sulfur hexafluoride (SF6) is one of the best ways to diagnose early latent insulation faults in gas-insulated equipment, and the occurrence of sudden accidents can be avoided effectively by finding early latent faults. Recently, functionalized graphene, a kind of gas sensing material, has been reported to show good application prospects in the gas sensor field. Therefore, calculations were performed to analyze the gas sensing properties of intrinsic graphene (Int-graphene) and functionalized graphene-based material, Ag-decorated graphene (Ag-graphene), for decomposition products of SF6, including SO2F2, SOF2, and SO2, based on density functional theory (DFT). We thoroughly investigated a series of parameters presenting gas-sensing properties of adsorbing process about gas molecule (SO2F2, SOF2, SO2) and double gas molecules (2SO2F2, 2SOF2, 2SO2) on Ag-graphene, including adsorption energy, net charge transfer, electronic state density, and the highest and lowest unoccupied molecular orbital. The results showed that the Ag atom significantly enhances the electrochemical reactivity of graphene, reflected in the change of conductivity during the adsorption process. SO2F2 and SO2 gas molecules on Ag-graphene presented chemisorption, and the adsorption strength was SO2F2 > SO2, while SOF2 absorption on Ag-graphene was physical adsorption. Thus, we concluded that Ag-graphene showed good selectivity and high sensitivity to SO2F2. The results can provide a helpful guide in exploring Ag-graphene material in experiments for monitoring the insulation status of SF6-insulated equipment based on detecting decomposition products of SF6. PMID:27809269

Decoupling of bilayer leaflets under gas supersaturation: nitrogen nanobubbles in a membrane and their implication in decompression sickness

NASA Astrophysics Data System (ADS)

Li, Jing; Zhang, Xianren; Cao, Dapeng

2018-05-01

Decompression sickness (also known as diver’s sickness) is a disease that arises from the formation of a bubble inside the body caused by rapid decompression from high atmospheric pressures. However, the nature of pre-existing micronuclei that are proposed for interpreting the formation and growth of the bubble, as well as their very existence, is still highly controversial. In this work, atomistic molecular dynamics simulations are employed to investigate the nucleation of gas bubbles under the condition of nitrogen supersaturation, in the presence of a lipid bilayer and lipid micelle representing other macromolecules with a smaller hydrophobic region. Our simulation results demonstrate that by crossing a small energy barrier, excess nitrogen molecules can enter the lipid bilayer nearly spontaneously, for which the hydrophobic core serves as a potential well for gas enrichment. At a rather low nitrogen supersaturation, gas molecules in the membrane are dispersed in the hydrophobic region of the bilayer, with a slight increase in membrane thickness. But as the level of gas supersaturation reaches a threshold, the accumulation of N2 molecules in the bilayer center causes the two leaflets to be decoupled and the formation of nanobubbles. Therefore, we propose a nucleation mechanism for bubble formation in a supersaturated solution of inert gas: a cell membrane acts as a potential well for gas enrichment, being an ideal location for forming nanobubbles that induce membrane damage at a high level of gas supersaturation. As opposed to previous models, the new mechanism involves forming gas nuclei in a very low-tension hydrophobic environment, and thus a rather low energy barrier is required and pre-existing bubble micronuclei are not needed.

A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2012-12-01

The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, nonaqueous liquid, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulations that predict the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. The phase equilibria for the ternary gas hydrate system within the gas hydrate stability range of composition, temperature and pressure, includes regions where the gas hydrate is in equilibrium with gas, nonaqueous liquid, or mixtures of gas and nonaqeuous liquid near the CO2-CH4-N2 mixture critical point. In these regions, solutions to cubic equations of state can be nonconvergent without accurate initial guesses. A hybrid tabular-cubic equation of state is described which avoids convergence issues, but conserves the characteristics and advantages of the cubic equation of state approaches to phase equilibria calculations. The application of interest will be the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

Reducing background contributions in fluorescence fluctuation time-traces for single-molecule measurements in solution.

PubMed

Földes-Papp, Zeno; Liao, Shih-Chu Jeff; You, Tiefeng; Barbieri, Beniamino

2009-08-01

We first report on the development of new microscope means that reduce background contributions in fluorescence fluctuation methods: i) excitation shutter, ii) electronic switches, and iii) early and late time-gating. The elements allow for measuring molecules at low analyte concentrations. We first found conditions of early and late time-gating with time-correlated single-photon counting that made the fluorescence signal as bright as possible compared with the fluctuations in the background count rate in a diffraction-limited optical set-up. We measured about a 140-fold increase in the amplitude of autocorrelated fluorescence fluctuations at the lowest analyte concentration of about 15 pM, which gave a signal-to-background advantage of more than two-orders of magnitude. The results of this original article pave the way for single-molecule detection in solution and in live cells without immobilization or hydrodynamic/electrokinetic focusing at longer observation times than are currently available.

HIGH RESOLUTION SPECTROSCOPY IN THE GAS PHASE: Even Large Molecules Have Well-Defined Shapes

NASA Astrophysics Data System (ADS)

Pratt, David W.

1998-10-01

A review of recent high-resolution microwave, infrared, and optical spectroscopy experiments demonstrates that remarkable progress has been made in the past 20 years in determining the equilibrium geometries of large polyatomic molecules and their clusters in the gas phase, and how these geometries change when the photon is absorbed. A special focus is on the dynamical information that can be obtained from such studies, particularly of electronically excited states.

Interstellar Alcohols

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.; Millar, T. J.

1995-01-01

We have investigated the gas-phase chemistry in dense cores where ice mantles containing ethanol and other alcohols have been evaporated. Model calculations show that methanol, ethanol, propanol, and butanol drive a chemistry leading to the formation of several large ethers and esters. Of these molecules, methyl ethyl ether (CH3OC2H5) and diethyl ether (C2H5)2O attain the highest abundances and should be present in detectable quantities within cores rich in ethanol and methanol. Gas-phase reactions act to destroy evaporated ethanol and a low observed abundance of gas-phase C,H,OH does not rule out a high solid-phase abundance. Grain surface formation mechanisms and other possible gas-phase reactions driven by alcohols are discussed, as are observing strategies for the detection of these large interstellar molecules.

Optimized cell geometry for buffer-gas-cooled molecular-beam sources

NASA Astrophysics Data System (ADS)

Singh, Vijay; Samanta, Amit K.; Roth, Nils; Gusa, Daniel; Ossenbrüggen, Tim; Rubinsky, Igor; Horke, Daniel A.; Küpper, Jochen

2018-03-01

We have designed, constructed, and commissioned a cryogenic helium buffer-gas source for producing a cryogenically cooled molecular beam and evaluated the effect of different cell geometries on the intensity of the produced molecular beam, using ammonia as a test molecule. Planar and conical entrance and exit geometries are tested. We observe a threefold enhancement in the NH3 signal for a cell with planar entrance and conical-exit geometry, compared to that for a typically used "boxlike" geometry with planar entrance and exit. These observations are rationalized by flow field simulations for the different buffer-gas cell geometries. The full thermalization of molecules with the helium buffer gas is confirmed through rotationally resolved resonance-enhanced multiphoton ionization spectra yielding a rotational temperature of 5 K.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A., E-mail: christopher.k.materese@nasa.gov

Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C{sub 6}H{sub 6}) or naphthalene (C{sub 10}H{submore » 8}) mixed in ices containing H{sub 2}O and NH{sub 3}. This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology.« less

UV PHOTODESORPTION OF METHANOL IN PURE AND CO-RICH ICES: DESORPTION RATES OF THE INTACT MOLECULE AND OF THE PHOTOFRAGMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bertin, Mathieu; Doronin, Mikhail; Philippe, Laurent

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7–14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10{sup −5} molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10{sup −6} molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH{sub 3}OHmore » ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH{sub 3}, OH, H{sub 2}CO, and CH{sub 3}O/CH{sub 2}OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH{sub 3}O, therefore, opening new gas phase chemical routes for the formation of complex molecules.« less

THERMALLY DRIVEN ATMOSPHERIC ESCAPE: TRANSITION FROM HYDRODYNAMIC TO JEANS ESCAPE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Volkov, Alexey N.; Johnson, Robert E.; Tucker, Orenthal J.

2011-03-10

Thermally driven escape from planetary atmospheres changes in nature from an organized outflow (hydrodynamic escape) to escape on a molecule-by-molecule basis (Jeans escape) with increasing Jeans parameter, {lambda}, the ratio of the gravitational to thermal energy of the atmospheric molecules. This change is described here for the first time using the direct simulation Monte Carlo method. When heating is predominantly below the lower boundary of the simulation region, R{sub 0}, and well below the exobase of a single-component atmosphere, the nature of the escape process changes over a surprisingly narrow range of Jeans parameters, {lambda}{sub 0}, evaluated at R{sub 0}.more » For an atomic gas, the transition occurs over {lambda}{sub 0} {approx} 2-3, where the lower bound, {lambda}{sub 0} {approx} 2.1, corresponds to the upper limit for isentropic, supersonic outflow. For {lambda}{sub 0} > 3 escape occurs on a molecule-by-molecule basis and we show that, contrary to earlier suggestions, for {lambda}{sub 0} > {approx}6 the escape rate does not deviate significantly from the familiar Jeans rate. In a gas composed of diatomic molecules, the transition shifts to {lambda}{sub 0} {approx} 2.4-3.6 and at {lambda}{sub 0} > {approx}4 the escape rate increases a few tens of percent over that for the monatomic gas. Scaling by the Jeans parameter and the Knudsen number, these results can be applied to thermally induced escape of the major species from solar and extrasolar planets.« less

Crystallographic studies of gas sorption in metal–organic frameworks

PubMed Central

Carrington, Elliot J.; Vitórica-Yrezábal, Iñigo J.; Brammer, Lee

2014-01-01

Metal–organic frameworks (MOFs) are a class of porous crystalline materials of modular design. One of the primary applications of these materials is in the adsorption and separation of gases, with potential benefits to the energy, transport and medical sectors. In situ crystallography of MOFs under gas atmospheres has enabled the behaviour of the frameworks under gas loading to be investigated and has established the precise location of adsorbed gas molecules in a significant number of MOFs. This article reviews progress in such crystallographic studies, which has taken place over the past decade, but has its origins in earlier studies of zeolites, clathrates etc. The review considers studies by single-crystal or powder diffraction using either X-rays or neutrons. Features of MOFs that strongly affect gas sorption behaviour are discussed in the context of in situ crystallographic studies, specifically framework flexibility, and the presence of (organic) functional groups and unsaturated (open) metal sites within pores that can form specific interactions with gas molecules. PMID:24892587

Carbon Nanotube Biosensors for Space Molecule Detection and Clinical Molecular Diagnostics

NASA Technical Reports Server (NTRS)

Han, Jie

2001-01-01

Both space molecule detection and clinical molecule diagnostics need to develop ultra sensitive biosensors for detection of less than attomole molecules such as amino acids for DNA. However all the electrode sensor systems including those fabricated from the existing carbon nanotubes, have a background level of nA (nanoAmp). This has limited DNA or other molecule detection to nA level or molecules whose concentration is, much higher than attomole level. A program has been created by NASA and NCI (National Cancer Institute) to exploit the possibility of carbon nanotube based biosensors to solve this problem for both's interest. In this talk, I will present our effort on the evaluation and novel design of carbon nanotubes as electrode biosensors with strategies to minimize background currents while maximizing signal intensity.The fabrication of nanotube electrode arrays, immobilization of molecular probes on nanotube electrodes and in vitro biosensor testing will also be discussed.

A flexible, transparent and high-performance gas sensor based on layer-materials for wearable technology

NASA Astrophysics Data System (ADS)

Zheng, Zhaoqiang; Yao, Jiandong; Wang, Bing; Yang, Guowei

2017-10-01

Gas sensors play a vital role among a wide range of practical applications. Recently, propelled by the development of layered materials, gas sensors have gained much progress. However, the high operation temperature has restricted their further application. Herein, via a facile pulsed laser deposition (PLD) method, we demonstrate a flexible, transparent and high-performance gas sensor made of highly-crystalline indium selenide (In2Se3) film. Under UV-vis-NIR light or even solar energy activation, the constructed gas sensors exhibit superior properties for detecting acetylene (C2H2) gas at room temperature. We attribute these properties to the photo-induced charger transfer mechanism upon C2H2 molecule adsorption. Moreover, no apparent degradation in the device properties is observed even after 100 bending cycles. In addition, we can also fabricate this device on rigid substrates, which is also capable to detect gas molecules at room temperature. These results unambiguously distinguish In2Se3 as a new candidate for future application in monitoring C2H2 gas at room temperature and open up new opportunities for developing next generation full-spectrum activated gas sensors.

A flexible, transparent and high-performance gas sensor based on layer-materials for wearable technology.

PubMed

Zheng, Zhaoqiang; Yao, Jiandong; Wang, Bing; Yang, Guowei

2017-10-13

Gas sensors play a vital role among a wide range of practical applications. Recently, propelled by the development of layered materials, gas sensors have gained much progress. However, the high operation temperature has restricted their further application. Herein, via a facile pulsed laser deposition (PLD) method, we demonstrate a flexible, transparent and high-performance gas sensor made of highly-crystalline indium selenide (In 2 Se 3 ) film. Under UV-vis-NIR light or even solar energy activation, the constructed gas sensors exhibit superior properties for detecting acetylene (C 2 H 2 ) gas at room temperature. We attribute these properties to the photo-induced charger transfer mechanism upon C 2 H 2 molecule adsorption. Moreover, no apparent degradation in the device properties is observed even after 100 bending cycles. In addition, we can also fabricate this device on rigid substrates, which is also capable to detect gas molecules at room temperature. These results unambiguously distinguish In 2 Se 3 as a new candidate for future application in monitoring C 2 H 2 gas at room temperature and open up new opportunities for developing next generation full-spectrum activated gas sensors.

Techniques for active passivation

DOEpatents

Roscioli, Joseph R.; Herndon, Scott C.; Nelson, Jr., David D.

2016-12-20

In one embodiment, active (continuous or intermittent) passivation may be employed to prevent interaction of sticky molecules with interfaces inside of an instrument (e.g., an infrared absorption spectrometer) and thereby improve response time. A passivation species may be continuously or intermittently applied to an inlet of the instrument while a sample gas stream is being applied. The passivation species may have a highly polar functional group that strongly binds to either water or polar groups of the interfaces, and once bound presents a non-polar group to the gas phase in order to prevent further binding of polar molecules. The instrument may be actively used to detect the sticky molecules while the passivation species is being applied.

Lithium-functionalized germanene: A promising media for CO2 capture

NASA Astrophysics Data System (ADS)

Mehdi Aghaei, S.; Monshi, M. M.; Torres, I.; Banakermani, M.; Calizo, I.

2018-02-01

Density functional theory (DFT) is employed to investigate the interactions of CO2 gas molecules with pristine and lithium-functionalized germanene. It is discovered that although a single CO2 molecule is weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy is found by utilizing Li-functionalized germanene as the adsorbent. Excitingly, the moderate adsorption energy at high CO2 coverage secures an easy release step. Moreover, the structure of Li-functionalized germanene can be fully recovered after removal of CO2 gas molecules. Our results suggest that Li-functionalized germanene show promise for CO2 sensing and capture with a storage capacity of 12.57 mol/kg.

SNSMIL, a real-time single molecule identification and localization algorithm for super-resolution fluorescence microscopy

PubMed Central

Tang, Yunqing; Dai, Luru; Zhang, Xiaoming; Li, Junbai; Hendriks, Johnny; Fan, Xiaoming; Gruteser, Nadine; Meisenberg, Annika; Baumann, Arnd; Katranidis, Alexandros; Gensch, Thomas

2015-01-01

Single molecule localization based super-resolution fluorescence microscopy offers significantly higher spatial resolution than predicted by Abbe’s resolution limit for far field optical microscopy. Such super-resolution images are reconstructed from wide-field or total internal reflection single molecule fluorescence recordings. Discrimination between emission of single fluorescent molecules and background noise fluctuations remains a great challenge in current data analysis. Here we present a real-time, and robust single molecule identification and localization algorithm, SNSMIL (Shot Noise based Single Molecule Identification and Localization). This algorithm is based on the intrinsic nature of noise, i.e., its Poisson or shot noise characteristics and a new identification criterion, QSNSMIL, is defined. SNSMIL improves the identification accuracy of single fluorescent molecules in experimental or simulated datasets with high and inhomogeneous background. The implementation of SNSMIL relies on a graphics processing unit (GPU), making real-time analysis feasible as shown for real experimental and simulated datasets. PMID:26098742

The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

NASA Astrophysics Data System (ADS)

Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

2018-02-01

Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

If You Were a Molecule in a Chromatography Column, What Would You See?

ERIC Educational Resources Information Center

Mattice, John

2008-01-01

To visualize what takes place in a chromatography column, enlarge the molecules to human size and expand the columns to keep the ratio of size of molecule to size of column the same. If we were molecules, what would the columns be like? A typical gas chromatography (GC) capillary column would be 50 x 10 [superscript 6] 6 km (31 million mi) long,…

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

PubMed

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Molecular and isotopic analyses of the hydrocarbon gases within gas hydrate-bearing rock units of the Prudhoe Bay-Kuparuk River area in northern Alaska

USGS Publications Warehouse

Valin, Zenon C.; Collett, Timothy S.

1992-01-01

Gas hydrates, which are crystalline substances of water molecules that encase gas molecules, have the potential for being a significant source of natural gas. World-wide estimates for the amount of gas contained in hydrates range from 1.1 x 105 to 2.7 x 108 trillion cubic feet. Gas hydrates exist in many Arctic regions, including the North Slope of Alaska. The two primary objectives of the U.S. Geological Survey Gas Hydrate Research Project are (1) to map the distribution of in-situ gas hydrates on the North Slope of Alaska, and (2) to evaluate the geologic parameters that control the distribution of these gas hydrates. To aid in this study, British Petroleum Exploration, ARCO Alaska, Exxon Company USA, and the Continental Oil Company allowed the U.S. Geological Survey to collect geochemical samples from drilling North Slope production wells. Molecular analysis of gaseous drill cutting and free-flowing gas samples from 10 production wells drilled in the Prudhoe Bay, Kuparuk River, and Milne Point oil fields indicates that methane is the primary hydrocarbon gas in the gas hydrate-bearing stratigraphic units. Isotopic data for several of these rock units indicate that the methane within the inferred gas hydrate occurences originated from both microbial and thermogenic processes.

Recording of absorption spectra by a three-beam integral technique with a tunable laser and external cavity

NASA Astrophysics Data System (ADS)

Korolenko, P. V.; Nikolaev, I. V.; Ochkin, V. N.; Tskhai, S. N.

2014-04-01

An integral method is considered for recording absorption using three laser beams transmitted through and reflected from an external cavity with the absorbing medium (R-ICOS). The method is the elaboration of a known single-beam ICOS method and allows suppression of the influence of radiation phase fluctuations in the resonator on recording weak absorption spectra. First of all, this reduces high-frequency instabilities and gives a possibility to record spectra during short time intervals. In this method, mirrors of the resonator may have moderate reflection coefficients. Capabilities of the method have been demonstrated by the examples of weak absorption spectra of atmospheric methane and natural gas in a spectral range around 1650 nm. With the mirrors having the reflection coefficients of 0.8-0.99, a spectrum can be recorded for 320 μs with the accuracy sufficient for detecting a background concentration of methane in atmosphere. For the acquisition time of 20 s, the absorption coefficients of ~2×10-8 cm-1 can be measured, which corresponds to a 40 times less molecule concentration than the background value.

Sorption of small molecules in polymeric media

NASA Astrophysics Data System (ADS)

Camboni, Federico; Sokolov, Igor M.

2016-12-01

We discuss the sorption of penetrant molecules from the gas phase by a polymeric medium within a model which is very close in spirit to the dual sorption mode model: the penetrant molecules are partly dissolved within the polymeric matrix, partly fill the preexisting voids. The only difference with the initial dual sorption mode situation is the assumption that the two populations of molecules are in equilibrium with each other. Applying basic thermodynamics principles we obtain the dependence of the penetrant concentration on the pressure in the gas phase and find that this is expressed via the Lambert W-function, a different functional form than the one proposed by dual sorption mode model. The Lambert-like isotherms appear universally at low and moderate pressures and originate from the assumption that the internal energy in a polymer-penetrant-void ternary mixture is (in the lowest order) a bilinear form in the concentrations of the three components. Fitting the existing data shows that in the domain of parameters where the dual sorption mode model is typically applied, the Lambert function, which describes the same behavior as the one proposed by the gas-polymer matrix model, fits the data equally well.

Communication: Gas-phase structural isomer identification by Coulomb explosion of aligned molecules

NASA Astrophysics Data System (ADS)

Burt, Michael; Amini, Kasra; Lee, Jason W. L.; Christiansen, Lars; Johansen, Rasmus R.; Kobayashi, Yuki; Pickering, James D.; Vallance, Claire; Brouard, Mark; Stapelfeldt, Henrik

2018-03-01

The gas-phase structures of four difluoroiodobenzene and two dihydroxybromobenzene isomers were identified by correlating the emission angles of atomic fragment ions created, following femtosecond laser-induced Coulomb explosion. The structural determinations were facilitated by confining the most polarizable axis of each molecule to the detection plane prior to the Coulomb explosion event using one-dimensional laser-induced adiabatic alignment. For a molecular target consisting of two difluoroiodobenzene isomers, each constituent structure could additionally be singled out and distinguished.

Preparation of a pure molecular quantum gas.

PubMed

Herbig, Jens; Kraemer, Tobias; Mark, Michael; Weber, Tino; Chin, Cheng; Nägerl, Hanns-Christoph; Grimm, Rudolf

2003-09-12

An ultracold molecular quantum gas is created by application of a magnetic field sweep across a Feshbach resonance to a Bose-Einstein condensate of cesium atoms. The ability to separate the molecules from the atoms permits direct imaging of the pure molecular sample. Magnetic levitation enables study of the dynamics of the ensemble on extended time scales. We measured ultralow expansion energies in the range of a few nanokelvin for a sample of 3000 molecules. Our observations are consistent with the presence of a macroscopic molecular matter wave.

Measurement and reduction of low-level radon background in the KATRIN experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fränkle, F. M.

The KArlsruhe TRItium Neutrino (KATRIN) experiment is a next generation, model independent, large scale experiment to determine the mass of the electron anti-neutrino by investigating the kinematics of tritium beta decay with a sensitivity of 200 meV/c{sup 2}. The measurement setup consists of a high luminosity windowless gaseous molecular tritium source (WGTS), a differential and cryogenic pumped electron transport and tritium retention section, a tandem spectrometer section (pre-spectrometer and main spectrometer) for energy analysis, followed by a detector system for counting transmitted beta decay electrons. Measurements performed at the KATRIN pre-spectrometer test setup showed that the decay of radon (Rn)more » atoms in the volume of the KATRIN spectrometers is a major background source. Rn atoms from low-level radon emanation of materials inside the vacuum region of the KATRIN spectrometers are able to penetrate deep into the magnetic flux tube so that the alpha decay of Rn contributes to the background. Of particular importance are electrons emitted in processes accompanying the Rn alpha decay, such as shake-off, internal conversion of excited levels in the Rn daughter atoms and Auger electrons. Lowenergy electrons (< 100 eV) directly contribute to the background in the signal region. High-energy electrons can be stored magnetically inside the volume of the spectrometer and are able to create thousands of secondary electrons via subsequent ionization processes with residual gas molecules. In order to reduce the Rn induced background different active and passive counter measures were developed and tested. This proceeding will give an overview on Rn sources within the KATRIN spectrometer, describes how Rn decays inside the spectrometer produce background events at the detector and presents different counter measures to reduce the Rn induced background.« less

Measurement and reduction of low-level radon background in the KATRIN experiment

NASA Astrophysics Data System (ADS)

Fränkle, F. M.

2013-08-01

The KArlsruhe TRItium Neutrino (KATRIN) experiment is a next generation, model independent, large scale experiment to determine the mass of the electron anti-neutrino by investigating the kinematics of tritium beta decay with a sensitivity of 200 meV/c2. The measurement setup consists of a high luminosity windowless gaseous molecular tritium source (WGTS), a differential and cryogenic pumped electron transport and tritium retention section, a tandem spectrometer section (pre-spectrometer and main spectrometer) for energy analysis, followed by a detector system for counting transmitted beta decay electrons. Measurements performed at the KATRIN pre-spectrometer test setup showed that the decay of radon (Rn) atoms in the volume of the KATRIN spectrometers is a major background source. Rn atoms from low-level radon emanation of materials inside the vacuum region of the KATRIN spectrometers are able to penetrate deep into the magnetic flux tube so that the alpha decay of Rn contributes to the background. Of particular importance are electrons emitted in processes accompanying the Rn alpha decay, such as shake-off, internal conversion of excited levels in the Rn daughter atoms and Auger electrons. Lowenergy electrons (< 100 eV) directly contribute to the background in the signal region. High-energy electrons can be stored magnetically inside the volume of the spectrometer and are able to create thousands of secondary electrons via subsequent ionization processes with residual gas molecules. In order to reduce the Rn induced background different active and passive counter measures were developed and tested. This proceeding will give an overview on Rn sources within the KATRIN spectrometer, describes how Rn decays inside the spectrometer produce background events at the detector and presents different counter measures to reduce the Rn induced background.

Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars

PubMed Central

Freissinet, C; Glavin, D P; Mahaffy, P R; Miller, K E; Eigenbrode, J L; Summons, R E; Brunner, A E; Buch, A; Szopa, C; Archer, P D; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P

2015-01-01

The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. Key Points First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition PMID:26690960

Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars.

PubMed

Freissinet, C; Glavin, D P; Mahaffy, P R; Miller, K E; Eigenbrode, J L; Summons, R E; Brunner, A E; Buch, A; Szopa, C; Archer, P D; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; Ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P

2015-03-01

The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150-300 parts per billion by weight (ppbw)) and C 2 to C 4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition.

Buffer Gas Modifiers Effect Resolution in Ion Mobility Spectrometry through Selective Ion-Molecule Clustering Reactions

PubMed Central

Fernández-Maestre, Roberto; Wu, Ching; Hill, Herbert H.

2013-01-01

RATIONALE When polar molecules (modifiers) are introduced into the buffer gas of an ion mobility spectrometer, most ion mobilities decrease due to the formation of ion-modifier clusters. METHODS We used ethyl lactate, nitrobenzene, 2-butanol, and tetrahydrofuran-2-carbonitrile as buffer gas modifiers and electrospray ionization ion mobility spectrometry (IMS) coupled to quadrupole mass spectrometry. Ethyl lactate, nitrobenzene, and tetrahydrofuran-2-carbonitrile had not been tested as buffer gas modifiers and 2-butanol had not been used with basic amino acids. RESULTS The ion mobilities of several diamines (arginine, histidine, lysine, and atenolol) were not affected or only slightly reduced when these modifiers were introduced into the buffer gas (3.4% average reduction in an analyte's mobility for the three modifiers). Intramolecular bridges caused limited change in the ion mobilities of diamines when modifiers were added to the buffer gas; these bridges hindered the attachment of modifier molecules to the positive charge of ions and delocalized the charge, which deterred clustering. There was also a tendency towards large changes in ion mobility when the mass of the analyte decreased; ethanolamine, the smallest compound tested, had the largest reduction in ion mobility with the introduction of modifiers into the buffer gas (61%). These differences in mobilities, together with the lack of shift in bridge-forming ions, were used to separate ions that overlapped in IMS, such as isoleucine and lysine, and arginine and phenylalanine, and made possible the prediction of separation or not of overlapping ions. CONCLUSIONS The introduction of modifiers into the buffer gas in IMS can selectively alter the mobilities of analytes to aid in compound identification and/or enable the separation of overlapping analyte peaks. PMID:22956312

Formation of a nanobubble and its effect on the structural ordering of water in a CH4-N2-CO2-H2O mixture.

PubMed

Kaur, Surinder Pal; Sujith, K S; Ramachandran, C N

2018-04-04

The replacement of methane (CH4) from its hydrate by a mixture of nitrogen (N2) and carbon dioxide (CO2) involves the dissociation of methane hydrate leading to the formation of a CH4-N2-CO2-H2O mixture that can significantly influence the subsequent steps of the replacement process. In the present work, we study the evolution of dissolved gas molecules in this mixture by applying classical molecular dynamics simulations. Our study shows that a higher CO2 : N2 ratio in the mixture enhances the formation of nanobubbles composed of N2, CH4 and CO2 molecules. To understand how the CO2 : N2 ratio affects nanobubble nucleation, the distribution of molecules in the bubble formed is examined. It is observed that unlike N2 and CH4, the density of CO2 in the bubble reaches a maximum at the surface of the bubble. The accumulation of CO2 molecules at the surface makes the bubble more stable by decreasing the excess pressure inside the bubble as well as surface tension at its interface with water. It is found that a frequent exchange of gas molecules takes place between the bubble and the surrounding liquid and an increase in concentration of CO2 in the mixture leads to a decrease in the number of such exchanges. The effect of nanobubbles on the structural ordering of water molecules is examined by determining the number of water rings formed per unit volume in the mixture. The role of nanobubbles in water structuring is correlated to the dynamic nature of the bubble arising from the exchange of gas molecules between the bubble and the liquid.

Infrared Matrix-Isolation Study of New Noble-Gas Compounds

NASA Astrophysics Data System (ADS)

Zhu, Cheng; Räsänen, Markku; Khriachtchev, Leonid

2016-06-01

We identify new noble-gas compounds in solid matrices using IR spectroscopy. The compounds under study belong to two types: HNgY and YNgY' where Ng is a noble-gas atom and Y and Y' are electronegative fragments. The experimental assignments are supported by ab initio calculations at the MP2(full) and CCSD(T) levels of theory with the def2-TZVPPD basis set. We have prepared and characterized two new HNgY compounds (noble-gas hydrides): HKrCCCl in a Kr matrix and HXeCCCl in a Xe matrix.I The synthesis of these compounds includes two steps: UV photolysis of HCCCl in a noble-gas matrix to form the H + CCCl fragments and annealing of the matrix to mobilize H atoms and to promote the H + Ng + CCCl = HNgCCCl reaction. An interesting observation in the experiments on HXeCCCl in a Xe matrix is the temperature-induced transformation of the three H-Xe stretching bands. This observation is explained by temperature-induced changes of local matrix morphology around the embedded HXeCCCl molecule. In these experiments, we have also obtained the IR spectrum of the CCCl radical, which is produced by photodecomposition of HCCCl. We have identified three new YNgY' compounds (fluorinated noble-gas cyanides): FKrCN in a Kr matrix and FXeCN and FXeNC in a Xe matrix.II These molecule are formed by photolysis of FCN in a noble-gas matrix due to locality of this process. The amount of these molecules increases upon thermal mobilization of the F atoms in the photolyzed matrix featuring the F + Ng + CN reaction.

Neutral vs zwitterionic glycine forms at the water/silica interface: structure, energies, and vibrational features from B3LYP periodic simulations.

PubMed

Rimola, Albert; Civalleri, Bartolomeo; Ugliengo, Piero

2008-12-16

B3LYP periodic calculations with a triple-xi-polarized Gaussian basis set have been used to study adsorption of glycine on a hydroxylated silica surface (2.2 OH/nm2) model derived from the (001) surface of edingtonite. The simulation envisages glycine adsorbed either as a gas-phase molecule or when microsolvated by up to five H20 molecules. Both neutral and zwitterionic forms of glycine have been considered and their structural, energetic, and spectroscopic vibrational features compared internally and with experiments. As a gas phase glycine sticks in its neutral form at the silica surface, the zwitterion being highly unstable and with transition-state character. When glycine is microsolvated at the silica interface, two H20 molecules render the zwitterion population comparable to that of the neutral form whereas with four H2O molecules the neutral glycine population is wiped out in favor of the zwitterion. With four H20 molecules the most stable structure shows no direct contact between glycine and the silica surface, H20 acting as a mediator via H-bond interactions. The B3LYP energies and structural data were also supported by comparing the scaled harmonic vibrational features with literature FTIR data of glycine adsorbed on an amorphous silica surface either from the gas phase or in water solution.

Complex molecules in the W51 North region

NASA Astrophysics Data System (ADS)

Rong, Jialei; Qin, Sheng-Li; Zapata, Luis A.; Wu, Yuefang; Liu, Tie; Zhang, Chengpeng; Peng, Yaping; Zhang, Li; Liu, Ying

2016-01-01

We present Submillimeter Array (SMA) molecular-line observations in two 2-GHz wide bands centred at 217.5 and 227.5 GHz, towards the massive star-forming region W51 North. We identified 84 molecular-line transitions from 17 species and their isotopologues. The molecular gas distribution of these lines mainly peaks in the continuum position of W51 North, and has a small tail extending to the west, probably associated with W51 d2. In addition to the commonly detected nitrogen- and oxygen-bearing species, we detected a large number of transitions of acetone (CH3COCH3) and methyl formate (CH3OCHO), which might suggest that these molecules are present in an early evolutionary stage of massive stars. We have also found that W51 North is an ethanol-rich source. There is no obvious difference in the molecular gas distributions between the oxygen-bearing and nitrogen-bearing molecules. Under the assumption of local thermodynamic equilibrium, with the XCLASS tool, the molecular column densities and rotation temperatures are estimated. We have found that the oxygen-bearing molecules have considerably higher column densities and fractional abundances than the nitrogen-bearing molecules. The rotation temperatures range from 100 to 200 K, suggesting that the molecular emission could originate from a warm environment. Finally, based on the gas distributions, fractional abundances and the rotation temperatures, we conclude that CH3OH, C2H5OH, CH3COCH3 and CH3CH2CN might be synthesized on the grain surface, while gas phase chemistry is responsible for the production of CH3OCH3, CH3OCHO and CH2CHCN.

High-pressure/low-temperature neutron scattering of gas inclusion compounds: Progress and prospects

PubMed Central

Zhao, Yusheng; Xu, Hongwu; Daemen, Luke L.; Lokshin, Konstantin; Tait, Kimberly T.; Mao, Wendy L.; Luo, Junhua; Currier, Robert P.; Hickmott, Donald D.

2007-01-01

Alternative energy resources such as hydrogen and methane gases are becoming increasingly important for the future economy. A major challenge for using hydrogen is to develop suitable materials to store it under a variety of conditions, which requires systematic studies of the structures, stability, and kinetics of various hydrogen-storing compounds. Neutron scattering is particularly useful for these studies. We have developed high-pressure/low-temperature gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments allowing in situ and real-time examination of gas uptake/release processes. We studied the formation of methane and hydrogen clathrates, a group of inclusion compounds consisting of frameworks of hydrogen-bonded H2O molecules with gas molecules trapped inside the cages. Our results reveal that clathrate can store up to four hydrogen molecules in each of its large cages with an intermolecular H2–H2 distance of only 2.93 Å. This distance is much shorter than that in the solid/metallic hydrogen (3.78 Å), suggesting a strong densification effect of the clathrate framework on the enclosed hydrogen molecules. The framework-pressurizing effect is striking and may exist in other inclusion compounds such as metal-organic frameworks (MOFs). Owing to the enormous variety and flexibility of their frameworks, inclusion compounds may offer superior properties for storage of hydrogen and/or hydrogen-rich molecules, relative to other types of compounds. We have investigated the hydrogen storage properties of two MOFs, Cu3[Co(CN)6]2 and Cu3(BTC)2 (BTC = benzenetricarboxylate), and our preliminary results demonstrate that the developed neutron-scattering techniques are equally well suited for studying MOFs and other inclusion compounds. PMID:17389387

Interstellar Processes Leading to Molecular Deuterium Enrichment and Their Detection

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Kliss, Mark (Technical Monitor)

2001-01-01

Large deuterium (D) enrichments in meteoritic materials indicate that interstellar organic materials survived incorporation into parent bodies within the forming Solar System. These enrichments are likelier due to one or more of four distinct astrochemical processes. These are (1) low temperature gas phase ion-molecule reactions; (2) low temperature gas-grain reactions; (3) gas phase unimolecular photodissociation, and (4) ultraviolet photolysis in D-enriched ice mantles. Each of these processes should be associated with molecular carriers having, distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.). These processes are reviewed and specific spectroscopic signatures for the detection of these processes in space are identified and described.

Laser absorption spectroscopy of water vapor confined in nanoporous alumina: wall collision line broadening and gas diffusion dynamics.

PubMed

Svensson, Tomas; Lewander, Märta; Svanberg, Sune

2010-08-02

We demonstrate high-resolution tunable diode laser absorption spectroscopy (TDLAS) of water vapor confined in nanoporous alumina. Strong multiple light scattering results in long photon pathlengths (1 m through a 6 mm sample). We report on strong line broadening due to frequent wall collisions (gas-surface interactions). For the water vapor line at 935.685 nm, the HWHM of confined molecules are about 4.3 GHz as compared to 2.9 GHz for free molecules (atmospheric pressure). Gas diffusion is also investigated, and in contrast to molecular oxygen (that moves rapidly in and out of the alumina), the exchange of water vapor is found very slow.

Optical and Electron Spin Resonance Studies of Destruction of Porous Structures Formed by Nitrogen-Rare Gas Nanoclusters in Bulk Superfluid Helium

NASA Astrophysics Data System (ADS)

McColgan, Patrick T.; Meraki, Adil; Boltnev, Roman E.; Lee, David M.; Khmelenko, Vladimir V.

2017-04-01

We studied optical and electron spin resonance spectra during destruction of porous structures formed by nitrogen-rare gas (RG) nanoclusters in bulk superfluid helium containing high concentrations of stabilized nitrogen atoms. Samples were created by injecting products of a radio frequency discharge of nitrogen-rare gas-helium gas mixtures into bulk superfluid helium. These samples have a high energy density allowing the study of energy release in chemical processes inside of nanocluster aggregates. The rare gases used in the studies were neon, argon, and krypton. We also studied the effects of changing the relative concentrations between nitrogen and rare gas on thermoluminescence spectra during destruction of the samples. At the beginning of the destructions, α -group of nitrogen atoms, Vegard-Kaplan bands of N_2 molecules, and β -group of O atoms were observed. The final destruction of the samples were characterized by a series bright flashes. Spectra obtained during these flashes contain M- and β -bands of NO molecules, the intensities of which depend on the concentration of molecular nitrogen in the gas mixture as well as the type of rare gas present in the gas mixture.

How well do static electronic dipole polarizabilities from gas-phase experiments compare with density functional and MP2 computations?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thakkar, Ajit J., E-mail: ajit@unb.ca; Wu, Taozhe

2015-10-14

Static electronic dipole polarizabilities for 135 molecules are calculated using second-order Møller-Plesset perturbation theory and six density functionals recently recommended for polarizabilities. Comparison is made with the best gas-phase experimental data. The lowest mean absolute percent deviations from the best experimental values for all 135 molecules are 3.03% and 3.08% for the LC-τHCTH and M11 functionals, respectively. Excluding the eight extreme outliers for which the experimental values are almost certainly in error, the mean absolute percent deviation for the remaining 127 molecules drops to 2.42% and 2.48% for the LC-τHCTH and M11 functionals, respectively. Detailed comparison enables us to identifymore » 32 molecules for which the discrepancy between the calculated and experimental values warrants further investigation.« less

An advanced molecule-surface scattering instrument for study of vibrational energy transfer in gas-solid collisions.

PubMed

Ran, Qin; Matsiev, Daniel; Wodtke, Alec M; Auerbach, Daniel J

2007-10-01

We describe an advanced and highly sensitive instrument for quantum state-resolved molecule-surface energy transfer studies under ultrahigh vacuum (UHV) conditions. The apparatus includes a beam source chamber, two differential pumping chambers, and a UHV chamber for surface preparation, surface characterization, and molecular beam scattering. Pulsed and collimated supersonic molecular beams are generated by expanding target molecule mixtures through a home-built pulsed nozzle, and excited quantum state-selected molecules were prepared via tunable, narrow-band laser overtone pumping. Detection systems have been designed to measure specific vibrational-rotational state, time-of-flight, angular and velocity distributions of molecular beams coming to and scattered off the surface. Facilities are provided to clean and characterize the surface under UHV conditions. Initial experiments on the scattering of HCl(v = 0) from Au(111) show many advantages of this new instrument for fundamental studies of the energy transfer at the gas-surface interface.

An optical switch

DOEpatents

Christophorou, L.G.; Hunter, S.R.

1987-04-30

The invention is a gas mixture for a diffuse discharge switch having an electron attaching gas wherein electron attachment is brought about by indirect excitation of molecules to long live states by exposure to laser light. 3 figs.

Aerothermodynamics of Satellite During Atmospheric Reentry for the Whole Range of Gas Rarefaction: Influence of Inelastic Intermolecular Collisions

NASA Astrophysics Data System (ADS)

Kozak, Dalton Vinicius; Sharipov, Felix

2012-08-01

The aerothermodynamic characteristics of the Brazilian satellite Satélite de Reentrada Atmosférica were calculated for orbital-flight and atmospheric-reentry conditions with the direct simulation Monte Carlo method for a diatomic gas. The internal modes of molecule energy in the intermolecular interaction, such as the rotational energy, were taken into account. The numerical calculations cover a range of gas rarefactions wide enough to embrace the free-molecule and hydrodynamic regimes. Two Mach numbers were considered: 10 and 20. Numerical results include the drag force of the satellite, the energy flux, pressure coefficient, and skin friction coefficient over the satellite surface, the density and temperature distributions, and streamlines of the gas flow around the satellite. The influence of the satellite temperature upon these characteristics was evaluated at different satellite temperatures.

Relaxation of heavy species and gas temperature in the afterglow of a N2 microwave discharge

NASA Astrophysics Data System (ADS)

Pintassilgo, Carlos D.; Guerra, Vasco

2017-10-01

In this paper we present a self-consistent kinetic model to study the temporal variation of the gas temperature in the afterglow of a 440 Pa microwave nitrogen discharge operating at 433 MHz in a 3.8 cm diameter tube. The initial conditions in the afterglow are determined by a kinetic model that solves the electron Boltzmann equation coupled to the gas thermal balance equation and a system of rate-balance equations for N2(X 1∑g+, v) molecules, electronically excited states of N2, ground and excited states of atomic nitrogen and the main positive ions. Once the initial concentrations of the heavy species and gas temperature are known, their relaxation in the afterglow is obtained from the solutions to the corresponding time-dependent equations. Modelling predictions are found to be in good agreement with previously measured values for the concentrations of N(4S) atoms and N2(A 3∑u+) molecules, and the radially averaged gas temperature Tg along the afterglow of a microwave discharge in N2 under the same working conditions. It is shown that gas heating in the afterglow comes essentially from the energy transfer involving non-resonant vibration-vibration (V-V) collisions between vibrationally excited nitrogen molecules, as well as from energy exchanges in vibration-translation (V-T) on N2-N collisions. Contribution to the topical issue "Plasma Sources and Plasma Processes (PSPP)", edited by Luis Lemos Alves, Thierry Belmonte and Tiberiu Minea

High Selective Gas Detection for small molecules based on Germanium selenide monolayer

NASA Astrophysics Data System (ADS)

Liu, Lian; Yang, Qun; Wang, Zeping; Ye, Huaiyu; Chen, Xianping; Fan, Xuejun; Zhang, Guoqi

2018-03-01

Predictive calculations based on density functional theory (DFT) are used here to study the electronic and optical properties of GeSe monolayer after adsorbing gas molecules (O2, NH3, SO2, H2, CO2, H2S, NO2, CH4, H2O, NO, CO). Our results reveal that for all the gas molecules considered, only NH3 is adsorbed on GeSe monolayer by physisorption. Whereas SO2 and NO2 are chemisorbed on GeSe monolayer with strong adsorption energies. In addition, the adsorption of O2, NO and NO2 distinctly enhances the optical absorbance and broaden the absorbance range of GeSe monolayer in visible light region. Also, it is found that the adsorption of H2S, NO and NH3 can reduce the work function of the GeSe monolayer. The results indicate that GeSe monolayer is not only a promising candidate for the sensing, capture, and storage of NH3, but also an anticipated disposable gas sensor or metal-free catalyst for detecting and catalyzing SO2 and NO2. Furthermore, it has excellent potential to be applied to optical sensors, solar cells, nanoelectronics or optoelectronics devices.

Carbon monoxide: present and future indications for a medical gas

PubMed Central

Choi, Augustine M. K.

2013-01-01

Gaseous molecules continue to hold new promise in molecular medicine as experimental and clinical therapeutics. The low molecular weight gas carbon monoxide (CO), and similar gaseous molecules (e.g., H2S, nitric oxide) have been implicated as potential inhalation therapies in inflammatory diseases. At high concentration, CO represents a toxic inhalation hazard, and is a common component of air pollution. CO is also produced endogenously as a product of heme degradation catalyzed by heme oxygenase enzymes. CO binds avidly to hemoglobin, causing hypoxemia and decreased oxygen delivery to tissues at high concentrations. At physiological concentrations, CO may have endogenous roles as a signal transduction molecule in the regulation of neural and vascular function and cellular homeostasis. CO has been demonstrated to act as an effective anti-inflammatory agent in preclinical animal models of inflammation, acute lung injury, sepsis, ischemia/reperfusion injury, and organ transplantation. Additional experimental indications for this gas include pulmonary fibrosis, pulmonary hypertension, metabolic diseases, and preeclampsia. The development of chemical CO releasing compounds constitutes a novel pharmaceutical approach to CO delivery with demonstrated effectiveness in sepsis models. Current and pending clinical evaluation will determine the usefulness of this gas as a therapeutic in human disease. PMID:23525151

Thermophoretic force and velocity of nanoparticles in the free molecule regime.

PubMed

Li, Zhigang; Wang, Hai

2004-08-01

We extend our previous gas-kinetic theory analysis of drag force in a uniform temperature field [Li and Wang, Phys. Rev. E. 68, 061206 (2003); 68, 061207 (2003)] to particle transport in fluids with nonuniform temperature. Formulations for drag and thermophoretic forces are proposed for nanoparticle transport in low-density gases. We specifically consider the influence of nonrigid body collision due to van der Waals or other forces between the particle and gas molecules and find that these forces play a notable role for particles a few nanometers in size. It is shown that the present formulations can be easily reduced to the classical result of Waldmann [Z. Naturforsch. A 14a, 589 (1959)] by assuming rigid body collision. From the force formulations we also obtain the equation governing the thermophoretic velocity. This velocity is found to be highly sensitive to the potential energy of interactions between gas molecules and particle, and as such Waldmann's thermophoretic velocity is not expected to be accurate for nanosized particles.

Kinetics and dynamics of near-resonant vibrational energy transfer in gas ensembles of atmospheric interest

NASA Astrophysics Data System (ADS)

McCaffery, Anthony J.

2018-03-01

This study of near-resonant, vibration-vibration (V-V) gas-phase energy transfer in diatomic molecules uses the theoretical/computational method, of Marsh & McCaffery (Marsh & McCaffery 2002 J. Chem. Phys. 117, 503 (doi:10.1063/1.1489998)) The method uses the angular momentum (AM) theoretical formalism to compute quantum-state populations within the component molecules of large, non-equilibrium, gas mixtures as the component species proceed to equilibration. Computed quantum-state populations are displayed in a number of formats that reveal the detailed mechanism of the near-resonant V-V process. Further, the evolution of quantum-state populations, for each species present, may be followed as the number of collision cycles increases, displaying the kinetics of evolution for each quantum state of the ensemble's molecules. These features are illustrated for ensembles containing vibrationally excited N2 in H2, O2 and N2 initially in their ground states. This article is part of the theme issue `Modern theoretical chemistry'.

Adsorption and Desorption of Hydrogen by Gas-Phase Palladium Clusters Revealed by In Situ Thermal Desorption Spectroscopy.

PubMed

Takenouchi, Masato; Kudoh, Satoshi; Miyajima, Ken; Mafuné, Fumitaka

2015-07-02

Adsorption and desorption of hydrogen by gas-phase Pd clusters, Pdn(+), were investigated by thermal desorption spectroscopy (TDS) experiments and density functional theory (DFT) calculations. The desorption processes were examined by heating the clusters that had adsorbed hydrogen at room temperature. The clusters remaining after heating were monitored by mass spectrometry as a function of temperature up to 1000 K, and the temperature-programmed desorption (TPD) curve was obtained for each Pdn(+). It was found that hydrogen molecules were released from the clusters into the gas phase with increasing temperature until bare Pdn(+) was formed. The threshold energy for desorption, estimated from the TPD curve, was compared to the desorption energy calculated by using DFT, indicating that smaller Pdn(+) clusters (n ≤ 6) tended to have weakly adsorbed hydrogen molecules, whereas larger Pdn(+) clusters (n ≥ 7) had dissociatively adsorbed hydrogen atoms on the surface. Highly likely, the nonmetallic nature of the small Pd clusters prevents hydrogen molecule from adsorbing dissociatively on the surface.

Monte Carlo calculations of diatomic molecule gas flows including rotational mode excitation

NASA Technical Reports Server (NTRS)

Yoshikawa, K. K.; Itikawa, Y.

1976-01-01

The direct simulation Monte Carlo method was used to solve the Boltzmann equation for flows of an internally excited nonequilibrium gas, namely, of rotationally excited homonuclear diatomic nitrogen. The semi-classical transition probability model of Itikawa was investigated for its ability to simulate flow fields far from equilibrium. The behavior of diatomic nitrogen was examined for several different nonequilibrium initial states that are subjected to uniform mean flow without boundary interactions. A sample of 1000 model molecules was observed as the gas relaxed to a steady state starting from three specified initial states. The initial states considered are: (1) complete equilibrium, (2) nonequilibrium, equipartition (all rotational energy states are assigned the mean energy level obtained at equilibrium with a Boltzmann distribution at the translational temperature), and (3) nonequipartition (the mean rotational energy is different from the equilibrium mean value with respect to the translational energy states). In all cases investigated the present model satisfactorily simulated the principal features of the relaxation effects in nonequilibrium flow of diatomic molecules.

First-principles study of Au–Cu alloy surface changes induced by gas adsorption of CO, NO, or O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhifallah, Marwa; Université de Gabes, Unité de recherche environnement, Catalyse et Analyse des Procédés, 6072 Gabes; Dhouib, Adnene

2016-07-14

The surface composition of bimetallics can be strongly altered by adsorbing molecules where the metal with the strongest interaction with the adsorbate segregates into the surface. To investigate the effect of reactive gas on the surface composition of Au–Cu alloy, we examined by means of density functional theory to study the segregation behavior of copper in gold matrices. The adsorption mechanisms of CO, NO, and O{sub 2} gas molecules on gold, copper, and gold-copper low index (111), (100), and (110) surfaces were analyzed from energetic and electronic points of view. Our results show a strong segregation of Cu toward themore » (110) surface in the presence of all adsorbed molecules. Interestingly, the Cu segregation toward the (111) and (100) surface could occur only in the presence of CO and at a lower extent in the presence of NO. The analysis of the electronic structure highlights the different binding characters of adsorbates inducing the Cu segregation.« less

Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface

NASA Astrophysics Data System (ADS)

Murina, Ezequiel L.; Fernández-Prini, Roberto; Pastorino, Claudio

2017-08-01

We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

Haze heats Pluto's atmosphere yet explains its cold temperature.

PubMed

Zhang, Xi; Strobel, Darrell F; Imanaka, Hiroshi

2017-11-15

Pluto's atmosphere is cold and hazy. Recent observations have shown it to be much colder than predicted theoretically, suggesting an unknown cooling mechanism. Atmospheric gas molecules, particularly water vapour, have been proposed as a coolant; however, because Pluto's thermal structure is expected to be in radiative-conductive equilibrium, the required water vapour would need to be supersaturated by many orders of magnitude under thermodynamic equilibrium conditions. Here we report that atmospheric hazes, rather than gases, can explain Pluto's temperature profile. We find that haze particles have substantially larger solar heating and thermal cooling rates than gas molecules, dominating the atmospheric radiative balance from the ground to an altitude of 700 kilometres, above which heat conduction maintains an isothermal atmosphere. We conclude that Pluto's atmosphere is unique among Solar System planetary atmospheres, as its radiative energy equilibrium is controlled primarily by haze particles instead of gas molecules. We predict that Pluto is therefore several orders of magnitude brighter at mid-infrared wavelengths than previously thought-a brightness that could be detected by future telescopes.

Laser photochemical lead isotopes separation for harmless nuclear power engineering

NASA Astrophysics Data System (ADS)

Bokhan, P. A.; Fateev, N. V.; Kim, V. A.; Zakrevsky, D. E.

2016-09-01

The collisional quenching of the metastable 3 P 1,2 and 1 D 2 lead atoms is studied experimentally in the gas flow of the lead atoms, reagent-molecules and a carrier gas Ar. The experimental parameters were similar to the conditions that are required in the operation of the experimental setup for photochemical isotope separation. Excited atoms are generated under electron impact conditions created by a gas glow discharge through the mixture of gases and monitored photoelectrically by attenuation of atomic resonance radiation from hollow cathode 208Pb lamp. The decay of the excited atoms has been studied in the presence various molecules and total cross section data are reported. The flow tube measurements has allowed to separate the physical and chemical quenching channels and measure the rates of the chemical reaction excited lead with N2O, CH2Cl2, SF6 and CuBr molecules. These results are discussed in the prospects of the obtaining isotopically modified lead as a promising coolant in the reactors on the fast-neutron.

A new interstellar molecule - Tricarbon monoxide

NASA Technical Reports Server (NTRS)

Matthews, H. E.; Irvine, W. M.; Friberg, P.; Brown, R. D.; Godfrey, P. D.

1984-01-01

The C3O molecule, whose pure rotational spectrum has only recently been studied in the laboratory, has been detected in the cold, dark interstellar Taurus Molecular Cloud 1. Since C3O is the first interstelar carbon chain molecule to contain oxygen, its existence places an important new constraint on chemical schemes for cold interstellar clouds. The abundance of C3O can be understood in terms of purely gas-phase ion-molecule chemistry.

Efficient rotational cooling of Coulomb-crystallized molecular ions by a helium buffer gas.

PubMed

Hansen, A K; Versolato, O O; Kłosowski, L; Kristensen, S B; Gingell, A; Schwarz, M; Windberger, A; Ullrich, J; López-Urrutia, J R Crespo; Drewsen, M

2014-04-03

The preparation of cold molecules is of great importance in many contexts, such as fundamental physics investigations, high-resolution spectroscopy of complex molecules, cold chemistry and astrochemistry. One versatile and widely applied method to cool molecules is helium buffer-gas cooling in either a supersonic beam expansion or a cryogenic trap environment. Another more recent method applicable to trapped molecular ions relies on sympathetic translational cooling, through collisional interactions with co-trapped, laser-cooled atomic ions, into spatially ordered structures called Coulomb crystals, combined with laser-controlled internal-state preparation. Here we present experimental results on helium buffer-gas cooling of the rotational degrees of freedom of MgH(+) molecular ions, which have been trapped and sympathetically cooled in a cryogenic linear radio-frequency quadrupole trap. With helium collision rates of only about ten per second--that is, four to five orders of magnitude lower than in typical buffer-gas cooling settings--we have cooled a single molecular ion to a rotational temperature of 7.5(+0.9)(-0.7) kelvin, the lowest such temperature so far measured. In addition, by varying the shape of, or the number of atomic and molecular ions in, larger Coulomb crystals, or both, we have tuned the effective rotational temperature from about 7 kelvin to about 60 kelvin by changing the translational micromotion energy of the ions. The extremely low helium collision rate may allow for sympathetic sideband cooling of single molecular ions, and eventually make quantum-logic spectroscopy of buffer-gas-cooled molecular ions feasible. Furthermore, application of the present cooling scheme to complex molecular ions should enable single- or few-state manipulations of individual molecules of biological interest.

Co(II)-doped MOF-5 nano/microcrystals: Solvatochromic behaviour, sensing solvent molecules and gas sorption property

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ji-Min; School of Chemistry and Chemical Engineering, Linyi University, Linyi 276005; Liu, Qing

2014-10-15

Co(II)-doped MOF-5 nano/microcrystals with controllable morphology and size were successfully obtained by solvothermal method. The products were characterized by powder X-ray diffraction (PXRD), energy dispersive spectrometry (EDS), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), inductively coupled plasma optical emission spectrometer (ICP-OES), elemental analysis, UV–vis and infrared (IR) spectroscopy. The factors influencing the crystal morphology and size were investigated. The gas sorption measurements reveal that highly crystalline particles have large Langmuir surface area. It was found that the Co(II)-doped MOF-5 shows enhanced hydrostability and the sorption profiles of the Co(II)-doped MOF-5 nano/microcrystals are dependent on the morphology and sizemore » of the particles. Porous Co(II)-doped MOF-5 is stable upon the removal of guest molecules and exhibits different colour with accommodating different solvent molecule, which means that it can act as solvatochromic sensing materials for recognition of solvent molecules. - Graphical abstract: Co(II)-doped MOF-5 nano/microcrystals with different shapes and sizes were synthesized by a facile hydrothermal method, which not only enhance gas sorption properties and structural stability of MOFs towards moisture, but also act as new sensing materials for sensing small molecules. - Highlights: • Co(II)-doped MOF-5 nano/microcrystals with controllable morphology and size were obtained. • Co(II)-doped MOF-5 nano/microcrystals enhance the structural stability towards moisture. • Co(II)-doped MOF-5 can act as new sensing material for sensing small molecules.« less

The molecular inventory around protostars: water, organic molecules, and the missing oxygen problem

NASA Astrophysics Data System (ADS)

Neufeld, David A.

2018-06-01

Massive star formation is accompanied by significant chemical evolution in the surrounding interstellar gas. Here, grains are heated up and icy mantles evaporate, releasing a rich inventory of water and organic molecules into the gas-phase within “hot core” regions surrounding massive protostars. Because molecules on the grain surface present broad infrared features without rotational structure, only the most abundant molecules can be identified unambiguously in the solid phase; once released into the gas-phase, however, where they are free to rotate, the constituents of grain mantles can be identified easily by means of rotational spectroscopy at millimeter and submillimeter wavelengths or through rovibrational spectroscopy in the mid-infrared. While observations of pure-rotational emission lines provide a broad view of hot core chemistry, absorption line spectroscopy of rovibrational transitions can probe the very hottest material closest to the protostar. With access to the mid-infrared spectral region from above 99% of Earth’s water vapor, SOFIA provides a unique platform for high-resolution rovibrational spectroscopy of water and organic molecules, many of which have vibrational transitions in the 5 – 8 micron spectral region that is unobservable from the ground. High spectral resolution is essential for disentangling the rotational structure and providing reliable measurements of the molecular column densities and temperatures. Future SOFIA observations will help elucidate the inventory of water and organic molecules around young protostars, and can address a puzzle related to the “oxygen budget” in the interstellar medium: surprisingly, the main interstellar reservoirs of the third-most abundant element in the Universe have yet to be identified.

The Zn12O12 cluster-assembled nanowires as a highly sensitive and selective gas sensor for NO and NO2.

PubMed

Yong, Yongliang; Su, Xiangying; Zhou, Qingxiao; Kuang, Yanmin; Li, Xiaohong

2017-12-13

Motivated by the recent realization of cluster-assembled nanomaterials as gas sensors, first-principles calculations are carried out to explore the stability and electronic properties of Zn 12 O 12 cluster-assembled nanowires and the adsorption behaviors of environmental gases on the Zn 12 O 12 -based nanowires, including CO, NO, NO 2 , SO 2 , NH 3 , CH 4 , CO 2 , O 2 and H 2 . Our results indicate that the ultrathin Zn 12 O 12 cluster-assembled nanowires are particularly thermodynamic stable at room temperature. The CO, NO, NO 2 , SO 2 , and NH 3 molecules are all chemisorbed on the Zn 12 O 12 -based nanowires with reasonable adsorption energies, but CH 4 , CO 2 , O 2 and H 2 molecules are only physically adsorbed on the nanowire. The electronic properties of the Zn 12 O 12 -based nanowire present dramatic changes after the adsorption of the NO and NO 2 molecules, especially their electric conductivity and magnetic properties, however, the other molecules adsorption hardly change the electric conductivity of the nanowire. Meanwhile, the recovery time of the nanowire sensor at T = 300 K is estimated at 1.5 μs and 16.7 μs for NO and NO 2 molecules, respectively. Furthermore, the sensitivities of NO and NO 2 are much larger than that of the other molecules. Our results thus conclude that the Zn 12 O 12 -based nanowire is a potential candidate for gas sensors with highly sensitivity for NO and NO 2 .

Electric-field controlled capture or release of phosgene molecule on graphene-based materials: First principles calculations

NASA Astrophysics Data System (ADS)

Zhang, Tong; Sun, Hao; Wang, Fengdi; Zhang, Wanqiao; Ma, Junmei; Tang, Shuwei; Gong, Hongwei; Zhang, Jingping

2018-01-01

Phosgene, one of the common chemicals in many industry areas, is extremely harmful to human and the environment. Thus, it is necessary to design the advanced materials to detect or remove phosgene effectively. In fact, detection or adsorption of some small gas molecules are not the most difficult to actualize. Whereas, one of the primary challenges is the gas molecules desorption from the adsorbent for the purpose of recycling of substrate materials since the small gas molecules interacts strongly with the substrates. In this work, the interaction between the phosgene molecule and pristine or Mn-doped graphene sheets with different electric field and charge state are investigated by using first-principles simulations. Our results show that the adsorption energy of phosgene on Mn-doped graphene is dramatically weakened by applying an external negative electric field but is obviously enhanced by introducing a positive electric field. These processes can be easily controlled by transform the direction of the electric field. Thus, introducing an external electric field or charge in the system may be an excellent method to control the phosgene molecule adsorption and desorption on Mn-doped graphene sheet. All energy needed is just a small quantity of electricity, which satisfies well the requirement of green chemistry and sustainable development. The mechanism and reason of reversible adsorption/desorption is also revealed in terms of energy, charge distribution and orbital analysis. Such spontaneous adsorption or desorption makes Mn-doped graphene to be used as an excellent reusable scavenger of phosgene.

Atmospheric Gaseous Plasma with Large Dimensions

NASA Astrophysics Data System (ADS)

Korenev, Sergey

2012-10-01

The forming of atmospheric plasma with large dimensions using electrical discharge typically uses the Dielectric Barrier Discharge (DBD). The study of atmospheric DBD was shown some problems related to homogeneous volume plasma. The volume of this plasma determines by cross section and gas gap between electrode and dielectric. The using of electron beam for volume ionization of air molecules by CW relativistic electron beams was shown the high efficiency of this process [1, 2]. The main advantage of this approach consists in the ionization of gas molecules by electrons in longitudinal direction determines by their kinetic energy. A novel method for forming of atmospheric homogeneous plasma with large volume dimensions using ionization of gas molecules by pulsed non-relativistic electron beams is presented in the paper. The results of computer modeling for delivered doses of electron beams in gases and ionization are discussed. The structure of experimental bench with plasma diagnostics is considered. The preliminary results of forming atmospheric plasma with ionization gas molecules by pulsed nanosecond non-relativistic electron beam are given. The analysis of potential applications for atmospheric volume plasma is presented. Reference: [1] S. Korenev. ``The ionization of air by scanning relativistic high power CW electron beam,'' 2002 IEEE International Conference on Plasma Science. May 2002, Alberta, Canada. [2] S. Korenev, I. Korenev. ``The propagation of high power CW scanning electron beam in air.'' BEAMS 2002: 14th International Conference on High-Power Particle Beams, Albuquerque, New Mexico (USA), June 2002, AIP Conference Proceedings Vol. 650(1), pp. 373-376. December 17.

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Thomas, J. D.; Witt, A. N.

2006-01-01

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

Large scale study of multiple-molecule queries

PubMed Central

2009-01-01

Background In ligand-based screening, as well as in other chemoinformatics applications, one seeks to effectively search large repositories of molecules in order to retrieve molecules that are similar typically to a single molecule lead. However, in some case, multiple molecules from the same family are available to seed the query and search for other members of the same family. Multiple-molecule query methods have been less studied than single-molecule query methods. Furthermore, the previous studies have relied on proprietary data and sometimes have not used proper cross-validation methods to assess the results. In contrast, here we develop and compare multiple-molecule query methods using several large publicly available data sets and background. We also create a framework based on a strict cross-validation protocol to allow unbiased benchmarking for direct comparison in future studies across several performance metrics. Results Fourteen different multiple-molecule query methods were defined and benchmarked using: (1) 41 publicly available data sets of related molecules with similar biological activity; and (2) publicly available background data sets consisting of up to 175,000 molecules randomly extracted from the ChemDB database and other sources. Eight of the fourteen methods were parameter free, and six of them fit one or two free parameters to the data using a careful cross-validation protocol. All the methods were assessed and compared for their ability to retrieve members of the same family against the background data set by using several performance metrics including the Area Under the Accumulation Curve (AUAC), Area Under the Curve (AUC), F1-measure, and BEDROC metrics. Consistent with the previous literature, the best parameter-free methods are the MAX-SIM and MIN-RANK methods, which score a molecule to a family by the maximum similarity, or minimum ranking, obtained across the family. One new parameterized method introduced in this study and two previously defined methods, the Exponential Tanimoto Discriminant (ETD), the Tanimoto Power Discriminant (TPD), and the Binary Kernel Discriminant (BKD), outperform most other methods but are more complex, requiring one or two parameters to be fit to the data. Conclusion Fourteen methods for multiple-molecule querying of chemical databases, including novel methods, (ETD) and (TPD), are validated using publicly available data sets, standard cross-validation protocols, and established metrics. The best results are obtained with ETD, TPD, BKD, MAX-SIM, and MIN-RANK. These results can be replicated and compared with the results of future studies using data freely downloadable from http://cdb.ics.uci.edu/. PMID:20298525

Detection of presence of chemical precursors

NASA Technical Reports Server (NTRS)

Li, Jing (Inventor); Meyyappan, Meyya (Inventor); Lu, Yijiang (Inventor)

2009-01-01

Methods and systems for determining if one or more target molecules are present in a gas, by exposing a functionalized carbon nanostructure (CNS) to the gas and measuring an electrical parameter value EPV(n) associated with each of N CNS sub-arrays. In a first embodiment, a most-probable concentration value C(opt) is estimated, and an error value, depending upon differences between the measured values EPV(n) and corresponding values EPV(n;C(opt)) is computed. If the error value is less than a first error threshold value, the system interprets this as indicating that the target molecule is present in a concentration C.apprxeq.C(opt). A second embodiment uses extensive statistical and vector space analysis to estimate target molecule concentration.

Hyperthermal Carbon Dioxide Interactions with Self-Assembled Monolayer Surfaces

DTIC Science & Technology

2013-09-08

comparison of the scattering behavior from the liquid and semi-solid surfaces to allow new insight into the pivotal initial step in gas -surface reaction...scattering dynamics of atoms and molecules on liquid and SAM surfaces, in order to deepen the understanding of gas -surface interactions at liquid and... gas - liquid and gas -SAM interface have developed a basic picture of the gas -surface collision dynamics. The previous experiments showed a bimodal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Razhev, A M; Kargapol'tsev, E S; Churkin, D S

Results of an experimental study of the influence of a gas mixture (laser active medium) composition on an output energy and total efficiency of gas-discharge excimer lasers on ArF* (193 nm), KrCl* (222 nm), KrF* (248 nm) and XeCl* (308 nm) molecules operating without a buffer gas are presented. The optimal ratios of gas components (from the viewpoint of a maximum output energy) of an active medium are found, which provide an efficient operation of laser sources. It is experimentally confirmed that for gas-discharge excimer lasers on halogenides of inert gases the presence of a buffer gas in an activemore » medium is not a necessary condition for efficient operation. For the first time, in two-component gas mixtures of repetitively pulsed gas-discharge excimer lasers on electron transitions of excimer molecules ArF*, KrCl*, KrF* and XeCl*, the pulsed energy of laser radiation obtained under pumping by a transverse volume electric discharge in a low-pressure gas mixture without a buffer gas reached up to 170 mJ and a high pulsed output power (of up to 24 MW) was obtained at a FWHM duration of the KrF-laser pulse of 7 ns. The maximal total efficiency obtained in the experiment with two-component gas mixtures of KrF and XeCl lasers was 0.8%. (lasers)« less

A pressure-amplifying framework material with negative gas adsorption transitions.

PubMed

Krause, Simon; Bon, Volodymyr; Senkovska, Irena; Stoeck, Ulrich; Wallacher, Dirk; Többens, Daniel M; Zander, Stefan; Pillai, Renjith S; Maurin, Guillaume; Coudert, François-Xavier; Kaskel, Stefan

2016-04-21

Adsorption-based phenomena are important in gas separations, such as the treatment of greenhouse-gas and toxic-gas pollutants, and in water-adsorption-based heat pumps for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers--or metal-organic frameworks (MOFs)--has made them attractive materials for such adsorption-based applications. The flexibility and guest-molecule-dependent response of MOFs give rise to unexpected and often desirable adsorption phenomena. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.

Prediction Metrics for Chemical Detection in Long-Wave Infrared Hyperspectral Imagery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chilton, Marie C.; Walsh, Stephen J.; Daly, Don S.

2009-01-29

A natural or anthropogenic process often generates a signature gas plume whose chemical constituents may be identified using hyperspectral imagery. A hyperspectral image is a pixel-indexed set of spectra where each spectrum reflects the chemical constituents of the plume, the atmosphere, the bounding background surface, and instrument noise. This study explored the relationship between gas absorbance and background emissivity across the long-wave infrared (LWIR) spectrum and how they affect relative gas detection sensitivity. The physics-based model for the observed radiance shows that high gas absorbance coupled with low background emissivity at a single wavenumber results in a stronger recorded radiance.more » Two sensitivity measures were developed to predict relative probability of detection using chemical absorbance and background emissivity: one focused on a single wavenumber while another accounted for the entire spectrum. The predictive abilities of these measures were compared to synthetic image analysis. This study simulated images with 499 distinct gases at each of 6 concentrations over 6 different background surfaces with the atmosphere and level of instrument noise held constant. The Whitened Matched Filter was used to define gas detection from an image spectrum. The estimate of a chemical’s probability of detection at a given concentration over a specific background was the proportion of detections in 500 trials. Of the 499 chemicals used in the images, 276 had estimated probabilities of detection below 0.2 across all backgrounds and concentrations; these chemicals were removed from the study. For 92.8 percent of the remaining chemicals, the single channel measure correctly predicted the background over which the chemical had the largest relative probability of detection. Further, the measure which accounted for information across all wavenumbers predicted the background over which the chemical had the largest relative probability of detection for 93.3 percent of the chemicals. These results suggest that the wavenumber with largest gas absorbance has the most influence over gas detection for this data. By furthering the in-silico experimentation with higher concentrations of gases not detectable in this experiment or by standardizing the gas absorbance spectra to unit vectors, these conclusions may be confirmed and generalized to more gases. This will help simplify image acquisition planning and the identification of unknowns in field collected images.« less

Diffusion and mobility of atomic particles in a liquid

NASA Astrophysics Data System (ADS)

Smirnov, B. M.; Son, E. E.; Tereshonok, D. V.

2017-11-01

The diffusion coefficient of a test atom or molecule in a liquid is determined for the mechanism where the displacement of the test molecule results from the vibrations and motion of liquid molecules surrounding the test molecule and of the test particle itself. This leads to a random change in the coordinate of the test molecule, which eventually results in the diffusion motion of the test particle in space. Two models parameters of interaction of a particle and a liquid are used to find the activation energy of the diffusion process under consideration: the gas-kinetic cross section for scattering of test molecules in the parent gas and the Wigner-Seitz radius for test molecules. In the context of this approach, we have calculated the diffusion coefficient of atoms and molecules in water, where based on experimental data, we have constructed the dependence of the activation energy for the diffusion of test molecules in water on the interaction parameter and the temperature dependence for diffusion coefficient of atoms or molecules in water within the models considered. The statistically averaged difference of the activation energies for the diffusion coefficients of different test molecules in water that we have calculated based on each of the presented models does not exceed 10% of the diffusion coefficient itself. We have considered the diffusion of clusters in water and present the dependence of the diffusion coefficient on the cluster size. The accuracy of the presented formulas for the diffusion coefficient of atomic particles in water is estimated to be 50%.

Chemiresistive and Gravimetric Dual-Mode Gas Sensor toward Target Recognition and Differentiation.

PubMed

Chen, Yan; Zhang, Hao; Feng, Zhihong; Zhang, Hongxiang; Zhang, Rui; Yu, Yuanyuan; Tao, Jin; Zhao, Hongyuan; Guo, Wenlan; Pang, Wei; Duan, Xuexin; Liu, Jing; Zhang, Daihua

2016-08-24

We demonstrate a dual-mode gas sensor for simultaneous and independent acquisition of electrical and mechanical signals from the same gas adsorption event. The device integrates a graphene field-effect transistor (FET) with a piezoelectric resonator in a seamless manner by leveraging multiple structural and functional synergies. Dual signals resulting from independent physical processes, i.e., mass attachment and charge transfer can reflect intrinsic properties of gas molecules and potentially enable target recognition and quantification at the same time. Fabrication of the device is based on standard Integrated Circuit (IC) foundry processes and fully compatible with system-on-a-chip (SoC) integration to achieve extremely small form factors. In addition, the ability of simultaneous measurements of mass adsorption and charge transfer guides us to a more precise understanding of the interactions between graphene and various gas molecules. Besides its practical functions, the device serves as an effective tool to quantitatively investigate the physical processes and sensing mechanisms for a large library of sensing materials and target analytes.

Adsorption behavior of COF2 and CF4 gas on the MoS2 monolayer doped with Ni: A first-principles study

NASA Astrophysics Data System (ADS)

Li, Yi; Zhang, Xiaoxing; Chen, Dachang; Xiao, Song; Tang, Ju

2018-06-01

CF4 and COF2 are the two main decomposition products of fluorocarbon gas insulating medium. We explored the gas sensing properties of Ni-MoS2 to CF4 and COF2 based on the density functional theory calculations. The adsorption energy, charge transfer, density of states and electron density difference have been discussed. It was found that the interaction between COF2 molecule and Ni-MoS2 is strong, and the adsorption energy is 0.723 eV. Ni-MoS2 acts as the electron donor and transfers some electrons to COF2 molecule during the interaction. The adsorption energy of CF4 on Ni-MoS2 is lower than that of COF2, and the interaction between them belongs to physical adsorption. Ni-MoS2 has the potential to be used as a gas sensor for COF2 detection using in the field of gas insulated switchgear on-line monitoring.

The H-theorem and equation of state for kinetic model of imperfect gas

NASA Astrophysics Data System (ADS)

Bishaev, A. M.; Rikov, V. A.; Abgaryan, M. V.

2018-03-01

In the offered article, having used earlier constructed kinetic model for imperfect gas, the equation of state for such gas which takes place which is able in a thermodynamic equilibrium is received and also expression for critical temperature as functions is received from an interaction potential between molecules.

First steps towards a gas-phase acidity ladder for derivatized fullerene dications

NASA Astrophysics Data System (ADS)

Petrie, Simon; Javahery, Gholamreza; Bohme, Diethard K.

1993-03-01

C2+60 can be derivatized by gas-phase ion/molecule reactions with polar hydrogen-bearing molecules. The adduct dications so produced may then undergo proton transfer to neutrals. The occurrence or absence of proton transfer as a secondary process gives information on the gas-phase acidity of the dicationic species C60·(XH)2+in. We have performed studies using a selected-ion flow tube at 294 ± 2 K and 0.35 ± 0.01 Torr, and have used observed reactivity of such dicationic fullerene adducts to determine upper or lower limits to their apparent and absolute gas-phase acidities. We present also a rationale for assessing the proton-transfer reactivity of dications via the apparent gas-phase acidity of these species, rather than the traditional use of gas-phase basicities or proton affinities. We propose that further studies of proton transfer from polycharged fullerene adducts may provide considerable useful information to model the reactivity of polyprotonated proteins and other large molecular polycatiions which can now be produced by techniques such as electrospray ionization.

The retrieval of atmospheric constituent mixing-ratio profiles from solar absorption spectra. Ph.D. Thesis. Interim Technical Report

NASA Technical Reports Server (NTRS)

Shaffer, W. A.

1983-01-01

Methods used to determine various atmospheric gas distributions are summarized. The experimentally determined mixing ratio profiles (the mixing ratio of a gas is the ratio of the number of gas molecules to the number of air molecules) of some atmospheric gases are shown. In most in situ experiments stratospheric gas samples are collected at several altitudes by balloon, aircraft, or rocket. These samples are then analyzed by various methods. Mixing ratio profiles of Ci, ClO, and OH were determined by laser induced fluorescence of samples. Others have analyzed gas samples by gas chromatography in order to determine the molecular abundances of CCl2F2, CCl4, CCl3F, CFCl3, CF2Cl2, CHClF2, CH3CCl3, CH4, CO, C2Cl3F3, C2Cl4, C2HCl3, C2H2, C2H4, C2H6, C3H8, C6H6, C7H8, H2, and N2O.

Target molecules detection by waveguiding in a photonic silicon membrane

DOEpatents

Letant, Sonia E [Livermore, CA; Van Buuren, Anthony [Livermore, CA; Terminello, Louis [Danville, CA; Hart, Bradley R [Brentwood, CA

2006-12-26

Disclosed herein is a porous silicon filter capable of binding and detecting biological and chemical target molecules in liquid or gas samples. A photonic waveguiding silicon filter with chemical and/or biological anchors covalently attached to the pore walls bind target molecules. The system uses transmission curve engineering principles to allow measurements to be made in situ and in real time to detect the presence of various target molecules and calculate the concentration of bound target.

Target molecules detection by waveguiding in a photonic silicon membrane

DOEpatents

Letant, Sonia; Van Buuren, Anthony; Terminello, Louis

2004-08-31

Disclosed herein is a photonic silicon filter capable of binding and detecting biological and chemical target molecules in liquid or gas samples. A photonic waveguiding silicon filter with chemical and/or biological anchors covalently attached to the pore walls selectively bind target molecules. The system uses transmission curve engineering principles to allow measurements to be made in situ and in real time to detect the presence of various target molecules and determine the concentration of bound target.

Oriented Polar Molecules in a Solid Inert-Gas Matrix: A Proposed Method for Measuring the Electric Dipole Moment of the Electron

NASA Astrophysics Data System (ADS)

Vutha, A.; Horbatsch, M.; Hessels, E.

2018-01-01

We propose a very sensitive method for measuring the electric dipole moment of the electron using polar molecules embedded in a cryogenic solid matrix of inert-gas atoms. The polar molecules can be oriented in the $\\hat{\\rm{z}}$ direction by an applied electric field, as has recently been demonstrated by Park, et al. [Angewandte Chemie {\\bf 129}, 1066 (2017)]. The trapped molecules are prepared into a state which has its electron spin perpendicular to $\\hat{\\rm{z}}$, and a magnetic field along $\\hat{\\rm{z}}$ causes precession of this spin. An electron electric dipole moment $d_e$ would affect this precession due to the up to 100~GV/cm effective electric field produced by the polar molecule. The large number of polar molecules that can be embedded in a matrix, along with the expected long coherence times for the precession, allows for the possibility of measuring $d_e$ to an accuracy that surpasses current measurements by many orders of magnitude. Because the matrix can inhibit molecular rotations and lock the orientation of the polar molecules, it may not be necessary to have an electric field present during the precession. The proposed technique can be applied using a variety of polar molecules and inert gases, which, along with other experimental variables, should allow for careful study of systematic uncertainties in the measurement.

Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2011-12-01

Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. This paper describes and demonstrates a numerical solution scheme for ternary hydrate systems that seeks a balance between accuracy and computational efficiency. This scheme uses a generalize cubic equation of state, functional forms for the hydrate equilibria and cage occupancies, variable switching scheme for phase transitions, and kinetic exchange of hydrate formers (i.e., CH4, CO2, and N2) between the mobile phases (i.e., aqueous, liquid CO2, and gas) and hydrate phase. Accuracy of the scheme will be evaluated by comparing property values and phase equilibria against experimental data. Computational efficiency of the scheme will be evaluated by comparing the base scheme against variants. The application of interest will the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

Raman spectral signatures as conformational probes of gas phase flexible molecules

NASA Astrophysics Data System (ADS)

Golan, Amir; Mayorkas, Nitzan; Rosenwaks, Salman; Bar, Ilana

2009-07-01

A novel application of ionization-loss stimulated Raman spectroscopy (ILSRS) for monitoring the spectral features of four conformers of a gas phase flexible molecule is reported. The Raman spectral signatures of four conformers of 2-phenylethylamine are well matched by the results of density functional theory calculations, showing bands uniquely identifying the structures. The measurement of spectral signatures by ILSRS in an extended spectral range, with a conventional laser source, is instrumental in facilitating the unraveling of intra- and intermolecular interactions that are significant in biological structure and activity.

The particles in town air

PubMed Central

Ellison, J. McK.

1965-01-01

Particles constitute an important part of air pollution, and their behaviour when suspended in air is very different from that of gas molecules: in particular, the mechanisms by which they become deposited on surfaces are different, and consequently the methods normally used for removing particles from the air, either for sampling or for cleaning it, rely mainly on mechanisms that do not enter into the behaviour of gas molecules. These mechanisms are described, and the ways in which they affect the problems of air pollution and its measurement are discussed. ImagesFIG. 8 PMID:14315713

Complex admixtures of clathrate hydrates in a water desalination method

DOEpatents

Simmons, Blake A [San Francisco, CA; Bradshaw, Robert W [Livermore, CA; Dedrick, Daniel E [Berkeley, CA; Anderson, David W [Riverbank, CA

2009-07-14

Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

Rapid and selective detection of acetone using hierarchical ZnO gas sensor for hazardous odor markers application.

PubMed

Jia, Qianqian; Ji, Huiming; Zhang, Ying; Chen, Yalu; Sun, Xiaohong; Jin, Zhengguo

2014-07-15

Hierarchical nanostructured ZnO dandelion-like spheres were synthesized via solvothermal reaction at 200°C for 4h. The products were pure hexagonal ZnO with large exposure of (002) polar facet. Side-heating gas sensor based on hierarchical ZnO spheres was prepared to evaluate the acetone gas sensing properties. The detection limit to acetone for the ZnO sensor is 0.25ppm. The response (Ra/Rg) toward 100ppm acetone was 33 operated at 230°C and the response time was as short as 3s. The sensor exhibited remarkable acetone selectivity with negligible response toward other hazardous gases and water vapor. The high proportion of electron depletion region and oxygen vacancies contributed to high gas response sensitivity. The hollow and porous structure of dandelion-like ZnO spheres facilitated the diffusion of gas molecules, leading to a rapid response speed. The largely exposed (002) polar facets could adsorb acetone gas molecules easily and efficiently, resulting in a rapid response speed and good selectivity of hierarchical ZnO spheres gas sensor at low operating temperature. Copyright © 2014 Elsevier B.V. All rights reserved.

Simulation of diatomic gas-wall interaction and accommodation coefficients for negative ion sources and accelerators.

PubMed

Sartori, E; Brescaccin, L; Serianni, G

2016-02-01

Particle-wall interactions determine in different ways the operating conditions of plasma sources, ion accelerators, and beams operating in vacuum. For instance, a contribution to gas heating is given by ion neutralization at walls; beam losses and stray particle production-detrimental for high current negative ion systems such as beam sources for fusion-are caused by collisional processes with residual gas, with the gas density profile that is determined by the scattering of neutral particles at the walls. This paper shows that Molecular Dynamics (MD) studies at the nano-scale can provide accommodation parameters for gas-wall interactions, such as the momentum accommodation coefficient and energy accommodation coefficient: in non-isothermal flows (such as the neutral gas in the accelerator, coming from the plasma source), these affect the gas density gradients and influence efficiency and losses in particular of negative ion accelerators. For ideal surfaces, the computation also provides the angular distribution of scattered particles. Classical MD method has been applied to the case of diatomic hydrogen molecules. Single collision events, against a frozen wall or a fully thermal lattice, have been simulated by using probe molecules. Different modelling approximations are compared.

Simulation of diatomic gas-wall interaction and accommodation coefficients for negative ion sources and accelerators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sartori, E., E-mail: emanuele.sartori@igi.cnr.it; Serianni, G.; Brescaccin, L.

2016-02-15

Particle-wall interactions determine in different ways the operating conditions of plasma sources, ion accelerators, and beams operating in vacuum. For instance, a contribution to gas heating is given by ion neutralization at walls; beam losses and stray particle production—detrimental for high current negative ion systems such as beam sources for fusion—are caused by collisional processes with residual gas, with the gas density profile that is determined by the scattering of neutral particles at the walls. This paper shows that Molecular Dynamics (MD) studies at the nano-scale can provide accommodation parameters for gas-wall interactions, such as the momentum accommodation coefficient andmore » energy accommodation coefficient: in non-isothermal flows (such as the neutral gas in the accelerator, coming from the plasma source), these affect the gas density gradients and influence efficiency and losses in particular of negative ion accelerators. For ideal surfaces, the computation also provides the angular distribution of scattered particles. Classical MD method has been applied to the case of diatomic hydrogen molecules. Single collision events, against a frozen wall or a fully thermal lattice, have been simulated by using probe molecules. Different modelling approximations are compared.« less

Ultrafast Magnetization of a Dense Molecular Gas with an Optical Centrifuge.

PubMed

Milner, A A; Korobenko, A; Milner, V

2017-06-16

Strong laser-induced magnetization of oxygen gas at room temperature and atmospheric pressure is achieved experimentally on the subnanosecond time scale. The method is based on controlling the electronic spin of paramagnetic molecules by means of manipulating their rotation with an optical centrifuge. Spin-rotational coupling results in a high degree of spin polarization on the order of one Bohr magneton per centrifuged molecule. Owing to the nonresonant interaction with the laser pulses, the demonstrated technique is applicable to a broad class of paramagnetic rotors. Executed in a high-density gas, it may offer an efficient way of generating macroscopic magnetic fields remotely (as shown in this work) and producing a large amount of spin-polarized electrons.

Ultrafast Magnetization of a Dense Molecular Gas with an Optical Centrifuge

NASA Astrophysics Data System (ADS)

Milner, A. A.; Korobenko, A.; Milner, V.

2017-06-01

Strong laser-induced magnetization of oxygen gas at room temperature and atmospheric pressure is achieved experimentally on the subnanosecond time scale. The method is based on controlling the electronic spin of paramagnetic molecules by means of manipulating their rotation with an optical centrifuge. Spin-rotational coupling results in a high degree of spin polarization on the order of one Bohr magneton per centrifuged molecule. Owing to the nonresonant interaction with the laser pulses, the demonstrated technique is applicable to a broad class of paramagnetic rotors. Executed in a high-density gas, it may offer an efficient way of generating macroscopic magnetic fields remotely (as shown in this work) and producing a large amount of spin-polarized electrons.

Detection system for a gas chromatograph

DOEpatents

Hayes, John M.; Small, Gerald J.

1984-01-01

A method and apparatus are described for the quantitative analysis of vaporizable compounds, and in particular of polycyclic aromatic hydrocarbons which may be induced to fluoresce. The sample to be analyzed is injected into a gas chromatography column and is eluted through a narrow orifice into a vacuum chamber. The free expansion of the eluted sample into the vacuum chamber creates a supersonic molecular beam in which the sample molecules are cooled to the extent that the excited vibrational and rotational levels are substantially depopulated. The cooled molecules, when induced to fluoresce by laser excitation, give greatly simplified spectra suitable for analytical purposes. The laser induced fluorimetry provides great selectivity, and the gas chromatograph provides quantitative transfer of the sample to the molecular beam.

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection.

PubMed

Matz, Laura M; Hill, Herbert H; Beegle, Luther W; Kanik, Isik

2002-04-01

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Mars low albedo regions: Possible map of near-surface

NASA Technical Reports Server (NTRS)

Huguenin, R. L.

1987-01-01

A freeze/thaw desorption mechanism is proposed in certain low albedo areas which could be the factor that instigated dust storms. It is widely accepted that the bulk of the episodic gas evolution (not necessarily the oxygen release) experienced during the humidification process in the Viking Gas Exhange Experiment (GEX) was caused by a familiar process in which more polar H2O molecules replace large quantities of other preadsorbed gas molecules on adsorption sites. The author suggests that a similar process could produce high pore pressures in soil that could disrupt the soil and eject dust at high velocity. The author also argued that association of sites of dust storms initiated with high thermal inertial areas may simply reflect repeated dust depletion.

Thermophoretic force on nonspherical particles in the free-molecule regime

NASA Astrophysics Data System (ADS)

Yu, Song; Wang, Jun; Xia, Guodong; Zong, Luxiang

2018-05-01

The present paper is devoted to studying the thermophoresis of a nonspherical convex particle suspended in a gas with nonuniform temperature distribution in the free-molecule regime. Based on the gas kinetic theory and the assumption of a rigid-body collision for the gas-particle interaction, analytical expressions for the thermophoretic forces are obtained for several typical nonspherical bodies, including cylinders, spheroids, needles, disks, and cuboids. The orientation dependences of the thermophoretic forces and thermophoretic velocities are evaluated based on these expressions. It is found that the influence of the pitching effect of the nonspheres can be significant. The expressions for the orientation-averaged thermophoretic forces are also obtained under the assumption of a uniform particle orientation distribution.

Simulation of PEP-II Accelerator Backgrounds Using TURTLE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barlow, R.J.; Fieguth, T.; /SLAC

2006-02-15

We present studies of accelerator-induced backgrounds in the BaBar detector at the SLAC B-Factory, carried out using LPTURTLE, a modified version of the DECAY TURTLE simulation package. Lost-particle backgrounds in PEP-II are dominated by a combination of beam-gas bremstrahlung, beam-gas Coulomb scattering, radiative-Bhabha events and beam-beam blow-up. The radiation damage and detector occupancy caused by the associated electromagnetic shower debris can limit the usable luminosity. In order to understand and mitigate such backgrounds, we have performed a full program of beam-gas and luminosity-background simulations, that include the effects of the detector solenoidal field, detailed modeling of limiting apertures in bothmore » collider rings, and optimization of the betatron collimation scheme in the presence of large transverse tails.« less

Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN nanosheet

NASA Astrophysics Data System (ADS)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh

2018-05-01

We have investigated the electronic properties, adsorptions strength and charge transfer using first principles calculations using density functional theory (DFT). The hexagonal boron nitride (h-BN) substrate shows metallic behavior, which helps to enhance the absorption process. The adsorption of three different orientations (S, D and T) of the H2S gas molecules to analyze the maximum adsorption strength from them onto a copper cluster (Cu4) based on h-BN nanosheet. The maximum adsorption energy of the H2S gas molecule is -1.50 eV for the S orientation and for D and U, it is -0.71 eV and -0.78 eV, respectively. The results show that Cu4 cluster helps to capture H2S gas from the environment and results are useful for the cleaning environment from the toxic gases.

Fabry-Perot interferometer measurement of static temperature and velocity for ASTOVL model tests

NASA Technical Reports Server (NTRS)

Kourous, Helen E.; Seacholtz, Richard G.

1995-01-01

A spectrally resolved Rayleigh/Mie scattering diagnostic was developed to measure temperature and wing-spanwise velocity in the vicinity of an ASTOVL aircraft model in the Lewis 9 x 15 Low Speed Wind Tunnel. The spectrum of argon-ion laser light scattered by the air molecules and particles in the flow was resolved with a Fabry-Perot interferometer. Temperature was extracted from the spectral width of the Rayleigh scattering component, and spanwise gas velocity from the gross spectral shift. Nozzle temperature approached 800 K, and the velocity component approached 30 m/s. The measurement uncertainty was about 5 percent for the gas temperature, and about 10 m/s for the velocity. The large difference in the spectral width of the Mie scattering from particles and the Rayleigh scattering from gas molecules allowed the gas temperature to be measured in flow containing both naturally occurring dust and LDV seed (both were present).

Photoacoustic infrared spectroscopy for conducting gas tracer tests and measuring water saturations in landfills

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jung, Yoojin; Han, Byunghyun; Mostafid, M. Erfan

2012-02-15

Highlights: Black-Right-Pointing-Pointer Photoacoustic infrared spectroscopy tested for measuring tracer gas in landfills. Black-Right-Pointing-Pointer Measurement errors for tracer gases were 1-3% in landfill gas. Black-Right-Pointing-Pointer Background signals from landfill gas result in elevated limits of detection. Black-Right-Pointing-Pointer Technique is much less expensive and easier to use than GC. - Abstract: Gas tracer tests can be used to determine gas flow patterns within landfills, quantify volatile contaminant residence time, and measure water within refuse. While gas chromatography (GC) has been traditionally used to analyze gas tracers in refuse, photoacoustic spectroscopy (PAS) might allow real-time measurements with reduced personnel costs and greater mobilitymore » and ease of use. Laboratory and field experiments were conducted to evaluate the efficacy of PAS for conducting gas tracer tests in landfills. Two tracer gases, difluoromethane (DFM) and sulfur hexafluoride (SF{sub 6}), were measured with a commercial PAS instrument. Relative measurement errors were invariant with tracer concentration but influenced by background gas: errors were 1-3% in landfill gas but 4-5% in air. Two partitioning gas tracer tests were conducted in an aerobic landfill, and limits of detection (LODs) were 3-4 times larger for DFM with PAS versus GC due to temporal changes in background signals. While higher LODs can be compensated by injecting larger tracer mass, changes in background signals increased the uncertainty in measured water saturations by up to 25% over comparable GC methods. PAS has distinct advantages over GC with respect to personnel costs and ease of use, although for field applications GC analyses of select samples are recommended to quantify instrument interferences.« less

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Frequency modulation upon nonstationary heating of the p - n junction in high-sensitive diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Andreev, Sergei N.; Nikolaev, I. V.; Ochkin, Vladimir N.; Savinov, Sergei Yu; Spiridonov, Maksim V.; Tskhai, Sergei N.

2007-04-01

A special type of modulation of the injection current of a diode laser is proposed at which the frequency modulation of radiation is not accompanied by the residual amplitude modulation. This method considerably reduces the influence of the diode laser radiation instability on the recorded absorption spectra. This allows a prolonged monitoring of small amounts of impurities in gas analysis by retaining a high sensitivity. Prolonged measurements of absorption spectra are performed at a relative absorption of 8×10-7. By using a 50-cm multipass cell with the optical length of 90 m, the absorption coefficient of 1.2×10-10 cm-1 was detected. As an example, the day evolution of the background concentrations of NO2 molecules was measured in the atmosphere.

Interaction of Gas Phase Oxalic Acid with Ammonia and its Atmospheric Implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Xiu-Qiu; Liu, Yi-Rong; Huang, Teng

Oxalic acid is believed to play an important role in the formation and growth of atmospheric organic aerosols. However, as a common organic acid, the understanding of the larger clusters formed by gas phase oxalic acid with multiple ammonia molecules is incomplete. In this work, the structural characteristics and thermodynamics of oxalic acid clusters with up to six ammonia molecules have been investigated at the PW91PW91/6-311++G(3df,3pd) level of theory. We found that oxalic acid forms relatively stable clusters with ammonia molecules, and that ionization events play a key role. The analyses of the thermodynamics and atmospheric relevance indicate that themore » heterodimer (H2C2O4)(NH3) shows an obvious relative concentration in the atmosphere, and thus likely participates in new particle formation. However, with increasing number of ammonia molecules, the concentration of clusters decreases gradually. Additionally, clusters of oxalic acid with ammonia molecules are predicted to form favorably in low temperature conditions and show high Rayleigh scattering intensities.« less

Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makarov, G N; Petin, A N

2016-03-31

We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with amore » surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation. (laser separation of isotopes)« less

Study on Characteristics of Co-firing Ammonia/Methane Fuels under Oxygen Enriched Combustion Conditions

NASA Astrophysics Data System (ADS)

Xiao, Hua; Wang, Zhaolin; Valera-Medina, Agustin; Bowen, Philip J.

2018-06-01

Having a background of utilising ammonia as an alternative fuel for power generation, exploring the feasibility of co-firing ammonia with methane is proposed to use ammonia to substitute conventional natural gas. However, improvement of the combustion of such fuels can be achieved using conditions that enable an increase of oxygenation, thus fomenting the combustion process of a slower reactive molecule as ammonia. Therefore, the present study looks at oxygen enriched combustion technologies, a proposed concept to improve the performance of ammonia/methane combustion. To investigate the characteristics of ammonia/methane combustion under oxygen enriched conditions, adiabatic burning velocity and burner stabilized laminar flame emissions were studied. Simulation results show that the oxygen enriched method can help to significantly enhance the propagation of ammonia/methane combustion without changing the emission level, which would be quite promising for the design of systems using this fuel for practical applications. Furthermore, to produce low computational-cost flame chemistry for detailed numerical analyses for future combustion studies, three reduced combustion mechanisms of the well-known Konnov's mechanism were compared in ammonia/methane flame simulations under practical gas turbine combustor conditions. Results show that the reduced reaction mechanisms can provide good results for further analyses of oxygen enriched combustion of ammonia/methane. The results obtained in this study also allow gas turbine designers and modellers to choose the most suitable mechanism for further combustion studies and development.

Utilization of UV and IR Supercontinua in Gas-Phase Subpicosecond Kinetic Spectroscopy

NASA Astrophysics Data System (ADS)

Glownia, J. H.; Misewich, J.; Sorokin, P. P.

Through the work of photochemists extending over many decades, there now exists a wealth of information on the various reactions that photoexcited gas phase molecules undergo. Most of this information relates to the product molecules that are formed, either as the direct result of a primary photochemical act, such as photodissociation, or through subsequent secondary reactions, involving collisions with other molecules in the gas. Recently, there has been an extensive effort directed at determining the exact energy distributions of the primary products formed in photodissociation. With the use of nanosecond tunable-laser techniques, such as laser-induced fluorescence (LIF) and coherent anti-Stokes Raman spectroscopy (CARS), scientists have successfully determined the nascent electronic, vibrational, and rotational energy distributions of various diatomic fragments such as CN, OH, NO, and O2 that are directly formed in the photodissociation of many kinds of molecules. The ready availability of high-quality, tunable, nanosecond lasers has made determination of the above-mentioned collisionless energy distributions a relatively straightforward process. The determination of product translational energies has long effectively been handled by angularly resolved time-of-flight (TOF) spectroscopy, or by sub-Doppler resolution spectroscopy, including a recently improved version of the latter, velocity-aligned Doppler spectroscopy (Xu et al., 1986).

Gas-phase spectra of MgO molecules: a possible connection from gas-phase molecules to planet formation

NASA Astrophysics Data System (ADS)

Kloska, Katherine A.; Fortenberry, Ryan C.

2018-02-01

A more fine-tuned method for probing planet-forming regions, such as protoplanetary discs, could be rovibrational molecular spectroscopy observation of particular premineral molecules instead of more common but ultimately less related volatile organic compounds. Planets are created when grains aggregate, but how molecules form grains is an ongoing topic of discussion in astrophysics and planetary science. Using the spectroscopic data of molecules specifically involved in mineral formation could help to map regions where planet formation is believed to be occurring in order to examine the interplay between gas and dust. Four atoms are frequently associated with planetary formation: Fe, Si, Mg and O. Magnesium, in particular, has been shown to be in higher relative abundance in planet-hosting stars. Magnesium oxide crystals comprise the mineral periclase making it the chemically simplest magnesium-bearing mineral and a natural choice for analysis. The monomer, dimer and trimer forms of (MgO)n with n = 1-3 are analysed in this work using high-level quantum chemical computations known to produce accurate results. Strong vibrational transitions at 12.5, 15.0 and 16.5 μm are indicative of magnesium oxide monomer, dimer and trimer making these wavelengths of particular interest for the observation of protoplanetary discs and even potentially planet-forming regions around stars. If such transitions are observed in emission from the accretion discs or absorptions from stellar spectra, the beginning stages of mineral and, subsequently, rocky body formation could be indicated.

Free energy study of H2O, N2O5, SO2, and O3 gas sorption by water droplets/slabs

NASA Astrophysics Data System (ADS)

Li, Wentao; Pak, Chi Yuen; Tse, Ying-Lung Steve

2018-04-01

Understanding gas sorption by water in the atmosphere is an active research area because the gases can significantly alter the radiation and chemical properties of the atmosphere. We attempt to elucidate the molecular details of the gas sorption of water and three common atmospheric gases (N2O5, SO2, and O3) by water droplets/slabs in molecular dynamics simulations. The system size effects are investigated, and we show that the calculated solvation free energy decreases linearly as a function of the reciprocal of the number of water molecules from 1/215 to 1/1000 in both the slab and the droplet systems. By analyzing the infinitely large system size limit by extrapolation, we find that all our droplet results are more accurate than the slab results when compared to the experimental values. We also show how the choice of restraints in umbrella sampling can affect the sampling efficiency for the droplet systems. The free energy changes were decomposed into the energetic ΔU and entropic -TΔS contributions to reveal the molecular details of the gas sorption processes. By further decomposing ΔU into Lennard-Jones and Coulombic interactions, we observe that the ΔU trends are primarily determined by local effects due to the size of the gas molecule, charge distribution, and solvation structure around the gas molecule. Moreover, we find that there is a strong correlation between the change in the entropic contribution and the mean residence time of water, which is spatially nonlocal and related to the mobility of water.

Discrete unified gas kinetic scheme for all Knudsen number flows. III. Binary gas mixtures of Maxwell molecules

NASA Astrophysics Data System (ADS)

Zhang, Yue; Zhu, Lianhua; Wang, Ruijie; Guo, Zhaoli

2018-05-01

Recently a discrete unified gas kinetic scheme (DUGKS) in a finite-volume formulation based on the Boltzmann model equation has been developed for gas flows in all flow regimes. The original DUGKS is designed for flows of single-species gases. In this work, we extend the DUGKS to flows of binary gas mixtures of Maxwell molecules based on the Andries-Aoki-Perthame kinetic model [P. Andries et al., J. Stat. Phys. 106, 993 (2002), 10.1023/A:1014033703134. A particular feature of the method is that the flux at each cell interface is evaluated based on the characteristic solution of the kinetic equation itself; thus the numerical dissipation is low in comparison with that using direct reconstruction. Furthermore, the implicit treatment of the collision term enables the time step to be free from the restriction of the relaxation time. Unlike the DUGKS for single-species flows, a nonlinear system must be solved to determine the interaction parameters appearing in the equilibrium distribution function, which can be obtained analytically for Maxwell molecules. Several tests are performed to validate the scheme, including the shock structure problem under different Mach numbers and molar concentrations, the channel flow driven by a small gradient of pressure, temperature, or concentration, the plane Couette flow, and the shear driven cavity flow under different mass ratios and molar concentrations. The results are compared with those from other reliable numerical methods. The results show that the proposed scheme is an effective and reliable method for binary gas mixtures in all flow regimes.

Conversion of laser energy to gas kinetic energy

NASA Technical Reports Server (NTRS)

Caledonia, G. E.

1976-01-01

Techniques for the gas phase absorption of laser radiation for ultimate conversion to gas kinetic energy are discussed. Particular emphasis is placed on absorption by the vibration rotation bands of diatomic molecules at high pressures. This high pressure absorption appears to offer efficient conversion of laser energy to gas translational energy. Bleaching and chemical effects are minimized and the variation of the total absorption coefficient with temperature is minimal.

Formation of complex organic molecules in cold objects: the role of gas-phase reactions

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

2015-04-01

While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

MalE of Group A Streptococcus Participates in the Rapid Transport of Maltotriose and Longer Maltodextrins▿ †

PubMed Central

Shelburne, Samuel A.; Fang, Han; Okorafor, Nnaja; Sumby, Paul; Sitkiewicz, Izabela; Keith, David; Patel, Payal; Austin, Celest; Graviss, Edward A.; Musser, James M.; Chow, Dar-Chone

2007-01-01

Study of the maltose/maltodextrin binding protein MalE in Escherichia coli has resulted in fundamental insights into the molecular mechanisms of microbial transport. Whether gram-positive bacteria employ a similar pathway for maltodextrin transport is unclear. The maltodextrin binding protein MalE has previously been shown to be key to the ability of group A Streptococcus (GAS) to colonize the oropharynx, the major site of GAS infection in humans. Here we used a multifaceted approach to elucidate the function and binding characteristics of GAS MalE. We found that GAS MalE is a central part of a highly efficient maltodextrin transport system capable of transporting linear maltodextrins that are up to at least seven glucose molecules long. Of the carbohydrates tested, GAS MalE had the highest affinity for maltotriose, a major breakdown product of starch in the human oropharynx. The thermodynamics and fluorescence changes induced by GAS MalE-maltodextrin binding were essentially opposite those reported for E. coli MalE. Moreover, unlike E. coli MalE, GAS MalE exhibited no specific binding of maltose or cyclic maltodextrins. Our data show that GAS developed a transport system optimized for linear maltodextrins longer than two glucose molecules that has several key differences from its well-studied E. coli counterpart. PMID:17259319

IR femtochemistry on the surface of wide-gap ionic crystals

NASA Astrophysics Data System (ADS)

Laptev, V. B.; Chekalin, S. V.; Dorofeyev, I. A.; Kompanets, V. O.; Pigulsky, S. V.; Ryabov, E. A.

2018-02-01

We have found and studied a phenomenon of the growth of films resulting from decomposition of some organic and silicon-containing molecules adsorbed on the surface of ionic crystals under the action of IR (1.4-5.4 µm) femtosecond radiation of a moderate intensity, ~1011 W cm-2. In the gas phase, these molecules do not decompose. Microstructured films consisting of amorphous carbon, graphite oxide, and silicon dioxide have been obtained. The formation of carbon films was accompanied by the appearance of different hydrocarbons in the gas phase. The extensive films of graphite oxide have been obtained. The decomposition of molecules on the surface is apparently caused by non-resonant ionization and subsequent deep fragmentation. The mechanisms of ionization at relatively low intensities of the femtosecond IR radiation have been discussed.

Characterization of Noble Gas Ion Beam Fabricated Single Molecule Nanopore Detectors

NASA Astrophysics Data System (ADS)

Rollings, Ryan; Ledden, Bradley; Shultz, John; Fologea, Daniel; Li, Jiali; Chervinsky, John; Golovchenko, Jene

2006-03-01

Nanopores fabricated with low energy noble gas ion beams in a silicon nitride membrane can be employed as the fundamental element of single biomolecule detection and characterization devices [1,2]. With the help of X-ray Photoelectron Spectroscopy (XPS) and Rutherford Backscattering (RBS), we demonstrate that the electrical noise properties, and hence ultimate sensitivity of nanopore single molecule detectors depends on ion beam species and nanopore annealing conditions. .1. Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169. 2. Li, J., M. Gershow, D. Stein, E. Brandin, and J.A. Golovchenko, DNA Molecules and Configurations in a Solid-state Nanopore Microscope. Nature Materials, 2003. 2: p. 611-615.

Gas-phase binding energies for non-covalent Aβ-40 peptide/small molecule complexes from CID mass spectrometry and RRKM theory.

PubMed

Mayer, Paul M; Martineau, Eric

2011-03-21

The gas-phase binding of small molecules to the Amyloid β-40 peptide generated by electrospray ionization has been explored with collision-induced dissociation mass spectrometry and kinetic rate theory. This study discusses a simple procedure used to theoretically model the experimental breakdown diagrams for the Aβ-40 peptide complexed with a series of aminosulfonate small molecules, namely homotaurine, 3-cyclohexylamino-2-hydroxy-1-propanesulfonic acid (CAPSO), 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)propane-1-sulfonic acid, 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)butane-1-sulfonic acid, and 3-(cyclohexylamino)propane-1-sulfonic acid. An alternative procedure employing an extrapolation procedure for k(E) is also discussed.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.

Review on hydroxylamine, a precursor to amino-acids

NASA Astrophysics Data System (ADS)

Lemaire, Jean Louis

2015-08-01

Does life on earth come from interstellar space (IS)?It has been recently demonstrated that part of the terrestrial water is of IS origin [Cleeves et al. Science 2014]. This raises the question whether materials like amino-acids or their pre-biotic molecular precursors could have been formed and brought to earth in the same way than water. Another question is whether these molecules were formed in the gas phase or through reactions on the surface/volume of ice-covered grains. This may then have occurred in the vicinity of proto-stellar cores or deep into a pristine dense molecular clouds at very low temperatures.As far as bio-related molecules are concerned, chemistry with nitrogen-bearing molecules (like NH3 and NO) is involved. I review recent experimental work showing that hydroxylamine (NH2OH) could be formed either by surface or by volume reactions in conditions close to those prevailing in dense media. They use either electron-UV irradiation of water-ammonia ices [Zheng & Kaiser JCPA 2010] or successive hydrogenation of solid nitric oxide[Congiu, Fedoseev & al. ApJL.2012] or the simple oxidation of ammonia [He, Vidali, Lemaire & Garrod, ApJ, 2015] or the reaction of ammonia with hydroxyl radicals in a rare gas matrix [Zins & Krim, 2014, 69th ISMS]. A step further, the synthesis of the simplest amino-acids, glycine (NH2CH2COOH) and L- or D-alanine (NH2CH3CHCOOH) has already been obtained via reactions in the gas phase involving NH2OH+ [Blagojevic & al. MNRAS 2003].In addition to several earlier models demonstrating that the formation of all these molecules is possible in the gas phase, a new recent three-phase gas-grain chemical kinetics model of hot cores [Garrod ApJ 2013] shows that the results of ammonia oxidation we obtain are plausible by surface/volume reactions.Although none of the aforementioned molecules (except glycine in a sample of cometary origin) has been yet detected in the IS, they all are considered by many observers and modelers as likely targets of detection with ALMA.A review of the present observational status will be presented and suggestions of conditions for future observations will be provided.

High sensitivity fluorescent single particle and single molecule detection apparatus and method

DOEpatents

Mathies, Richard A.; Peck, Konan; Stryer, Lubert

1990-01-01

Apparatus is described for ultrasensitive detection of single fluorescent particles down to the single fluorescent molecule limit in a fluid or on a substrate comprising means for illuminating a predetermined volume of the fluid or area of the substrate whereby to emit light including background light from the fluid and burst of photons from particles residing in the area. The photon burst is detected in real time to generate output representative signal. The signal is received and the burst of energy from the fluorescent particles is distinguished from the background energy to provide an indication of the number, location or concentration of the particles or molecules.

Reactive Desorption and Radiative Association as Possible Drivers of Complex Molecule Formation in the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Vasyunin, A. I.; Herbst, Eric

2013-05-01

The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed "warm-up" scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

Assessment of atmospheric distribution of polycyclic aromatic hydrocarbons using a molecular structure model

NASA Astrophysics Data System (ADS)

Turk Sekulić, Maja; Okuka, Marija; Šenk, Nevena; Radonić, Jelena; Vojinović Miloradov, Mirjana; Vidicki, Branko

2013-07-01

In this paper, a comparison of experimentally obtained and SPARC software v4.6 modelled values of gas/particle partitioning coefficients was conducted to determine whether the evaluation of atmospheric distribution of PAH molecules can be performed using a molecular structure model. Partitioning coefficients were calculated for sixteen EPA PAHs, in thirty-nine samples of ambient air collected at nineteen urban, industrial, highly contaminated and background sites in the Republic of Serbia and Bosnia and Herzegovina. For obtaining samples of ambient air, the conventional high volume (Hi-Vol) methodology was applied, whereby gaseous and particulate phase data collection was conducted simultaneously by glass fibre filters (GFFs) and polyurethane foam filters (PUFs). The best prediction was for PAHs with 5 or more rings (benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)perylene and benzo(ghi)perylene). For evaluating the applicability of SPARC software predictions of gas/particle partitioning coefficients for the existing conditions, the results were compared with those obtained by applying other frequently used and highly ranked theoretical models of phase distributions, namely Junge-Pankow adsorption model, KOA absorption model, Dachs-Eisenreich dual model and PP-LFER model.

Spectroscopy of reactive species produced by low-energy atmospheric-pressure plasma on conductive target material surface

NASA Astrophysics Data System (ADS)

Yamada, Hiromasa; Sakakita, Hajime; Kato, Susumu; Kim, Jaeho; Kiyama, Satoru; Fujiwara, Masanori; Itagaki, Hirotomo; Okazaki, Toshiya; Ikehara, Sanae; Nakanishi, Hayao; Shimizu, Nobuyuki; Ikehara, Yuzuru

2016-10-01

A method for blood coagulation using low-energy atmospheric-pressure plasma (LEAPP) is confirmed as an alternative procedure to reduce tissue damage caused by heat. Blood coagulation using LEAPP behaves differently depending on working gas species; helium is more effective than argon in promoting fast coagulation. To analyse the difference in reactive species produced by helium and argon plasma, spectroscopic measurements were conducted without and with a target material. To compare emissions, blood coagulation experiments using LEAPP for both plasmas were performed under almost identical conditions. Although many kinds of reactive species such as hydroxyl radicals and excited nitrogen molecules were observed with similar intensity in both plasmas, intensities of nitrogen ion molecules and nitric oxide molecules were extremely strong in the helium plasma. It is considered that nitrogen ion molecules were mainly produced by penning ionization by helium metastable. Near the target, a significant increase in the emissions of reactive species is observed. There is a possibility that electron acceleration was induced in a local electric field formed on the surface. However, in argon plasma, emissions from nitrogen ion were not measured even near the target surface. These differences between the two plasmas may be producing the difference in blood coagulation behaviour. To control the surrounding gas of the plasma, a gas-component-controllable chamber was assembled. Filling the chamber with O2/He or N2/He gas mixtures selectively produces either reactive oxygen species or reactive nitrogen species. Through selective treatments, this chamber would be useful in studying the effects of specific reactive species on blood coagulation.

Charge transfer and adsorption-desorption kinetics in carbon nanotube and graphene gas sensing

NASA Astrophysics Data System (ADS)

Liang, Sang-Zi; Chen, Gugang; Harutyunyan, Avetik; Cole, Milton; Sofo, Jorge

2014-03-01

Detection of molecules in the gas phase by carbon nanotube and graphene has great application potentials due to the high sensitivity and surface-to-volume ratio. In chemiresistor, the conductance of the materials has been proposed to change as a result of charge transfer from the adsorbed molecules. Due to self-interaction errors, calculations using LDA or GGA density functionals have an innate disadvantage in dealing with charge transfer situations. A model which takes into consideration the dielectric interaction between the graphene surface and the molecule is employed to estimate the distance where charge transfer becomes favorable. Adsorption-desorption kinetics is studied with a modified Langmuir model, including sites from which the molecules do not desorb within the experimental time. Assuming a constant mobility, the model reproduces existing experimental conductance data. Its parameters provide information about the microscopic process during the detection and varying them allows optimization of aspects of sensor performance, including sensitivity, detection limit and response time. This work is supported by Honda Research Institute USA, Inc.

Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

DOE PAGES

Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; ...

2016-12-13

The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO 2, SO 2, C 2H 4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained bymore » ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. Lastly, these findings may provide alternative strategies for gas storage, delivery and separation.« less

The molecular composition of dense interstellar clouds

NASA Technical Reports Server (NTRS)

Allen, M.; Robinson, G. W.

1977-01-01

Presented in this paper is an ab initio chemical model for dense interstellar clouds that incorporates 598 grain surface reactions, with small grains providing the reaction area. Gas-phase molecules are depleted through collisions with grains. The abundances of 372 chemical species are calculated as a function of time and are found to be of sufficient magnitude to explain most observations. Peak abundances are achieved on time scales of the order of 100,000 to 1 million years, depending on cloud density and kinetic temperature. The reaction rates for ion-molecule chemistry are approximately the same, indicating that surface and gas-phase chemistry may be coupled in certain regions. The composition of grain mantles is shown to be a function of grain radius. In certain grain-size ranges, large molecules containing two or more heavy atoms are more predominant than lighter 'ices' - H2O, NH3, and CH4. It is possible that absorption due to these large molecules in the mantle may contribute to the observed 3-micron band in astronomical spectra.

Elasticity and Stability of Clathrate Hydrate: Role of Guest Molecule Motions.

PubMed

Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

2017-05-02

Molecular dynamic simulations were performed to determine the elastic constants of carbon dioxide (CO 2 ) and methane (CH 4 ) hydrates at one hundred pressure-temperature data points, respectively. The conditions represent marine sediments and permafrost zones where gas hydrates occur. The shear modulus and Young's modulus of the CO 2 hydrate increase anomalously with increasing temperature, whereas those of the CH 4 hydrate decrease regularly with increase in temperature. We ascribe this anomaly to the kinetic behavior of the linear CO 2 molecule, especially those in the small cages. The cavity space of the cage limits free rotational motion of the CO 2 molecule at low temperature. With increase in temperature, the CO 2 molecule can rotate easily, and enhance the stability and rigidity of the CO 2 hydrate. Our work provides a key database for the elastic properties of gas hydrates, and molecular insights into stability changes of CO 2 hydrate from high temperature of ~5 °C to low decomposition temperature of ~-150 °C.

Pressure and temperature dependences of the reaction of OH with nitric acid

NASA Technical Reports Server (NTRS)

Stachnik, R. A.; Molina, L. T.; Molina, M. J.

1986-01-01

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Summary of Research

NASA Technical Reports Server (NTRS)

dePater, I.; Hollenbach, D. J.; Charnley, S. B.

1999-01-01

In protostellar cores where the dust temperature has been raised above 100K and subsequently allowed to fall below the condensation temperature of methanol, recondensation on to cooling grains removes methanol molecules from the gas at rates.faster (about 1000 times) than those of chemical reactions. Molecular recondensation can have a profound effect on the chemical composition of hot cores. The methanol chemistry of hot cores is solved analytically and the trend in molecule binding energies required is compared with theoretical and experimental values. It is demonstrated, through a model calculation incorporating recondensation, that it yields a consistent explanation of the similarity of the CH3OH , CH3OCH3 and HCOOCH3 abundances measured in G34.3 and W3(H2O). These observations suggest that the latter molecules could not be derived from CH3OH through gas phase reactions. The manner in which molecular recondensation could affect the interpretation of hot core chemistry in general, particularly of organic molecules, is briefly discussed.

Selective Gas Capture Ability of Gas-Adsorbent-Incorporated Cellulose Nanofiber Films.

PubMed

Shah, Kinjal J; Imae, Toyoko

2016-05-09

The 2,2,6,6-tetramethylpiperidine-1-oxyl radical-oxidized cellulose nanofibers (TOCNF) were hybridized with cation and anion-exchange organoclays, where poly(amido amine) dendrimers were loaded to enhance the functionality of gas adsorption, since dendrimers have the high adsorbability and the enough selectivity on the gas adsorption. The thin films were prepared from the organoclay-TOCNF hybrids and supplied to the gas adsorption. The adsorption of CO2 and NH3 gases increased with an increasing amount of organoclays in TOCNF films, but the behavior of the increase depended on gases, clays, and dendrimers. The hydrotalcite organoclay-TOCNF films displayed the highest adsorption of both gases, but the desorption of CO2 gas from hydrotalcite organoclay-TOCNF films was drastically high in comparison with the other systems. While the CO2 gas is adsorbed and remained on cationic dendrimer sites in cation-exchange organoclay-TOCNF films, the CO2 gas is adsorbed on cationic clay sites in anion exchange organoclay-TOCNF films, and it is easily desorbed from the films. The NH3 adsorption is inversive to the CO2 adsorption. Then the CO2 molecules adsorbed on the cationic dendrimers and the NH3 molecules adsorbed on the anionic dendrimers are preferably captured in these adsorbents. The present research incorporated dendrimers will be contributing to the development of gas-specialized adsorbents, which are selectively storable only in particular gases.

First-principles investigation on defect-induced silicene nanoribbons - A superior media for sensing NH3, NO2 and NO gas molecules

NASA Astrophysics Data System (ADS)

Walia, Gurleen Kaur; Randhawa, Deep Kamal Kaur

2018-04-01

In this paper, the electronic and transport properties of armchair silicene nanoribbons (ASiNRs) are analyzed for their application as highly selective and sensitive gas molecule sensors. The study is focused on sensing three nitrogen based gases; ammonia (NH3), nitrogen dioxide (NO2) and nitric oxide (NO), which depending upon their adsorption energy and charge transfer, form bonds of varying strength with ASiNRs. The negligible band gap of ASiNRs is tuned by adding a defect in ASiNRs. Adsorption of NH3 leads to the opening of band gap whereas on adsorption of NO2 and NO, ASiNRs exhibit metallic nature. Distinctly divergent electronic and transport properties of ASiNRs are observed and on adsorption of NH3, NO2 and NO, renders them suitable for sensing them. All gas molecules show stronger adsorption on defective ASiNRs (D-ASiNRs) as compared to pristine ASiNRs (P-ASiNRs). The work reveals that introduction of defect can drastically improve the sensitivity of ASiNRs.

On the Relative "Transparency" of Gas-phase Coronene Molecules to Low-energy Electrons: Effects on the Interstellar Medium

NASA Astrophysics Data System (ADS)

Carelli, F.; Gianturco, F. A.

2011-12-01

Free, gas-phase polycyclic aromatic hydrocarbons (PAHs) are understood to play an important role in the interstellar medium (ISM), as they are thought to significantly contribute to both diffused and unidentified infrared interstellar bands. They are also considered fundamental blocks of the interstellar dust, whose nature has important implications for a plethora of physical and chemical nanoscopic processes within the ISM. Since free electrons represent a versatile alternative way to transport energy in the interstellar space, in this paper we compute from quantum scattering methods the angular redistributions of free electrons by gas-phase coronene molecules, the latter of which are believed to be one of the most representative PAHs, in order to assess their role in describing the efficiency of electron deflection by this molecule. The associated rates can provide useful information about the coupling mechanism between external radio-frequency fields and complex molecular plasmas containing neutral and ionized PAHs. They can also yield information on the possible presence of such species in the dust phase of the medium.

Spectroscopic investigation of a dielectric barrier discharge in modified atmosphere packaging

NASA Astrophysics Data System (ADS)

Milosavljević, Vladimir; Cullen, Patrick J.

2017-11-01

Diagnostics of a dielectric barrier discharge (DBD), in a sealed package (with and without meat) filled with gas mixtures of oxygen and carbon-dioxide (O2-CO2), is reported. The generation and evaluation of the plasma chemistry induced within the confines of the sealed package is studied. The plasma discharges were analyzed by optical emission spectroscopy (OES) and optical absorption spectroscopy (OAS) over a range of plasma process parameters. The study includes a detailed experimental investigation of the spatial and temporal spectroscopic data and links them with plasma kinetics. The results from the spectral radiation from package provide information about the electron energy distribution function. The experimental data indicates that the humidity level in the package with and without meat is unchanged, and that the gas temperature was not significantly modified. Oxygen and nitrogen radicals (trapped gas atmosphere and modified atmosphere) are increased in the package containing meat; at the same time there is no evidence of the presence of carbon monoxide molecules. The role of the nitrogen molecule in the quenching of O2 and CO2 molecules is also evaluated.

Molecular adsorption on graphene

NASA Astrophysics Data System (ADS)

Kong, Lingmei; Enders, Axel; Rahman, Talat S.; Dowben, Peter A.

2014-11-01

Current studies addressing the engineering of charge carrier concentration and the electronic band gap in epitaxial graphene using molecular adsorbates are reviewed. The focus here is on interactions between the graphene surface and the adsorbed molecules, including small gas molecules (H2O, H2, O2, CO, NO2, NO, and NH3), aromatic, and non-aromatic molecules (F4-TCNQ, PTCDA, TPA, Na-NH2, An-CH3, An-Br, Poly (ethylene imine) (PEI), and diazonium salts), and various biomolecules such as peptides, DNA fragments, and other derivatives. This is followed by a discussion on graphene-based gas sensor concepts. In reviewing the studies of the effects of molecular adsorption on graphene, it is evident that the strong manipulation of graphene’s electronic structure, including p- and n-doping, is not only possible with molecular adsorbates, but that this approach appears to be superior compared to these exploiting edge effects, local defects, or strain. However, graphene-based gas sensors, albeit feasible because huge adsorbate-induced variations in the relative conductivity are possible, generally suffer from the lack of chemical selectivity.

The Zodiacal Cloud Model applied to the Martian atmosphere. Diurnal variations in meteoric ion layers

NASA Astrophysics Data System (ADS)

Carrillo-Sánchez, J. D.; Plane, J. M. C.; Withers, P.; Fallows, K.; Nesvorny, D.; Pokorný, P.

2016-12-01

Sporadic metal layers have been detected in the Martian atmosphere by radio occultation measurements using the Mars Express Orbiter and Mars Global Surveyor spacecraft. More recently, metallic ion layers produced by the meteor storm event following the close encounter between Comet Siding Spring (C/2013 A1) and Mars were identified by the Imaging UltraViolet Spectrograph (IUVS) and the Neutral Gas and Ion Mass Spectrometer (NGIMS) on the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft. Work is now in progress to detect the background metal layers produced by the influx of sporadic meteors. In this study we predict the likely appearance of these layers. The Zodiacal Dust Cloud (ZDC) model for particle populations released by asteroids (AST), and dust grains from Jupiter Family Comets (JFCs) and Halley-Type Comets (HTCs) has been combined with a Monte Carlo sampling method and the Chemical ABlation MODel (CABMOD) to predict the ablation rates of Na, K, Fe, Si, Mg, Ca and Al above 40 km altitude in the Martian atmosphere. CABMOD considers the standard treatment of meteor physics, including the balance of frictional heating by radiative losses and the absorption of heat energy through temperature increases, melting phase transitions and vaporization, as well as sputtering by inelastic collisions with the air molecules. The vertical injection profiles are input into the Leeds 1-D Mars atmospheric model which includes photo-ionization, and gas-phase ion-molecule and neutral chemistry, in order to explore the evolution of the resulting metallic ions and atoms. We conclude that the dominant contributor in the Martian's atmosphere is the JFCs over other sources. Finally, we explore the changes of the neutral and ionized Na, Mg and Fe layers over a diurnal cycle.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

NASA Astrophysics Data System (ADS)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

Fluctuations in microwave background radiation due to secondary ionization of the intergalactic gas in the universe

NASA Technical Reports Server (NTRS)

Sunyayev, R. A.

1979-01-01

Secondary heating and ionization of the intergalactic gas at redshifts z approximately 10-30 could lead to the large optical depth of the Universe for Thomson scattering and could smooth the primordial fluctuations formed at z approximately 1500. It is shown that the gas motions connected with the large scale density perturbations at z approximately 10-15 must lead to the generation of secondary fluctuations of microwave background. The contribution of the rich clusters of galaxies and young galaxies to the fluctuations of microwave background is also estimated.

Comparison of gas-solid chromatography and MM2 force field molecular binding energies for greenhouse gases on a carbonaceous surface.

PubMed

Rybolt, Thomas R; Bivona, Kevin T; Thomas, Howard E; O'Dell, Casey M

2009-10-01

Gas-solid chromatography was used to determine B(2s) (gas-solid virial coefficient) values for eight molecular adsorbates interacting with a carbon powder (Carbopack B, Supelco). B(2s) values were determined by multiple size variant injections within the temperature range of 313-553 K. The molecular adsorbates included: carbon dioxide (CO(2)); tetrafluoromethane (CF(4)); hexafluoroethane (C(2)F(6)); 1,1-difluoroethane (C(2)H(4)F(2)); 1-chloro-1,1-difluoroethane (C(2)H(3)ClF(2)); dichlorodifluoromethane (CCl(2)F(2)); trichlorofluoromethane (CCl(3)F); and 1,1,1-trichloroethane (C(2)H(3)Cl(3)). Two of these molecules are of special interest because they are "super greenhouse gases". The global warming potential, GWP, for CF(4) is 6500 and for C(2)F(6) is 9200 relative to the reference value of 1 for CO(2). The GWP index considers both radiative blocking and molecular lifetime. For these and other industrial greenhouse gases, adsorptive trapping on a carbonaceous solid, which depends on molecule-surface binding energy, could avoid atmospheric release. The temperature variations of the gas-solid virial coefficients in conjunction with van't Hoff plots were used to find the experimental adsorption energy or binding energy values (E(*)) for each adsorbate. A molecular mechanics based, rough-surface model was used to calculate the molecule-surface binding energy (Ecal(*)) using augmented MM2 parameters. The surface model consisted of parallel graphene layers with two separated nanostructures each containing 17 benzene rings arranged in linear strips. The separation of the parallel nanostructures had been optimized in a prior study to appropriately represent molecule-surface interactions for Carbopack B. Linear regressions of E(*) versus Ecal(*) for the current data set of eight molecules and the same surface model gave E(*)=0.926 Ecal(*) and r(2)=0.956. A combined set of the current and prior Carbopack B adsorbates studied (linear alkanes, branched alkanes, cyclic alkanes, ethers, and halogenated hydrocarbons) gave a data set with 33 molecules and a regression of E(*)=0.991 Ecal(*) and r(2)=0.968. These results indicated a good correlation between the experimental and the MM2 computed molecule-surface binding energies.

OT2_jhewitt_2: Understanding Shock Oxygen Chemistry in Interacting Supernova Remnants

NASA Astrophysics Data System (ADS)

Hewitt, J.

2011-09-01

Supernova remnants interacting with dense moelcular clouds provide astrochemical laboratories to study heating and cooling of the dense ISM, shock chemistry, destruction and sputtering of dust, and the reformation of molecules. Water is expected to be a major coolant for shocks into dense gas, yet the number of remnants in which IR lines of hydroxyl and water are detected is very limited. We propose Herschel PACS, SPIRE and HIFI observations of three remnants with particularly high shocked gas densities, high dust and IR line luinosities, and extreme ionization environments. The scientific objectives of this proposal are: (1) to determine the abundance and excitation of oxygen-bearing molecules, and (2) to study the effects of variable ionization sources on oxygen chemistry in dense molecular gas shocked by powerful supernova remnant blast waves.

Detection system for a gas chromatograph. [. cap alpha. -methylnaphthalene,. beta. -methylnapthalene

DOEpatents

Hayes, J.M.; Small, G.J.

1982-04-26

A method and apparatus are described for the quantitative analysis of vaporizable compounds, and in particular of polycyclic aromatic hydrocarbons which may be induced to fluoresce. The sample to be analyzed is injected into a gas chromatography column and is eluted through a narrow orifice into a vacuum chamber. The free expansion of the eluted sample into the vacuum chamber creates a supersonic molecular beam in which the sample molecules are cooled to the extent that the excited vibrational and rotational levels are substantially depopulated. The cooled molecules, when induced to fluoresce by laser excitation, give greatly simplified spectra suitable for analytical purposes. The laser induced fluorimetry provides great selectivity, and the gas chromatograph provides quantitative transfer of the sample to the molecular beam. 3 figures, 2 tables.

Method and source for producing a high concentration of positively charged molecular hydrogen or deuterium ions

DOEpatents

Ehlers, Kenneth W.; Leung, Ka-Ngo

1988-01-01

A high concentration of positive molecular ions of hydrogen or deuterium gas is extracted from a positive ion source having a short path length of extracted ions, relative to the mean free path of the gas molecules, to minimize the production of other ion species by collision between the positive ions and gas molecules. The ion source has arrays of permanent magnets to produce a multi-cusp magnetic field in regions remote from the plasma grid and the electron emitters, for largely confining the plasma to the space therebetween. The ion source has a chamber which is short in length, relative to its transverse dimensions, and the electron emitters are at an even shorter distance from the plasma grid, which contains one or more extraction apertures.

Interstellar abundances - Gas and dust

NASA Technical Reports Server (NTRS)

Field, G. B.

1974-01-01

Data on abundances of interstellar atoms, ions and molecules in front of zeta Oph are assembled and analyzed. The gas-phase abundances of at least 11 heavy elements are significantly lower, relative to hydrogen, than in the solar system. The abundance deficiencies of certain elements correlate with the temperatures derived theoretically for particle condensation in stellar atmospheres or nebulae, suggesting that these elements have condensed into dust grains near stars. There is evidence that other elements have accreted onto such grains after their arrival in interstellar space. The extinction spectrum of zeta Oph can be explained qualitatively and, to a degree, quantitatively by dust grains composed of silicates, graphite, silicon carbide, and iron, with mantles composed of complex molecules of H, C, N, and O. This composition is consistent with the observed gas-phase deficiencies.

Angular motion of a PAH molecule in interstellar environment

NASA Technical Reports Server (NTRS)

Rouan, D.; Leger, Alain; Omont, A.; Giard, Martin

1989-01-01

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Researchers Use NRAO Telescope to Study Formation Of Chemical Precursors to Life

NASA Astrophysics Data System (ADS)

2006-08-01

In just two years of work, an international research team has discovered eight new complex, biologically-significant molecules in interstellar space using the National Science Foundation's Robert C. Byrd Green Bank Telescope (GBT) in West Virginia. "This is a feat unprecedented in the 35-year history of searching for complex molecules in space and suggests that a universal prebiotic chemistry is at work," said Jan M. Hollis of the NASA Goddard Space Flight Center, leader of the research team. Chemistry Cycle The Cosmic Chemistry Cycle CREDIT: Bill Saxton, NRAO/AUI/NSF Full Size Image Files Interactive Graphic With "Mouseover" Text Blocks Chemical Cycle Graphic (above image, JPEG, 129K) Graphic With Text Blocks (JPEG, 165K) High-Res TIFF (44.2M) High-Res TIFF With Text Blocks (44.2M) Green Bank Telescope and Molecule Diagrams (JPEG, 58K) Green Bank Telescope and Molecule Diagrams (TIFF, 21M) New Molecules: Chemical Diagrams (PDF, 64K) The new discoveries are helping scientists unlock the secrets of how the molecular precursors to life can form in the giant clouds of gas and dust in which stars and planets are born. "The first of the many chemical processes that ultimately led to life on Earth probably took place even before our planet was formed. The GBT has taken the leading role in exploring the origin of biomolecules in interstellar clouds," said Phil Jewell of the National Radio Astronomy Observatory (NRAO). The eight new molecules discovered with the GBT bring the total to 141 different molecular species found in interstellar space. About 90 percent of those interstellar molecules contain carbon, which is required for a molecule to be classified as organic. The newly-discovered molecules all contain carbon and are composed of 6 to 11 atoms each. These results suggest, the scientists say, that chemical evolution occurs routinely in the gas and dust from which stars and planets eventually are born. The mass of an interstellar cloud is 99 percent gas and one percent dust. The GBT discoveries have been made in just two prototypical interstellar clouds. The molecules acetamide (CH3CONH2), cyclopropenone (H2C3O), propenal (CH2CHCHO), propanal (CH3CH2CHO), and ketenimine (CH2CNH) were found in a cloud called Sagittarius B2(N), which is near the center of our Milky Way Galaxy some 26,000 light years from Earth. This star-forming region is the largest repository of complex interstellar molecules known. The molecules methyl-cyano-diacetylene (CH3C5N), methyl-triacetylene (CH3C6H), and cyanoallene (CH2CCHCN) were found in the Taurus Molecular Cloud (TMC-1), which is relatively nearby at a distance of 450 light years. The starless TMC-1 cloud is dark and cold with a temperature of only 10 degrees above absolute zero and may eventually evolve into a star-forming region. "The discovery of these large organic molecules in the coldest regions of the interstellar medium has certainly changed the belief that large organic molecules would only have their origins in hot molecular cores. It has forced us to rethink the paradigms of interstellar chemistry," said Anthony Remijan of the NRAO. These large molecules found with the GBT are built up from smaller ones, the scientists say, by two principal mechanisms. In the first, simple chemical reactions add an atom to a molecular structure residing on the surface of a dust grain. As an example of this process, the researchers cite a molecule called cyclopropenylidene (c-C3H2, where "c-" means cyclic), which contains three carbon atoms in a ring. Cyclopropenylidene was discovered in interstellar space in 1987, and is known to be highly reactive. In 2005, using the GBT, scientists discovered another molecule, cyclopropenone (c-H2C3O), which can be produced by adding an oxygen atom to cyclopropenylidene. The second method for constructing larger molecules from smaller ones involves neutral-radical reactions that can occur within the gas in an interstellar cloud. For example, in 2006, the scientists discovered acetamide (CH3CONH2), which can be formed when a previously-discovered neutral molecule called formamide (HCONH2) combines with radicals such as CH2 and CH3, also previously discovered. Acetamide is particularly interesting because it contains a peptide bond which is the means for linking amino acids together to form proteins. Once interstellar molecules are ejected from dust grains into the gas phase, presumably by shock waves, they are free to rotate end-over-end. As gas molecules change their rotational modes, they can emit or absorb radiation at precise radio frequencies, called transitions, that are unique to each type of molecule. By detecting several rotational transitions, astronomers can unambiguously identify a specific interstellar molecule. "It is important to note that likely interstellar molecule candidates are first studied in gas-phase laboratory experiments so that transition frequencies are known in advance of an interstellar experiment," said Frank Lovas of the National Institute of Standards and Technology. Along the line of sight from the interstellar cloud to the telescope, thousands of billions of molecules undergo the exact same transition, producing a signal strong enough to be detected by sensitive equipment. For this type of work, the GBT is the world's most sensitive tool that can be accurately pointed and track astronomical objects. In addition to Hollis, Jewell, Remijan, and Lovas, the research team included Lewis Snyder of the University of Illinois; Harald Mollendal of the University of Oslo, Norway; Vadim Ilyushin of the Institute of Radio Astronomy of the National Academy of Sciences of the Ukraine; and Isabell Kleiner of the Universite Paris, France. The astronomers' reports on their results appeared in 8 separate editions of the Astrophysical Journal. The National Radio Astronomy Observatory is a facility of the National Science Foundation, operated under cooperative agreement by Associated Universities, Inc.

Simulating the formation of carbon-rich molecules on an idealized graphitic surface

NASA Astrophysics Data System (ADS)

Marshall, David W.; Sadeghpour, H. R.

2016-01-01

There is accumulating evidence for the presence of complex molecules, including carbon-bearing and organic molecules, in the interstellar medium. Much of this evidence comes to us from studies of chemical composition, photo- and mass spectroscopy in cometary, meteoritic and asteroid samples, indicating a need to better understand the surface chemistry of astrophysical objects. There is also considerable interest in the origins of life-forming and life-sustaining molecules on the Earth. Here, we perform reactive molecular dynamics simulations to probe the formation of carbon-rich molecules and clusters on carbonaceous surfaces resembling dust grains and meteoroids. Our results show that large chains form on graphitic surfaces at low temperatures (100-500 K) and smaller fullerene-like molecules form at higher temperatures (2000-3000 K). The formation is faster on the surface than in the gas at low temperatures but slower at high temperatures as surface interactions prevent small clusters from coagulation. We find that for efficient formation of molecular complexity, mobility about the surface is important and helps to build larger carbon chains on the surface than in the gas phase at low temperatures. Finally, we show that the temperature of the surface strongly determines what kind of structures forms and that low turbulent environments are needed for efficient formation.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, David K.; Potter, Thomas F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, D.K.; Potter, T.F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber. 25 figs.

Diffusivity of dicarboxylic acids molecules to secondary organic material governed by particle phase state

NASA Astrophysics Data System (ADS)

Han, Y.; Gong, Z.; Liu, P.; de Sá, S. S.; McKinney, K. A.; Martin, S. T.

2017-12-01

Atmospheric secondary organic material (SOM) from oxidation of volatile organic compounds can exist in amorphous solid, semisolid, and liquid states depending on a range of factors such as relative humidity (RH), temperature, and reaction history. The phase state of SOM affects the dynamic exchange and reactivity between particles and gas-phase molecules. Dicarboxylic acids are ubiquitous in ambient atmosphere and the uptake of which may lead to substantial changes in hygroscopicity, absorption property, and light scattering of aerosol particles. This study investigates the diffusivity of dicarboxylic acids to the matrix of SOM particles. SOM was generated from dark ozonolysis of a-pinene in Harvard Environmental Chamber. The produced SOM particles were passed through an ozone scrubber to remove gas-phase chemistry before being led into a flask reactor, where gas-phase dicarboxylic acid was injected continuously and RH was varied from 5% to 85%. The probe dicarboxylic acids molecules including malonic acid and a-ketoglutaric acid have been investigated for the uptake to SOM particles. Organic composition in the outflow of the flask was measured with a high-resolution time-of-flight aerosol mass spectrometer. The mass fractions of tracer ions in total organic mass for both malonic acid and a-ketoglutaric acid increased substantially with the increase of RH values. The tracer ions of malonic acid were also more abundant in a-pinene SOM particles with increased gas-phase concentrations. These results suggest that the diffusion of the studied dicarboxylic acids molecules to a-pinene SOM particles was enhanced at increased RH values, which is possibly due to the phase transition of a-pinene SOM particles from non-liquid to liquid states. Therefore, particle phase state may be an important factor governing the diffusivity of dicarboxylic acids molecules to a-pinene SOM. Further dicarboxylic acids with various functional groups will be investigated to understand the effects of volatility and structure on their diffusivity.

Measurement of partial pressures in vacuum technology and vacuum physics

NASA Technical Reports Server (NTRS)

Huber, W. K.

1986-01-01

It is pointed out that the measurement of gaseous pressures of less than 0.0001 torr is based on the ionization of gas atoms and molecules due to collisions with electrons. The particle density is determined in place of the pressure. The ionization cross sections for molecules of various gases are discussed. It is found that the true pressure in a vacuum system cannot be determined with certainty if it is unknown which gas is present. Effects of partial pressure determination on the condition of the vacuum system are discussed together with ion sources, systems of separation, and ion detection.

Improved ion source

DOEpatents

Leung, K.N.; Ehlers, K.W.

1982-05-04

A magnetic filter for an ion source reduces the production of undesired ion species and improves the ion beam quality. High-energy ionizing electrons are confined by the magnetic filter to an ion source region, where the high-energy electrons ionize gas molecules. One embodiment of the magnetic filter uses permanent magnets oriented to establish a magnetic field transverse to the direction of travel of ions from the ion source region to the ion extraction region. In another embodiment, low energy 16 eV electrons are injected into the ion source to dissociate gas molecules and undesired ion species into desired ion species,

Ion source

DOEpatents

Leung, Ka-Ngo; Ehlers, Kenneth W.

1984-01-01

A magnetic filter for an ion source reduces the production of undesired ion species and improves the ion beam quality. High-energy ionizing electrons are confined by the magnetic filter to an ion source region, where the high-energy electrons ionize gas molecules. One embodiment of the magnetic filter uses permanent magnets oriented to establish a magnetic field transverse to the direction of travel of ions from the ion source region to the ion extraction region. In another embodiment, low energy 16 eV electrons are injected into the ion source to dissociate gas molecules and undesired ion species into desired ion species.

The electronic structure of VO in its ground and electronically excited states: A combined matrix isolation and quantum chemical (MRCI) study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hübner, Olaf; Hornung, Julius; Himmel, Hans-Jörg, E-mail: hans-jorg.himmel@aci.uni-heidelberg.de

2015-07-14

The electronic ground and excited states of the vanadium monoxide (VO) molecule were studied in detail. Electronic absorption spectra for the molecule isolated in Ne matrices complement the previous gas-phase spectra. A thorough quantum chemical (multi-reference configuration interaction) study essentially confirms the assignment and characterization of the electronic excitations observed for VO in the gas-phase and in Ne matrices and allows the clarification of open issues. It provides a complete overview over the electronically excited states up to about 3 eV of this archetypical compound.

Effect of laser fluence and ambient gas pressure on surface morphology and chemical composition of hydroxyapatite thin films deposited using pulsed laser deposition

NASA Astrophysics Data System (ADS)

Nishikawa, Hiroaki; Hasegawa, Tsukasa; Miyake, Akiko; Tashiro, Yuichiro; Komasa, Satoshi; Hashimoto, Yoshiya

2018-01-01

The dependence of the surface morphology and chemical composition of hydroxyapatite (HA) thin films on the laser fluence and ambient gas pressure during their formation by pulsed laser deposition was studied as the first step to investigate the effect of physical and chemical interactions between the ablated chemical species and ambient gas molecules on HA film formation. It was found that a higher fluence could decrease the number of large protrusions on the surface of HA thin films. However, too high a fluence caused a phosphorus deficiency from the stoichiometric value, particularly in the case of lower ambient gas pressure. It was also found that for lower fluences, the atomic species among the ablated chemical species were easily scattered by collision processes with ambient gas molecules. This was caused by the lower velocity of the ablated chemical species and higher ambient gas pressure, which induced a shorter mean free path. In addition, these collision processes played an important role in the adsorption, migration, and re-evaporation of the ablated chemical species on the substrate via chemical reactions.

Adsorption of gas molecules on a manganese phthalocyanine molecular device and its possibility as a gas sensor.

PubMed

Zou, Dongqing; Zhao, Wenkai; Cui, Bin; Li, Dongmei; Liu, Desheng

2018-01-17

A theoretical investigation of the gas detection performance of manganese(ii) phthalocyanine (MnPc) molecular junctions for six different gases (NO, CO, O 2 , CO 2 , NO 2 , and NH 3 ) is executed through a non-equilibrium Green's function technique in combination with spin density functional theory. Herein, we systematically studied the adsorption structural configurations, the adsorption energy, the charge transfer, and the spin transport properties of the MnPc molecular junctions with these gas adsorbates. Remarkably, NO adsorption can achieve an off-state of the Mn spin; this may be an effective measure to switch the molecular spin. In addition, our results indicate that by measuring spin filter efficiency and the changes in total current through the molecular junctions, the CO, NO, O 2 , and NO 2 gas molecules can be detected selectively. However, the CO 2 and NH 3 gas adsorptions are difficult to be detected due to weak van der Waals interaction between these two gases and central Mn atom. Our findings provide important clues to the application of nanosensors for highly sensitive and selective based on MnPc molecular junction systems.

Miniature Oxidizer Ionizer for a Fuel Cell

NASA Technical Reports Server (NTRS)

Hartley, Frank

2006-01-01

A proposed miniature device for ionizing the oxygen (or other oxidizing gas) in a fuel cell would consist mostly of a membrane ionizer using the same principles as those of the device described in the earlier article, Miniature Bipolar Electrostatic Ion Thruster (NPO-21057). The oxidizing gas would be completely ionized upon passage through the holes in the membrane ionizer. The resulting positively charged atoms or molecules of oxidizing gas could then, under the influence of the fringe fields of the ionizer, move toward the fuel-cell cathode that would be part of a membrane/electrode assembly comprising the cathode, a solid-electrolyte membrane, and an anode. The electro-oxidized state of the oxidizer atoms and molecules would enhance transfer of them through the cathode, thereby reducing the partial pressure of the oxidizer gas between the ionizer and the fuel-cell cathode, thereby, in turn, causing further inflow of oxidizer gas through the holes in the membrane ionizer. Optionally the ionizer could be maintained at a positive electric potential with respect to the cathode, in which case the resulting electric field would accelerate the ions toward the cathode.

A simple fast pulse gas valve using a dynamic pressure differential as the primary closing mechanism

NASA Astrophysics Data System (ADS)

Thomas, J. C.; Hwang, D. Q.; Horton, R. D.; Rogers, J. H.; Raman, R.

1993-06-01

In this article we describe a simple fast pulse gas valve developed for use in a plasma discharge experiment. The valve delivers 1017-1019 molecules per pulse varied by changing the voltage on the electromagnetic driver power supply. Valve pulse widths are observed to be less than 300 μs full width at half maximum with a rise time of less than 100 μs resulting in a maximum gas flow rate of ˜1022 molecules per second. An optical transmission technique was used to determine the mechanical opening and closing characteristics of the valve piston. A fast ionization gauge (FIG) was used for diagnosis of the temporal character of the gas pulse while the total gas throughput was determined by measuring the change in pressure per pulse in a small test chamber with a convectron tube gauge. Calibration of the FIG was accomplished by comparing the net change in pressure in a large chamber as measured by the FIG to the net change in pressure in a small test chamber as measured by the convectron tube gauge.

Influence of Background H2O on the Collision-Induced Dissociation Products Generated from [UO2NO3]+

NASA Astrophysics Data System (ADS)

Van Stipdonk, Michael J.; Iacovino, Anna; Tatosian, Irena

2018-04-01

Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H2O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ion traps (Van Stipdonk et al. J. Am. Soc. Mass Spectrom. 14, 1205-1214, 2003). In the present study, we revisited the dissociation of complexes composed of uranyl nitrate cation [UVIO2(NO3)]+ coordinated by alcohol ligands (methanol and ethanol) using the 2-D LIT. With relatively low levels of background H2O, collision-induced dissociation (CID) of [UVIO2(NO3)]+ primarily creates [UO2(O2)]+ by the ejection of NO. However, CID (using He as collision gas) of [UVIO2(NO3)]+ creates [UO2(H2O)]+ and UO2 + when the 2-D LIT is used with higher levels of background H2O. Based on the results presented here, we propose that product ion spectrum in the previous experiments was the result of a two-step process: initial formation of [UVIO2(O2)]+ followed by rapid exchange of O2 for H2O by ion-molecule reaction. Our experiments illustrate the impact of residual H2O in ion trap instruments on the product ions generated by CID and provide a more accurate description of the intrinsic dissociation pathway for [UVIO2(NO3)]+. [Figure not available: see fulltext.

Molecular-dynamics study on characteristics of energy and tangential momentum accommodation coefficients

NASA Astrophysics Data System (ADS)

Yamaguchi, Hiroki; Matsuda, Yu; Niimi, Tomohide

2017-07-01

Gas-surface interaction is studied by the molecular dynamics method to investigate qualitatively characteristics of accommodation coefficients. A large number of trajectories of gas molecules colliding to and scattering from a surface are statistically analyzed to calculate the energy (thermal) accommodation coefficient (EAC) and the tangential momentum accommodation coefficient (TMAC). Considering experimental measurements of the accommodation coefficients, the incident velocities are stochastically sampled to represent a bulk condition. The accommodation coefficients for noble gases show qualitative coincidence with experimental values. To investigate characteristics of these accommodation coefficients in detail, the gas-surface interaction is parametrically studied by varying the molecular mass of gas, the gas-surface interaction strength, and the molecular size of gas, one by one. EAC increases with increasing every parameter, while TMAC increases with increasing the interaction strength, but decreases with increasing the molecular mass and the molecular size. Thus, contradictory results in experimentally measured TMAC for noble gases could result from the difference between the surface conditions employed in the measurements in the balance among the effective parameters of molecular mass, interaction strength, and molecular size, due to surface roughness and/or adsorbed molecules. The accommodation coefficients for a thermo-fluid dynamics field with a temperature difference between gas and surface and a bulk flow at the same time are also investigated.

Impact of ambient gases on the mechanism of [Cs8Nb6O19]-promoted nerve-agent decomposition.

PubMed

Kaledin, Alexey L; Driscoll, Darren M; Troya, Diego; Collins-Wildman, Daniel L; Hill, Craig L; Morris, John R; Musaev, Djamaladdin G

2018-02-28

The impact of ambient gas molecules (X), NO 2 , CO 2 and SO 2 on the structure, stability and decontamination activity of Cs 8 Nb 6 O 19 polyoxometalate was studied computationally and experimentally. It was found that Cs 8 Nb 6 O 19 absorbs these molecules more strongly than it adsorbs water and Sarin (GB) and that these interactions hinder nerve agent decontamination. The impacts of diamagnetic CO 2 and SO 2 molecules on polyoxoniobate Cs 8 Nb 6 O 19 were fundamentally different from that of NO 2 radical. At ambient temperatures, weak coordination of the first NO 2 radical to Cs 8 Nb 6 O 19 conferred partial radical character on the polyoxoniobate and promoted stronger coordination of the second NO 2 adsorbent to form a stable diamagnetic Cs 8 Nb 6 O 19 /(NO 2 ) 2 species. Moreover, at low temperatures, NO 2 radicals formed stable dinitrogen tetraoxide (N 2 O 4 ) that weakly interacted with Cs 8 Nb 6 O 19 . It was found that both in the absence and presence of ambient gas molecules, GB decontamination by the Cs 8 Nb 6 O 19 species proceeds via general base hydrolysis involving: (a) the adsorption of water and the nerve agent on Cs 8 Nb 6 O 19 /(X), (b) concerted hydrolysis of a water molecule on a basic oxygen atom of the polyoxoniobate and nucleophilic addition of the nascent OH group to the phosphorus center of Sarin, and (c) rapid reorganization of the formed pentacoordinated-phosphorus intermediate, followed by dissociation of either HF or isopropanol and formation of POM-bound isopropyl methyl phosphonic acid (i-MPA) or methyl phosphonofluoridic acid (MPFA), respectively. The presence of the ambient gas molecules increases the energy of the intermediate stationary points relative to the asymptote of the reactants and slightly increases the hydrolysis barrier. These changes closely correlate with the Cs 8 Nb 6 O 19 -X complexation energy. The most energetically stable intermediates of the GB hydrolysis and decontamination reaction were found to be Cs 8 Nb 6 O 19 /X-MPFA-(i-POH) and Cs 8 Nb 6 O 19 /X-(i-MPA)-HF both in the absence and presence of ambient gas molecules. The high stability of these intermediates is due to, in part, the strong hydrogen bonding between the adsorbates and the protonated [Cs 8 Nb 6 O 19 /X/H] + -core. Desorption of HF or/and (i-POH) and regeneration of the catalyst required deprotonation of the [Cs 8 Nb 6 O 19 /X/H] + -core and protonation of the phosphonic acids i-MPA and MPFA. This catalyst regeneration is shown to be a highly endothermic process, which is the rate-limiting step of the GB hydrolysis and decontamination reaction both in the absence and presence of ambient gas molecules.

The influence of the dispersion corrections on the performance of DFT method in modeling HNgY noble gas molecules and their complexes

NASA Astrophysics Data System (ADS)

Cukras, Janusz; Sadlej, Joanna

2018-01-01

The letter reports a comparative assessment of the usefulness of the two different Grimme's corrections for evaluating dispersion interaction (DFT-D3 and DFT-D3BJ) for the representative molecules of the family of noble-gas hydrides HXeY and their complexes with the HZ molecules, where Y and Z are F/Cl/OH/SH. with special regard to the dispersion term calculated by means of the symmetry-adapted perturbation theory (at the SAPT0 level). The results indicate that despite differences in the total interactions energy (DFT + corrections) versus SAPT0 results, the sequence of contributions of the individual dispersion terms is still maintained. Both dispersion corrections perform similarly and they improve the results suggesting that it is worthwhile to include them in calculations.

DFT STUDY OF CO AND NO ADSORPTION ON BORON NITRIDE (BN)n = 3 - 5 NANOCLUSTERS

NASA Astrophysics Data System (ADS)

Zahedi, Ehsan; Pangh, Abdolhakim; Ghorbanpour, Hamed

2015-11-01

Interaction of CO and NO molecules by different orientations on (BN)n=3-5 clusters have been studied at the B3LYP/6-311+G* level of theory. Total electronic energies have been corrected for geometrical counterpoise (gCP) and dispersion (D3) energies at the B3LYP/6-31G* level. Formation of a new sigma bond between the gas and (BN)3 cluster, atom in molecules (AIM) results, density of states spectrums (DOS), molecular electrostatic potential (MEP) surfaces, and visualization of wave function of molecular orbitals in the nearest bonding regions to the Fermi level have confirmed that adsorption of CO by carbon end atom, and NO by nitrogen end atom is covalent in nature, so that the charge transfer is occurred from gas molecule to the cluster.

Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases

NASA Astrophysics Data System (ADS)

Tokatli, A.; Ucun, F.; Sütçü, K.; Osmanoğlu, Y. E.; Osmanoğlu, Ş.

2018-02-01

In this study the conformational behavior of cycloheximide in the gas and solution (CHCl3) phases has theoretically been investigated by spectroscopic and quantum chemical properties using density functional theory (wB97X-D) method with 6-31++G(d,p) basis set, for the first time. The calculated IR results reveal that in the ground state the molecule exits as a mixture of the chair and twist-boat conformers in the gas phase, while the calculated NMR results reveal that it only exits as the chair conformer in the solution phase. In order to obtain the contributions coming from intramolecular interactions to the stability of the conformers in the gas and solution phases, the quantum theory of atoms in molecules (QTAIM), noncovalent interactions (NCI) method, and natural bond orbital analysis (NBO) have been employed. The QTAIM and NCI methods indicated that by intramolecular interactions with bond critical point (BCP) the twist-boat conformer is more stabilized than the chair conformer, while by steric interactions it is more destabilized. Considering that these interactions balance each other, the stabilities of the conformers are understood to be dictated by the van der Waals interactions. The NBO analyses show that the hyperconjugative and steric effects play an important role in the stabilization in the gas and solution phases. Furthermore, to get a better understanding of the chemical behavior of this important antibiotic drug we have evaluated and, commented the global and local reactivity descriptors of the both conformers. Finally, the EPR analysis of γ-irradiated cycloheximide has been done. The comparison of the experimental and calculated data have showed the inducement of a radical structure of (CH2)2ĊCH2 in the molecule. The experimental EPR spectrum has also confirmed that the molecule simultaneously exists in the chair and twist-boat conformers in the solid phase.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM

NASA Astrophysics Data System (ADS)

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-01

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt1/Fe2O3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water–gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe2O3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H2O molecules to the CO or H2 significantly accelerates the sintering of the Fe2O3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal–support interaction.

High-performance, room-temperature, and no-humidity-impact ammonia sensor based on heterogeneous nickel oxide and zinc oxide nanocrystals.

PubMed

Wang, Jian; Yang, Pan; Wei, Xiaowei

2015-02-18

NiO nanocones decorated with ZnO nanothorns on NiO foil substrates are shown to be an ammonia sensor with excellent comprehensive performance, which could, in real-time, detect and monitor NH3 in the surrounding environment. Gas-sensing measurements indicate that assembling nanocones decorated with nanothorns on NiO foil substrate is an effective strategy for simultaneously promoting the stability, reproducibility, and sensitivity of the sensor, because the NiO foil substrate as a whole can quickly and stably transfer electrons between the gas molecules and the sensing materials and the large specific surface area of both nanocones and nanothorns provide good accessibility of the gas molecules to the sensing materials. Moreover, p-type NiO, with majority charge carriers of holes, has higher binding affinity for the electron-donating ammonia, resulting in a significant increase in selectivity toward NH3 over other organic gases. Compared with the NiO nanowires and pure NiO nanocones, the heterogeneous NiO nanocones/ZnO nanothorns exhibit less dependence on the temperature and humidity in response/recovery speed and sensitivity of sensing NH3. Our investigation indicates that two factors are responsible for reducing the dependence on the gas sensing characteristics under various environmental conditions. One is that the n-type ZnO nanothorns growing on the surface of nanocones, with majority charge carriers of electrons, speed up adsorption and desorption of gas molecules. The other is that the abundant cone-shaped and thornlike superstructures on the substrate are favorable for constructing a hydrophobic surface, which prevents the gas sensing material from being wetted.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM.

PubMed

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-18

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt 1 /Fe 2 O 3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water-gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe 2 O 3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H 2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H 2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H 2 O molecules to the CO or H 2 significantly accelerates the sintering of the Fe 2 O 3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal-support interaction.

Terahertz Frequency-Domain Spectroscopy of Low-Pressure Acetonitrile Gas by a Photomixing Terahertz Synthesizer Referenced to Dual Optical Frequency Combs

NASA Astrophysics Data System (ADS)

Hsieh, Yi-Da; Kimura, Hiroto; Hayashi, Kenta; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Inaba, Hajime; Minoshima, Kaoru; Hindle, Francis; Yasui, Takeshi

2016-09-01

A terahertz (THz) frequency synthesizer based on photomixing of two near-infrared lasers with a sub-THz to THz frequency offset is a powerful tool for spectroscopy of polar gas molecules due to its broad spectral coverage; however, its frequency accuracy and resolution are relatively low. To tune the output frequency continuously and widely while maintaining its traceability to a frequency standard, we developed a photomixing THz synthesizer phase-locked to dual optical frequency combs (OFCs). While the phase-locking to dual OFCs ensured continuous tuning within a spectral range of 120 GHz, in addition to the traceability to the frequency standard, use of a broadband uni-traveling carrier photodiode for photomixing enabled the generation of CW-THz radiation within a frequency range from 0.2 to 1.5 THz. We demonstrated THz frequency-domain spectroscopy of gas-phase acetonitrile CH3CN and its isotope CH3 13CN in the frequency range of 0.600-0.720 THz using this THz synthesizer. Their rotational transitions were assigned with a frequency accuracy of 8.42 × 10-8 and a frequency resolution of 520 kHz. Furthermore, the concentration of the CH3CN gas at 20 Pa was determined to be (5.41 ± 0.05) × 1014 molecules/cm3 by curve fitting analysis of the measured absorbance spectrum, and the mixture ratio of the mixed CH3CN/CH3 13CN gas was determined to be 1:2.26 with a gas concentration of 1014-1015 molecules/cm3. The developed THz synthesizer is highly promising for high-precision THz-FDS of low-pressure molecular gases and will enable the qualitative and quantitative analyses of multiple gases.

Magnetoassociation of KRb Feshbach molecules

NASA Astrophysics Data System (ADS)

Cumby, Tyler; Perreault, John; Shewmon, Ruth; Jin, Deborah

2010-03-01

I will discuss experiments in which we study the creation of ^40K^87Rb Feshbach molecules via magnetoassociation. We measure the molecule number as a function of the magnetic-field sweep rate through the interspecies Feshbach resonance and explore the dependence of association on the initial atom gas conditions. This study of the Feshbach molecule creation process may be relevant to the production of ultracold polar molecules, where magnetoassociated Feshbach molecules can be a crucial first step [1].[4pt] [1] K.-K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Peer, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye, Science, 2008, 322, 231- 235.

Magnetoassociation of KRb Feshbach molecules

NASA Astrophysics Data System (ADS)

Cumby, Tyler; Perreault, John; Shewmon, Ruth; Jin, Deborah

2010-03-01

I will discuss experiments in which we study the creation of ^40K^87Rb Feshbach molecules via magnetoassociation. We measure the molecule number as a function of the magnetic-field sweep rate through the interspecies Feshbach resonance and explore the dependence of association on the initial atom gas conditions. This study of the Feshbach molecule creation process may be relevant to the production of ultracold polar molecules, where magnetoassociated Feshbach molecules can be a crucial first step [1].[4pt] [1] K.-K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Peer, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye, Science, 2008, 322, 231-235.

Adsorption properties of argon on Ti doped SBA-15.

PubMed

Kim, Euikwoun; Lee, Sang-Hwa; Kim, Jaeyong

2014-11-01

Thermodynamic properties of argon on Ti doped Santa barbara amorphous No. 15 (SBA-15) were investigated in the temperature range of 77-89 K to understand the interaction of gas molecules with porous materials. When the total amount of adsorbed molecules is plotted as a function of the equilibrium vapor pressure of the adsorbed Ar, the results exhibit two distinct isotherm steps. The first step appears at the beginning of the isotherm while the second step locates at 0.7 of the normalized pressure. The existence of the second isotherm step which spanned in the normalized pressure from 0.7 to 0.9 is confirmed when the isotherm data were plotted in terms of the 2-dimensional compressibility values. The total amount of adsorbed molecules forming the second isotherm step is 2.5 times greater than the one for the first step. These adsorption behaviors are typical patterns noted from porous materials and far different from the ones observed from non-pore materials. Our observations demonstrate that most of adsorbed molecules reside in the pores and the height of the second isotherm step is strongly associated with filling pores with gas molecules.

Formation of ions and radicals from icy grains in comets

NASA Technical Reports Server (NTRS)

Jackson, William M.; Gerth, Christopher; Hendricks, Charles

1991-01-01

Ion and radical formation in comets are thought to occur primarily by photodissociation of gas phase molecules. Experimental evidence and theoretical calculations are presented that show that some of the radical and ions can come directly from ice grains. The experimental evidence suggest that if the frozen molecules on the surface of grains undergo direct dissociation then they may be able to release radicals directly in the gas phase. If the molecules undergo predissociation it is unlikely that they will release radicals in the gas phase since they should be quenched. Calculations of this direct photodissociation mechanism further indicate that even if the parent molecule undergoes direct dissociation, the yield will not be high enough to explain the rays structure in comets unless the radicals are stored in the grains and then released when the grain evaporates. Calculations were also performed to determine the maximum number of ions that can be stored in an icy grain's radius. This number is compared with the ratio of the ion to neutral molecular density. The comparison suggests that some of the ions observed near the nucleus of the comet could have originally been present in the cometary nucleus. It is also pointed out that the presence of these ions in icy grains could lead to radical formation via electron recombination. Finally, an avalanche process was evaluated as another means of producing ions in comets.

Chemical indices and methods of multivariate statistics as a tool for odor classification.

PubMed

Mahlke, Ingo T; Thiesen, Peter H; Niemeyer, Bernd

2007-04-01

Industrial and agricultural off-gas streams are comprised of numerous volatile compounds, many of which have substantially different odorous properties. State-of-the-art waste-gas treatment includes the characterization of these molecules and is directed at, if possible, either the avoidance of such odorants during processing or the use of existing standardized air purification techniques like bioscrubbing or afterburning, which however, often show low efficiency under ecological and economical regards. Selective odor separation from the off-gas streams could ease many of these disadvantages but is not yet widely applicable. Thus, the aim of this paper is to identify possible model substances in selective odor separation research from 155 volatile molecules mainly originating from livestock facilities, fat refineries, and cocoa and coffee production by knowledge-based methods. All compounds are examined with regard to their structure and information-content using topological and information-theoretical indices. Resulting data are fitted in an observation matrix, and similarities between the substances are computed. Principal component analysis and k-means cluster analysis are conducted showing that clustering of indices data can depict odor information correlating well to molecular composition and molecular shape. Quantitative molecule describtion along with the application of such statistical means therefore provide a good classification tool of malodorant structure properties with no thermodynamic data needed. The approximate look-alike shape of odorous compounds within the clusters suggests a fair choice of possible model molecules.

Computational Investigations of Rovibrational Quenching of HD due to Collisions in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Goodman Veazey, Clark; Wan, Yier; Yang, Benhui H.; Stancil, P.

2017-06-01

When conducting an examination of distant astronomical objects, scientists rely on measurements derived from astronomical observations of these objects, which are primarily collected using spectroscopy. In order to interpret spectroscopic data collected on astronomical objects, it is necessary to have a background of accurate dynamical information on interstellar molecules at one’s disposal. Seeing as most of the observable infrared radiation in the universe is emitted by molecules excited by collisional processes in the interstellar gas, generating accurate data on the rate of molecular collisions is of salient interest to astronomical endeavors.The collisional system we will be focusing on here is He-HD, an atom-diatom system in which He collides with HD. We are primarily interested in the cooling capabilities of this system, as these species are predicted to have played an important role in the formation of primordial stars, which emerged from a background composed solely of Hydrogen, Helium, and their compounds. HD is being investigated because it has a finite dipole moment and is hence a powerful radiator, and He due to its relative abundance in the early universe. Using a hybrid OpenMP/MPI adaption (vrrm) of a public-domain scattering package, cross sections for He-HD collisions are computed for a swathe of both rotational and vibrational states across a range of relevant kinetic energies, then integrated to produce rate coefficients. Due to the vast computational requirements for performing these operations, the use of high-powered computational resources is necessary.The work of CV was funded by a UGA Center for Undergraduate Research Opportunities award. We thank the University of Georgia GACRC and NERSC at Lawrence-Berkeley for computational resources and Brendan McLaughlin for assistance.

Radio-frequency capacitive discharge with flowing liquid electrodes at reduced gas pressures

NASA Astrophysics Data System (ADS)

Gaisin, Al. F.; Son, E. E.; Petryakov, S. Yu.

2017-07-01

Results are presented from experimental studies of the electrophysical and spectral characteristics of the low-temperature plasma of a radio-frequency capacitive discharge excited between two flowing liquid electrodes at gas pressures of 103-105 Pa. The plasma composition, the electron density, and the vibrational and rotational temperatures of gas molecules are estimated. The types and shapes of discharge are described, and the thermal and gas-hydrodynamic processes in the discharge zone are analyzed.

Ghostly Specter Haunts the ‘Coldest Place in the Universe’

NASA Image and Video Library

2013-10-28

The Boomerang nebula, called the "coldest place in the universe," reveals its true shape to the Atacama Large Millimeter/submillimeter Array (ALMA) telescope. The background blue structure, as seen in visible light by NASA's Hubble Space Telescope, shows a classic double-lobe shape with a very narrow central region. ALMA’s resolution and ability to see the cold gas molecules reveals the nebula’s more elongated shape, as seen in red. Image credit: NRAO/AUI/NSF/NASA/STScI/JPL-Caltech Read more about this image from NASA's Jet Propulsion Laboratory (JPL) here: 1.usa.gov/17o22Rz NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

Characterization and Identification of Natural Terpenic Resins employed in “Madonna con Bambino e Angeli” by Antonello da Messina using Gas Chromatography–Mass Spectrometry

PubMed Central

2012-01-01

Background Natural resins were frequently employed as adhesives or as components of oleo-resinous media in paintings in the past. The identification of vegetable resins is still an open problem. The aim of this paper is to analyze by GC-MS some vegetable resins frequently employed in paintings, such as Venice turpentine, dammar, copal, elemi in order to identify their main component in raw and aged samples. Some molecules are proposed as chemical “markers” to identify these natural resins. Results The results obtained on standards allowed us to successfully analyze sample collected from one work of art: the Madonna with the Infant and Angels by Antonello da Messina (XV century). Conclusion The results obtained confirm that the painting the artist originally used a mixture of linseed oil and natural resin (Venice turpentine) as binding medium. PMID:22721351

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

Field Tests of a Gas-Filter Imaging Radiometer for Methane, CH4,: A Prototype for Geostationary Remote Infrared Pollution Sounder, GRIPS

NASA Astrophysics Data System (ADS)

Dickerson, R. R.; Fish, C. S.; Brent, L. C.; Burrows, J. P.; Fuentes, J. D.; Gordley, L. L.; Jacob, D. J.; Schoeberl, M. R.; Salawitch, R. J.; Ren, X.; Thompson, A. M.

2013-12-01

Gas filter radiometry is a powerful tool for measuring infrared active trace gases. Methane (CH4) is the second most important greenhouse gas and is more potent molecule for molecule than carbon dioxide (CO2). Unconventional natural gas recovery has the potential to show great environmental benefits relative to coal, but only if fugitive leakage is held below 3% and leak rates remain highly uncertain. We present design specifications and initial field/aircraft test results for an imaging remote sensing device to measure column content of methane. The instrument is compared to in situ altitude profiles measured with cavity ring-down. This device is an airborne prototype for the Geostationary Remote Infrared Pollution Sounder, GRIPS, a satellite instrument designed to monitor CH4, CO2, CO, N2O and AOD from geostationary orbit, with capabilities for great advances in air quality and climate research. GRIPS: The Geostationary Remote Infrared Pollution Sounder

Ni-catalysed WO3 nanostructures grown by electron beam rapid thermal annealing for NO2 gas sensing

NASA Astrophysics Data System (ADS)

Chandrasekaran, Gopalakrishnan; Sundararaj, Anuraj; Therese, Helen Annal; Jeganathan, K.

2015-07-01

Ni-catalysed WO3 (Ni-WO3) nanowires and nanosheets were grown on Si (100) substrates using electron beam evaporation followed by electron beam-assisted rapid thermal annealing process. Gas-sensing measurements were performed for various concentrations of NO2 in dry air at a temperature range of 50-400 °C. Nanowires and nanosheets show optimum sensor response of 229 and 197 at operating temperatures of 200 and 250 °C, respectively, for 100 ppm of NO2 exposure. Nanowires demonstrated a rapid response time of 66 s, but a slow recovery time of 204 s owing to poor rate of desorption of the adsorbed NO2 gas molecules from the internal porous structure of nanowires. In contrast, the recovery time for nanosheet was 126 s due to higher desorption rate of the adhered NO2 molecules associated with low surface area and less porous structure of nanosheet. The gas-sensing mechanism of WO3 nanostructure is discussed briefly.

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates.

PubMed

Qiao, Zhen-An; Chai, Song-Hai; Nelson, Kimberly; Bi, Zhonghe; Chen, Jihua; Mahurin, Shannon M; Zhu, Xiang; Dai, Sheng

2014-04-16

High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

Detection of martian amino acids by chemical derivatization coupled to gas chromatography: in situ and laboratory analysis.

PubMed

Rodier, C; Vandenabeele-Trambouze, O; Sternberg, R; Coscia, D; Coll, P; Szopa, C; Raulin, F; Vidal-Madjar, C; Cabane, M; Israel, G; Grenier-Loustalot, M F; Dobrijevic, M; Despois, D

2001-01-01

If there is, or ever was, life in our solar system beyond the Earth, Mars is the most likely place to search for. Future space missions will have then to take into account the detection of prebiotic molecules or molecules of biological significance such as amino acids. Techniques of analysis used for returned samples have to be very sensitive and avoid any chemical or biological contamination whereas in situ techniques have to be automated, fast and low energy consuming. Several possible methods could be used for in situ amino acid analyses on Mars, but gas chromatography would likely be the most suitable. Returned samples could be analyzed by any method in routine laboratory use such as gas chromatography, already successfully performed for analyses of organic matter including amino acids from martian meteorites. The derivatization step, which volatilizes amino acids to perform both in situ and laboratory analysis by gas chromatography, is discussed here. c2001 COSPAR. Published by Elsevier Science Ltd. All rights reserved.

The ARO Working Group Meeting on Ignition Processes, June 1978.

DTIC Science & Technology

1980-03-01

great variety of products are formed from HMX and RDX , including several which cannot be readily explained by the propellant molecules simply breaking...nascent product from HMX is N20, which indicates that some chemistry has taken place somewhere (Figure I shows the HMX and RDX molecules for reference...who described his research into the gas phase unimolecular decomposition of molecules used as explosives (TNT, HMX , RDX ). The purpose of this research

Effects of adatom and gas molecule adsorption on the physical properties of tellurene: a first principles investigation.

PubMed

Wang, Xiao Hua; Wang, Da Wei; Yang, Ai Jun; Koratkar, Nikhil; Chu, Ji Feng; Lv, Pin Lei; Rong, Ming Zhe

2018-02-07

Tellurene is a new member of the two-dimensional (2D) materials' family, whose existence has been recently confirmed by first principles calculation and experimental work. Tellurene is also the first 2D mono-elemental material of group-VI predicted by scientists, and investigations of its basic properties are still in their infancy. In this study, we use first principles calculation based on density functional theory to investigate the adsorption of nineteen typical adatoms (Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Ag, Au, Pd, Pt, B, N, O, Si, Cl, and Al), and five typical gas molecules (H 2 , O 2 , H 2 O, NO 2 , and NH 3 ) on α-phase as well as β-phase tellurene sheets. Our calculations shows that most adatoms are chemisorbed on tellurene sheets with large adsorption energies. Moreover, some of the adatoms are observed to give rise to distinct structural deformations and even local reconstructions. We report that a variety of electronic states are induced by the adatoms, which implies that different electronic structures can be engineered by the adsorption of adatoms. In fact, n-type doping, p-type doping, half-metal, and spin-gapless semiconductor features can be acquired by doping adatoms on tellurene sheets. Our calculations also show that the five gas molecules are all physisorbed on tellurene sheets, and no splitting behaviors are observed. Therefore, the adsorption of the five gas molecules has a weak effect on the electronic properties of tellurene. To conclude, our results indicate that adatom engineering may be used to greatly expand the potential applications of 2D tellurene.

Magnetic Trapping and Coherent Control of Laser-Cooled Molecules

NASA Astrophysics Data System (ADS)

Williams, H. J.; Caldwell, L.; Fitch, N. J.; Truppe, S.; Rodewald, J.; Hinds, E. A.; Sauer, B. E.; Tarbutt, M. R.

2018-04-01

We demonstrate coherent microwave control of the rotational, hyperfine, and Zeeman states of ultracold CaF molecules, and the magnetic trapping of these molecules in a single, selectable quantum state. We trap about 5 ×103 molecules for almost 2 s at a temperature of 70 (8 ) μ K and a density of 1.2 ×105 cm-3. We measure the state-specific loss rate due to collisions with background helium.

Gas density effect on dropsize of simulated fuel sprays

NASA Technical Reports Server (NTRS)

Ingebo, Robert D.

1989-01-01

Two-phase flow in pneumatic two-fluid fuel nozzles was investigated experimentally to determine the effect of atomizing-gas density and gas mass-flux on liquid-jet breakup in sonic-velocity gas-flow. Dropsize data were obtained for the following atomizing-gases: nitrogen; argon; carbon dioxide; and helium. They were selected to cover a gas molecular-weight range of 4 to 44. Atomizing-gas mass-flux ranged from 6 to 50 g/sq cm-sec and four differently sized two-fluid fuel nozzles were used having orifice diameters that varied from 0.32 to 0.56 cm. The ratio of liquid-jet diameter to SMD, D sub o/D sub 32, was correlated with aerodynamic and liquid-surface forces based on the product of the Weber and Reynolds number, We*Re, and gas-to-liquid density ratio, rho sub g/rho sub l. To correlate spray dropsize with breakup forces produced by using different atomizing-gases, a new molecular-scale dimensionless group was derived. The derived dimensionless group was used to obtain an expression for the ratio of liquid-jet diameter to SMD, D sub o/D sub 32. The mathematical expression of this phenomenon incorporates the product of the Weber and Reynolds number, liquid viscosity, surface tension, acoustic gas velocity, the RMS velocity of gas molecules, the acceleration of gas molecules due to gravity, and gas viscosity. The mathematical expression encompassing these parameters agrees well with the atomization theory for liquid-jet breakup in high velocity gas flow. Also, it was found that at the same gas mass-flux, helium was considerably more effective than nitrogen in producing small droplet sprays with SMD's in the order of 5 micrometers.

Gas hydrates of outer continental margins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kvenvolden, K.A.

1990-05-01

Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf ofmore » Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.« less

Understanding the influence of external perturbation on aziridinium ion formation

NASA Astrophysics Data System (ADS)

Sinha, Sourab; Bhattacharyya, Pradip Kr

2018-01-01

A density functional theory study is performed to understand the effect of discrete water molecules during Az+ ion formation in nitrogen mustards. A comparative study in gas phase, and implicit and explicit solvation models of three drug molecules (mustine, chlorambucil and melphalan) is reported. Noteworthy changes in the structure and C-N stretching frequencies of the transition states have been observed in the presence of explicit water molecules. Presence of explicit water molecules reduces the positive charge around the tricyclic Az+ ring, and hence stabilising it. Both activation energy and rate constants are seen to be significantly affected in the presence of discrete water molecules.

Selective CO2 gas adsorption in the narrow crystalline cavities of flexible peptide metallo-macrocycles.

PubMed

Miyake, Ryosuke; Kuwata, Chika; Masumoto, Yui

2015-02-21

Crystalline peptide Ni(ii)-macrocycles (BF4(-) salt) exhibited moderate CO2 gas adsorption (ca. 6-7 CO2 molecules per macrocycle) into very narrow cavities (narrowest part <2 Å), accompanied by the expansion of the cavities. The BF4(-) salt demonstrated selective uptake of CO2 gas in preference to CH4 and N2 gases.

Gas-Phase Synthesis and Characterization of CH4-Loaded Hydroquinone Clathrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.; Lee, Y; Takeya, S

2010-01-01

A CH{sub 4}-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the {alpha}-form of crystalline HQ and CH{sub 4} gas at 12 MPa and room temperature. Solid-state {sup 13}C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH{sub 4} molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH{sub 4} molecules, that is, 0.69 CH{sub 4} per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH{sub 4}-loaded HQ clathrate adopts the {beta}-form ofmore » HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 {angstrom} and c = 5.5038 {angstrom}. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH{sub 4}-loaded HQ clathrate is stable up to 368 K and gradually transforms to the {alpha}-form by releasing the confined CH{sub 4} gases between 368-378 K. Using solid-state {sup 13}C CP/MAS NMR, the reaction kinetics between the {alpha}-form HQ and CH{sub 4} gas is qualitatively described in terms of the particle size of the crystalline HQ.« less

Molecular Composition and Chemistry of Isolated Dense Cores

NASA Astrophysics Data System (ADS)

Cook, Amanda; Boogert, A.

2009-01-01

The composition of molecular clouds and the envelopes and disks surrounding low mass protostars within them is still poorly known. There is little doubt that a large fraction of the molecules is frozen on grains, but the abundance of several crucial species (e.g. ammonia, methanol, ions) in the ices is still uncertain. In addition, prominent spectral features discovered decades ago are still not securely identified (e.g. the 6.85-micron absorption band). Gas phase and grain surface chemistry play pivotal roles in molecule formation, but numerous other processes could have significant impacts as well: shocks, thermal heating, irradiation of ices by ultraviolet photons and cosmic rays. Complex species could be formed this way, profoundly influencing cloud, disk and planetary/cometary chemistry. We have obtained Spitzer/IRS spectra of an unprecedented sample of sight-lines tracing 25 dense isolated cores. These cores physically differ from the large, cluster-forming molecular clouds (e.g. Ophiuchus, Perseus) that are commonly studied: they are less turbulent, colder, less dense, and likely longer lived. These IRS spectra of isolated cores thus provide unique information on ice formation and destruction mechanisms. Toward the same cores, we observed 33 highly extincted background stars as well, tracing the quiescent cloud medium against which the ices around protostars can be contrasted.

Young Stars Emerge from Orion Head

NASA Image and Video Library

2007-05-17

This image from NASA's Spitzer Space Telescope shows infant stars "hatching" in the head of the hunter constellation, Orion. Astronomers suspect that shockwaves from a supernova explosion in Orion's head, nearly three million years ago, may have initiated this newfound birth. The region featured in this Spitzer image is called Barnard 30. It is located approximately 1,300 light-years away and sits on the right side of Orion's "head," just north of the massive star Lambda Orionis. Wisps of green in the cloud are organic molecules called polycyclic aromatic hydrocarbons. These molecules are formed anytime carbon-based materials are burned incompletely. On Earth, they can be found in the sooty exhaust from automobile and airplane engines. They also coat the grills where charcoal-broiled meats are cooked. Tints of orange-red in the cloud are dust particles warmed by the newly forming stars. The reddish-pink dots at the top of the cloud are very young stars embedded in a cocoon of cosmic gas and dust. Blue spots throughout the image are background Milky Way along this line of sight. This composite includes data from Spitzer's infrared array camera instrument, and multiband imaging photometer instrument. Light at 4.5 microns is shown as blue, 8.0 microns is green, and 24 microns is red. http://photojournal.jpl.nasa.gov/catalog/PIA09411

Young Stars Emerge from Orion's Head

NASA Technical Reports Server (NTRS)

2007-01-01

This image from NASA's Spitzer Space Telescope shows infant stars 'hatching' in the head of the hunter constellation, Orion. Astronomers suspect that shockwaves from a supernova explosion in Orion's head, nearly three million years ago, may have initiated this newfound birth

The region featured in this Spitzer image is called Barnard 30. It is located approximately 1,300 light-years away and sits on the right side of Orion's 'head,' just north of the massive star Lambda Orionis.

Wisps of green in the cloud are organic molecules called polycyclic aromatic hydrocarbons. These molecules are formed anytime carbon-based materials are burned incompletely. On Earth, they can be found in the sooty exhaust from automobile and airplane engines. They also coat the grills where charcoal-broiled meats are cooked.

Tints of orange-red in the cloud are dust particles warmed by the newly forming stars. The reddish-pink dots at the top of the cloud are very young stars embedded in a cocoon of cosmic gas and dust. Blue spots throughout the image are background Milky Way along this line of sight.

This composite includes data from Spitzer's infrared array camera instrument, and multiband imaging photometer instrument. Light at 4.5 microns is shown as blue, 8.0 microns is green, and 24 microns is red.

Influence of oxygen concentration on ethylene removal using dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Takahashi, Katsuyuki; Motodate, Takuma; Takaki, Koichi; Koide, Shoji

2018-01-01

Ethylene gas is decomposed using a dielectric barrier discharge plasma reactor for long-period preservation of fruits and vegetables. The oxygen concentration in ambient gas is varied from 2 to 20% to simulate the fruit and vegetable transport container. The experimental results show that the efficiency of ethylene gas decomposition increases with decreasing oxygen concentration. The reactions of ethylene molecules with ozone are analyzed by Fourier transform infrared spectrometry. The analysis results show that the oxidization process by ozone is later than that by oxygen atoms. The amount of oxygen atoms that contribute to ethylene removal increases with decreasing oxygen concentration because the reaction between oxygen radicals and oxygen molecules is suppressed at low oxygen concentrations. Ozone is completely removed and the energy efficiency of C2H4 removal is increased using manganese dioxide as a catalyst.

Evaporation of liquid droplets of nano- and micro-meter size as a function of molecular mass and intermolecular interactions: experiments and molecular dynamics simulations.

PubMed

Hołyst, Robert; Litniewski, Marek; Jakubczyk, Daniel

2017-09-13

Transport of heat to the surface of a liquid is a limiting step in the evaporation of liquids into an inert gas. Molecular dynamics (MD) simulations of a two component Lennard-Jones (LJ) fluid revealed two modes of energy transport from a vapour to an interface of an evaporating droplet of liquid. Heat is transported according to the equation of temperature diffusion, far from the droplet of radius R. The heat flux, in this region, is proportional to temperature gradient and heat conductivity in the vapour. However at some distance from the interface, Aλ, (where λ is the mean free path in the gas), the temperature has a discontinuity and heat is transported ballistically i.e. by direct individual collisions of gas molecules with the interface. This ballistic transport reduces the heat flux (and consequently the mass flux) by the factor R/(R + Aλ) in comparison to the flux obtained from temperature diffusion. Thus it slows down the evaporation of droplets of sizes R ∼ Aλ and smaller (practically for sizes from 10 3 nm down to 1 nm). We analyzed parameter A as a function of interactions between molecules and their masses. The rescaled parameter, A(k B T b /ε 11 ) 1/2 , is a linear function of the ratio of the molecular mass of the liquid molecules to the molecular mass of the gas molecules, m 1 /m 2 (for a series of chemically similar compounds). Here ε 11 is the interaction parameter between molecules in the liquid (proportional to the enthalpy of evaporation) and T b is the temperature of the gas in the bulk. We tested the predictions of MD simulations in experiments performed on droplets of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. They were suspended in an electrodynamic trap and evaporated into dry nitrogen gas. A changes from ∼1 (for ethylene glycol) to approximately 10 (for tetraethylene glycol) and has the same dependence on molecular parameters as obtained for the LJ fluid in MD simulations. The value of x = A(k B T b /ε 11 ) 1/2 is of the order of 1 (for water x = 1.8, glycerol x = 1, ethylene glycol x = 0.4, tetraethylene glycol x = 2.1 evaporating into dry nitrogen at room temperature and for Lennard-Jones fluids x = 2 for m 1 /m 2 = 1 and low temperature).

On the uncertainty in single molecule fluorescent lifetime and energy emission measurements

NASA Technical Reports Server (NTRS)

Brown, Emery N.; Zhang, Zhenhua; Mccollom, Alex D.

1995-01-01

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least square methods agree and are optimal when the number of detected photons is large however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67% of those can be noise and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous poisson processes, we derive the exact joint arrival time probably density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. the ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background nose and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

On the Uncertainty in Single Molecule Fluorescent Lifetime and Energy Emission Measurements

NASA Technical Reports Server (NTRS)

Brown, Emery N.; Zhang, Zhenhua; McCollom, Alex D.

1996-01-01

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least squares methods agree and are optimal when the number of detected photons is large, however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67 percent of those can be noise, and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous Poisson processes, we derive the exact joint arrival time probability density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. The ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background noise and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

GC in Environmental Analysis

ERIC Educational Resources Information Center

Gosink, Thomas A.

1975-01-01

Gas chromatography can be used to quantitate various gases, complex organic molecules, metals, anions, and pesticides in the lab or in the field. Important advances in gas chromatography and how they directly apply to environmental analyses plus suggestions where they will be of importance to environmental chemists are discussed. (BT)

Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

NASA Technical Reports Server (NTRS)

Bergin, E. A.; Langer, W. D.; Goldsmith, P. F.

1995-01-01

We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

A molecular dynamics study of model SI clathrate hydrates: the effect of guest size and guest-water interaction on decomposition kinetics.

PubMed

Das, Subhadip; Baghel, Vikesh Singh; Roy, Sudip; Kumar, Rajnish

2015-04-14

One of the options suggested for methane recovery from natural gas hydrates is molecular replacement of methane by suitable guests like CO2 and N2. This approach has been found to be feasible through many experimental and molecular dynamics simulation studies. However, the long term stability of the resultant hydrate needs to be evaluated; the decomposition rate of these hydrates is expected to depend on the interaction between these guest and water molecules. In this work, molecular dynamics simulation has been performed to illustrate the effect of guest molecules with different sizes and interaction strengths with water on structure I (SI) hydrate decomposition and hence the stability. The van der Waals interaction between water of hydrate cages and guest molecules is defined by Lennard Jones potential parameters. A wide range of parameter spaces has been scanned by changing the guest molecules in the SI hydrate, which acts as a model gas for occupying the small and large cages of the SI hydrate. All atomistic simulation results show that the stability of the hydrate is sensitive to the size and interaction of the guest molecules with hydrate water. The increase in the interaction of guest molecules with water stabilizes the hydrate, which in turn shows a slower rate of hydrate decomposition. Similarly guest molecules with a reasonably small (similar to Helium) or large size increase the decomposition rate. The results were also analyzed by calculating the structural order parameter to understand the dynamics of crystal structure and correlated with the release rate of guest molecules from the solid hydrate phase. The results have been explained based on the calculation of potential energies felt by guest molecules in amorphous water, hydrate bulk and hydrate-water interface regions.

Organic positive ions in aircraft gas-turbine engine exhaust

NASA Astrophysics Data System (ADS)

Sorokin, Andrey; Arnold, Frank

Volatile organic compounds (VOCs) represent a significant fraction of atmospheric aerosol. However the role of organic species emitted by aircraft (as a consequence of the incomplete combustion of fuel in the engine) in nucleation of new volatile particles still remains rather speculative and requires a much more detailed analysis of the underlying mechanisms. Measurements in aircraft exhaust plumes have shown the presence of both different non-methane VOCs (e.g. PartEmis project) and numerous organic cluster ions (MPIK-Heidelberg). However the link between detected organic gas-phase species and measured mass spectrum of cluster ions is uncertain. Unfortunately, up to now there are no models describing the thermodynamics of the formation of primary organic cluster ions in the exhaust of aircraft engines. The aim of this work is to present first results of such a model development. The model includes the block of thermodynamic data based on proton affinities and gas basicities of organic molecules and the block of non-equilibrium kinetics of the cluster ions evolution in the exhaust. The model predicts important features of the measured spectrum of positive ions in the exhaust behind aircraft. It is shown that positive ions emitted by aircraft engines into the atmosphere mostly consist of protonated and hydrated organic cluster ions. The developed model may be explored also in aerosol investigations of the background atmosphere as well as in the analysis of the emission of fine aerosol particles by automobiles.

Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

NASA Astrophysics Data System (ADS)

Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

2017-12-01

The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

Understanding about How Different Foaming Gases Effect the Interfacial Array Behaviors of Surfactants and the Foam Properties.

PubMed

Sun, Yange; Qi, Xiaoqing; Sun, Haoyang; Zhao, Hui; Li, Ying

2016-08-02

In this paper, the detailed behaviors of all the molecules, especially the interfacial array behaviors of surfactants and diffusion behaviors of gas molecules, in foam systems with different gases (N2, O2, and CO2) being used as foaming agents were investigated by combining molecular dynamics simulation and experimental approaches for the purpose of interpreting how the molecular behaviors effect the properties of the foam and find out the key factors which fundamentally determine the foam stability. Sodium dodecyl sulfate SDS was used as the foam stabilizer. The foam decay and the drainage process were determined by Foamscan. A texture analyzer (TA) was utilized to measure the stiffness and viscoelasticity of the foam films. The experimental results agreed very well with the simulation results by which how the different gas components affect the interfacial behaviors of surfactant molecules and thereby bring influence on foam properties was described.

Molecular dynamics simulations of the surface tension of oxygen-supersaturated water

NASA Astrophysics Data System (ADS)

Jain, S.; Qiao, L.

2017-04-01

In this work, non-reactive molecular dynamic simulations were conducted to determine the surface tension of water as a function of the concentration of the dissolved gaseous molecules (O2), which would in turn help to predict the pressure inside the nanobubbles under supersaturation conditions. Knowing the bubble pressure is a prerequisite for understanding the mechanisms behind the spontaneous combustion of the H2/O2 gases inside the nanobubbles. First, the surface tension of pure water was determined using the planar interface method and the Irving and Kirkwood formula. Next, the surface tension of water containing four different supersaturation concentrations (S) of O2 gas molecules was computed considering the curved interface of a nanobubble. The surface tension of water was found to decrease with an increase in the supersaturation ratio or the concentration of the dissolved O2 gas molecules.

A New Radio Spectral Line Survey of Planetary Nebulae: Exploring Radiatively-driven Heating and Chemistry of Molecular Gas

NASA Astrophysics Data System (ADS)

Bublitz, Jesse; Kastner, Joel H.; Santander-García, Miguel; Montez, Rodolfo; Alcolea, Javier; Balick, Bruce; Bujarrabal, Valentín

2018-01-01

We report the results of a survey of mm-wave molecular line emission from nine nearby (<1.5 kpc), well-studied, molecule-rich planetary nebulae (PNe) with the Institut de Radioastronomie Millimétrique (IRAM) 30 m telescope. Our sample comprises molecule-rich PNe spanning a wide range of central star UV luminosities as well as central star and nebular X-ray emission properties. Nine molecular line frequencies were chosen to investigate the molecular chemistry of these nebulae. New detections of one or more of five molecules -- the molecular mass tracer 13CO and the chemically important trace species HCO+, CN, HCN, and HNC -- were made in at least one PN. We present analysis of emission line flux ratios that are potential diagnostics of the influence that ultraviolet and X-ray radiation have on the chemistry of residual molecular gas in PNe.

Molecular complexes in close and far away

PubMed Central

Klemperer, William; Vaida, Veronica

2006-01-01

In this review, gas-phase chemistry of interstellar media and some planetary atmospheres is extended to include molecular complexes. Although the composition, density, and temperature of the environments discussed are very different, molecular complexes have recently been considered as potential contributors to chemistry. The complexes reviewed include strongly bound aggregates of molecules with ions, intermediate-strength hydrogen bonded complexes (primarily hydrates), and weakly bonded van der Waals molecules. In low-density, low-temperature environments characteristic of giant molecular clouds, molecular synthesis, known to involve gas-phase ion-molecule reactions and chemistry at the surface of dust and ice grains is extended here to involve molecular ionic clusters. At the high density and high temperatures found on planetary atmospheres, molecular complexes contribute to both atmospheric chemistry and climate. Using the observational, laboratory, and theoretical database, the role of molecular complexes in close and far away is discussed. PMID:16740667

The sensitivity of gas-phase models of dense interstellar clouds to changes in dissociative recombination branching ratios

NASA Technical Reports Server (NTRS)

Millar, T. J.; Defrees, D. J.; Mclean, A. D.; Herbst, E.

1988-01-01

The approach of Bates to the determination of neutral product branching ratios in ion-electron dissociative recombination reactions has been utilized in conjunction with quantum chemical techniques to redetermine branching ratios for a wide variety of important reactions of this class in dense interstellar clouds. The branching ratios have then been used in a pseudo time-dependent model calculation of the gas phase chemistry of a dark cloud resembling TMC-1 and the results compared with an analogous model containing previously used branching ratios. In general, the changes in branching ratios lead to stronger effects on calculated molecular abundances at steady state than at earlier times and often lead to reductions in the calculated abundances of complex molecules. However, at the so-called 'early time' when complex molecule synthesis is most efficient, the abundances of complex molecules are hardly affected by the newly used branching ratios.

The Buffer-Gas Positron Accumulator and Resonances in Positron-Molecule Interactions

NASA Technical Reports Server (NTRS)

Surko, C.M.

2007-01-01

This is a personal account of the development of our buffer-gas positron trap and the new generation of cold beams that these traps enabled. Dick Drachman provided much appreciated advice to us from the time we started the project. The physics underlying trap operation is related to resonances (or apparent resonances) in positron-molecule interactions. Amusingly, experiments enabled by the trap allowed us to understand these processes. The positron-resonance "box score" to date is one resounding "yes," namely vibrational Feshbach resonances in positron annihilation on hydrocarbons; a "probably" for positron-impact electronic excitation of CO and NZ;an d a "maybe" for vibrational excitation of selected molecules. Two of these processes enabled the efficient operation of the trap, and one almost killed it in infancy. We conclude with a brief overview of further applications of the trapping technology discussed here, such as "massive" positron storage and beams with meV energy resolution.

Emulating porphyrins with a rippled multivacancy graphene system

NASA Astrophysics Data System (ADS)

Mombrú, Dominique; Faccio, Ricardo; Mombrú, Alvaro W.

2018-04-01

The interaction between a complex porphyrin-like system formed by an iron atom and multivacant graphene layer and O2, CO and CO2 molecules is studied, using Density Functional Theory (DFT) calculations. The multivacancy graphene system used for this study, consists in the removal of a 1,4-dimethybenzene-like moiety, in a 6 × 6 supercell. This removal and the structural optimization subsequently performed, yield to a biaxial vacancy, where the location of an iron atom embedded in it, lead to a system with resemblance to iron-porphyrin systems. This similar structure could be used to form complexes where gas molecules are allowed to interact with these iron-octavacant graphene systems. The study focuses on the structure of the system and the net magnetic moment for different gas molecules: O2, CO2 and CO. Rippling in the vacant graphene is enhanced through this interaction.

Theoretical and experimental studies of the structure and vibrational spectra of NTO

NASA Astrophysics Data System (ADS)

Sorescu, Dan C.; Sutton, Teressa R. L.; Thompson, Donald L.; Beardall, David; Wight, Charles A.

1996-10-01

The structure and vibrational spectra of the high explosive 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) have been determined by ab initio molecular orbital calculations at the Hartree-Fock and second-order Møller-Plesset levels and by density functional theory (B3LYP). Experimental frequencies for the molecule have been determined from infrared spectra of pure NTO films and NTO molecules isolated in an argon matrix at 21 K. A force field for gas phase NTO has been obtained based on calculated results at the MP2/6-311G∗∗ level. In addition, a force field for solid state NTO has been constructed using the experimental vibrational frequencies for NTO films and scaled ab initio vibrational frequencies. Differences between the solid state and gas phase results indicate that the environment and preparation procedure exert a marked influence on the spectral characteristics of the NTO molecule.

Methyl group transfer upon gas phase decomposition of protonated methyl benzoate and similar compounds.

PubMed

Frański, Rafał; Gierczyk, Błażej; Zalas, Maciej; Jankowski, Wojciech; Hoffmann, Marcin

2018-05-01

Gas phase decompositions of protonated methyl benzoate and its conjugates have been studied by using electrospray ionization-collision induced dissociation-tandem mass spectrometry. Loss of CO 2 molecule, thus transfer of methyl group, has been observed. In order to better understand this process, the theoretical calculations have been performed. For methyl benzoate conjugates, it has been found that position of substituent affects the loss of CO 2 molecule, not the electron donor/withdrawing properties of the substituent. Therefore, electrospray ionization-mass spectrometry in positive ion mode may be useful for differentiation of isomers of methyl benzoate conjugates. Copyright © 2018 John Wiley & Sons, Ltd.

Red-shifting and blue-shifting OH groups on metal oxide surfaces - towards a unified picture.

PubMed

Kebede, Getachew G; Mitev, Pavlin D; Briels, Wim J; Hermansson, Kersti

2018-05-09

We analyse the OH vibrational signatures of 56 structurally unique water molecules and 34 structurally unique hydroxide ions in thin water films on MgO(001) and CaO(001), using DFT-generated anharmonic potential energy surfaces. We find that the OH stretching frequencies of intact water molecules on the surface are always downshifted with respect to the gas-phase species while the OH- groups are either upshifted or downshifted. Despite these differences, the main characteristics of the frequency shifts for all three types of surface OH groups (OHw, OsH and OHf) can be accounted for by one unified expression involving the in situ electric field from the surrounding environment, and the gas-phase molecular properties of the vibrating species (H2O or OH-). The origin behind the different red- and blueshift behaviour can be traced back to the fact that the molecular dipole moment of a gas-phase water molecule increases when an OH bond is stretched, but the opposite is true for the hydroxide ion. We propose that familiarity with the relations presented here will help surface scientists in the interpretation of vibrational OH spectra for thin water films on ionic crystal surfaces.

Serial single molecule electron diffraction imaging: diffraction background of superfluid helium droplets

NASA Astrophysics Data System (ADS)

Zhang, Jie; He, Yunteng; Lei, Lei; Alghamdi, Maha; Oswalt, Andrew; Kong, Wei

2017-08-01

In an effort to solve the crystallization problem in crystallography, we have been engaged in developing a method termed "serial single molecule electron diffraction imaging" (SS-EDI). The unique features of SS-EDI are superfluid helium droplet cooling and field-induced orientation: together the two features constitute a molecular goniometer. Unfortunately, the helium atoms surrounding the sample molecule also contribute to a diffraction background. In this report, we analyze the properties of a superfluid helium droplet beam and its doping statistics, and demonstrate the feasibility of overcoming the background issue by using the velocity slip phenomenon of a pulsed droplet beam. Electron diffraction profiles and pair correlation functions of ferrocene-monomer-doped droplets and iodine-nanocluster-doped droplets are presented. The timing of the pulsed electron gun and the effective doping efficiency under different dopant pressures can both be controlled for size selection. This work clears any doubt of the effectiveness of superfluid helium droplets in SS-EDI, thereby advancing the effort in demonstrating the "proof-of-concept" one step further.

Molecular diagnostics of interstellar shocks

NASA Technical Reports Server (NTRS)

Hartquist, T. W.; Dalgarno, A.; Oppenheimer, M.

1980-01-01

The chemistry of molecules in shocked regions of the interstellar gas is considered and calculations are carried out for a region subjected to a shock at a velocity of 8 km/sec. Substantial enhancements are predicted in the concentrations of the molecules H2S, SO, and SiO compared to those anticipated in cold interstellar clouds.

Molecular diagnostics of interstellar shocks

NASA Astrophysics Data System (ADS)

Hartquist, T. W.; Dalgarno, A.; Oppenheimer, M.

1980-02-01

The chemistry of molecules in shocked regions of the interstellar gas is considered and calculations are carried out for a region subjected to a shock at a velocity of 8 km/sec. Substantial enhancements are predicted in the concentrations of the molecules H2S, SO, and SiO compared to those anticipated in cold interstellar clouds.

Parallel mass spectrometry (APCI-MS and ESI-MS) for lipid analysis

USDA-ARS?s Scientific Manuscript database

Coupling the condensed phase of HPLC with the high vacuum necessary for ion analysis in a mass spectrometer requires quickly evaporating large amounts of liquid mobile phase to release analyte molecules into the gas phase, along with ionization of those molecules, so they can be detected by the mass...

A quorum-sensing molecule acts as a morphogen controlling gas vesicle organelle biogenesis and adaptive flotation in an enterobacterium

PubMed Central

Ramsay, Joshua P.; Williamson, Neil R.; Spring, David R.; Salmond, George P. C.

2011-01-01

Gas vesicles are hollow intracellular proteinaceous organelles produced by aquatic Eubacteria and Archaea, including cyanobacteria and halobacteria. Gas vesicles increase buoyancy and allow taxis toward air–liquid interfaces, enabling subsequent niche colonization. Here we report a unique example of gas vesicle-mediated flotation in an enterobacterium; Serratia sp. strain ATCC39006. This strain is a member of the Enterobacteriaceae previously studied for its production of prodigiosin and carbapenem antibiotics. Genes required for gas vesicle synthesis mapped to a 16.6-kb gene cluster encoding three distinct homologs of the main structural protein, GvpA. Heterologous expression of this locus in Escherichia coli induced copious vesicle production and efficient cell buoyancy. Gas vesicle morphogenesis in Serratia enabled formation of a pellicle-like layer of highly vacuolated cells, which was dependent on oxygen limitation and the expression of ntrB/C and cheY-like regulatory genes within the gas-vesicle gene cluster. Gas vesicle biogenesis was strictly controlled by intercellular chemical signaling, through an N-acyl homoserine lactone, indicating that in this system the quorum-sensing molecule acts as a morphogen initiating organelle development. Flagella-based motility and gas vesicle morphogenesis were also oppositely regulated by the small RNA-binding protein, RsmA, suggesting environmental adaptation through physiological control of the choice between motility and flotation as alternative taxis modes. We propose that gas vesicle biogenesis in this strain represents a distinct mechanism of mobility, regulated by oxygen availability, nutritional status, the RsmA global regulatory system, and the quorum-sensing morphogen. PMID:21873216

A quorum-sensing molecule acts as a morphogen controlling gas vesicle organelle biogenesis and adaptive flotation in an enterobacterium.

PubMed

Ramsay, Joshua P; Williamson, Neil R; Spring, David R; Salmond, George P C

2011-09-06

Gas vesicles are hollow intracellular proteinaceous organelles produced by aquatic Eubacteria and Archaea, including cyanobacteria and halobacteria. Gas vesicles increase buoyancy and allow taxis toward air-liquid interfaces, enabling subsequent niche colonization. Here we report a unique example of gas vesicle-mediated flotation in an enterobacterium; Serratia sp. strain ATCC39006. This strain is a member of the Enterobacteriaceae previously studied for its production of prodigiosin and carbapenem antibiotics. Genes required for gas vesicle synthesis mapped to a 16.6-kb gene cluster encoding three distinct homologs of the main structural protein, GvpA. Heterologous expression of this locus in Escherichia coli induced copious vesicle production and efficient cell buoyancy. Gas vesicle morphogenesis in Serratia enabled formation of a pellicle-like layer of highly vacuolated cells, which was dependent on oxygen limitation and the expression of ntrB/C and cheY-like regulatory genes within the gas-vesicle gene cluster. Gas vesicle biogenesis was strictly controlled by intercellular chemical signaling, through an N-acyl homoserine lactone, indicating that in this system the quorum-sensing molecule acts as a morphogen initiating organelle development. Flagella-based motility and gas vesicle morphogenesis were also oppositely regulated by the small RNA-binding protein, RsmA, suggesting environmental adaptation through physiological control of the choice between motility and flotation as alternative taxis modes. We propose that gas vesicle biogenesis in this strain represents a distinct mechanism of mobility, regulated by oxygen availability, nutritional status, the RsmA global regulatory system, and the quorum-sensing morphogen.

Molecules in interstellar clouds. [physical and chemical conditions of star formation and biological evolution

NASA Technical Reports Server (NTRS)

Irvine, W. M.; Hjalmarson, A.; Rydbeck, O. E. H.

1981-01-01

The physical conditions and chemical compositions of the gas in interstellar clouds are reviewed in light of the importance of interstellar clouds for star formation and the origin of life. The Orion A region is discussed as an example of a giant molecular cloud where massive stars are being formed, and it is pointed out that conditions in the core of the cloud, with a kinetic temperature of about 75 K and a density of 100,000-1,000,000 molecules/cu cm, may support gas phase ion-molecule chemistry. The Taurus Molecular Clouds are then considered as examples of cold, dark, relatively dense interstellar clouds which may be the birthplaces of solar-type stars and which have been found to contain the heaviest interstellar molecules yet discovered. The molecular species identified in each of these regions are tabulated, including such building blocks of biological monomers as H2O, NH3, H2CO, CO, H2S, CH3CN and H2, and more complex species such as HCOOCH3 and CH3CH2CN.

Atomic and molecular data for spacecraft re-entry plasmas

NASA Astrophysics Data System (ADS)

Celiberto, R.; Armenise, I.; Cacciatore, M.; Capitelli, M.; Esposito, F.; Gamallo, P.; Janev, R. K.; Laganà, A.; Laporta, V.; Laricchiuta, A.; Lombardi, A.; Rutigliano, M.; Sayós, R.; Tennyson, J.; Wadehra, J. M.

2016-06-01

The modeling of atmospheric gas, interacting with the space vehicles in re-entry conditions in planetary exploration missions, requires a large set of scattering data for all those elementary processes occurring in the system. A fundamental aspect of re-entry problems is represented by the strong non-equilibrium conditions met in the atmospheric plasma close to the surface of the thermal shield, where numerous interconnected relaxation processes determine the evolution of the gaseous system towards equilibrium conditions. A central role is played by the vibrational exchanges of energy, so that collisional processes involving vibrationally excited molecules assume a particular importance. In the present paper, theoretical calculations of complete sets of vibrationally state-resolved cross sections and rate coefficients are reviewed, focusing on the relevant classes of collisional processes: resonant and non-resonant electron-impact excitation of molecules, atom-diatom and molecule-molecule collisions as well as gas-surface interaction. In particular, collisional processes involving atomic and molecular species, relevant to Earth (N2, O2, NO), Mars (CO2, CO, N2) and Jupiter (H2, He) atmospheres are considered.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

Non Covalent Interactions in Large Diamondoid Dimers in the Gas Phase - a Microwave Study

NASA Astrophysics Data System (ADS)

Perez, Cristobal; Sekutor, Marina; Fokin, Andrey A.; Blomeyer, Sebastian; Vishnevskiy, Yury V.; Mitzel, Norbert W.; Schreiner, Peter R.; Schnell, Melanie

2017-06-01

Accurate structure determination of large molecules still represents an ambitious challenge. Interesting benchmark systems for structure determination are large diamondoid dimers, whose structures are governed by strong intramolecular interactions. Recently, diamondoid dimers with unusually long central C-C bonds (up to 1.71 Å) were synthesized. This long central C-C bond was rationalized by numerous CH...HC-type dispersion attractions between the two halves of the molecule. The thermodynamic stabilization of molecules equipped with bulky groups has provided a conceptually new rationale, since until then it had been assumed that such molecules are highly unstable. We performed a broadband CP-FTMW spectroscopy study in the 2-8 GHz frequency range on oxygen-substituted diamondoid dimers (C_{26}H_{34}O_2, 28 heavy atoms) as well as diadamantyl ether to provide further insight into their structures. The experimental data are compared with results from quantum-chemical calculations and gas-phase electron diffraction. For the ether, we even obtained ^{13}C and ^{18}O isotopologues to generate the full heavy-atom substitution structure.

New measurements on water ice photodesorption and product formation under ultraviolet irradiation

NASA Astrophysics Data System (ADS)

Cruz-Diaz, Gustavo A.; Martín-Doménech, Rafael; Moreno, Elena; Muñoz Caro, Guillermo M.; Chen, Yu-Jung

2018-03-01

The photodesorption of icy grain mantles has been claimed to be responsible for the abundance of gas-phase molecules towards cold regions. Being water a ubiquitous molecule, it is crucial to understand its role in photochemistry and its behaviour under an ultraviolet field. We report new measurements on the ultraviolet (UV) photodesorption of water ice and its H2, OH, and O2 photoproducts using a calibrated quadrupole mass spectrometer. Solid water was deposited under ultra-high-vacuum conditions and then UV-irradiated at various temperatures starting from 8 K with a microwave discharged hydrogen lamp. Deuterated water was used for confirmation of the results. We found a photodesorption yield of 1.3 × 10-3 molecules per incident photon for water and 0.7 × 10-3 molecules per incident photon for deuterated water at the lowest irradiation temperature, 8 K. The photodesorption yield per absorbed photon is given and comparison with astrophysical scenarios, where water ice photodesorption could account for the presence of gas-phase water towards cold regions in the absence of a thermal desorption process, is addressed.

Adsorption and Transport of Methane Molecules through One-Dimensional Channels in Dipeptide-Based Materials

NASA Astrophysics Data System (ADS)

Paradiso, Daniele; Perelli Cippo, Enrico; Gorini, Giuseppe; Rossi, Giorgio; Larese, John Z.

The development of new materials for use in energy and environmental applications is of great interest, in particular in the areas of gas separation and carbon capture, where molecular transport plays a significant role. The dipeptides are organic molecules that offer an attractive possibility in such areas, because they form open hexagonal crystalline structures (space group P61) with quasi one-dimensional channels of tunable pore diameters in the range 3-6 Å. These molecular crystals exhibit selective adsorption, as well as, water and gas transport properties: these are believed to result from collective vibrations of the crystal structure that are coupled to the motions of the guest molecules within the channels. Current studies focus on characterizing the system methane and L-Isoleucyl-L-Valine (IV): this was initially done with high-resolution adsorption isotherms; then, high-resolution Inelastic Neutron Scattering measurements at the Spallation Neutron Source (BASIS spectrometer) revealed clear rotational tunneling peaks, offering details to unravel the potential energy surface of the system, as well as, evidences that channels flexibility and dynamical motion of the molecules have influence on the dipeptides adsorption properties.

Water-assisted dehalogenation of thionyl chloride in the presence of water molecules.

PubMed

Yeung, Chi Shun; Ng, Ping Leung; Guan, Xiangguo; Phillips, David Lee

2010-04-01

A second-order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT) investigation of the dehalogenation reactions of thionyl chloride is reported, in which water molecules (up to seven) were explicitly involved in the reaction complex. The dehalogenation processes of thionyl chloride were found to be dramatically catalyzed by water molecules. The reaction rate became significantly faster as more water molecules became involved in the reaction complex. The dehalogenation processes can be reasonably simulated by the gas-phase water cluster models, which reveals that water molecules can help to solvate the thionyl chloride molecules and activate the release of the Cl(-) leaving group. The computed activation energies were used to compare the calculations to available experimental data.

Excited State Energetics and Dynamics of Large Molecules, Complexes and Clusters

DTIC Science & Technology

1988-07-01

tetracene. Ar (n=l-5) complexes, providing central information on microscopic solvent shifts. These studies were extended to M-metal atom com - plexes...corresponding to the bare molecule. At higher 2. Experimental stagnation pressures of Ar (p = 80-150 Toff) the contributions of van der Waals DPB. Ar, com - Our...gas aromatic-molecule complexes were docu- So - S1 transition of the trans-stilbene (TS)-Ar com - mented experimentally to lie in the rango - 30- plex

Photoacoustic infrared spectroscopy for conducting gas tracer tests and measuring water saturations in landfills.

PubMed

Jung, Yoojin; Han, Byunghyun; Mostafid, M Erfan; Chiu, Pei; Yazdani, Ramin; Imhoff, Paul T

2012-02-01

Gas tracer tests can be used to determine gas flow patterns within landfills, quantify volatile contaminant residence time, and measure water within refuse. While gas chromatography (GC) has been traditionally used to analyze gas tracers in refuse, photoacoustic spectroscopy (PAS) might allow real-time measurements with reduced personnel costs and greater mobility and ease of use. Laboratory and field experiments were conducted to evaluate the efficacy of PAS for conducting gas tracer tests in landfills. Two tracer gases, difluoromethane (DFM) and sulfur hexafluoride (SF(6)), were measured with a commercial PAS instrument. Relative measurement errors were invariant with tracer concentration but influenced by background gas: errors were 1-3% in landfill gas but 4-5% in air. Two partitioning gas tracer tests were conducted in an aerobic landfill, and limits of detection (LODs) were 3-4 times larger for DFM with PAS versus GC due to temporal changes in background signals. While higher LODs can be compensated by injecting larger tracer mass, changes in background signals increased the uncertainty in measured water saturations by up to 25% over comparable GC methods. PAS has distinct advantages over GC with respect to personnel costs and ease of use, although for field applications GC analyses of select samples are recommended to quantify instrument interferences. Copyright © 2011 Elsevier Ltd. All rights reserved.

PIC code modeling of spacecraft charging potential during electron beam injection into a background of neutral gas and plasma, part 1

NASA Technical Reports Server (NTRS)

Koga, J. K.; Lin, C. S.; Winglee, R. M.

1989-01-01

Injections of nonrelativistic electron beams from an isolated equipotential conductor into a uniform background of plasma and neutral gas were simulated using a 2-D electrostatic particle code. The ionization effects on spacecraft charging are examined by including interactions of electrons with neutral gas. The simulations show that the conductor charging potential decreases with increasing neutral background density due to the production of secondary electrons near the conductor surface. In the spacecraft wake, the background electrons accelerated towards the charged spacecraft produce an enhancement of secondary electrons and ions. Simulations run for longer times indicate that the spacecraft potential is further reduced and short wavelength beam-plasma oscillations appear. The results are applied to explain the spacecraft charging potential measured during the SEPAC experiments from Spacelab 1.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

PubMed

Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

2018-02-21

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Plasma discharge elemental detector for a mass spectrometer

NASA Astrophysics Data System (ADS)

Heppner, R. A.

1983-06-01

A material to be analyzed is injected into a mirowave-induced plasma discharge unit, in which the material is carried with a flow of buffer gas through an intense microwave energy field which produces a plasma discharge in the buffer gas. As the material exits from the plasma discharge, the material is sampled and conveyed along a capillary transfer tube to a mass spectrometer where it is analyzed. The plasma discharge causes dissociation of complex organic molecules into simpler molecules which return to the neutral ground state before they are analyzed in the mass spectrometer. The buffer gas is supplied to one end portion of the discharge tube and is withdrawn from the other end portion by a vacuum pump which maintains a subatmospheric pressure in the discharge tube. The sample material is injected by a capillary injection tube into the buffer gas flow as it enters the plasma discharge zone. The dissociated materials are sampled by an axial sampling tube having an entrance where the buffer gas exits from the plasma discharge zone. The sample material may be supplied by a gas chromatography having a capillary effluent line connected to the capillary injection tube, so that the effluent material is injected into the microwave induced plasma discharge. The microwave field is produced by a cavity resonator through which the discharge tube passes.

Noble metal (Pt or Au)-doped monolayer MoS2 as a promising adsorbent and gas-sensing material to SO2, SOF2 and SO2F2: a DFT study

NASA Astrophysics Data System (ADS)

Chen, Dachang; Zhang, Xiaoxing; Tang, Ju; Cui, Hao; Li, Yi

2018-02-01

We explored the adsorption of SO2, SOF2, and SO2F2 on Pt- or Au-doped MoS2 monolayer based on density functional theory. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. SO2 and SOF2 exhibit strong chemical interactions with Pt-doped MoS2 based on large adsorption energy, charge transfer, and changes of electron orbitals in gas molecule. SO2 also shows obvious chemisorption on Au-doped MoS2 with apparent magnetism transfer from Au to gas molecules. The adsorption of SO2F2 on Pt-MoS2 and SOF2 on Au-MoS2 exhibits weaker chemical interactions and SO2F2 losses electrons when adsorbed on Pt-MoS2 which is different from other gas adsorption. The adsorption of SO2F2 on Au-MoS2 represents no obvious chemical interaction but physisorption. The gas-sensing properties are also evaluated based on DFT results. This work could provide prospects and application value for typical noble metal-doped MoS2 as gas-sensing materials.

Water Vapor Sensors Go Sky-High to Assure Aircraft Safety

NASA Technical Reports Server (NTRS)

2006-01-01

JPL used a special tunable diode laser, which NASA scientists could tune to different wavelengths, like a radio being tuned to different frequencies, to accurately target specific molecules and detect small traces of gas. This tunable diode laser was designed to emit near-infrared light at wavelengths absorbed by the gas or gases being detected. The light energy being absorbed by the target gas is related to the molecules present. This is usually measured in parts per million or parts per billion. Multiple measurements are made every second, making the system quick to respond to variations in the target gas. NASA scientists developed this technology as part of the 1999 Mars Polar Lander mission to explore the possibility of life-giving elements on Mars. NASA has since used the tunable diode laser-based gas sensor on aircraft and on balloons to successfully study weather and climate, global warming, emissions from aircraft, and numerous other areas where chemical gas analysis is needed. SpectraSensors, Inc., was formed in 1999 as a spinoff company of JPL, to commercialize tunable diode laser-based analyzers for industrial gas-sensing applications (Spinoff 2000). Now, the San Dimas, California-based firm has come back to the market with a new product featuring the NASA-developed instrument for atmospheric monitoring. This instrument is now helping aircraft avoid hazardous weather conditions and enabling the National Weather Service to provide more accurate weather forecasts.

A monobromobimane-based assay to measure the pharmacokinetic profile of reactive sulphide species in blood

PubMed Central

Wintner, Edward A; Deckwerth, Thomas L; Langston, William; Bengtsson, Asa; Leviten, Dina; Hill, Paul; Insko, Michael A; Dumpit, Ronald; VandenEkart, Emily; Toombs, Christopher F; Szabo, Csaba

2010-01-01

Background and purpose: Hydrogen sulphide (H2S) is a labile, endogenous metabolite of cysteine, with multiple biological roles. The development of sulphide-based therapies for human diseases will benefit from a reliable method of quantifying H2S in blood and tissues. Experimental approach: Concentrations of reactive sulphide in saline and freshly drawn whole blood were quantified by reaction with the thio-specific derivatization agent monobromobimane, followed by reversed-phase fluorescence HPLC and/or mass spectrometry. In pharmacokinetic studies, male rats were exposed either to intravenous infusions of sodium sulphide or to H2S gas inhalation, and levels of available blood sulphide were measured. Levels of dissolved H2S/HS- were concomitantly measured using an amperometric sensor. Key results: Monobromobimane was found to rapidly and quantitatively derivatize sulphide in saline or whole blood to yield the stable small molecule sulphide dibimane. Extraction and quantification of this bis-bimane derivative were validated via reversed-phase HPLC separation coupled to fluorescence detection, and also by mass spectrometry. Baseline levels of sulphide in blood were in the range of 0.4–0.9 µM. Intravenous administration of sodium sulphide solution (2–20 mg·kg−1·h−1) or inhalation of H2S gas (50–400 ppm) elevated reactive sulphide in blood in a dose-dependent manner. Each 1 mg·kg−1·h−1 of sodium sulphide infusion into rats was found to be pharmacokinetically equivalent to approximately 30 ppm of H2S gas inhalation. Conclusions and implications: The monobromobimane derivatization method is a sensitive and reliable means to measure reactive sulphide species in whole blood. Using this method, we have established a bioequivalence between infused sodium sulphide and inhaled H2S gas. PMID:20590590

Quantum rotor model for a Bose-Einstein condensate of dipolar molecules.

PubMed

Armaitis, J; Duine, R A; Stoof, H T C

2013-11-22

We show that a Bose-Einstein condensate of heteronuclear molecules in the regime of small and static electric fields is described by a quantum rotor model for the macroscopic electric dipole moment of the molecular gas cloud. We solve this model exactly and find the symmetric, i.e., rotationally invariant, and dipolar phases expected from the single-molecule problem, but also an axial and planar nematic phase due to many-body effects. Investigation of the wave function of the macroscopic dipole moment also reveals squeezing of the probability distribution for the angular momentum of the molecules.

Extending HHG spectroscopy to new molecular species

NASA Astrophysics Data System (ADS)

McGrath, F.; Hawkins, P.; Simpson, E.; Siegel, T.; Diveki, Z.; Austin, D.; Zair, A.; Castillejo, M.; Marangos, J. P.

2014-03-01

We present technical and experimental advances for performing HHG experiments in a range of substituted benzene molecules starting in the liquid phase. We demonstrate sub 3% fluctutaions in the harmonic signal generated in a benzene vapour backed continuous flow gas jet using a mid-IR laser source. The longer drive wavelength is necessary as the target molecules have low ionization potential and exhibit femtosecond timescale dynamics. We present the acquisition of stable and reproducible harmonic spectra from a range of substituted benzene molecules and the dependence of HHG upon the ellipticity of the laser beam was measured for a number of molecules.

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

NASA Technical Reports Server (NTRS)

Kress, M. E.; Tielens, A. G. G. M.; Roberge, W. G.

1998-01-01

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Slowing of Femtosecond Laser-Generated Nanoparticles in a Background Gas

DOE PAGES

Rouleau, Christopher M.; Puretzky, Alexander A.; Geohegan, David B.

2014-11-25

The slowing of Pt nanoparticles in argon background gas was characterized by Rayleigh scattering imaging using a plume of nanoparticles generated by femtosecond laser through thin film ablation (fs-TTFA) of 20 nanometers-thick Pt films. The ablation was performed at threshold laser energy fluences for complete film removal to provide a well-defined plume consisting almost entirely of nanoparticles traveling with a narrow velocity distribution, providing a unique system to unambiguously characterize the slowing of nanoparticles during interaction with background gases. Nanoparticles of ~200 nm diameter were found to decelerate in background Ar gas with pressures less than 50 Torr in goodmore » agreement with a linear drag model in the Epstein regime. Based on this model, the stopping distance of small nanoparticles in the plume was predicted and tested by particle collection in an off-axis geometry, and size distribution analysis by transmission electron microscopy. These results permit a basis to interpret nanoparticle propagation through background gases in laser ablation plumes that contain mixed components.« less

Assessing the Rayleigh Intensity Remote Leak Detection Technique

NASA Technical Reports Server (NTRS)

Clements, Sandra

2001-01-01

Remote sensing technologies are being considered for efficient, low cost gas leak detection. An exploratory project to identify and evaluate remote sensing technologies for application to gas leak detection is underway. During Phase 1 of the project, completed last year, eleven specific techniques were identified for further study. One of these, the Rayleigh Intensity technique, would make use of changes in the light scattered off of gas molecules to detect and locate a leak. During the 10-week Summer Faculty Fellowship Program, the scatter of light off of gas molecules was investigated. The influence of light scattered off of aerosols suspended in the atmosphere was also examined to determine if this would adversely affect leak detection. Results of this study indicate that in unconditioned air, it will be difficult, though perhaps not impossible, to distinguish between a gas leak and natural variations in the aerosol content of the air. Because information about the particle size distribution in clean room environments is incomplete, the applicability in clean rooms is uncertain though more promising than in unconditioned environments. It is suggested that problems caused by aerosols may be overcome by using the Rayleigh Intensity technique in combination with another remote sensing technique, the Rayleigh Doppler technique.

High Resolution Spectroscopy and Dynamics: from Jet Cooled Radicals to Gas-Liquid Interfaces

NASA Astrophysics Data System (ADS)

Sharp-Williams, E.; Roberts, M. A.; Roscioli, J. R.; Gisler, A. W.; Ziemkiewicz, M.; Nesbitt, D. J.; Dong, F.; Perkins, B. G., Jr.

2010-06-01

This talk will attempt to reflect recent work in our group involving two quite different but complementary applications of high resolution molecular spectroscopy for detailed study of intramolecular as well as intermolecular dynamics in small molecules. The first is based on direct infrared absorption spectroscopy in a 100 KHz slit supersonic discharge, which provides a remarkably versatile and yet highly sensitive probe for study of important chemical transients such as open shell combustion species and molecular ions under jet cooled (10-20K), sub-Doppler conditions. For this talk will focus on gas phase spectroscopic results for a series of unsaturated hydrocarbon radical species (ethynyl, vinyl, and phenyl) reputed to be critical intermediates in soot formation. Secondly, we will discuss recent applications of high resolution IR and velocity map imaging spectroscopy toward quantum state resolved collision dynamics of jet cooled molecules from gas-room temperature ionic liquid (RTIL) and gas-self assembled monolayer (SAM) interfaces. Time permitting, we will also present new results on hyperthermal scattering of jet cooled NO radical from liquid Ga, which offer a novel window into non-adiabatic energy transfer and electron-hole pair dynamics at the gas-molten metal interface.

Comparison of combustion characteristics of ASTM A-1, propane, and natural-gas fuels in an annular turbojet combustor

NASA Technical Reports Server (NTRS)

Wear, J. D.; Jones, R. E.

1973-01-01

The performance of an annular turbojet combustor using natural-gas fuel is compared with that obtained using ASTM A-1 and propane fuels. Propane gas was used to simulate operation with vaporized kerosene fuels. The results obtained at severe operating conditions and altitude relight conditions show that natural gas is inferior to both ASTM A-1 and propane fuels. Combustion efficiencies were significantly lower and combustor pressures for relight were higher with natural-gas fuel than with the other fuels. The inferior performance of natural gas is shown to be caused by the chemical stability of the methane molecule.

Gas-surface interactions using accommodation coefficients for a dilute and a dense gas in a micro- or nanochannel: heat flux predictions using combined molecular dynamics and Monte Carlo techniques.

PubMed

Nedea, S V; van Steenhoven, A A; Markvoort, A J; Spijker, P; Giordano, D

2014-05-01

The influence of gas-surface interactions of a dilute gas confined between two parallel walls on the heat flux predictions is investigated using a combined Monte Carlo (MC) and molecular dynamics (MD) approach. The accommodation coefficients are computed from the temperature of incident and reflected molecules in molecular dynamics and used as effective coefficients in Maxwell-like boundary conditions in Monte Carlo simulations. Hydrophobic and hydrophilic wall interactions are studied, and the effect of the gas-surface interaction potential on the heat flux and other characteristic parameters like density and temperature is shown. The heat flux dependence on the accommodation coefficient is shown for different fluid-wall mass ratios. We find that the accommodation coefficient is increasing considerably when the mass ratio is decreased. An effective map of the heat flux depending on the accommodation coefficient is given and we show that MC heat flux predictions using Maxwell boundary conditions based on the accommodation coefficient give good results when compared to pure molecular dynamics heat predictions. The accommodation coefficients computed for a dilute gas for different gas-wall interaction parameters and mass ratios are transferred to compute the heat flux predictions for a dense gas. Comparison of the heat fluxes derived using explicit MD, MC with Maxwell-like boundary conditions based on the accommodation coefficients, and pure Maxwell boundary conditions are discussed. A map of the heat flux dependence on the accommodation coefficients for a dense gas, and the effective accommodation coefficients for different gas-wall interactions are given. In the end, this approach is applied to study the gas-surface interactions of argon and xenon molecules on a platinum surface. The derived accommodation coefficients are compared with values of experimental results.

Seismic reflections identify finite differences in gas hydrate resources

USGS Publications Warehouse

Dillon, William P.; Max, M.

1999-01-01

Gas hydrate is a gas-bearing, ice-like crystalline solid. The substance's build ing blocks consist of a gas molecule (generally methane) sur-rounded by a cage of water molecules. The total amount of methane in hydrate in the world is immense - the most recent speculative estimate centers on values of 21x1015 cu meters. Thus, it may represent a future energy resource. This estimate was presented by Keith Kvenvolden at the International Symposium on Methane Hydrates, Resources in the Near Future, sponsor ed by Japanese National Oil Company (Tokyo, October, 1998).But, as with any natural resource, there is a need to find naturally occurring concentrations in order to effectively extract gas. We need to answer four basic questions:Do methane hydrate concentrations suitable for methane extraction exist?How can we recognize these concentrations?Where are concentrations located?What processes control methane hydrate concentrations?Gas hydrate occurs naturally at the pressure/ temperature/chemical conditions that are present within ocean floor sediments at water depths greater than about 500 meters. The gas hydrate stability zone (GHSZ) extends from the sea bottom downward to a depth where the natural increase in temperature causes the hydrate to melt (dissociate), even though the downward pressure increase is working to increase gas hydrate stability.Thus, the base of the GHSZ tends to parallel the seafloor at any given water depth (pressure), because the sub-seafloor isotherms (depths of constant temperature) generally parallel the seafloor. The layer at which gas hydrate is stable commonly extends from the sea floor to several hundred meters below it. The gas in most gas hydrates is methane, generated by bacteria in the sediments. In some cases, it can be higher carbon-number, thermogenic hydrocarbon gases that rise from greater depths.

How micron-sized dust particles determine the chemistry of our Universe

PubMed Central

Dulieu, François; Congiu, Emanuele; Noble, Jennifer; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Minissale, Marco; Cazaux, Stéphanie

2013-01-01

In the environments where stars and planets form, about one percent of the mass is in the form of micro-meter sized particles known as dust. However small and insignificant these dust grains may seem, they are responsible for the production of the simplest (H2) to the most complex (amino-acids) molecules observed in our Universe. Dust particles are recognized as powerful nano-factories that produce chemical species. However, the mechanism that converts species on dust to gas species remains elusive. Here we report experimental evidence that species forming on interstellar dust analogs can be directly released into the gas. This process, entitled chemical desorption (fig. 1), can dominate over the chemistry due to the gas phase by more than ten orders of magnitude. It also determines which species remain on the surface and are available to participate in the subsequent complex chemistry that forms the molecules necessary for the emergence of life. PMID:23439221

The effect of carrier gas flow rate and source cell temperature on low pressure organic vapor phase deposition simulation by direct simulation Monte Carlo method

PubMed Central

Wada, Takao; Ueda, Noriaki

2013-01-01

The process of low pressure organic vapor phase deposition (LP-OVPD) controls the growth of amorphous organic thin films, where the source gases (Alq3 molecule, etc.) are introduced into a hot wall reactor via an injection barrel using an inert carrier gas (N2 molecule). It is possible to control well the following substrate properties such as dopant concentration, deposition rate, and thickness uniformity of the thin film. In this paper, we present LP-OVPD simulation results using direct simulation Monte Carlo-Neutrals (Particle-PLUS neutral module) which is commercial software adopting direct simulation Monte Carlo method. By estimating properly the evaporation rate with experimental vaporization enthalpies, the calculated deposition rates on the substrate agree well with the experimental results that depend on carrier gas flow rate and source cell temperature. PMID:23674843

Linear free-energy relationships between a single gas-phase ab initio equilibrium bond length and experimental pKa values in aqueous solution.

PubMed

Alkorta, Ibon; Popelier, Paul L A

2015-02-02

Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKa values in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups, meta/para substitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKa values can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKa units for 5 drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Buffer Gas Cooled Molecule Source for Cpmmw Spectroscopy

NASA Astrophysics Data System (ADS)

Zhou, Yan; Grimes, David; Barnum, Timothy J.; Klein, Ethan; Field, Robert W.

2014-06-01

We have built a new molecular beam source that implements 20 K Neon buffer gas cooling for the study of the spectra of small molecules. In particular, laser ablation of BaF2 pellets has been optimized to produce a molecular beam of BaF with a number density more than 100 times greater than what we have previously obtained from a typical Smalley-type photoablation supersonic beam source. Moreover, the forward beam velocity of 150 m/s in our apparatus represents an approximate 10-fold reduction, improving spectroscopic resolution from 500 kHz to better than 50 kHz at 100 GHz in a chirped-pulse millimeter-wave experiment in which resolution is limited by Doppler broadening. Novel improvements in our buffer gas source and advantages for CPmmW spectroscopy studies will be discussed. We thank David Patterson, John Barry, John Doyle, and David DeMille for help in the design of our source.

Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

PubMed

El-Shall, M Samy

2008-07-01

Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information on the oligomers formed by gas-phase polymerization can be obtained using the mass-selected ion mobility technique where the measured collision cross-sections of the selected oligomer ions and collision-induced dissociation can provide fairly accurate structural identifications. The identification of the structures of the dimers and trimers formed in the gas-phase thermal polymerization of styrene confirms that the polymerization proceeds according to the Mayo mechanism. Similarly, the ion mobility technique has been utilized to confirm the formation of benzene cations by intracluster polymerization following the ionization of acetylene clusters. Finally, it has been shown that polymerization of styrene vapor on the surface of activated nanoparticles can lead to the incorporation of a variety of metal and metal oxide nanoparticles within polystyrene films. The ability to probe the reactivity and structure of the small growing oligomers in the gas phase can provide fundamental insight into mechanisms of polymerization that are difficult to obtain from condensed-phase studies. These experiments are also important for understanding the growth mechanisms of complex organics in flames, combustion processes, interstellar clouds, and solar nebula where gas-phase reactions, cluster polymerization, and surface catalysis on dust nanoparticles represent the major synthetic pathways. This research can lead to the discovery of novel initiation mechanisms and reaction pathways with applications in the synthesis of oligomers and nanocomposites with unique and improved properties.

Laser-stimulated desorption of organic molecules from surfaces, as a method of increasing the efficiency of ion mobility spectrometry analysis.

PubMed

Akmalov, Artem E; Chistyakov, Alexander A; Kotkovskii, Gennadii E

2017-08-01

Application of laser-induced desorption was investigated as a method of increasing the efficiency of gas phase analyzers on principles of field asymmetric ion mobility spectrometry. Mass spectrometric data of investigations of laser desorption of pentaerythritoltetranitrate molecules and cyclotetramethylenetetranitramine molecules from quartz substrate under vacuum were obtained. Laser sources a Nd 3+ :YAG with nanosecond pulse duration (λ = 532 nm) and a continuous wave diode laser (λ = 440 nm) were used. It was shown that both laser sources have different desorption abilities. This is expressed in various time of appearance of desorbed products that is caused by different heating mechanisms of surface layer. The desorbed quantity under action of both laser sources exceeds the detection threshold for all modern gas phase analyzers. It should be noted that despite the presence of surface dissociation of explosives under laser radiation, the quantity of nondissociated molecules is large enough for detection by ion mobility and field asymmetric ion mobility spectrometers. The optimal parameters of laser radiation for effective removal (evaporation) molecules of low-volatile compounds from surfaces are defined. The conclusion about preferable use of a Nd 3+ :YAG laser for increasing the detection ability of detectors based on ion mobility spectrometry was made.

Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry

PubMed Central

Balucani, Nadia

2009-01-01

The formation of complex organic molecules in a reactor filled with gaseous mixtures possibly reproducing the primitive terrestrial atmosphere and ocean demonstrated more than 50 years ago that inorganic synthesis of prebiotic molecules is possible, provided that some form of energy is provided to the system. After that groundbreaking experiment, gas-phase prebiotic molecules have been observed in a wide variety of extraterrestrial objects (including interstellar clouds, comets and planetary atmospheres) where the physical conditions vary widely. A thorough characterization of the chemical evolution of those objects relies on a multi-disciplinary approach: 1) observations allow us to identify the molecules and their number densities as they are nowadays; 2) the chemistry which lies behind their formation starting from atoms and simple molecules is accounted for by complex reaction networks; 3) for a realistic modeling of such networks, a number of experimental parameters are needed and, therefore, the relevant molecular processes should be fully characterized in laboratory experiments. A survey of the available literature reveals, however, that much information is still lacking if it is true that only a small percentage of the elementary reactions considered in the models have been characterized in laboratory experiments. New experimental approaches to characterize the relevant elementary reactions in laboratory are presented and the implications of the results are discussed. PMID:19564951

Crystal structure and theoretical studies of derivative of imidazo-1,2,4-triazine

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Sztanke, Krzysztof

2016-09-01

In this study, we present the result of X-ray structure analysis of methyl [8-(3-chlorophenyl)-4-oxo-2,3,4,6,7,8-heksahydroimidazo[2,1-c][1,2,4]triazin-3-yl]acetate (1). The molecule conformation is flat, with a chlorophenyl substituent and the ester moiety lying in the plain of the heterobicyclic scaffold. Its conformation is stabilized by an intramolecular Nsbnd H…O hydrogen bond. Within the crystalline structure of 1, molecules associate with one another by weak Csbnd H…O, Csbnd H…Cl and Csbnd H…π bonds. The molecular and crystal structure of 1 was compared with the previously described structurally similar compound possessing the same bicyclic rigid core and similar chemical nature of the functional ester moiety. Very interesting differences in molecules geometry and association were observed. Non-covalent bonds within the crystals are additionally visualized by determination of Hirshfeld surfaces. Moreover, the quantum chemical calculation for 1 in the gas phase were carried out. The DFT calculation methods was used to optimize of molecule geometry and obtain molecular energy profiles with respect to selected torsion angles. The quantum chemical conformational analysis that was carried out for compound 1 in the gas phase suggests that in the solid state the molecules adopt the minimum energy conformation.

Experimental Investigations of the Internal Energy of Molecules Evaporated via Laser-induced Acoustic Desorption into a Fourier-transform Ion Cyclotron Resonance Mass Spectrometer (LIAD/FT-ICR)

PubMed Central

Shea, Ryan C.; Petzold, Christopher J.; Liu, Ji-ang; Kenttämaa, Hilkka I.

2008-01-01

The internal energy of neutral gas-phase organic and biomolecules, evaporated by means of laser-induced acoustic desorption (LIAD) into a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR), was investigated through several experimental approaches. The desorbed molecules were demonstrated not to undergo degradation during the desorption process by collecting LIAD-evaporated molecules and subjecting them to analysis by electrospray ionization/quadrupole ion trap mass spectrometry. Previously established gas-phase basicity (GB) values were remeasured for LIAD-evaporated organic molecules and biomolecules with the use of the bracketing method. No endothermic reactions were observed. The remeasured basicity values are in close agreement with the values reported in the literature. The amount of internal energy deposited during LIAD is concluded to be less than a few kcal/mol. Chemical ionization with a series of proton transfer reagents was employed to obtain a breakdown curve for a protonated dipeptide, val-pro, evaporated by LIAD. Comparison of this breakdown curve with a previously published analogous curve obtained by using substrate-assisted laser desorption (SALD) to evaporate the peptide suggests that the molecules evaporated via LIAD have less internal energy than those evaporated via SALD. PMID:17263513

Motion of a Distinguishable Impurity in the Bose Gas: Arrested Expansion Without a Lattice and Impurity Snaking

NASA Astrophysics Data System (ADS)

Robinson, Neil J.; Caux, Jean-Sébastien; Konik, Robert M.

2016-04-01

We consider the real-time dynamics of an initially localized distinguishable impurity injected into the ground state of the Lieb-Liniger model. Focusing on the case where integrability is preserved, we numerically compute the time evolution of the impurity density operator in regimes far from analytically tractable limits. We find that the injected impurity undergoes a stuttering motion as it moves and expands. For an initially stationary impurity, the interaction-driven formation of a quasibound state with a hole in the background gas leads to arrested expansion—a period of quasistationary behavior. When the impurity is injected with a finite center-of-mass momentum, the impurity moves through the background gas in a snaking manner, arising from a quantum Newton's cradlelike scenario where momentum is exchanged back and forth between the impurity and the background gas.

Motion of a distinguishable Impurity in the Bose gas: Arrested expansion without a lattice and impurity snaking

DOE PAGES

Neil J. Robinson; Caux, Jean -Sebastien; Konik, Robert M.

2016-04-07

We consider the real-time dynamics of an initially localized distinguishable impurity injected into the ground state of the Lieb-Liniger model. Focusing on the case where integrability is preserved, we numerically compute the time evolution of the impurity density operator in regimes far from analytically tractable limits. We find that the injected impurity undergoes a stuttering motion as it moves and expands. For an initially stationary impurity, the interaction-driven formation of a quasibound state with a hole in the background gas leads to arrested expansion—a period of quasistationary behavior. In conclusion, when the impurity is injected with a finite center-of-mass momentum,more » the impurity moves through the background gas in a snaking manner, arising from a quantum Newton’s cradlelike scenario where momentum is exchanged back and forth between the impurity and the background gas.« less

SLOW-NEUTRON SCATTERING BY MOLECULES OF LIQUID METHANE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogalska, Z.

1962-10-01

The total slow neutron scattering cross section of liquid methane molecules as a function of neutron energy was measured. Agreement between experimental results and the theoretical curve, calculated on the basis of the Krieger and Nelkin theory for gaseous methane, was found. The most reasonable interpretation of this agreement was attributed to the fact that there exists a free rotation of molecules in liquid methane. It might be concluded that a free rotation is maintained at the transition from gas to liquid. (auth)

Origins and trends in ethane and propane in the United Kingdom from 1993 to 2012

NASA Astrophysics Data System (ADS)

Derwent, R. G.; Field, R. A.; Dumitrean, P.; Murrells, T. P.; Telling, S. P.

2017-05-01

Continuous, high frequency in situ observations of ethane and propane began in the United Kingdom in 1993 and have continued through to the present day at a range of kerbside, urban background and rural locations. Whilst other monitored C2 - C8 hydrocarbons have shown dramatic declines in concentrations by close to or over an order of magnitude, ethane and propane levels have remained at or close to their 1993 values. Urban ethane sources appear to be dominated by natural gas leakage. Background levels of ethane associated with long range transport are rising. However, natural gas leakage is not the sole source of urban propane. Oil and gas operations lead to elevated propane levels in urban centres when important refinery operations are located nearby. Weekend versus weekday average diurnal curves for ethane and propane at an urban background site in London show the importance of natural gas leakage for both ethane and propane, and road traffic sources for propane. The road traffic source of propane was tentatively identified as arising from petrol-engined motor vehicle refuelling and showed a strong downwards trend at the long-running urban background and rural sites. The natural gas leakage source of ethane and propane in the observations exhibits an upwards trend whereas that in the UK emission inventory trends downwards. Also, inventory emissions for natural gas leakage appeared to be significantly underestimated compared with the observations. In addition, the observed ethane to propane ratio found here for natural gas leakage strongly disagreed with the inventory ratio.

A novel nano-photonics biosensor concept for rapid molecular diagnostics

NASA Astrophysics Data System (ADS)

Klunder, Dion J. W.; van Herpen, Maarten M. J. W.; Kolesnychenko, Aleksey; Hornix, Eefje; Kahya, Nicoletta; de Boer, Ruth; Stapert, Henk

2008-04-01

We present a novel nano-photonics biosensor concept that offers an ultra-high surface specificity and excellent suppression of background signals due to the sample fluid on top of the biosensor. In our contribution, we will briefly discuss the operation principle and fabrication of the biosensor, followed by a more detailed discussion on the experimentally determined performance parameters. Recent results on detection of fluorescently labeled molecules in a highly fluorescent background will be shown, and we will give an outlook on real-time detection of bio-molecules such as proteins and nucleic acids.

Theoretical Studies of Chemical Reactions following Electronic Excitation

NASA Technical Reports Server (NTRS)

Chaban, Galina M.

2003-01-01

The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.

Fuel cell with ionization membrane

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2007-01-01

A fuel cell is disclosed comprising an ionization membrane having at least one area through which gas is passed, and which ionizes the gas passing therethrough, and a cathode for receiving the ions generated by the ionization membrane. The ionization membrane may include one or more openings in the membrane with electrodes that are located closer than a mean free path of molecules within the gas to be ionized. Methods of manufacture are also provided.

Broadband laser amplifier based on gas-phase dimer molecules pumped by the Sun.

PubMed

Pe'er, I; Vishnevitsky, I; Naftali, N; Yogev, A

2001-09-01

We report the design and experimental realization of a solar-pumped dimer gas-laser amplifier. The amplifying medium is Te(2) gas, which is capable of amplifying laser signals over a broad spectral range. A gain of 42% was measured at a wavelength of 632.8 nm. We also present studies of the material characteristics and a brief review of the study of other candidate materials for solar pumping.

Catalytic Reactor For Oxidizing Mercury Vapor

DOEpatents

Helfritch, Dennis J.

1998-07-28

A catalytic reactor (10) for oxidizing elemental mercury contained in flue gas is provided. The catalyst reactor (10) comprises within a flue gas conduit a perforated corona discharge plate (30a, b) having a plurality of through openings (33) and a plurality of projecting corona discharge electrodes (31); a perforated electrode plate (40a, b, c) having a plurality of through openings (43) axially aligned with the through openings (33) of the perforated corona discharge plate (30a, b) displaced from and opposing the tips of the corona discharge electrodes (31); and a catalyst member (60a, b, c, d) overlaying that face of the perforated electrode plate (40a, b, c) opposing the tips of the corona discharge electrodes (31). A uniformly distributed corona discharge plasma (1000) is intermittently generated between the plurality of corona discharge electrode tips (31) and the catalyst member (60a, b, c, d) when a stream of flue gas is passed through the conduit. During those periods when corona discharge (1000) is not being generated, the catalyst molecules of the catalyst member (60a, b, c, d) adsorb mercury vapor contained in the passing flue gas. During those periods when corona discharge (1000) is being generated, ions and active radicals contained in the generated corona discharge plasma (1000) desorb the mercury from the catalyst molecules of the catalyst member (60a, b, c, d), oxidizing the mercury in virtually simultaneous manner. The desorption process regenerates and activates the catalyst member molecules.

Chemical Analysis of a "Miller-Type" Complex Prebiotic Broth. Part II: Gas, Oil, Water and the Oil/Water-Interface

NASA Astrophysics Data System (ADS)

Scherer, Sabrina; Wollrab, Eva; Codutti, Luca; Carlomagno, Teresa; da Costa, Stefan Gomes; Volkmer, Andreas; Bronja, Amela; Schmitz, Oliver J.; Ott, Albrecht

2017-12-01

We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡ C or C≡ N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps.

Photodissociation and caging of HBr and HI molecules on the surface of large rare gas clusters.

PubMed

Baumfalk, R; Nahler, N H; Buck, U

2001-01-01

Photodissociation experiments were carried out at a wavelength of 243 nm for single HBr and HI molecules adsorbed on the surface of large Nen, Arn, Krn and Xen clusters. The average size is about = 130; the size ranges = 62-139 for the system HBr-Arn and = 110-830 for HI-Xen were covered. In this way the dependence of the photodissociation dynamics on both the size and the rare gas host cluster was investigated. The main observable is the kinetic energy distribution of the outgoing H atoms. The key results are that we do not find any size dependence for either system but that we observe a strong dependence on the rare gas clusters. All systems exhibit H atoms with no energy loss that indicate direct cage exit and those with nearly zero energy that are an indication of complete caging. The intensity ratio of caged to uncaged H atoms is largest for Nen, decreases with increasing mass of the cage atoms, and is weakest for Xen. On the basis of accompanying calculations this behaviour is attributed to the large amplitude motion of the light H atom. This leads to direct cage exit and penetration of the atom through the cluster with different energy transfer per collision depending on the rare gas atoms. The differences between HBr and HI molecules are attributed to different surface states, a flat and an encapsulated site.

Chemical Analysis of a "Miller-Type" Complex Prebiotic Broth : Part II: Gas, Oil, Water and the Oil/Water-Interface.

PubMed

Scherer, Sabrina; Wollrab, Eva; Codutti, Luca; Carlomagno, Teresa; da Costa, Stefan Gomes; Volkmer, Andreas; Bronja, Amela; Schmitz, Oliver J; Ott, Albrecht

2017-12-01

We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡C or C≡N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps.

Flue gas adsorption on periodic mesoporous phenylene-silica: a DFT approach.

PubMed

Lourenço, Mirtha A O; Ferreira, Paula; Gomes, José R B

2018-06-20

Periodic mesoporous organosilicas (PMOs) were suggested as potential adsorbents for CO2/CH4 separation because of their large affinities towards CO2 and low interaction with CH4. Herewith, we present a comprehensive computational study on the binding properties of flue gas species with the pore walls of periodic mesoporous phenylene-silica (Ph-PMO) for understanding the possible impact of other gaseous species in the CO2/CH4 separation. The calculations considered three exchange-correlation functionals (PBE, PBE-D2 and M06-2X) based on the density functional theory and the walls of the periodic mesoporous phenylene-silica were modelled within the cluster model approach. The components of the flue gas considered were the diatomic CO, H2, N2, O2 and NO molecules, the triatomic CO2, H2O, H2S and SO2 species, the tetratomic SO3 and NH3 gases and the pentatomic CH4 molecule. The calculated data demonstrate that the presence of H2O, SO2, NH3, H2S and SO3 is a significant threat to CO2 capture by Ph-PMO and suggest that the Ph-PMO material would present high selectivity for CO2 over CH4, CO, H2 or N2 adsorption. The adsorption behaviour of flue gas components in Ph-PMO can be directly related to the experimental proton affinities, basicities or even the polarizabilities of the gaseous molecules.

First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

PubMed

Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

2017-06-16

To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.

Unravelling the chemical characteristics of YSOs

NASA Astrophysics Data System (ADS)

van Dishoeck, Ewine F.

1999-10-01

The formation of stars is accompanied by orders of magnitude changes in the physical conditions, with densities in the envelopes and disks increasing from 104 cm-3 to > 1013 cm-3 and temperatures from ~ 10 K in the cold quiescent gas to 10,000 K in shocked regions. The abundances and excitation of the various molecules respond to these changes, and are therefore excellent probes of the physical evolution of YSOs. Moreover, a comprehensive inventory of the chemical composition of envelopes and disks at different evolutionary stages is essential to study the chemistry of matter as it is incorporated into new solar systems. Recent observations of the envelopes of YSOs using single-dish telescopes and millimeter interferometers clearly reveal the potential of submillimeter lines to probe these physical and chemical changes. However, the existing data generally lack the spatial resolution to separate the different physical components, such as the warm inner envelope or `hot core', the region of interaction of the outflow with the envelope and any possible circumstellar disk. ALMA will be essential to provide an `unblurred' view of the YSO environment and unravel the chemical evolution during star formation. In this talk, an overview will be given of recent single-dish and interferometer results of the chemistry in the envelopes and disks around low- and high-mass young stellar objects. Together with ISO data on solid-state material, these observations lead to a chemical scenario in which both gas-phase and gas-grain chemistry (in particular freeze-out and evaporation) play an important role. The evaporated molecules drive a rich chemistry in the warm gas, which can result in complex organic molecules. The potential of ALMA to test chemical theories and determine the composition of gas and dust as it enters forming planetary systems will be illustrated.

Prospects for P-bearing molecules in cometary atmospheres

NASA Astrophysics Data System (ADS)

Boice, Daniel; de Almeida, Amaury

Phosphorus is a key element in all known forms of life and phosphorus-bearing compounds have been observed in space. Phosphorus is ubiquitous in meteorites, albeit in small quantities, with phosphates being found in stoney meteorites and phosphides have been identified in iron meteorites. It has been detected as part of the dust component in comet Halley but searches for P-bearing species in the gas phase in comets have been unsuccessful. Based of its moderate cosmic abundance (eighteenth most abundant element, [P]/[N] = 4 x 10-3 ) and the positive identification of P-bearing species in the interstellar medium (such as, PN, PC, HCP and PO), we would expect simple molecules, diatomics (like PH, PO, PC, PS), triatomics (like HCP and PH2 ), and possibly other polyatomics (like phosphine PH3 and diphosphine P2 H4 ), to exist in cometary ices, hence released into the gas phase upon ice sublimation. Our fluid dynamics model with chemistry of cometary comae (SUISEI) has been adapted to study this problem. SUISEI produces cometocentric abundances of the coma gas species; velocities of the bulk gas, light atomic and molecular hydrogen with escape, and electrons; gas and electron temperatures; column densities to facilitate comparison with observations; coma energy budget quantities; attenuation of the solar irradiance; and other quantities that can be related readily to observations. We present results from the first quantitative study of phosphorus-bearing molecules in comets to identify likely species containing phosphorus to aid in future searches for this important element in comets, possibly shedding light on issues of comet formation (time and place) and matters of the prebiotic to biotic evolution of life. Acknowledgements. This work was supported by the NSF Planetary Astronomy Program.

Uncertain Henry's law constants compromise equilibrium partitioning calculations of atmospheric oxidation products

NASA Astrophysics Data System (ADS)

Wang, Chen; Yuan, Tiange; Wood, Stephen A.; Goss, Kai-Uwe; Li, Jingyi; Ying, Qi; Wania, Frank

2017-06-01

Gas-particle partitioning governs the distribution, removal, and transport of organic compounds in the atmosphere and the formation of secondary organic aerosol (SOA). The large variety of atmospheric species and their wide range of properties make predicting this partitioning equilibrium challenging. Here we expand on earlier work and predict gas-organic and gas-aqueous phase partitioning coefficients for 3414 atmospherically relevant molecules using COSMOtherm, SPARC Performs Automated Reasoning in Chemistry (SPARC), and poly-parameter linear free-energy relationships. The Master Chemical Mechanism generated the structures by oxidizing primary emitted volatile organic compounds. Predictions for gas-organic phase partitioning coefficients (KWIOM/G) by different methods are on average within 1 order of magnitude of each other, irrespective of the numbers of functional groups, except for predictions by COSMOtherm and SPARC for compounds with more than three functional groups, which have a slightly higher discrepancy. Discrepancies between predictions of gas-aqueous partitioning (KW/G) are much larger and increase with the number of functional groups in the molecule. In particular, COSMOtherm often predicts much lower KW/G for highly functionalized compounds than the other methods. While the quantum-chemistry-based COSMOtherm accounts for the influence of intra-molecular interactions on conformation, highly functionalized molecules likely fall outside of the applicability domain of the other techniques, which at least in part rely on empirical data for calibration. Further analysis suggests that atmospheric phase distribution calculations are sensitive to the partitioning coefficient estimation method, in particular to the estimated value of KW/G. The large uncertainty in KW/G predictions for highly functionalized organic compounds needs to be resolved to improve the quantitative treatment of SOA formation.

The early stages of massive star formation: tracing the physical and chemical conditions in hot cores

NASA Astrophysics Data System (ADS)

Calcutt, Hannah

2015-04-01

Molecules are essential to the formation of stars, by allowing radiation to escape the cloud and cooling to occur. Over 180 molecules have been detected in interstellar environments, ranging from comets to interstellar clouds. Their spectra are useful probes of the conditions in which these molecules form. Comparison of rest frequencies to observed frequencies can provide information about the velocity of gas and indicate physical structures. The density, temperature, and excitation conditions of gas can be determined directly from the spectra of molecules. Furthermore, by taking a chemical inventory of a particular object, one can gain an understanding of the chemical processes occurring within a cloud. The class of molecules known as complex molecules (>6 atoms), are of particular interest when probing the conditions in massive starforming environments, as they are observed to trace a more compact region than smaller molecules. This thesis details the work of my PhD, to explore how complex molecules can be used to trace the physical and chemical conditions in hot cores (HCs), one of the earliest stages of massive star formation. This work combines both the observations and chemical modelling of several different massive star-forming regions. We identify molecular transitions observed in the spectra of these regions, and calculate column densities and rotation temperatures of these molecules (Chapters 2 and 3). In Chapter 4, we chemically model the HCs, and perform a comparison between observational column densities and chemical modelling column densities. In Chapter 5, we look at the abundance ratio of three isomers, acetic acid, glycolaldehyde, and methyl formate, to ascertain whether this ratio can be used as an indicator of HC evolution. Finally, we explore the chemistry of the HC IRAS 17233-3606, to identify emission features in the spectra, and determine column densities and rotation temperatures of the detected molecules.

Study of Molecular-Shape Selectivity of Zeolites by Gas Chromatography

ERIC Educational Resources Information Center

Chao, Pei-Yu; Chuang, Yao-Yuan; Ho, Grace Hsiuying; Chuang, Shiow-Huey; Tsai, Tseng-Chang; Lee, Chi-Young; Tsai, Shang-Tien; Huang, Jun-Fu

2008-01-01

A sorption experiment using a gas chromatograph is described that can help students understand the "molecular-shape selectivity" behavior of zeolites in the subnano regime. Hexane isomers are used as probe molecules to demonstrate the sorption phenomena. In the experiment, a zeolite adsorbs certain hexane isomers with molecular sizes smaller than…

Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond.

PubMed

Li, Li; Yang, Deshuai; Fisher, Trevor R; Qiao, Qi; Yang, Zhen; Hu, Na; Chen, Xiangshu; Huang, Liangliang

2017-10-24

The loading-dependent diffusion behavior of CH 4 , CO 2 , SO 2 , and their binary mixtures in ZIF-10 has been investigated in detail by using classical molecular dynamics simulations. Our simulation results demonstrate that the self-diffusion coefficient D i of CH 4 molecules decreases sharply and monotonically with the loading while those of both CO 2 and SO 2 molecules initially display a slight increase at low uptakes and follow a slow decrease at high uptakes. Accordingly, the interaction energies between CH 4 molecules and ZIF-10 remain nearly constant regardless of the loading due to the absence of hydrogen bonds (HBs), while the interaction energies between CO 2 (or SO 2 ) and ZIF-10 decease rapidly with the loading, especially at small amounts of gas molecules. Such different loading-dependent diffusion and interaction mechanisms can be attributed to the relevant HB behavior between gas molecules and ZIF-10. At low loadings, both the number and strength of HBs between CO 2 (or SO 2 ) molecules and ZIF-10 decrease obviously as the loading increases, which is responsible for the slight increase of their diffusion coefficients. However, at high loadings, their HB strength increases with the loading. Similar loading-dependent phenomena of diffusion, interaction, and HB behavior can be observed for CH 4, CO 2 , and SO 2 binary mixtures in ZIF-10, only associated with some HB competition between CO 2 and SO 2 molecules in the case of the CO 2 /SO 2 mixture.

Gas Heating, Chemistry and Photoevaporation in Protostellar Disks

NASA Technical Reports Server (NTRS)

Hollenbach, David

2004-01-01

We model the thermal balance, the chemistry, and the radiative transfer in dusty disks orbiting young, low mass stars. These models are motivated by observations of infrared and ultraviolet transitions of H2 from protoplanetary disks, as well as millimeter and submillimeter observations of other molecules such as CO, and infrared continuum observations of the dust. The dust grains are heated primarily by the stellar radiation and the infrared radiation field produced by the dust itself. The gas is heated by collisions with warmer dust grains, X-rays from the region close to the stellar surface, UV pumping of hydrogen molecules, and the grain photoelectric heating mechanism initiated by UV photons from the central star. We treat cases where the gas to dust ratio is high, because the dust has settled to the midplane and coagulated into relatively large objects. We discuss situations in which the infrared emission from H2 can be detected, and how the comparison of the observations with our models can deduce physical parameters such as the mass and the density and temperature distribution of the gas.

Insights into the structure of mixed CO 2/CH 4 in gas hydrates

DOE PAGES

Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; ...

2015-05-12

The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH 4 for energy production while simultaneously sequestering CO 2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH 4) 1-x(CO 2) x·5.75H 2O provides a model system to study how the distinct bonding and shapes of CH 4 and CO 2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO 2/CH 4 gas hydrates. CO 2-rich hydrates had smaller lattice parameters, which were attributed tomore » the higher affinity of the CO 2 molecule interacting with H 2O molecules that form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH 4/CO 2 gas hydrate.« less

Hydrogen gas treatment prolongs replicative lifespan of bone marrow multipotential stromal cells in vitro while preserving differentiation and paracrine potentials.

PubMed

Kawasaki, Haruhisa; Guan, Jianjun; Tamama, Kenichi

2010-07-02

Cell therapy with bone marrow multipotential stromal cells/mesenchymal stem cells (MSCs) represents a promising approach in the field of regenerative medicine. Low frequency of MSCs in adult bone marrow necessitates ex vivo expansion of MSCs after harvest; however, such a manipulation causes cellular senescence with loss of differentiation, proliferative, and therapeutic potentials of MSCs. Hydrogen molecules have been shown to exert organ protective effects through selective reduction of hydroxyl radicals. As oxidative stress is one of the key insults promoting cell senescence in vivo as well as in vitro, we hypothesized that hydrogen molecules prevent senescent process during MSC expansion. Addition of 3% hydrogen gas enhanced preservation of colony forming early progenitor cells within MSC preparation and prolonged the in vitro replicative lifespan of MSCs without losing differentiation potentials and paracrine capabilities. Interestingly, 3% hydrogen gas treatment did not decrease hydroxyl radical, protein carbonyl, and 8-hydroxydeoxyguanosine, suggesting that scavenging hydroxyl radical might not be responsible for these effects of hydrogen gas in this study. Copyright 2010 Elsevier Inc. All rights reserved.

Hydrogen gas treatment prolongs replicative lifespan of bone marrow multipotential stromal cells in vitro while preserving differentiation and paracrine potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawasaki, Haruhisa; Davis Heart and Lung Research Institute, The Ohio State University, Columbus, OH 43210; Guan, Jianjun

2010-07-02

Cell therapy with bone marrow multipotential stromal cells/mesenchymal stem cells (MSCs) represents a promising approach in the field of regenerative medicine. Low frequency of MSCs in adult bone marrow necessitates ex vivo expansion of MSCs after harvest; however, such a manipulation causes cellular senescence with loss of differentiation, proliferative, and therapeutic potentials of MSCs. Hydrogen molecules have been shown to exert organ protective effects through selective reduction of hydroxyl radicals. As oxidative stress is one of the key insults promoting cell senescence in vivo as well as in vitro, we hypothesized that hydrogen molecules prevent senescent process during MSC expansion.more » Addition of 3% hydrogen gas enhanced preservation of colony forming early progenitor cells within MSC preparation and prolonged the in vitro replicative lifespan of MSCs without losing differentiation potentials and paracrine capabilities. Interestingly, 3% hydrogen gas treatment did not decrease hydroxyl radical, protein carbonyl, and 8-hydroxydeoxyguanosine, suggesting that scavenging hydroxyl radical might not be responsible for these effects of hydrogen gas in this study.« less

Simulation of beam-induced plasma in gas-filled rf cavities

DOE PAGES

Yu, Kwangmin; Samulyak, Roman; Yonehara, Katsuya; ...

2017-03-07

Processes occurring in a radio-frequency (rf) cavity, filled with high pressure gas and interacting with proton beams, have been studied via advanced numerical simulations. Simulations support the experimental program on the hydrogen gas-filled rf cavity in the Mucool Test Area (MTA) at Fermilab, and broader research on the design of muon cooling devices. space, a 3D electromagnetic particle-in-cell (EM-PIC) code with atomic physics support, was used in simulation studies. Plasma dynamics in the rf cavity, including the process of neutral gas ionization by proton beams, plasma loading of the rf cavity, and atomic processes in plasma such as electron-ion andmore » ion-ion recombination and electron attachment to dopant molecules, have been studied. Here, through comparison with experiments in the MTA, simulations quantified several uncertain values of plasma properties such as effective recombination rates and the attachment time of electrons to dopant molecules. Simulations have achieved very good agreement with experiments on plasma loading and related processes. Lastly, the experimentally validated code space is capable of predictive simulations of muon cooling devices.« less

The Postshock Chemical Lifetimes of Outflow Tracers and a Possible New Mechanism to Produce Water Ice Mantles

NASA Technical Reports Server (NTRS)

Bergin, Edwin A.; Melnick, Gary J.; Neufeld, David A.

1998-01-01

We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of the chemical legacy in the wake of C-type shocks. We concentrate this study on the chemistry of H2O and O2, two molecules which are predicted to have abundances that are significantly affected in shock-heated gas. Two models are presented: (1) a three-stage model of preshock, shocked, and postshock gas; and (2) a Monte Carlo cloud simulation where we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. For both models we separately examine the pure gas-phase chemistry as well as the chemistry including the interactions of molecules with grain surfaces. In agreement with previous studies, we find that shock velocities in excess of 10 km/s are required to convert all of the oxygen not locked in CO into H2O before the gas has an opportunity to cool. For pure gas phase models the lifetime of the high water abundances, or "H2O legacy," in the postshock gas is approximately (4-7) x 10(exp 5) yr, independent of the gas density. A density dependence for the lifetime of H2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. Through the Monte Carlo cloud simulation we demonstrate that the time-average abundance of H2O, the weighted average of the amount of time gas spends in preshock, shock, and postshock stages, is a sensitive function of the frequency of shocks. Thus we predict that the abundance of H2O, and to a lesser extent O2, can be used to trace the history of shock activity in molecular gas. We use previous large-scale surveys of molecular outflows to constrain the frequency of 10 km/s shocks in regions with varying star formation properties and discuss the observations required to test these results. We discuss the postshock lifetimes for other possible outflow tracers (e.g., SiO and CH3OH) and show that the differences between the lifetimes for various tracers can produce potentially observable chemical variations between younger and older outflows. For gas-grain models we find that the abundance of water-ice on grain surfaces can be quite large and is comparable to that observed in molecular clouds. This offers a possible alternative method to create water mantles without resorting to grain surface chemistry: gas heating and chemical modification due to a C-type shock and subsequent depletion of the gas-phase species onto grain mantles.

49 CFR 172.540 - POISON GAS placard.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false POISON GAS placard. 172.540 Section 172.540... SECURITY PLANS Placarding § 172.540 POISON GAS placard. (a) Except for size and color, the POISON GAS... the POISON GAS placard and the symbol must be white. The background of the upper diamond must be black...

49 CFR 172.540 - POISON GAS placard.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 2 2012-10-01 2012-10-01 false POISON GAS placard. 172.540 Section 172.540... SECURITY PLANS Placarding § 172.540 POISON GAS placard. (a) Except for size and color, the POISON GAS... the POISON GAS placard and the symbol must be white. The background of the upper diamond must be black...

49 CFR 172.540 - POISON GAS placard.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false POISON GAS placard. 172.540 Section 172.540... SECURITY PLANS Placarding § 172.540 POISON GAS placard. (a) Except for size and color, the POISON GAS... the POISON GAS placard and the symbol must be white. The background of the upper diamond must be black...

49 CFR 172.540 - POISON GAS placard.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false POISON GAS placard. 172.540 Section 172.540... SECURITY PLANS Placarding § 172.540 POISON GAS placard. (a) Except for size and color, the POISON GAS... the POISON GAS placard and the symbol must be white. The background of the upper diamond must be black...

49 CFR 172.540 - POISON GAS placard.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false POISON GAS placard. 172.540 Section 172.540... SECURITY PLANS Placarding § 172.540 POISON GAS placard. (a) Except for size and color, the POISON GAS... the POISON GAS placard and the symbol must be white. The background of the upper diamond must be black...

In situ measurement of gas composition changes in radio frequency plasmas using a quartz sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Atsushi; Nonaka, Hidehiko

2009-09-15

A simple method using a quartz sensor (Q-sensor) was developed to observe gas composition changes in radio frequency (rf) plasmas. The output depends on the gases' absolute pressure, molecular weight, and viscosity. The pressure-normalized quartz sensor output depends only on the molecular weight and viscosity of the gas. Consequently, gas composition changes can be detected in the plasmas if a sensor can be used in the plasmas. Influences imparted by the plasmas on the sensor, such as those by reactive particles (e.g., radicals and ions), excited species, electrons, temperature, and electric potentials during measurements were investigated to test the applicabilitymore » of this quartz sensor measurement to plasma. The Q-sensor measurement results for rf plasmas with argon, hydrogen, and their mixtures are reproducible, demonstrating that the Q-sensor measurement is applicable for plasmas. In this work, pressure- and temperature-normalized Q-sensor output (NQO) were used to obtain the gas composition information of plasma. Temperature-normalization of the Q-sensor output enabled quartz sensor measurements near plasma electrodes, where the quartz sensor temperature increases. The changes in NQO agreed with results obtained by gas analysis using a quadrupole mass spectrometer. Results confirmed that the change in NQO is mainly attributable to changes in the densities and kinds of gas molecules in the plasma gas phase, not by other extrinsic influences of plasma. For argon, hydrogen, and argon-hydrogen plasmas, these changes correspond to reduction in nitrogen, production of carbon monoxide, and dissociation of hydrogen molecules, respectively. These changes in NQO qualitatively and somewhat quantitatively agreed with results obtained using gas analysis, indicting that the measurement has a potential application to obtain the gas composition in plasmas without disturbing industrial plasma processes.« less

Intercomparison of stratospheric water vapor observed by satellite experiments - Stratospheric Aerosol and Gas Experiment II versus Limb Infrared Monitor of the Stratosphere and Atmospheric Trace Molecule Spectroscopy

NASA Technical Reports Server (NTRS)

Chiou, E. W.; Mccormick, M. P.; Mcmaster, L. R.; Chu, W. P.; Larsen, J. C.; Rind, D.; Oltmans, S.

1993-01-01

A comparison is made of the stratospheric water vapor measurements made by the satellite sensors of the Stratospheric Aerosol and Gas Experiment II (SAGE II), the Nimbus-7 LIMS, and the Spacelab 3 Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment. It was found that, despite differences in the measurement techniques, sampling bias, and observational periods, the three experiments have disclosed a generally consistent pattern of stratospheric water vapor distribution. The only significant difference occurs at high southern altitudes in May below 18 km, where LIMS measurements were 2-3 ppmv greater than those of SAGE II and ATMOS.

Immobilized fluid membranes for gas separation

DOEpatents

Liu, Wei; Canfield, Nathan L; Zhang, Jian; Li, Xiaohong Shari; Zhang, Jiguang

2014-03-18

Provided herein are immobilized liquid membranes for gas separation, methods of preparing such membranes and uses thereof. In one example, the immobilized membrane includes a porous metallic host matrix and an immobilized liquid fluid (such as a silicone oil) that is immobilized within one or more pores included within the porous metallic host matrix. The immobilized liquid membrane is capable of selective permeation of one type of molecule (such as oxygen) over another type of molecule (such as water). In some examples, the selective membrane is incorporated into a device to supply oxygen from ambient air to the device for electrochemical reactions, and at the same time, to block water penetration and electrolyte loss from the device.

Tunable laser heterodyne spectrometer measurements of atmospheric species

NASA Technical Reports Server (NTRS)

Allario, F.; Katzberg, S. J.; Hoell, J. M.

1983-01-01

It is pointed out that spectroscopic measurements conducted with the aid of tunable laser heterodyne spectrometers in the 3-30 micron range of the electromagnetic spectrum have the potential to measure the vertical profiles of tenuous gas molecules in the atmosphere with ultra high spectral resolution and great sensitivity. Programs related to the realization of this potential have been conducted for some time, and a Laser Heterodyne Spectrometer (LHS) experiment was developed. The present investigation has the objective to provide an overview of the LHS concept for measuring the vertical profiles of tenuous gas molecules in the upper atmosphere from space and airborne platforms, and to discuss the sensitivity ranges for this technique.

The Mark of a Dying Star

NASA Technical Reports Server (NTRS)

2006-01-01

Six hundred and fifty light-years away in the constellation Aquarius, a dead star about the size of Earth, is refusing to fade away peacefully. In death, it is spewing out massive amounts of hot gas and intense ultraviolet radiation, creating a spectacular object called a 'planetary nebula.'

In this false-color image, NASA's Hubble and Spitzer Space Telescopes have teamed up to capture the complex structure of the object, called the Helix nebula, in unprecedented detail. The composite picture is made up of visible data from Hubble and infrared data from Spitzer.

The dead star, called a white dwarf, can be seen at the center of the image as a white dot. All of the colorful gaseous material seen in the image was once part of the central star, but was lost in the death throes of the star on its way to becoming a white dwarf. The intense ultraviolet radiation being released by the white dwarf is heating and destabilizing the molecules in its surrounding environment, starting from the inside out.

Like an electric stovetop slowly heating up from the center first, the hottest and most unstable gas molecules can be seen at the center of the nebula as wisps of blue. The transition to more stable and cooler molecules is clearly depicted as the color of the gas changes from very hot (blue) to hot (yellow) and warm (red).

A striking feature of the Helix, first revealed by ground-based images, is its collection of thousands of filamentary structures, or strands of gas. In this image the filaments can be seen under the transparent blue gas as red lines radiating out from the center. Astronomers believe that the molecules in these filaments are able to stay cooler and more stable because dense clumps of materials are shielding them from ultraviolet radiation.

This image is a composite showing ionized H-alpha (green) and O III (blue) gases from the Hubble Space Telescope, and molecular hydrogen (red) from Spitzer observations at 4.5 and 8.0 microns.

Single-molecule fluorescence detection: autocorrelation criterion and experimental realization with phycoerythrin.

PubMed Central

Peck, K; Stryer, L; Glazer, A N; Mathies, R A

1989-01-01

A theory for single-molecule fluorescence detection is developed and then used to analyze data from subpicomolar solutions of B-phycoerythrin (PE). The distribution of detected counts is the convolution of a Poissonian continuous background with bursts arising from the passage of individual fluorophores through the focused laser beam. The autocorrelation function reveals single-molecule events and provides a criterion for optimizing experimental parameters. The transit time of fluorescent molecules through the 120-fl imaged volume was 800 microseconds. The optimal laser power (32 mW at 514.5 nm) gave an incident intensity of 1.8 x 10(23) photons.cm-2.s-1, corresponding to a mean time of 1.1 ns between absorptions. The mean incremental count rate was 1.5 per 100 microseconds for PE monomers and 3.0 for PE dimers above a background count rate of 1.0. The distribution of counts and the autocorrelation function for 200 fM monomer and 100 fM dimer demonstrate that single-molecule detection was achieved. At this concentration, the mean occupancy was 0.014 monomer molecules in the probed volume. A hard-wired version of this detection system was used to measure the concentration of PE down to 1 fM. This single-molecule counter is 3 orders of magnitude more sensitive than conventional fluorescence detection systems. PMID:2726766

Effects of Post-Treatment Hydrogen Gas Inhalation on Uveitis Induced by Endotoxin in Rats.

PubMed

Yan, Weiming; Chen, Tao; Long, Pan; Zhang, Zhe; Liu, Qian; Wang, Xiaocheng; An, Jing; Zhang, Zuoming

2018-06-07

BACKGROUND Molecular hydrogen (H2) has been widely reported to have benefiicial effects in diverse animal models and human disease through reduction of oxidative stress and inflammation. The aim of this study was to investigate whether hydrogen gas could ameliorate endotoxin-induced uveitis (EIU) in rats. MATERIAL AND METHODS Male Sprague-Dawley rats were divided into a normal group, a model group, a nitrogen-oxygen (N-O) group, and a hydrogen-oxygen (H-O) group. EIU was induced in rats of the latter 3 groups by injection of lipopolysaccharide (LPS). After that, rats in the N-O group inhaled a gas mixture of 67% N2 and 33% O2, while those in the H-O group inhaled a gas mixture of 67% H2 and 33% O2. All rats were graded according to the signs of uveitis after electroretinography (ERG) examination. Protein concentration in the aqueous humor (AqH) was measured. Furthermore, hematoxylin-eosin staining and immunostaining of anti-ionized calcium-binding adapter molecule 1 (Iba1) in the iris and ciliary body (ICB) were carried out. RESULTS No statistically significant differences existed in the graded score of uveitis and the b-wave peak time in the Dark-adapted 3.0 ERG among the model, N-O, and H-O groups (P>0.05), while rats of the H-O group showed a lower concentration of AqH protein than that of the model or N-O group (P<0.05). The number of the infiltrating cells in the ICB of rats from the H-O group was not significantly different from that of the model or N-O group (P>0.05), while the activation of microglia cells in the H-O group was somewhat reduced (P<0.05). CONCLUSIONS Post-treatment hydrogen gas inhalation did not ameliorate the clinical signs, or reduce the infiltrating cells of EIU. However, it inhibited the elevation of protein in the AqH and reduced the microglia activation.

Plasma conversion of methane into higher hydrocarbons at surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sackinger, W.M.; Kamath, V.A.

1995-12-31

Natural gas is widely abundant, is easily withdrawn from reservoirs, is commonly produced as an associated gas along with crude oil production, and is found in many geologic settings as a resource separate from oil. A much larger fraction of the natural gas may be produced from a gas reservoir, as compared with a crude oil reservoir. However, natural gas is normally transported by pipeline, and the energy throughput of such a pipeline is perhaps only 20% to 30% of the throughput of an oil pipeline of the same size and cost. Gas is difficult to transport in moderate quantitiesmore » at low cost, as it must either have a special pipeline or must be liquified into LNG, shipped in cryogenic LNG tankers, and regasified chemical stability of methane has made it difficult to convert it directly into conventional hydrocarbon fuel mixtures, and has also impeded its use as a feedstock for petrochemical production. Experiments are described in which a methane plasma is created, and the resulting methyl and hydrogen ions have been accelerated within a microchannel array so that they interact with neutral methane molecules on the inside surfaces of the microchannels. No catalysts are used, and the device operates at room temperature. Impact energies of the ions are in the range of 15 ev to greater than 100 ev, and the energy delivered in the interaction at the surfaces has caused the production of larger hydrocarbon molecules, such as C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}, along with C{sub 3}, C{sub 4}, C{sub 5}, C{sub 6}, C{sub 7}, and C{sub 8} molecules. Conversion effectiveness is greater at higher pressure, due to the increased ionic activity. The costs of production of the plasma conversion devices are projected to be quite low, and the technology appears to be commercially and economically feasible.« less

Investigation of industrial-scale carbon dioxide reduction using pulsed electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrov, G. M.; Apruzese, J. P.; Petrova, Tz. B.

Carbon dioxide is the most important greenhouse gas contributing to global warming. To help mitigate increasing CO{sub 2} concentrations, we investigate a method of carbon dioxide reduction using high-power electron beams, which can be used on an industrial scale. A series of experiments are conducted in which the reduction of CO{sub 2} is measured for different gas compositions and power deposition rates. An electron beam deposition model is applied to compute reduction rates of CO{sub 2} and energy cost for breaking a CO{sub 2} molecule in flue gas and pure carbon dioxide at atmospheric pressure. For flue gas consisting ofmore » 82% N{sub 2}, 6% O{sub 2}, and 12% CO{sub 2}, the calculated energy cost is 85 eV per molecule. In order to dissociate 50% of the CO{sub 2} molecules, beam energy density deposition on the order of 20 J/cm{sup 3} is required. Electron beam irradiation of 12.6 liter gas volume containing 90% CO{sub 2} and 10% CH{sub 4} at beam energy density deposition of 4.2 J/cm{sup 3}, accumulated over 43 shots in a 20 min interval, reduced the CO{sub 2} concentration to 78%. Analogous experiments with a gas mixture containing 11.5% CO{sub 2}, 11.5% CH{sub 4}, and balance of Ar, reduced the CO{sub 2} concentration to below 11% with energy deposition 0.71 J/cm{sup 3}, accumulated over 10 shots in a 5 min interval. The experimental data and the theoretical predictions of CO{sub 2} reduction using pulsed electron beams are in agreement within the experimental error. Other techniques to enhance the removal of CO{sub 2} with pulsed electron beams are also explored, yielding new possible avenues of research.« less

Reliable energy level alignment at physisorbed molecule-metal interfaces from density functional theory.

PubMed

Egger, David A; Liu, Zhen-Fei; Neaton, Jeffrey B; Kronik, Leeor

2015-04-08

A key quantity for molecule-metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal-molecule interfaces. The method builds on the "DFT+Σ" approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule-metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

Pre-cometary ice composition from hot core chemistry.

PubMed

Tornow, Carmen; Kührt, Ekkehard; Motschmann, Uwe

2005-10-01

Pre-cometary ice located around star-forming regions contains molecules that are pre-biotic compounds or pre-biotic precursors. Molecular line surveys of hot cores provide information on the composition of the ice since it sublimates near these sites. We have combined a hydrostatic hot core model with a complex network of chemical reactions to calculate the time-dependent abundances of molecules, ions, and radicals. The model considers the interaction between the ice and gas phase. It is applied to the Orion hot core where high-mass star formation occurs, and to the solar-mass binary protostar system IRAS 16293-2422. Our calculations show that at the end of the hot core phase both star-forming sites produce the same prebiotic CN-bearing molecules. However, in the Orion hot core these molecules are formed in larger abundances. A comparison of the calculated values with the abundances derived from the observed line data requires a chemically unprocessed molecular cloud as the initial state of hot core evolution. Thus, it appears that these objects are formed at a much younger cloud stage than previously thought. This implies that the ice phase of the young clouds does not contain CN-bearing molecules in large abundances before the hot core has been formed. The pre-biotic molecules synthesized in hot cores cause a chemical enrichment in the gas phase and in the pre-cometary ice. This enrichment is thought to be an important extraterrestrial aspect of the formation of life on Earth and elsewhere.

Theoretical studies of the extraterrestrial chemistry of biogenic elements and compounds

NASA Technical Reports Server (NTRS)

Defrees, D. J.

1991-01-01

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.

Quantum chemical approach for condensed-phase thermochemistry (IV): Solubility of gaseous molecules

NASA Astrophysics Data System (ADS)

Ishikawa, Atsushi; Kamata, Masahiro; Nakai, Hiromi

2016-07-01

The harmonic solvation model (HSM) was applied to the solvation of gaseous molecules and compared to a procedure based on the ideal gas model (IGM). Examination of 25 molecules showed that (i) the accuracy of ΔGsolv was similar for both methods, but the HSM shows advantages for calculating ΔHsolv and TΔSsolv; (ii) TΔSsolv contributes more than ΔHsolv to ΔGsolv in the HSM, i.e. the solvation of gaseous molecules is entropy-driven, which agrees well with experimental understanding (the IGM does not show this); (iii) the temperature dependence of Henry's law coefficient was correctly reproduced with the HSM.

Concentration of Natural Gas Hydrate Beneath the Permafrost Zone: Implications for Geochemical and Hydrologic Investigations

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Namikawa, T.

2004-12-01

Gas hydrates are ice-like solids made of water molecules containing various gas molecules. The geological evaluations have suggested worldwide methane contents of gas hydrate beneath deep sea floors as well as permafrost-related zones to about twice the total reserves of conventional and unconventional hydrocarbon. Scientific and economic interests are increasing in gas hydrate as a new energy resource and a potential greenhouse gas. In 1998 and 2002 Mallik wells were drilled in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data, anomalies of chloride contents in pore waters, core temperature depression as well as visible gas hydrates have confirmed the highly saturated pore-space hydrate as intergranular pore filling within sandy layers, whose saturations are higher than 70% in pore volume. Muddy sediments scarcely contain gas hydrate. The Nankai Trough runs along the Japanese Island, where forearc basins and accretionary prisms developed extensively and BSRs (bottom simulating reflectors) have been recognized widely. The METI Nankai Trough wells in 2000 also revealed the presence of pore-space hydrate filling intergranular pore of sandy layers. It is remarked that there are many similar features in appearance and characteristics between the Mallik and Nankai Trough areas with observations of well-interconnected and highly saturated pore-space hydrate. It is necessary for evaluating subsurface fluid flow behaviors to know both porosity and permeability of gas hydrate-bearing sandy sediments, and measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sands revealed important geologic and sedimentologic controls on the formation and concentration of gas hydrate. It is suggested that the distribution of a porous and coarser-grained sandy sediments is one of the most important factors to control the occurrence of gas hydrates, as well as physicochemical conditions.

Conversion of laser energy to gas kinetic energy

NASA Technical Reports Server (NTRS)

Caledonia, G. E.

1975-01-01

Techniques for the gas phase absorption of laser radiation for conversion to gas kinetic energy are discussed. Absorption by inverse Bremsstrahlung, in which laser energy is converted at a gas kinetic rate in a spectrally continuous process, is briefly described, and absorption by molecular vibrational rotation bands is discussed at length. High pressure absorption is proposed as a means of minimizing gas bleaching and dissociation, the major disadvantages of the molecular absorption process. A band model is presented for predicting the molecular absorption spectra in the high pressure absorption region and is applied to the CO molecule. Use of a rare gas seeded with Fe(CO)5 for converting vibrational modes to translation modes is described.

Particle dynamics during nanoparticle synthesis by laser ablation in a background gas

NASA Astrophysics Data System (ADS)

Nakata, Yoshiki; Muramoto, Junichi; Okada, Tatsuo; Maeda, Mitsuo

2002-02-01

Particle dynamics during Si nanoparticle synthesis in a laser-ablation plume in different background gases were investigated by laser-spectroscopic imaging techniques. Two-dimensional laser induced fluorescence and ultraviolet Rayleigh scattering techniques were used to visualize the spatial distribution of the Si atoms and nanoparticles grown, respectively. We have developed a visualization technique called re-decomposition laser-induced fluorescence to observe small nanoparticles (hereafter called clusters) which are difficult to observe by the conventional imaging techniques. In this article, the whole process of nanoparticle synthesis in different background gases of He, Ne, Ar, N2 and O2 was investigated by these techniques. In He, Ne, Ar and N2 background gases at 10 Torr, the clustering of the Si atoms started 200, 250, 300 and 800 μs after ablation, respectively. The growth rate of the clusters in He background gas was much larger than that in the other gases. The spatial distributions of the Si nanoparticles were mushroom like in He, N2 and O2, and column like in Ne and Ar. It is thought that the difference in distribution was caused by differences in the flow characteristics of the background gases, which would imply that the viscosity of the background gas is one of the main governing parameters.

An approach to spin-resolved molecular gas microscopy

NASA Astrophysics Data System (ADS)

Covey, Jacob P.; De Marco, Luigi; Acevedo, Óscar L.; Rey, Ana Maria; Ye, Jun

2018-04-01

Ultracold polar molecules are an ideal platform for studying many-body physics with long-range dipolar interactions. Experiments in this field have progressed enormously, and several groups are pursuing advanced apparatus for manipulation of molecules with electric fields as well as single-atom-resolved in situ detection. Such detection has become ubiquitous for atoms in optical lattices and tweezer arrays, but has yet to be demonstrated for ultracold polar molecules. Here we present a proposal for the implementation of site-resolved microscopy for polar molecules, and specifically discuss a technique for spin-resolved molecular detection. We use numerical simulation of spin dynamics of lattice-confined polar molecules to show how such a scheme would be of utility in a spin-diffusion experiment.

The Atacama Large Millimeter/submillimeter Array (alma): Early Results

NASA Astrophysics Data System (ADS)

Wootten, Alwyn

2012-06-01

New radioastronomical instruments, such as ALMA or the Jansky VLA, have increased spectral throughput by orders of magnitude over previously available capabilities. ALMA brings orders of magnitude increases in spectral sensitivity and spatial resolution over what has previously been available. These increased capabilities open new possibilities for studies of complex molecules in the interstellar medium. Complex interstellar molecules may form on the surfaces of interstellar grains, after which they may be liberated into the gas phase by shocks, radiation, or other external influences. Emission from complex molecules may be diluted owing to the large number of transitions large molecules may undergo, particularly in warm regions of interstellar clouds. High sensitivity and spatial resolution are necessary to explore the distributions and relationships of these molecules. Of particular interest are the distributions of large organic molecules. Observations which establish the relationships between various large molecules are now emerging from these new instruments and will be discussed.

Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

PubMed

Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

2016-02-18

Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

Development of a low pressure microwave excited plasma and its application to the formation of microcrystalline silicon films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kikukawa, Daisuke; Hori, Masaru; Honma, Koichiro

2006-11-15

Microwave excited plasma source operating at a low pressure of 1.5 Pa was newly developed. This plasma source was successfully applied to the formation of hydrogenated microcrystalline silicon films in a glass substrate with a mixture gas of silane (SiH{sub 4}), hydrogen (H{sub 2}), and xenon (Xe). It was found that the crystallinity of films was dramatically improved with decreasing pressure. The crystalline fraction was evaluated to be 82% at a substrate temperature of 400 deg. C, a mixture gas of SiH{sub 4}/H{sub 2}/Xe: 5/200/30 SCCM, and a total pressure of 1.5 Pa by Raman spectroscopy. The absolute density ofmore » hydrogen atoms and the behavior of higher radicals and molecules in the mixture gas were evaluated using vacuum ultraviolet absorption spectroscopy and quadrupole mass spectrometer, respectively. H atom densities were of the order of 10{sup 11} cm{sup -3}. The fraction of H atom density increased, while higher radicals and molecules decreased with decrease in the total pressure. The increase in H atom density and decrease in higher radicals and molecules improved the crystallinity of films in low pressures below 10 Pa.« less

Photophysics of sunscreen molecules in the gas phase: a stepwise approach towards understanding and developing next-generation sunscreens

PubMed Central

Rodrigues, Natércia D. N.; Staniforth, Michael

2016-01-01

The relationship between exposure to ultraviolet (UV) radiation and skin cancer urges the need for extra photoprotection, which is presently provided by widespread commercially available sunscreen lotions. Apart from having a large absorption cross section in the UVA and UVB regions of the electromagnetic spectrum, the chemical absorbers in these photoprotective products should also be able to dissipate the excess energy in a safe way, i.e. without releasing photoproducts or inducing any further, harmful, photochemistry. While sunscreens are tested for both their photoprotective capability and dermatological compatibility, phenomena occurring at the molecular level upon absorption of UV radiation are largely overlooked. To date, there is only a limited amount of information regarding the photochemistry and photophysics of these sunscreen molecules. However, a thorough understanding of the intrinsic mechanisms by which popular sunscreen molecular constituents dissipate excess energy has the potential to aid in the design of more efficient, safer sunscreens. In this review, we explore the potential of using gas-phase frequency- and time-resolved spectroscopies in an effort to better understand the photoinduced excited-state dynamics, or photodynamics, of sunscreen molecules. Complementary computational studies are also briefly discussed. Finally, the future outlook of expanding these gas-phase studies into the solution phase is considered. PMID:27956888