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Sample records for adsorbed gas molecules

  1. 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

    2015-06-01

    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. PMID:26049513

  2. Does Moisture Influence the Chemical Detection of Gas Molecules Adsorbed on Single-Wall Carbon Nanotubes?

    NASA Astrophysics Data System (ADS)

    Yu, Ming; Tian, W. Q.; Jayanthi, C. S.; Wu, S. Y.

    2009-03-01

    In this work, the role of water in the detection of hydrazine (N2H4) by a single-wall carbon nanotube (SWCNT) is investigated using first principles electronic structure calculations (DFT/GGA--USPP)[1]. This calculation is undertaken to interpret the experimental resistivity measurements for N2H4 adsorbed on SWCNT that reveal an n-type behavior [2]. Our preliminary theoretical studies of the adsorption of N2H4 on SWCNT revealed physisorption for N2H4 and an unaltered band structure for the SWCNT [3]. This prompted us to look into the role of water on the bonding of N2H4 to the SWCNT. We found that, by introducing a monolayer of water film on the (8,0) SWCNT, the adsorption of N2H4 can introduce occupied states near the Fermi level, exhibiting an n-type behavior. However, the introduction of just few water molecules was not sufficient to influence the electronic structure of N2H4/SWCNT. Presently, we are studying the influence of water films on the chemical detection of a variety of other gas molecules (N2, NH3, etc.) by SWCNTs, and the results from such studies will also be reported. [1]. G. Kresse et al. Phys. Rev. B 54, 11169 (1996). [2]. S. Desai, et al. (APS, March 2008). [3]. M. Yu, et al. (APS, March 2008).

  3. Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS{sub 2}

    SciTech Connect

    Zhou, Changjie; Zhu, Huili; Yang, Weihuang

    2015-06-07

    Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS{sub 2} upon adsorption of various gas molecules (H{sub 2}, O{sub 2}, H{sub 2}O, NH{sub 3}, NO, NO{sub 2}, 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 WS{sub 2} with a low degree of charge transfer and accept charge from the monolayer, except for NH{sub 3}, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS{sub 2} are not significantly altered upon adsorption of H{sub 2}, H{sub 2}O, NH{sub 3}, and CO, whereas the lowest unoccupied molecular orbitals of O{sub 2}, NO, and NO{sub 2} are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS{sub 2}. 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 WS{sub 2}. 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.

  4. Hydrophobic Porous Material Adsorbs Small Organic Molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Hickey, Gregory S.

    1994-01-01

    Composite molecular-sieve material has pore structure designed specifically for preferential adsorption of organic molecules for sizes ranging from 3 to 6 angstrom. Design based on principle that contaminant molecules become strongly bound to surface of adsorbent when size of contaminant molecules is nearly same as that of pores in adsorbent. Material used to remove small organic contaminant molecules from vacuum systems or from enclosed gaseous environments like closed-loop life-support systems.

  5. Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

    SciTech Connect

    Van den Bossche, M.; Grönbeck, H.; Martin, N. M.; Gustafson, J.; Lundgren, E.; Hakanoglu, C.; Weaver, J. F.

    2014-07-21

    Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

  6. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  7. Imaging the wave functions of adsorbed molecules

    PubMed Central

    Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

    2014-01-01

    The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust. PMID:24344291

  8. Adsorbed natural gas storage with activated carbon

    SciTech Connect

    Sun, Jian; Brady, T.A.; Rood, M.J.

    1996-12-31

    Despite technical advances to reduce air pollution emissions, motor vehicles still account for 30 to 70% emissions of all urban air pollutants. The Clean Air Act Amendments of 1990 require 100 cities in the United States to reduce the amount of their smog within 5 to 15 years. Hence, auto emissions, the major cause of smog, must be reduced 30 to 60% by 1998. Natural gas con be combusted with less pollutant emissions. Adsorbed natural gas (ANG) uses adsorbents and operates with a low storage pressure which results in lower capital costs and maintenance. This paper describes the production of an activated carbon adsorbent produced from an Illinois coal for ANG.

  9. Gas storage using fullerene based adsorbents

    NASA Technical Reports Server (NTRS)

    Loutfy, Raouf O. (Inventor); Lu, Xiao-Chun (Inventor); Li, Weijiong (Inventor); Mikhael, Michael G. (Inventor)

    2000-01-01

    This invention is directed to the synthesis of high bulk density high gas absorption capacity adsorbents for gas storage applications. Specifically, this invention is concerned with novel gas absorbents with high gravimetric and volumetric gas adsorption capacities which are made from fullerene-based materials. By pressing fullerene powder into pellet form using a conventional press, then polymerizing it by subjecting the fullerene to high temperature and high inert gas pressure, the resulting fullerene-based materials have high bulk densities and high gas adsorption capacities. By pre-chemical modification or post-polymerization activation processes, the gas adsorption capacities of the fullerene-based adsorbents can be further enhanced. These materials are suitable for low pressure gas storage applications, such as oxygen storage for home oxygen therapy uses or on-board vehicle natural gas storage. They are also suitable for storing gases and vapors such as hydrogen, nitrogen, carbon dioxide, and water vapor.

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

    PubMed

    Shah, Kinjal J; Imae, Toyoko

    2016-05-01

    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. PMID:27035217

  11. Analysis of Adsorbed Natural Gas Tank Technology

    NASA Astrophysics Data System (ADS)

    Knight, Ernest; Schultz, Conrad; Rash, Tyler; Dohnke, Elmar; Stalla, David; Gillespie, Andrew; Sweany, Mark; Seydel, Florian; Pfeifer, Peter

    With gasoline being an ever decreasing finite resource and with the desire to reduce humanity's carbon footprint, there has been an increasing focus on innovation of alternative fuel sources. Natural gas burns cleaner, is more abundant, and conforms to modern engines. However, storing compressed natural gas (CNG) requires large, heavy gas cylinders, which limits space and fuel efficiency. Adsorbed natural gas (ANG) technology allows for much greater fuel storage capacity and the ability to store the gas at a much lower pressure. Thus, ANG tanks are much more flexible in terms of their size, shape, and weight. Our ANG tank employs monolithic nanoporous activated carbon as its adsorbent material. Several different configurations of this Flat Panel Tank Assembly (FPTA) along with a Fuel Extraction System (FES) were examined to compare with the mass flow rate demands of an engine.

  12. Adsorbed molecules in external fields: Effect of confining potential.

    PubMed

    Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

    2016-12-01

    We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials. PMID:27387127

  13. Inhomogeneous distribution of organic molecules adsorbed in sol gel glasses

    NASA Astrophysics Data System (ADS)

    Meneses-Nava, M. A.; Chávez-Cerda, S.; Sánchez-Villicaña, V.; Sánchez-Mondragón, J. J.; King, T. A.

    1999-09-01

    The effects of the porous matrix upon the radiative characteristics of quinine sulphate doped sol-gel glasses are investigated. The broadenings of the absorption and fluorescence spectra are explained by the attachment of the molecules on distorted sites or in a non-planar fashion, creating an inhomogeneous distribution of adsorbed molecules. For this reason, each emitting center relaxes with its own characteristics. This inhomogeneous distribution is also supported by the non-exponential and the wavelength dependence of the fluorescence decay.

  14. Probing atomic positions of adsorbed ammonia molecules in zeolite.

    PubMed

    Ye, Lin; Lo, Benedict T W; Qu, Jin; Wilkinson, Ian; Hughes, Tim; Murray, Claire A; Tang, Chiu C; Tsang, Shik Chi Edman

    2016-02-25

    Atomic positions and interactions between adsorbed guest molecules, such as ammonia in H-ZSM-5 microporous solids, are for the first time revealed by making use of the change in the periodical scattering parameter using in situ synchrotron powder X-ray diffraction combined with refinement within experimental errors. PMID:26833032

  15. Hydrogen molecule on lithium adsorbed graphene: A DFT study

    NASA Astrophysics Data System (ADS)

    Kaur, Gagandeep; Gupta, Shuchi; Gaganpreet, Dharamvir, Keya

    2016-05-01

    Electronic structure calculations for the adsorption of molecular hydrogen on lithium (Li) decorated and pristine graphene have been studied systematically using SIESTA code [1] within the framework of the first-principle DFT under the Perdew-Burke-Ernzerhof (PBE) form of the generalized gradient approximation (GGA)[2], including spin polarization. The energy of adsorption of hydrogen molecule on graphene is always enhanced by the presence of co-adsorbed lithium. The most efficient adsorption configuration is when H2 is lying parallel to lithium adsorbed graphene which is in contrast to its adsorption on pristine graphene (PG) where it prefers perpendicular orientation.

  16. Candidate Source of Flux Noise in SQUIDs: Adsorbed Oxygen Molecules.

    PubMed

    Wang, Hui; Shi, Chuntai; Hu, Jun; Han, Sungho; Yu, Clare C; Wu, R Q

    2015-08-14

    A major obstacle to using superconducting quantum interference devices (SQUIDs) as qubits is flux noise. We propose that the heretofore mysterious spins producing flux noise could be O_{2} molecules adsorbed on the surface. Using density functional theory calculations, we find that an O_{2} molecule adsorbed on an α-alumina surface has a magnetic moment of ~1.8 μ_{B}. The spin is oriented perpendicular to the axis of the O-O bond, the barrier to spin rotations is about 10 mK. Monte Carlo simulations of ferromagnetically coupled, anisotropic XY spins on a square lattice find 1/f magnetization noise, consistent with flux noise in Al SQUIDs. PMID:26317742

  17. Theory of raman scattering from molecules adsorbed at semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1983-09-01

    A theory is presented to calculate the Raman polarizability of an adsorbed molecule at a semiconductor surface, where the electronic excitation in the molecular site interacts with excitons (elementary excitations in the semiconductor) through non-radiative energy transfer between them, in an intermediate state in the Raman scattering process. The Raman polarizability thus calculated is found to exhibit a peak at the energy corresponding to a resonant excitation of excitons, thereby suggesting the possibility of surface enhanced Raman scattering on semiconductor surfaces. The mechanism studied here can also give an explanation of a recent observation of the Raman excitation profiles of p-NDMA and p-DMAAB adsorbed on ZnO or TiO 2, where those profiles were best described by assuming a resonant intermediate state of the exciton transition in the semiconductors. It is also demonstrated that in addition to vibrational Raman scattering, excitonic Raman scattering of adsorbed molecules will occur in the coupled molecule-semiconductor system, where the molecular returns to its ground electronic state by leaving an exciton in the semiconductor. A spectrum of the excitonic Raman scattering is expected to appear in the background of the vibrational Raman band and to be characterized by the electronic structure of excitons. A desirable experiment is suggested for an examination of the theory.

  18. A simple model for electronic properties of surface adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Dhakal, Rajesh; Schwalm, William

    We adapt a minimal approximation to one electron quantum theory of molecules referred as Fast Accurate Kinetic Energy method. This in principle handles large complex molecular structures with less computational effort to compute electronic properties of adsorbed molecules. Kinetic energy integrals are calculated accurately but multi-electron potential energy integrals are approximated. The neighboring atom interactions are included also. For layers of isopthalic acids formed on pyrolytic graphite the configuration changes as a function of length of hydrocarbon tails. We study properties of this system as a function of tail length.

  19. Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks

    SciTech Connect

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas–gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  20. SPR-MS: from identifying adsorbed molecules to image tissues

    NASA Astrophysics Data System (ADS)

    Masson, Jean-François; Breault-Turcot, Julien; Forest, Simon; Chaurand, Pierre

    2015-03-01

    Surface plasmon resonance (SPR) sensors have become valuable analytical sensors for biomolecule detection. While SPR is heralded with high sensitivity, label-free and real-time detection, nonspecific adsorption and detection of ultralow concentrations remain issues. Nonspecific adsorption can be minimized using adequate surface chemistry. For example, we have employed peptide monolayers to reduce nonspecific adsorption of crude serum or cell lysate. It is important to uncover the nature of molecules nonspecifically adsorbing to surfaces in these biofluids, to further improve understanding of the nonspecific adsorption processes. Mass spectrometry (MS) provides a complementary tool to SPR to identify biomolecule adsorbed to surface. Trypsic digestion of the proteins adsorbed to surfaces led to identification of characteristic peptides from the proteins involved in nonspecific adsorption. Nonspecific adsorption in crude cell lysate results mainly from lipids, as confirmed with SPR and MS but proteins were observed on some surfaces. In another application of SPR and MS, imaging SPR can be used in combination to imaging MS to image tissue sections. Thin sections of mouse liver were inserted in the fluidic chamber of a SPRi instrument and proteins were transferred to the SPRi chip. The SPR chip was then imaged using MALDI imaging MS to identify the biomolecules that were transferred to the SPRi chip.

  1. Controlling spins in adsorbed molecules by a chemical switch

    PubMed Central

    Wäckerlin, Christian; Chylarecka, Dorota; Kleibert, Armin; Müller, Kathrin; Iacovita, Cristian; Nolting, Frithjof; Jung, Thomas A.; Ballav, Nirmalya

    2010-01-01

    The development of chemical systems with switchable molecular spins could lead to the architecture of materials with controllable magnetic or spintronic properties. Here, we present conclusive evidence that the spin of an organometallic molecule coupled to a ferromagnetic substrate can be switched between magnetic off and on states by a chemical stimulus. This is achieved by nitric oxide (NO) functioning as an axial ligand of cobalt(II)tetraphenylporphyrin (CoTPP) ferromagnetically coupled to nickel thin-film (Ni(001)). On NO addition, the coordination sphere of Co2+ is modified and a NO–CoTPP nitrosyl complex is formed, which corresponds to an off state of the Co spin. Thermal dissociation of NO from the nitrosyl complex restores the on state of the Co spin. The NO-induced reversible off–on switching of surface-adsorbed molecular spins observed here is attributed to a spin trans effect. PMID:20975713

  2. Dynamics of photoinduced electron transfer from adsorbed molecules into solids

    NASA Astrophysics Data System (ADS)

    Gundlach, L.; Ernstorfer, R.; Willig, F.

    2007-08-01

    Ultrafast interfacial electron transfer from the donor orbital of organic chromophores into empty electronic acceptor states of a semiconductor and of a metal was investigated by two-photon photoemission spectroscopy (2PPE). Experimental tools and procedures have been developed for carrying out wet-chemistry preparation of the molecule/solid interface. The organic chromophore perylene was investigated with several different bridge/anchor groups on TiO2(110). One perylene compound was investigated for comparison on Ag(110). Angle and polarization dependent 2PPE measurements revealed the orientation of the perylene chromophore on the surface as controlled by the adsorption geometry of the respective anchor group on TiO2. UPS measurements gave the position of the HOMO level of the chromophore with respect to the Fermi level of the solid. The donor level of each molecule was found high enough to fulfill the “wide band limit” of heterogeneous electron transfer dynamics. Time constants for heterogeneous electron transfer were extracted from 2PPE transients. A difference by a factor of four was found, 13 fs against 47 fs, when a conjugated bond was exchanged for a saturated bond in the otherwise identical bridge group. The two different contributions to the 2PPE transients arising firstly from the excited state of the chromophore and secondly from the injected electrons were separated by measuring the latter contribution separately in the case of instantaneous interfacial electron transfer realized with catechol as adsorbate. The time scales measured for the electron transfer step and for the subsequent electron escape process from the surface into the bulk of TiO2 showed both good agreement with recent theoretical predictions of other groups for these systems.

  3. Polarizabilities of Adsorbed and Assembled Molecules: Measuring the Conductance through Buried Contacts

    PubMed Central

    2010-01-01

    We have measured the polarizabilities of four families of molecules adsorbed to Au{111} surfaces, with structures ranging from fully saturated to fully conjugated, including single-molecule switches. Measured polarizabilities increase with increasing length and conjugation in the adsorbed molecules and are consistent with theoretical calculations. For single-molecule switches, the polarizability reflects the difference in substrate−molecule electronic coupling in the ON and OFF conductance states. Calculations suggest that the switch between the two conductance states is correlated with an oxidation state change in a nitro functional group in the switch molecules. PMID:21077677

  4. Quasielastic neutron scattering from adsorbed water molecules on pyrogenic silica surfaces

    NASA Astrophysics Data System (ADS)

    Tumanov, A. A.; Zarko, V. I.

    1994-04-01

    Quasielastic neutron scattering (QNS) from hydrated samples of high dispersion (Aerosil) and of porous dioxide silicon was investigated. The broadening of the QNS peak analysis permits one to obtain the effective diffusion coefficient D of adsorbed water molecules. It was obtained that the D-value increases with silica hydration. The mean square displacement of the water molecules from equilibrium < x2> equals approximately 0.1 Å 2 and does not depend on the quantity of adsorbed water.

  5. Agricultural Waste as Sources for Mercury Adsorbents in Gas Applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Increased emphasis on reduction of mercury emissions from coal fired electric power plants have resulted in environmental regulations that may in the future require application of activated carbons as mercury sorbents. The sorbents could be injected into the flue gas stream where it adsorbs the mer...

  6. Agricultural By-products as Mercury Adsorbents in Gas Applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Increased emphasis on reduction of mercury emissions from coal fired electric power plans have resulted in environmental regulations that may in the future require application of activated carbons as mercury sorbents. The sorbents could be injected into the flue gas stream where is adsorbs the merc...

  7. Analysis of Adsorbate-Adsorbate and Adsorbate-Adsorbent Interactions to Decode Isosteric Heats of Gas Adsorption.

    PubMed

    Madani, S Hadi; Sedghi, Saeid; Biggs, Mark J; Pendleton, Phillip

    2015-12-21

    A qualitative interpretation is proposed to interpret isosteric heats of adsorption by considering contributions from three general classes of interaction energy: fluid-fluid heat, fluid-solid heat, and fluid-high-energy site (HES) heat. Multiple temperature adsorption isotherms are defined for nitrogen, T=(75, 77, 79) K, argon at T=(85, 87, 89) K, and for water and methanol at T=(278, 288, 298) K on a well-characterized polymer-based, activated carbon. Nitrogen and argon are subjected to isosteric heat analyses; their zero filling isosteric heats of adsorption are consistent with slit-pore, adsorption energy enhancement modelling. Water adsorbs entirely via specific interactions, offering decreasing isosteric heat at low pore filling followed by a constant heat slightly in excess of water condensation enthalpy, demonstrating the effects of micropores. Methanol offers both specific adsorption via the alcohol group and non-specific interactions via its methyl group; the isosteric heat increases at low pore filling, indicating the predominance of non-specific interactions. PMID:26538339

  8. Theory of optical excitation of adsorbed rare gas atoms

    NASA Astrophysics Data System (ADS)

    Tsukada, Masaru; Brenig, Wilhelm

    1985-03-01

    Optical absorption spectra of rare-gas atoms adsorbed on metal surfaces exhibit a bimodal behavior, which, according to Cunningham, Greenlaw and Flynn, can be correlated with the difference I' - φ (where I' is the ionization energy of the excited (gas phase) state of the rare gas atom and φ the work function of the metal) controlling the energetics of charge transfer from the excited atom to the metal. In this paper we propose a model which allows to treat this charge transfer and some accompanying many-body effects in detail. Strong Coulomb attraction between the core hole and the excited electron on the adatom is taken into account as well as the interaction with surface plasmons. An improved charge transfer criterion is obtained which, besides the important parameter I∗ - φ, involves additional parameters such as the adsorbate-metal coupling strength and the plasmon frequency.

  9. Relaxation dynamics of surface-adsorbed water molecules in nanoporous silica probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ru; Liu, Kao-Hsiang; Mou, Chung-Yuan; Sun, Chi-Kuang

    2015-08-01

    Relaxation dynamics of an exclusively adsorbed water molecule in mesoporous silica MCM-41-S was studied by using terahertz spectroscopy. With the temperature controlled from 0 to 50 °C, we observed strongly frequency- and temperature-dependent dielectric relaxation responses, implying that, unlike ice, surface-adsorbed water molecules retained flourishing picosecond dynamics. Based on the Debye relaxation model, a relaxation time constant was found to increase from 1.77 to 4.83 ps when the water molecule was cooled from 50 to 0 °C. An activation energy of ˜15 kJ/mol, which was in close agreement with a hydrogen-bonding energy, was further extracted from the Arrhenius analysis. Combined with previous molecular dynamics simulations, our results indicate that the reorientation relaxation originated from the "flip-flop" rotation of a three hydrogen-bonded surface-adsorbed water molecule.

  10. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  11. Auger electron spectroscopy as a tool for measuring intramolecular charges of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Magkoev, T. T.

    A way for the determination of the values of intramolecular charges of adsorbed molecules of some binary dielectrics, based on Auger electron spectroscopy (AES), is proposed. These values can be obtained from the coverage dependences of the ratios of intensities of anion KL 23L 23 and KL 1L 1 Auger transitions, which are sensitive to the amount of charge at the 2p-orbitals. As an example, MgO adsorbed on Mo(110) is presented.

  12. Auger electron spectroscopy as a tool for measuring intramolecular charges of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Magkoev, T. T.

    1993-10-01

    A way for the determination of the values of intramolecular charges of adsorbed molecules of some binary dielectrics, based on Auger electron spectroscopy (AES), is proposed. These values can be obtained from the coverage dependences of the ratios of intensities of anion KL 23L 23 and KL 1L 1 Auger transitions, which are sensitive to the amount of charge at the 2p-orbitals. As an example, MgO adsorbed on Mo(110) is presented.

  13. Transient magnetization of core excited organic molecules adsorbed on graphene

    NASA Astrophysics Data System (ADS)

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    This work presents a density functional theory based computational investigation of electronic and magnetic properties of physisorbed and chemisorbed organic molecules on graphene in the ground state and core excited one at low molecular coverage. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, it is found that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the contrary, when graphene is covalently functionalized, the system is magnetic in the ground state presenting two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. This project has received funding from the European Union Seventh Framework Programme under grant agreement n∘ 607232 [THINFACE].

  14. Rotational Spectromicroscopy: Imaging the Orbital Interaction between Molecular Hydrogen and an Adsorbed Molecule

    NASA Astrophysics Data System (ADS)

    Li, Shaowei; Yuan, Dingwang; Yu, Arthur; Czap, Gregory; Wu, Ruqian; Ho, W.

    2015-05-01

    A hydrogen molecule can diffuse freely on the surface and be trapped above an adsorbed molecule within the junction of a scanning tunneling microscope. The trapped dihydrogen exhibits the properties of a free rotor. Here we show that the intermolecular interaction between dihydrogen and Mg-porphyrin (MgP) can be visualized by imaging j =0 to 2 rotational excitation of dihydrogen. The interaction leads to a weakened H-H bond and modest electron donation from the dihydrogen to the lowest unoccupied molecular orbital of MgP, a process similarly observed for the interaction between dihydrogen and an adsorbed Au atom.

  15. Rotational Spectromicroscopy: Imaging the Orbital Interaction between Molecular Hydrogen and an Adsorbed Molecule.

    PubMed

    Li, Shaowei; Yuan, Dingwang; Yu, Arthur; Czap, Gregory; Wu, Ruqian; Ho, W

    2015-05-22

    A hydrogen molecule can diffuse freely on the surface and be trapped above an adsorbed molecule within the junction of a scanning tunneling microscope. The trapped dihydrogen exhibits the properties of a free rotor. Here we show that the intermolecular interaction between dihydrogen and Mg-porphyrin (MgP) can be visualized by imaging j=0 to 2 rotational excitation of dihydrogen. The interaction leads to a weakened H-H bond and modest electron donation from the dihydrogen to the lowest unoccupied molecular orbital of MgP, a process similarly observed for the interaction between dihydrogen and an adsorbed Au atom. PMID:26047242

  16. Hollow-fiber-based adsorbers for gas separation by pressure-swing adsorption

    SciTech Connect

    Feng, X.; Pan, C.Y.; McMinis, C.W.; Ivory, J.; Ghosh, D.

    1998-07-01

    Hollow-fiber-based adsorbers for gas separation by pressure-swing adsorption (PSA) was studied experimentally. The high efficiency of hollow-fiber-based adsorbers for gas separation was illustrated by hydrogen separation using fine-powder-activated carbon and molecular sieve as adsorbents. The adsorption equilibrium and dynamics of the hollow-fiber adsorbers were determined. The pressure drop of the gas flowing through the adsorbers was also examined. The adsorbers were tested for hydrogen separation from nitrogen, carbon dioxide, and a multicomponent gas mixture simulating ammonia synthesis purge gas. The PSA systems using the hollow-fiber adsorbers were very effective for hydrogen purification. The high separation efficiency is derived from the fast mass-transfer rate and low pressure drop, two key features of hollow-fiber-based adsorbers.

  17. Dynamics of Molecules Adsorbed in Zeolitic Systems: Neutron Scattering and MD Simulation Studies

    SciTech Connect

    Mitra, S.; Sharma, V. K.; Mukhopadhyay, R.

    2011-07-15

    Zeolites represent a class of technologically important materials because of their characteristic properties of molecular sieving and catalysis, which makes them indispensable in the petroleum industries. While the catalytic properties depend upon many factors, a major role is played by the dynamics of hydrocarbon gases. In order to be able to tailor make these materials for use in industry for catalytic and sieving purposes, it is important to understand the dynamical properties of the guest molecules adsorbed in the zeolitic materials. It is of interest to study the effects of size and shape of guest molecules and also the host zeolitic structure, governing the diffusion mechanism of the adsorbed species. Here we report the results of Quasielastic Neutron Scattering (QENS) and classical molecular dynamics (MD) simulation studies of two hydrocarbons namely acetylene and propylene adsorbed in two structurally different zeolites Na-Y and ZSM-5.

  18. Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator.

    PubMed

    Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita; Baltic, Romana; Rusponi, Stefano; Diller, Katharina; Patthey, François; Pivetta, Marina; Lan, Yanhua; Klyatskaya, Svetlana; Ruben, Mario; Brune, Harald; Dreiser, Jan

    2016-07-01

    TbPc2 single-molecule magnets adsorbed on a magnesium oxide tunnel barrier exhibit record magnetic remanence, record hysteresis opening, perfect out-of-plane alignment of the magnetic easy axes, and self-assembly into a well-ordered layer. PMID:27159732

  19. Dynamics of water molecules adsorbed by silica and resin SGK-7

    NASA Astrophysics Data System (ADS)

    Lisichkin, Yu. V.; Sakharova, L. A.; Tumanov, A. A.

    2014-01-01

    This paper has presented neutron spectroscopy data on the dynamics of light water molecules adsorbed in the cation exchanger (ion-exchange resin) SGK-7 and on the surface of aerosils (highly dispersed pyrogenic silica) with different levels of hydration. The measurements have been performed on a DIN-2PI spectrometer (Frank Laboratory of Neutron Physics of the Joint Institute for Nuclear Research, Dubna, Russia). The characteristics of the diffusive and vibrational motions of adsorbed water molecules have been determined from the experimental neutron scattering spectra. The data obtained in the quasi-elastic neutron scattering region have been analyzed using a model accounting for the effects of restricted translational and rotational diffusion. The results have demonstrated a significant decrease in the diffusion mobility of adsorbed water molecules as compared to conventional (bulk) water. In particular, the self-diffusion coefficient decreases several times, and the diffusion rate is the lower, the smaller is the thickness of the hydration layer. The dependences of the intensity and half-width of the quasi-elastic scattering peak on the magnitude of the neutron momentum transfer q in the scattering process exhibit a nonmonotonic character. This indicates manifestation of the effects of restricted translational diffusion, rotational diffusion, and jump diffusion. The partial distributions of vibrational frequencies of hydrogen atoms of water molecules adsorbed by the cation exchanger and aerosils have been obtained from the inelastic neutron scattering data.

  20. Sustainable catalyst supports for carbon dioxide gas adsorbent

    NASA Astrophysics Data System (ADS)

    Mazlee, M. N.

    2016-07-01

    The adsorption of carbon dioxide (CO2) become the prime attention nowadays due to the fact that increasing CO2 emissions has been identified as a contributor to global climate change. Major sources of CO2 emissions are thermoelectric power plants and industrial plants which account for approximately 45% of global CO2 emissions. Therefore, it is an urgent need to develop an efficient CO2 reduction technology such as carbon capture and storage (CCS) that can reduce CO2 emissions particularly from the energy sector. A lot of sustainable catalyst supports have been developed particularly for CO2 gas adsorbent applications.

  1. Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

    SciTech Connect

    P. Rudolf; R. Raval; P. Dumas; Gwyn P. Williams

    2002-04-01

    Infrared (IR) spectroscopy of chemisorbed C{sub 60} on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm{sup -1} per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C{sub 60>}/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules.

    Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C{sub 60} molecules, which results in rather small values ({approx}2 x 10{sup 9}s{sup -1} for Ag and Au, and {approx}1.6 x 10{sup 9}s{sup -1} for Cu), consistent with a marked metallic character of the adsorbed molecules.

    Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C{sub 60} deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron-phonon coupling with induced surface states.

  2. Aggregated Gas Molecules: Toxic to Protein?

    PubMed Central

    Zhang, Meng; Zuo, Guanghong; Chen, Jixiu; Gao, Yi; Fang, Haiping

    2013-01-01

    The biological toxicity of high levels of breathing gases has been known for centuries, but the mechanism remains elusive. Earlier work mainly focused on the influences of dispersed gas molecules dissolved in water on biomolecules. However, recent studies confirmed the existence of aggregated gas molecules at the water-solid interface. In this paper, we have investigated the binding preference of aggregated gas molecules on proteins with molecular dynamics simulations, using nitrogen (N2) gas and the Src-homology 3 (SH3) domain as the model system. Aggregated N2 molecules were strongly bound by the active sites of the SH3 domain, which could impair the activity of the protein. In contrast, dispersed N2 molecules did not specifically interact with the SH3 domain. These observations extend our understanding of the possible toxicity of aggregates of gas molecules in the function of proteins. PMID:23588597

  3. Rod-like cyanophenyl probe molecules nanoconfined to oxide particles: Density of adsorbed surface species

    NASA Astrophysics Data System (ADS)

    Frunza, Stefan; Frunza, Ligia; Ganea, Constantin Paul; Zgura, Irina; Brás, Ana Rita; Schönhals, Andreas

    2016-02-01

    Surface layers have already been observed by broadband dielectric spectroscopy for composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules. The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.

  4. Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

    NASA Astrophysics Data System (ADS)

    Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

    2003-04-01

    Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

  5. Adsorbed Oxygen Molecules as a Possible Source of Flux Noise in SQUIDs

    NASA Astrophysics Data System (ADS)

    Shi, Chuntai; Wang, Hui; Hu, Jun; Yu, Clare; Wu, Ruqian

    2015-03-01

    One of the dominant source of flux noise in SQUIDs is flux noise which has been attributed to mysterious fluctuating magnetic spins on the surface. We propose that the spins producing flux noise could be adsorbed O2 molecules that have a magnetic moment of about 2 μB. Using density functional calculations, we studied O2 molecules adsorbed on a sapphire surface. We find that the barrier for spin rotation is small enough to allow almost free spin reorientation due to thermal excitations at low temperatures. Monte Carlo simulations of a 2D XY spin model yields 1 / f noise where f is frequency. This work was supported by 1000 Talent Program of China through Fudan University. Work at UCI was supported by DOE-BES (Grant No. DE-FG02-05ER46237) and the Army Research Office (Grant No. W911NF-10-1-0494).

  6. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    NASA Astrophysics Data System (ADS)

    Katoch, Neha; Kapoor, Pooja; Sharma, Munish; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G0 to 2G0 suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  7. Orientation and heat capacity of horizontally adsorbed molecules in electric fields

    NASA Astrophysics Data System (ADS)

    Liao, Ying-Yen

    2014-02-01

    The orientation and the heat capacity of horizontally adsorbed molecules are investigated in static electric fields. We evaluate the energy spectrum and the wave function to probe the rotational characteristics of the molecule. Numerical results indicate that the electric field and the effect of quantum confinement lead to anticrossing behaviors in the energy levels. The orientation reveals a stepped feature due to the anticrossing in the ground state. Moreover, the heat capacity displays two peaks near the anticrossing. By means of comparison, each peak of the heat capacity corresponds to a particular degree of orientation.

  8. Preparation and performance of chitosan encapsulated activated charcoal (ACCB) adsorbents for small molecules.

    PubMed

    Chandy, T; Sharma, C P

    1993-01-01

    A technique is described to encapsulate activated charcoal for haemoperfusion to be used in an artificial liver support. Activated charcoal was encapsulated within chitosan matrix (ACCB) in different concentrations, and was used as the supports for perfusion of a mixture of solutes, having molecular weight ranges from 60 to 69,000; under a flow rate of 8 ml/min. It seems the ACCB may be a good adsorbent system for the removal of toxic uric acid, creatinine, bilirubin, etc., from solutions; while larger molecules such as albumin are adsorbed less. The encapsulated charcoal did not leach out from the matrix during perfusion, and the system may be useful for detoxification of blood. The haemolytic potential of ACCB has been compatible with polystyrene control tubes. However, further studies are needed to determine their behaviour under clinical conditions. PMID:8263676

  9. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    PubMed Central

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-01-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures. PMID:26891851

  10. Homeotropic orientation of a nematic liquid crystal by bent-core molecules adsorbed on its surface

    NASA Astrophysics Data System (ADS)

    Hwang, Jiyong; Yang, Seungbin; Lee, Hyojin; Kim, Jongyoon; Lee, Ji-Hoon; Kang, Shin-Woong; Choi, E.-Joon

    2015-06-01

    We reported the promotion of a homeotropic alignment of a nematic liquid crystal (NLC) by bent-core liquid-crystal (BLC) Molecules adsorbed its surface. The BLC was mixed at various concentrations with the NLC, and the mixtures were injected into an empty cell with a cell gap of 13 μm. Although the pure NLC showed a heterogeneous orientation, the BLC-NLC mixture was gradually transformed to a homeotropic alignment with increasing concentration of the BLC. We investigated the surface topography of the samples by using an atomic force microscopy (AFM) and found that the BLC molecules were segregated into a polyimide (PI) surface and formed protrusion domains with diameters of 50-100 nm. The BLC protrusions might promote the homeotropic orientation of the NLC molecules.

  11. Ultra-sensitive fluorescence spectroscopy of isolated surface-adsorbed molecules using an optical nanofiber.

    PubMed

    Stiebeiner, A; Rehband, O; Garcia-Fernandez, R; Rauschenbeutel, A

    2009-11-23

    The strong radial confinement and the pronounced evanescent field of the guided light in optical nanofibers yield favorable conditions for ultra-sensitive surface spectroscopy of molecules deposited on the fiber. Using the guided mode of the nanofiber for both excitation and fluorescence collection, we present spectroscopic measurements on 3,4,9,10-perylenetetracarboxylic dianhydride molecules (PTCDA) at ambient conditions. Surface coverages as small as 1 per thousand of a compact monolayer still give rise to fluorescence spectra with a good signal to noise ratio. Moreover, we analyze and quantify the self-absorption effects due to reabsorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist. PMID:19997412

  12. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    NASA Astrophysics Data System (ADS)

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-02-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures.

  13. Heat capacity measurements of atoms and molecules adsorbed on evaporated metal films

    SciTech Connect

    Kenny, T.W.

    1989-05-01

    Investigations of the properties of absorbed monolayers have received great experimental and theoretical attention recently, both because of the importance of surface processes in practical applications such as catalysis, and the importance of such systems to the understanding of the fundamentals of thermodynamics in two dimensions. We have adapted the composite bolometer technology to the construction of microcalorimeters. For these calorimeters, the adsorption substrate is an evaporated film deposited on one surface of an optically polished sapphire wafer. This approach has allowed us to make the first measurements of the heat capacity of submonolayer films of /sup 4/He adsorbed on metallic films. In contrast to measurements of /sup 4/He adsorbed on all other insulating substrates, we have shown that /sup 4/He on silver films occupies a two-dimensional gas phase over a broad range of coverages and temperatures. Our apparatus has been used to study the heat capacity of Indium flakes. CO multilayers, /sup 4/He adsorbed on sapphire and on Ag films and H/sub 2/ adsorbed on Ag films. The results are compared with appropriate theories. 68 refs., 19 figs.

  14. Structure formation in adsorbed overlayers comprising functional cross-shaped molecules: A Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Kasperski, Adam; Nieckarz, Damian; Szabelski, Paweł

    2015-11-01

    Surface confined self-assembly of functional star-shaped organic molecules is a promising method to create nanoporous networks with tailorable structure and functions. In this work we use the Monte Carlo simulation method to demonstrate how the morphology of these supramolecular assemblies can be tuned by manipulating intrinsic parameters of the building blocks and modified by the presence of co-adsorbed metal atoms. To that purpose we study the 2D self-assembly of planar cruciform molecules modeled as collections of interconnected segments, some of which were activated to represent discrete interaction centers. We consider a few exemplary adsorbed systems in which the molecules with different size, aspect ratio and intramolecular distribution of active centers form superstructures stabilized by short-range segment-segment interactions or by metal-segment interactions. These two situations correspond to supramolecular assemblies sustained by, for example, hydrogen bonding and metal-organic ligand coordination, respectively. The simulated results show that proper encoding of intramolecular interactions into the cruciform building bricks allows for directing the self-assembly towards largely diversified structures ranging from nanoclusters to porous grids. The obtained findings can facilitate designing and optimization of molecular networks comprising cross-shaped units including functionalized porphyrins and phthalocyanines and they can be helpful in preliminary selection of these building blocks.

  15. First-principles study of SF6 decomposed gas adsorbed on Au-decorated graphene

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoxing; Yu, Lei; Gui, Yingang; Hu, Weihua

    2016-03-01

    We theoretically investigated the decomposed gaseous components of sulfur hexafluoride (SF6), namely, H2S, SO2, SOF2, and SO2F2, adsorbed on pristine and Au-embedded graphene based on the revised Perdew-Burke-Ernzerhof calculation, which empirically includes a dispersion correction (DFT-D) for van der Waals interaction with standard generalized gradient approximation. Pristine graphene exhibits weak adsorption and absence of charge transfer, which indicates barely satisfactory sensing for decomposed components. The Au atom introduces magnetism to the pristine graphene after metal-embedded decoration as well as enhances conductivity. All four molecules induce certain hybridization between the molecules and Au-graphene, which results in chemical interactions. SOF2 and SO2F2 exhibit a strong chemisorption interaction with Au-graphene, while H2S and SO2 exhibit quasi-molecular binding effects. Only H2S exhibits n-type doping to Au-graphene, whereas the rest gases exhibit p-type doping. Magnetic moments fluctuate substantially in the original Au-graphene when H2S and SO2 are adsorbed. While the adsorption effects of SOF2 and SO2F2 generate magnetism quenching. The charge transfer mechanism is also discussed in this paper. These results will shed light on the valuable application of Au-embedded graphene for selective gas sensing and spintronics.

  16. Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Liu, Wei; Poltavsky, Igor; Stecher, Thomas; Oberhofer, Harald; Reuter, Karsten; Tkatchenko, Alexandre

    2016-04-01

    We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C12 H10 N2 on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 1024 s-1 that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems.

  17. Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111).

    PubMed

    Maurer, Reinhard J; Liu, Wei; Poltavsky, Igor; Stecher, Thomas; Oberhofer, Harald; Reuter, Karsten; Tkatchenko, Alexandre

    2016-04-01

    We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C_{12}H_{10}N_{2} on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 10^{24}  s^{-1} that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems. PMID:27104719

  18. Alignment and assembly of adsorbed collagen molecules induced by anisotropic chemical nanopatterns.

    PubMed

    Denis, Frédéric A; Pallandre, Antoine; Nysten, Bernard; Jonas, Alain M; Dupont-Gillain, Christine C

    2005-10-01

    Collagen, a protein widely used to control cell-material interactions, is known to self-assemble in solution. Supramolecular structures also form on material surfaces following collagen adsorption. Herein, we report the use of anisotropic, flat, surface chemical nanopatterns, which consist of alkyl-terminated tracks drawn in an oligo(ethylene glycol)-terminated matrix, to direct collagen adsorption. As revealed by atomic force microscopy, the spontaneous collagen adsorption performed on such patterned substrates results in the accumulation of collagen on the hydrophobic tracks. Moreover, the width of the tracks (30-90 nm), which is much smaller than the length of the collagen molecule (approximately 300 nm), is the origin of preferential alignment of the molecules and of their assembly into continuous bundles of adsorbed collagen. This chemical guidance effect due to self-confinement of proteins upon adsorption may bring novel and valuable applications, specifically in biomaterials science and cell growth control. PMID:17193383

  19. Molecular resonant dissociation of surface-adsorbed molecules by plasmonic nanoscissors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenglong; Sheng, Shaoxiang; Zheng, Hairong; Xu, Hongxing; Sun, Mengtao

    2014-04-01

    The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis, photosynthesis and the degradation of plastic, it is hard to break individual molecular bonds for those molecules adsorbed on the surface because of the weak light-absorption in molecules and the redistribution of the resulting vibrational energy both inside the molecule and to its surrounding environment. Here we show how to overcome these obstacles with a plasmonic hot-electron mediated process and demonstrate a new method that allows the sensitive control of resonant dissociation of surface-adsorbed molecules by `plasmonic' scissors. To that end, we used a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup to dissociate resonantly excited NC2H6 fragments from Malachite green. The surface plasmons (SPs) excited at the sharp metal tip not only enhance the local electric field to harvest the light incident from the laser, but crucially supply `hot electrons' whose energy can be transferred to individual bonds. These processes are resonant Raman, which result in some active chemical bonds and then weaken these bonds, followed by dumping in lots of indiscriminant energy and breaking the weakest bond. The method allows for sensitive control of both the rate and probability of dissociation through their dependence on the density of hot electrons, which can be manipulated by tuning the laser intensity or tunneling current/bias voltage in the HV-TERS setup, respectively. The concepts of plasmonic scissors open up new versatile avenues for the deep understanding of in situ surface-catalyzed chemistry.The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis

  20. Dissociative electron attachment and charging of SF6 adsorbed on rare-gas films

    NASA Astrophysics Data System (ADS)

    Weik, Fritz; Illenberger, Eugen

    1998-10-01

    Electron stimulated desorption (ESD) of fragment ions in the energy range between 0 and 18 eV from SF6 adsorbed on rare-gas films (Kr, Xe) is reported. The ESD results are compared with previous experiments on dissociative electron attachment (DA) to gas-phase SF6. At energies characteristic for the respective rare-gas substrate strong resonant enhancements in the ESD yield of F- are observed. This enhancement is explained by the appearance of an "electron-exciton complex" in the rare-gas film (the analogue to the anionic Feshbach resonances in single atoms) which couples to the first dipole allowed excitation of the SF6 molecule. After electron and energy transfer, the highly excited SF6*- ion dissociates at the surface resulting in the desorption of F- fragments. At low electron energies (in the range from 0 to 0.6 eV) charging of the rare-gas film covered with SF6 is observed. From these experiments a charging cross section of 2.1(±1.8)×10-15 cm2 is derived.

  1. Single-Molecule Magnets: Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator (Adv. Mater. 26/2016).

    PubMed

    Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita; Baltic, Romana; Rusponi, Stefano; Diller, Katharina; Patthey, François; Pivetta, Marina; Lan, Yanhua; Klyatskaya, Svetlana; Ruben, Mario; Brune, Harald; Dreiser, Jan

    2016-07-01

    In Tb(Pc)2 single-molecule magnets, where Pc is phthalocyanine, adsorbed on magnesium oxide, the fluctuations of the terbium magnetic moment are strongly suppressed in contrast to the adsorption on silver. On page 5195, J. Dreiser and co-workers investigate that the molecules are perfectly organized by self-assembly, as seen in the scanning tunnelling microscopy image (top part of the design). The molecules are probed by circularly polarized X-rays depicted as green spirals. PMID:27383020

  2. Imaging the wave functions of adsorbed molecules using angle-resolved photoemmision data

    NASA Astrophysics Data System (ADS)

    Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

    2014-03-01

    The frontier electronic orbitals of molecules are the prime determinants of the respective compounds' chemical, electronic, and optical properties. Although orbitals are very powerful concepts, experimentally only the electron densities and energy levels are directly observable. As has been shown in recent publications, angle-resolved photoemission (ARPES) intensity maps of organic molecular layers are related to the absolute value of the Fourier transform of the initial state molecular orbital. However, the lost phase information impedes the back-transformation of the orbital into real space. Here, we show how molecular orbital images as well as the absent phase information can be retrieved by applying an iterative procedure which takes experimental ARPES maps as input and only assumes spatial confinement of the orbital. The method is demonstrated for several molecular orbitals of two proto-typical pi-conjugated molecules: the LUMO, HOMO, and HOMO-1 of pentacene, and the LUMO and HOMO of PTCDA. The technique is simple and robust and further emphasizes the capabilities of ARPES looking at spatial distributions of wave functions of adsorbed molecules thereby complementing data obtained from scanning probe methods.

  3. Room temperature differential conductance measurements of triethylamine molecules adsorbed on Si(001).

    PubMed

    Naitabdi, Ahmed; Rochet, François; Carniato, Stéphane; Bournel, Fabrice; Gallet, Jean-Jacques

    2016-08-17

    We have measured the differential conductance of the triethylamine molecule (N(CH2CH3)3) adsorbed on Si(001)-2 × 1 at room temperature using scanning tunneling spectroscopy. Triethylamine can be engaged in a dative bonding with a silicon dimer, forming a Si-Si-N(CH2CH3)3 unit. We have examined the datively bonded adduct, either as an isolated molecule, or within an ordered molecular domain (reconstructed 4 × 2). The differential conductance curves, supported by DFT calculations, show that in the explored energy window (±2.5 near the Fermi level) the main features stem from the uncapped dangling bonds of the reacted dimer and of the adjacent unreacted ones that are electronically coupled The formation of a molecular domain, in which one dimer in two is left unreacted, is reflected in a shift of the up dimer atom occupied level away from the Fermi level, likely due to an increased π-bonding strength. In stark contrast with the preceding, pairs of dissociated molecule (a minority species) are electronically decoupled from the dimer dangling bond states. DFT calculation show that the lone-pair of the Si-N(CH2CH3)2 is a shallow level, that is clearly seen in the differential conductance curve. PMID:27499070

  4. Effect of resonance dipole-dipole interaction on spectra of adsorbed SF6 molecules.

    PubMed

    Dobrotvorskaia, Anna N; Kolomiitsova, Tatiana D; Petrov, Sergey N; Shchepkin, Dmitriy N; Smirnov, Konstantin S; Tsyganenko, Alexey A

    2015-09-01

    Adsorption of SF6 on zinc oxide and on silicalite-1 was investigated by a combination of IR spectroscopy with the calculations of spectra by means of a modernized model, developed previously for liquids. Comparison of the experimental spectra and the results of modeling shows that the complex band shapes in spectra of adsorbed molecules with extremely high absorbance are due to the strong resonance dipole-dipole interaction (RDDI) rather that the surface heterogeneity or the presence of specific surface sites. Perfect agreement between calculated and observed spectra was found for ZnO, while some dissimilarity in band intensities for silicalite-1 was attributed to complicated geometry of molecular arrangement in the channels. PMID:25897721

  5. Interactions of gas molecules with monolayer MoSe2: A first principle study

    NASA Astrophysics Data System (ADS)

    Sharma, Munish; Jamdagni, Pooja; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We present a first principle study of interaction of toxic gas molecules (NO, NO2 and SO2) with monolayer MoSe2. The predicted order of sensitivity of gas molecule is NO2 > SO2 > NO. Adsorbed molecules strongly influence the electronic behaviour of monolayer MoSe2 by inducing impurity levels in the vicinity of Fermi energy. NO and SO2 is found to induce p-type doping effect while semiconductor to metallic transitions occur on NO2 adsorption. Our findings may guide the experimentalist for fabricating sensor devices based on MoSe2 monolayer.

  6. Gas biology: tiny molecules controlling metabolic systems.

    PubMed

    Kajimura, Mayumi; Nakanishi, Tsuyoshi; Takenouchi, Toshiki; Morikawa, Takayuki; Hishiki, Takako; Yukutake, Yoshinori; Suematsu, Makoto

    2012-11-15

    It has been recognized that gaseous molecules and their signaling cascades play a vital role in alterations of metabolic systems in physiologic and pathologic conditions. Contrary to this awareness, detailed mechanisms whereby gases exert their actions, in particular in vivo, have been unclear because of several reasons. Gaseous signaling involves diverse reactions with metal centers of metalloproteins and thiol modification of cysteine residues of proteins. Both the multiplicity of gas targets and the technical limitations in accessing local gas concentrations make dissection of exact actions of any gas mediator a challenge. However, a series of advanced technologies now offer ways to explore gas-responsive regulatory processes in vivo. Imaging mass spectrometry combined with quantitative metabolomics by capillary-electrophoresis/mass spectrometry reveals spatio-temporal profiles of many metabolites. Comparing the metabolic footprinting of murine samples with a targeted deletion of a specific gas-producing enzyme makes it possible to determine sites of actions of the gas. In this review, we intend to elaborate on the ideas how small gaseous molecules interact with metabolic systems to control organ functions such as cerebral vascular tone and energy metabolism in vivo. PMID:22516267

  7. Electronic structure and binding geometry of tetraphenylporphyrin-derived molecules adsorbed on metal and metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Coh, Senia

    Tetraphenylporphyrin (TPP)-derived molecules have been studied extensively as efficient photosensitizers when chemisorbed on the metal oxide substrates in dye-sensitized solar cells. Still, many fundamental electronic properties of the dye/oxide interface are not understood and need careful consideration. In this thesis we present a comprehensive study of the electronic structure, energy level alignment and the adsorption geometry of the TPP-derived dye molecules adsorbed on TiO2(110), ZnO(1120) and Ag(100) single crystal surfaces using ultra-high vacuum (UHV) based surface sensitive techniques. The alignment of the molecular energy levels with respect to the TiO 2 and ZnO band edges for all TPP-derived molecules we studied was found to be insensitive to either the nature of the functional groups located on the phenyl rings, presence of zinc as a central metal ion and different binding geometry of the molecules. Binding geometry, molecule-molecule interaction and the aggregation effects in the adsorbed layer, that were observed in the UV-visible spectra of the molecules adsorbed on ZnO substrate were not observed in the ultraviolet photoemission (UPS) and inverse photoemission (IPS) spectra of the occupied and unoccupied molecular states. Using near edge X-ray absorption fine structure (NEXAFS) and scanning tunneling microscopy (STM), binding geometry of the two representative TPP-derivatives was directly determined to be upright, with the porphyrin ring under large angle with respect to the surface for the p-ZnTCPP molecules and with the porphyrin ring parallel to the surface for the m-ZnTCPP molecules. We observe that the energies and the energy level alignment of the ZnTPP molecular levels measured in UPS and IPS depend on the substrate on which the molecules are adsorbed (Ag(100) or TiO2(110) single crystal surfaces). The differences are attributed to different charge screening properties of these two materials. Image charges created in the substrates during

  8. Adsorption of gas molecules on monolayer MoS2 and effect of applied electric field

    NASA Astrophysics Data System (ADS)

    Yue, Qu; Shao, Zhengzheng; Chang, Shengli; Li, Jingbo

    2013-10-01

    Using first-principles calculations, we investigate the adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO) on monolayer MoS2. The most stable adsorption configuration, adsorption energy, and charge transfer are obtained. It is shown that all the molecules are weakly adsorbed on the monolayer MoS2 surface and act as charge acceptors for the monolayer, except NH3 which is found to be a charge donor. Furthermore, we show that charge transfer between the adsorbed molecule and MoS2 can be significantly modulated by a perpendicular electric field. Our theoretical results are consistent with the recent experiments and suggest MoS2 as a potential material for gas sensing application.

  9. Adsorption of gas molecules on monolayer MoS2 and effect of applied electric field.

    PubMed

    Yue, Qu; Shao, Zhengzheng; Chang, Shengli; Li, Jingbo

    2013-01-01

    : Using first-principles calculations, we investigate the adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO) on monolayer MoS2. The most stable adsorption configuration, adsorption energy, and charge transfer are obtained. It is shown that all the molecules are weakly adsorbed on the monolayer MoS2 surface and act as charge acceptors for the monolayer, except NH3 which is found to be a charge donor. Furthermore, we show that charge transfer between the adsorbed molecule and MoS2 can be significantly modulated by a perpendicular electric field. Our theoretical results are consistent with the recent experiments and suggest MoS2 as a potential material for gas sensing application. PMID:24134512

  10. The analysis of surface-adsorbed organic molecules by alkali-assisted MIES combined with UPS(He I)

    NASA Astrophysics Data System (ADS)

    Günster, J.; Ochs, D.; Dieckhoff, S.; Kempter, V.

    1996-12-01

    Metastable impact electron spectroscopy (MIES) in combination with UPS(He I) is applied to the study of s-triazine and triethoxytriazine molecules adsorbed on Si(100) either alone or in combination with cesium atoms. It is demonstrated that the presence of the Cs atoms facilitates the identification of the adsorbed species considerably. It is concluded that (i) non-dissociative adsorption of the studied organic molecules occurs whereby the basal rings of the molecules lie flat on the silicon surface, in accordance with previous studies by Bu and Lin, (ii) the binding of the molecules to the surface is mainly via the lone pair orbitals of the nitrogen in the ring, and (iii) s-triazine reacts strongly with oxygen which bonds to the carbon atoms of the triazine ring.

  11. Determination of maximal amount of minor gases adsorbed in a shale sample by headspace gas chromatography.

    PubMed

    Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

    2014-02-01

    In this paper, we present a novel method for determining the maximal amount of ethane, a minor gas species, adsorbed in a shale sample. The method is based on the time-dependent release of ethane from shale samples measured by headspace gas chromatography (HS-GC). The study includes a mathematical model for fitting the experimental data, calculating the maximal amount gas adsorbed, and predicting results at other temperatures. The method is a more efficient alternative to the isothermal adsorption method that is in widespread use today. PMID:24411088

  12. Barriers to intramolecular rotation determined from the temperature dependence of the Henry constant in the region of adsorbed molecule rigidity failure

    NASA Astrophysics Data System (ADS)

    Dolgonosov, A. M.; Prudkovskii, A. G.

    2008-05-01

    A distribution for the rigid and nonrigid adsorbed molecule forms was found. Adsorbed molecule rigidity failure was shown to be accompanied by a weak nonlinear effect, which manifested itself as a temperature dependence of the Henry constant. A method for the determination of the barrier to intramolecular rotation from the temperature dependence of the molecule adsorption constant was suggested. Barriers to rotation about the C-C and C-O bonds were determined for several molecules.

  13. Direct comparison of the electronic coupling efficiency of sulfur and selenium alligator clips for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.

    2003-05-01

    Scanning tunneling microscopy experiments have been performed to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol (DT) self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S, whatever the tunneling conditions.

  14. Direct comparison of the electronic coupling efficiency of sulfur and selenium anchoring groups for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.; Lagoute, J.; Zambelli, T.; Gauthier, S.

    2002-08-01

    We performed air and ultra-high vacuum scanning tunneling microscopy experiments in order to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S whatever the tunneling conditions.

  15. Adsorbent comparisons for anesthetic gas capture in hospital air emissions.

    PubMed

    Mehrata, Mina; Moralejo, Carol; Anderson, William A

    2016-08-23

    For the development of emission control strategies, activated carbon, zeolite, molecular sieves, and a silica gel were tested for adsorption of the newer anesthetic gases isoflurane, sevoflurane, and desflurane from air. The activated carbon Norit GCA 48 was selected for the best performance, and adsorption isotherms at room temperature were developed for the three anesthetics. Equilibrium capacities for this carbon were in the range of 500 to 1,000 mg g(-1) for these anesthetics at partial pressures ranging from 5 to 45 Torr, with the most volatile compound (desflurane) showing the least favorable adsorption. Activated carbons are therefore suggested for use as effective adsorbents in emission control of these anesthetic gases from hospitals. PMID:27222158

  16. Tunneling Spectroscopy Studies of Urea, Thiourea, and Selected Phosphonate Molecules Adsorbed on Aluminum Oxide

    NASA Astrophysics Data System (ADS)

    Crowder, Charles D.

    Experimental and calculated inelastic electron tunneling intensities were compared for several of the vibrational modes of thiourea adsorbed on aluminum oxide. The partial charge model of Kirtley, Scalapino, and Hansma was used to compute the theoretical intensities of each mode. The required partial charges were determined using a method developed by Momany. Essentially, the Coulomb potential resulting from point charges located at atom sites was fitted to the quantum mechanical electrostatic potential of a molecule calculated from Hartree-Fock theory. The effect of a vibrational mode pattern on the electrostatic potential of a molecule was investigated. This effect could not be acceptably modeled with a single point charge located on each atom, so one charge was used to represent the positive nucleus of each atom and a second charge was used to represent the valence cloud. The valence charge was allowed to move independently of the nuclear charge during a molecular vibration, and the motions of the two charges were found to be very different for hydrogen atoms. This model gave very reasonable agreement between the theoretical and observed relative intensities for the in plane vibrational modes of thiourea. An acceptable set of out of plane force constants could not be found. This caused problems in the interpretation of the out of plane relative intensities. Based on the in plane modes, it was concluded that thiourea bonded to aluminum oxide with the sulfur atom near the oxide and the sulfur-carbon bond perpendicular to the aluminum oxide surface. Quantum mechanical electrostatic potentials were also calculated for urea, phosphoric acid (PA), methylphosphonic acid (MPA), hydroxymethylphosphonic acid (HMP), and nitrotrismethylphosphonic acid (NTMP). Electron tunneling spectra were taken for PA, HMP and NTMP, and the observed frequencies were compared to values obtained from Fourier transform infrared, infrared and Raman spectroscopy. Upward shifts in the P=O and P

  17. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  18. Effects of molecule-insulator interaction on geometric property of a single phthalocyanine molecule adsorbed on an ultrathin NaCl film

    NASA Astrophysics Data System (ADS)

    Miwa, Kuniyuki; Imada, Hiroshi; Kawahara, Shota; Kim, Yousoo

    2016-04-01

    The adsorption structure and orientation of a metal-free phthalocyanine (H2Pc ) and a magnesium phthalocyanine (MgPc) on a bilayer of NaCl films were investigated both theoretically and experimentally by means of first-principles calculations based on density functional theory and by scanning tunneling microscopy. H2Pc is adsorbed with its center over the sodium cation, and H-N bonds in the molecule are aligned with the [100] or [010] surface direction of a bilayer (001)-terminated NaCl film. The most stable structures of MgPc on the NaCl film show two kinds of orientations corresponding to the molecule rotated by ±7∘ relative to the [110] surface direction, with the Mg cation positioned over the chlorine anion in both cases. The energetic barrier for switching between these orientations is as low as 9.0 meV, and during an STM measurement, an orientational change of MgPc can be observed. The interaction between the adsorbed molecule and the NaCl film were analyzed in terms of dispersion interaction, Mg-Cl chemical bonding, and electrostatic interaction. It is found that the small electrostatic interaction between the molecule and the film gives a dominant contribution to determining the molecular orientation. Our detailed and comprehensive studies of the molecule-insulator interaction will provide knowledge to understand and control the properties of molecules on an insulating material.

  19. Adsorbed Natural Gas Storage in Optimized High Surface Area Microporous Carbon

    NASA Astrophysics Data System (ADS)

    Romanos, Jimmy; Rash, Tyler; Nordwald, Erik; Shocklee, Joshua Shawn; Wexler, Carlos; Pfeifer, Peter

    2011-03-01

    Adsorbed natural gas (ANG) is an attractive alternative technology to compressed natural gas (CNG) or liquefied natural gas (LNG) for the efficient storage of natural gas, in particular for vehicular applications. In adsorbants engineered to have pores of a few molecular diameters, a strong van der Walls force allows reversible physisorption of methane at low pressures and room temperature. Activated carbons were optimized for storage by varying KOH:C ratio and activation temperature. We also consider the effect of mechanical compression of powders to further enhance the volumetric storage capacity. We will present standard porous material characterization (BET surface area and pore-size distribution from subcritical N2 adsorption) and methane isotherms up to 250 bar at 293K. At sufficiently high pressure, specific surface area, methane binding energy and film density can be extracted from supercritical methane adsorption isotherms. Research supported by the California Energy Commission (500-08-022).

  20. Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

    SciTech Connect

    Britton, Andrew J.; Weston, Matthew; O'Shea, James N.; Taylor, J. Ben; Rienzo, Anna; Mayor, Louise C.

    2011-10-28

    The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2{sup '}-bipyridyl-4,4{sup '}-dicarboxylato) -ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the {pi}*-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.

  1. Comparison of Gas and Adsorbed Phase X-ray Photoemission Spectra of Oxidized Organics on Ice

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Bluhm, H.

    2011-12-01

    Most uptake studies of small chain organics on ice surfaces at near ambient conditions have been performed using flow tube and other methods which monitor the disappearance of the gas phase. We will present results using synchrotron based, ambient pressure X-ray photoemission spectroscopy which allows for the probing of the ice surface directly at near ambient conditions. C 1s XPS and C K-edge NEXAFS gas phase and adsorbed phase spectra will be compared for 2-propanol, acetone, and 1-propanal on ice at -45 C. Uptake experiments give rise to first order Langmuirian isotherms. Acetone and 2-propanol show little difference in the photoemission spectra between the gas phase and adsorbed phase, suggesting that adsorption occurs molecularly. However, adsorption of 1-propanal shows evidence of chemical transformation (oxidation) at the interface of ice. Further studies are underway to better understand this adsorption behavior.

  2. 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. PMID:26331549

  3. Preparation of sodium humate/{alpha}-aluminum oxide adsorbents for flue gas desulfurization

    SciTech Connect

    Sun, Z.G.; Gao, H.Y.; Hu, G.X.; Li, Y.H.

    2009-06-15

    A new composite adsorbent of sodium humate (HNa)=alpha-aluminium oxide ({alpha}-Al{sub 2}O{sub 3}) for flue gas desulfurization (FGD) was prepared using the impregnation method. Both the adsorbent of {alpha}-Al{sub 2}O{sub 3} and HNa={alpha}-Al{sub 2}O{sub 3} were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy dispersive X-ray spectrometer (EDS), and scanning electron microscope (SEM). Desulfurization activity of the adsorbent impregnated with ammonia (NH{sub 4}OH) was investigated in a fixed-bed quartz reactor. Experimental results indicate that HNa, which coats the {alpha}-Al{sub 2}O{sub 3} fibers impregnated with HNa solution, improved the property of {alpha}-Al{sub 2}O{sub 3} support for FGD. On the other hand, the HNa-coating on the adsorbent of HNa/{alpha}-Al{sub 2}O{sub 3} impregnated with NH{sub 4}OH played an important role in enhancing the desulfurization property of the {alpha}-Al{sub 2}O{sub 3}. Due to the strong adsorption capability of HNa, more NH{sub 4}OH was adsorbed in the adsorbent of HNa/{alpha}-Al{sub 2}O{sub 3} the longer a high sulfur dioxide (SO{sub 2}) conversation rate was maintained. In addition, because the desulfurization product was a compound fertilizer consisting of ammonium sulfate ((NH{sub 4}){sub 2}SO{sub 4}), ammonium humate (HNH{sub 4}), and HNa, the recycling use of {alpha}-Al{sub 2}O{sub 3} was also easily achieved. Thus, this study can provide a new cost-effective way to remove SO{sub 2} from flue gas.

  4. A thermal energy storage system for adsorbent low-pressure natural gas storage

    SciTech Connect

    Blazek, C.F.; Jasionowski, W.J.; Kountz, K.J.; Tiller, A.J.; Gauthier, S.W.; Takagishi, S.K.

    1992-12-31

    Carbon-based adsorbents were determined to be the best enhanced storage media that would store more natural gas at low pressures than achieved with compression only. Thermal energy storage (TES) was previously demonstrated to be a potentially promising technique to mitigate heat effects associated with low-pressure carbon adsorption systems for natural gas storage. Further investigations were conducted to develop information for the design of an optimized adsorption system that incorporates TES heat management. The selection of appropriate phase-change materials and nucleating agents, encapsulant materials, and corrosion inhibitors for a TES heat management system are discussed and the results of extended thermal cyclic behavior are presented. Engineering analyses and finite element analyses are employed to calculate adsorption rates, heat generation, temperatures, and heat transfer within the adsorbent bed. The size, volume, and arrangement of components for an operational TES system designed to accommodate fast-fill within a defined time limit is presented.

  5. A thermal energy storage system for adsorbent low-pressure natural gas storage

    SciTech Connect

    Blazek, C.F.; Jasionowski, W.J.; Kountz, K.J.; Tiller, A.J. ); Gauthier, S.W.; Takagishi, S.K. )

    1992-01-01

    Carbon-based adsorbents were determined to be the best enhanced storage media that would store more natural gas at low pressures than achieved with compression only. Thermal energy storage (TES) was previously demonstrated to be a potentially promising technique to mitigate heat effects associated with low-pressure carbon adsorption systems for natural gas storage. Further investigations were conducted to develop information for the design of an optimized adsorption system that incorporates TES heat management. The selection of appropriate phase-change materials and nucleating agents, encapsulant materials, and corrosion inhibitors for a TES heat management system are discussed and the results of extended thermal cyclic behavior are presented. Engineering analyses and finite element analyses are employed to calculate adsorption rates, heat generation, temperatures, and heat transfer within the adsorbent bed. The size, volume, and arrangement of components for an operational TES system designed to accommodate fast-fill within a defined time limit is presented.

  6. A Study of Condition Assessment Method of Gas-Insulated Switchgear based on the Adsorbent (Part I)

    NASA Astrophysics Data System (ADS)

    Shinkai, Hiroyuki; Amano, Takaaki; Goshima, Hisashi; Yashima, Masafumi

    We have proposed the condition assessment method of the GIS based on the gas analysis. This method utilizes the accumulation of SF6 decomposition gas which is generated by the partial discharge or overheating and has a advantage that does not receive the influence of electrical noise. However, the decomposition gas is adsorbed by the adsorbent that was installed at the equipment as soon as it is generated. Therefore, an efficient separation and sensitive analysis method of the decomposition gas from the adsorbent are necessary. In this report, we proposed the simple separation and sensitive analysis method of decomposition gas. The decomposition gas in the adsorbent was separated as the aqueous solution by immersing the adsorbent in the purified water, and adsorbent aqueous solution was analyzed by water quality meter and ion chromatograph. As the result of water quality meter analysis, the characteristics of aqueous solution including the decomposition gas were greatly different from the one that doesn't contain decomposition gas. As the result of ion chromatograph analysis, the ingredient of the decomposition gas was able to be detected directly from aqueous solution. Therefore, it was shown that these proposed method are very useful for condition assessment method of GIS.

  7. Adsorbing H₂S onto a single graphene sheet: A possible gas sensor

    SciTech Connect

    Reshak, A. H.; Auluck, S.

    2014-09-14

    The electronic structure of pristine graphene sheet and the resulting structure of adsorbing a single molecule of H₂S on pristine graphene in three different sites (bridge, top, and hollow) are studied using the full potential linearized augmented plane wave method. Our calculations show that the adsorption of H₂S molecule on the bridge site opens up a small direct energy gap of about 0.1 eV at symmetry point M, while adsorption of H₂S on top site opens a gap of 0.3 eV around the symmetry point K. We find that adsorbed H₂S onto the hollow site of pristine graphene sheet causes to push the conduction band minimum and the valence band maximum towards Fermi level resulting in a metallic behavior. Comparing the angular momentum decomposition of the atoms projected electronic density of states of pristine graphene sheet with that of H₂S–graphene for three different cases, we find a significant influence of the location of the H₂S molecule on the electronic properties especially the strong hybridization between H₂S molecule and graphene sheet.

  8. Mercury removal from incineration flue gas by organic and inorganic adsorbents.

    PubMed

    Jurng, Jongsoo; Lee, Tai Gyu; Lee, Gyo Woo; Lee, Sung-Jun; Kim, Byung Hwa; Seier, Jochen

    2002-06-01

    Experiments were performed to investigate various adsorbents for their mercury removal capabilities from incineration flue gases. Four different materials were tested; Zeolite, Bentonite, activated carbon (AC), and wood char. Real incineration off-gas and in-lab simulated combustion flue gases (N2 + Hg) were used. Three cylindrical-shaped sorbent columns with 5 cm in diameter and 20 cm in length were used. The gas flow rate was fixed at 660 l/h at all times. Concentrations of NO, CO, O2, CO2, SO2, H2O, HCl, and mercury were continuously monitored. Mercury removal efficiencies of natural Zeolite and Bentonite were found to be much lower than those of the referenced AC. Amount of Hg removed were 9.2 and 7.4 microg/g of Zeolite and Bentonite, respectively. Removal efficiencies of each layer consisted of inorganic adsorbents were no higher than 7%. No significant improvement was observed with sulfur impregnation onto the inorganic adsorbents. Organic adsorbents (wood char and AC) showed much higher mercury removal efficiencies than those of inorganic ones (Zeolite and Bentonite). Mercury removal efficiency of wood char reached over 95% in the first layer, showing almost same effectiveness as AC which currently may be the most effective adsorbents for mercury. Amount of mercury captured by wood char was approximately 0.6 mg/g of wood char, close to the amount captured by AC tested in this study. Hence, wood char, made from the waste woods through a gasification process, should be considered as a possible alternative to relatively expensive AC. PMID:12108697

  9. Charge-transfer photodissociation of adsorbed molecules via electron image states

    SciTech Connect

    Jensen, E. T.

    2008-01-28

    The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

  10. Adsorbed states of chlorophenol on Cu(110) and controlled switching of single-molecule junctions

    NASA Astrophysics Data System (ADS)

    Okuyama, H.; Kitaguchi, Y.; Hattori, T.; Ueda, Y.; Ferrer, N. G.; Hatta, S.; Aruga, T.

    2016-06-01

    A molecular junction of substituted benzene (chlorophenol) is fabricated and controlled by using a scanning tunneling microscope (STM). Prior to the junction formation, the bonding geometry of the molecule on the surface is characterized by STM and electron energy loss spectroscopy (EELS). EELS shows that the OH group of chlorophenol is dissociated on Cu(110) and that the molecule is bonded nearly flat to the surface via an O atom, with the Cl group intact. We demonstrate controlled contact of an STM tip to the "available" Cl group and lift-up of the molecule while it is anchored to the surface via an O atom. The asymmetric bonding motifs of the molecule to the electrodes allow for reversible control of the junction.

  11. Adsorbed states of chlorophenol on Cu(110) and controlled switching of single-molecule junctions.

    PubMed

    Okuyama, H; Kitaguchi, Y; Hattori, T; Ueda, Y; Ferrer, N G; Hatta, S; Aruga, T

    2016-06-28

    A molecular junction of substituted benzene (chlorophenol) is fabricated and controlled by using a scanning tunneling microscope (STM). Prior to the junction formation, the bonding geometry of the molecule on the surface is characterized by STM and electron energy loss spectroscopy (EELS). EELS shows that the OH group of chlorophenol is dissociated on Cu(110) and that the molecule is bonded nearly flat to the surface via an O atom, with the Cl group intact. We demonstrate controlled contact of an STM tip to the "available" Cl group and lift-up of the molecule while it is anchored to the surface via an O atom. The asymmetric bonding motifs of the molecule to the electrodes allow for reversible control of the junction. PMID:27369529

  12. How hottest geometries and adsorptive parameters influence the SER(R)S spectra of Methylene Blue molecules adsorbed on nanocolloidal gold particles of varied sizes?

    PubMed

    Roy, Sannak Dutta; Ghosh, Manash; Chowdhury, Joydeep

    2015-12-01

    The SER(R)S spectra of Methylene Blue (MB) molecule adsorbed on gold nanocolloidal particles (AuNCs) have been investigated. The adsorptive parameters of the molecule adsorbed on AuNCs have been evaluated with the aid of Fluorescence Spectroscopy study. Fluorescence spectroscopic studies have been further applied to understand the concentration of probe molecule actually adsorbed on AuNC surfaces. Gigantic enhancements ∼10(6)-10(16) orders of magnitude have been recorded for the enhanced Raman bands in the SER(R)S spectra. Three-dimensional Finite Difference Time Domain (3D-FDTD) simulations studies have been carried out to predict the distributions of electric fields around the possible nanoaggregated hot geometries considered to be responsible for the huge enhancements of SER(R)S bands of the MB molecule. PMID:26172467

  13. Absence of a charge-transfer instability for rare-gas atoms adsorbed on metals

    NASA Astrophysics Data System (ADS)

    Lang, N. D.; Williams, A. R.; Himpsel, F. J.; Reihl, B.; Eastman, D. E.

    1982-08-01

    Recent optical-absorption experiments on rare-gas atoms bonded to metals dramatically segregate various rare-gas-metal systems into two classes. Cunningham, Greenlaw, and Flynn have hypothesized that these two classes are characterized by the presence or absence of charge transfer from the (excited) rare-gas atom to the metal, and that such charge transfer is controlled by the sign of the difference Φ-I*, where Φ is the metal work function and I* is the energy required to ionize the rare-gas atom in its lowest excited state. Flynn and Chen have, in addition, collected data describing the dipole moments of adsorbed Xe; these also suggest a dramatic dependence on the quantity Φ-I*. As a test of this hypothesis, we have measured the dipole moment of Xe adsorbed on a low-work-function substrate [Gd(0001), with Φ=3.3+/-0.1 eV for the clean surface]. The central new result is that both the Gd measurement and a variety of existing experimental data are inconsistent with the interpretation emphasizing Φ-I*. New calculations using the atom-on-jellium model are also introduced to supplement the discussion. Our analysis suggests that the behavior seen in the optical-absorption measurements could represent a physical effect even more unusual than the charge-transfer instability proposed by Flynn et al.

  14. Novel Applications of Buffer-gas Cooling to Cold Atoms, Diatomic Molecules, and Large Molecules

    NASA Astrophysics Data System (ADS)

    Drayna, Garrett Korda

    Cold gases of atoms and molecules provide a system for the exploration of a diverse set of physical phenomena. For example, cold gasses of magnetically and electrically polar atoms and molecules are ideal systems for quantum simulation and quantum computation experiments, and cold gasses of large polar molecules allow for novel spectroscopic techniques. Buffer-gas cooling is a robust and widely applicable method for cooling atoms and molecules to temperatures of approximately 1 Kelvin. In this thesis, I present novel applications of buffer-gas cooling to obtaining gases of trapped, ultracold atoms and diatomic molecules, as well as the study of the cooling of large organic molecules. In the first experiment of this thesis, a buffer-gas beam source of atoms is used to directly load a magneto-optical trap. Due to the versatility of the buffer-gas beam source, we obtain trapped, sub-milliKelvin gases of four different lanthanide species using the same experimental apparatus. In the second experiment of this thesis, a buffer-gas beam is used as the initial stage of an experiment to directly laser cool and magneto-optically trap the diatomic molecule CaF. In the third experiment of this thesis, buffer-gas cooling is used to study the cooling of the conformational state of large organic molecules. We directly observe conformational relaxation of gas-phase 1,2-propanediol due to cold collisions with helium gas. Lastly, I present preliminary results on a variety of novel applications of buffer-gas cooling, such as mixture analysis, separation of chiral mixtures, the measurement of parity-violation in chiral molecules, and the cooling and spectroscopy of highly unstable reaction intermediates.

  15. Nanovalved Adsorbents for CH4 Storage.

    PubMed

    Song, Zhuonan; Nambo, Apolo; Tate, Kirby L; Bao, Ainan; Zhu, Minqi; Jasinski, Jacek B; Zhou, Shaojun J; Meyer, Howard S; Carreon, Moises A; Li, Shiguang; Yu, Miao

    2016-05-11

    A novel concept of utilizing nanoporous coatings as effective nanovalves on microporous adsorbents was developed for high capacity natural gas storage at low storage pressure. The work reported here for the first time presents the concept of nanovalved adsorbents capable of sealing high pressure CH4 inside the adsorbents and storing it at low pressure. Traditional natural gas storage tanks are thick and heavy, which makes them expensive to manufacture and highly energy-consuming to carry around. Our design uses unique adsorbent pellets with nanoscale pores surrounded by a coating that functions as a valve to help manage the pressure of the gas and facilitate more efficient storage and transportation. We expect this new concept will result in a lighter, more affordable product with increased storage capacity. The nanovalved adsorbent concept demonstrated here can be potentially extended for the storage of other important gas molecules targeted for diverse relevant functional applications. PMID:27124722

  16. Poultry manure as raw material for mercury adsorbents in gas applications

    SciTech Connect

    Klasson, K.T.; Lima, I.M.; Boihem, L.L.

    2009-09-30

    The quantity of poultry manure generated each year is large, and technologies that take advantage of the material should be explored. At the same time, increased emphasis on the reduction of mercury emissions from coal-fired electric power plants has resulted in environmental regulations that may, in the future, require application of activated carbons as mercury sorbents. The sorbents could be injected into the flue gas stream, where they could adsorb the mercury. The sorbents (now containing mercury) would be removed via filtration or other means from the flue gas. Our preliminary work has demonstrated that activated carbon made from poultry manure can adsorb mercury from air with good efficiency. In laboratory experiments, an activated carbon made from turkey cake manure removed the majority of elemental mercury from a hot air stream. Other activated carbons made from chicken and turkey litter manure were also efficient. In general, unwashed activated carbons made from poultry manure were more efficient in removing mercury than their acid-washed counterparts. The results suggest that the adsorption of mercury was mainly due to chemisorption on the surface of the carbon. Other potential uses for the activated carbons are the removal of mercury from air and natural gas.

  17. Tunneling properties of nonplanar molecules in a gas medium

    SciTech Connect

    Bahrami, Mohammad; Bassi, Angelo

    2011-12-15

    We propose a simple, general, and accurate formula for analyzing the tunneling between classical configurations of a nonplanar molecule in a gas medium, as a function of the thermodynamic parameters of the gas. We apply it to two interesting cases: (i) the shift to zero frequency of the inversion line of ammonia, upon an increase in the pressure of the gas; and (ii) the destruction of the coherent tunneling of D{sub 2}S{sub 2} molecules in a He gas. In both cases, we compare our analysis with previous theoretical and experimental results.

  18. Hindered and modulated rotational states and spectra of adsorbed diatomic molecules

    SciTech Connect

    Shih, Y.T.; Chuu, D.S.; Mei, W.N.

    1996-10-01

    Both vertical and horizontal adsorption configurations of a diatomic molecule were modeled as the rigid rotor with which the spatial motion was confined by a finite conical well. In addition to the polar hindering potential, a sinusoidal azimuthal modulation, which bears the local symmetry of the adsorption site, was incorporated. Eigenfunctions for different models were expressed analytically in terms of the hypergeometric functions, and eigenvalues were solved numerically. We found that the rotational energy levels exhibit oscillatory behavior when plotted as functions of the hindrance angle. This particular phenomenon was interpreted as the occurrence of resonance transmission of the rotor wave function at certain hindrance condition. We also found that the rotational levels were grouped into bands when the azimuthal modulation strength was increased. The solutions were used to calculate the rotational-state distribution of desorbed molecules, and agreement with the previous experiment was obtained. {copyright} {ital 1996 The American Physical Society.}

  19. Novel simulated moving-bed adsorber for the fractionation of gas mixtures.

    PubMed

    Rao, D P; Sivakumar, S V; Mandal, Susmita; Kota, Sridevi; Ramaprasad, B S G

    2005-03-25

    The separation of propylene-propane mixture is an energy intensive operation commercially practiced using cryogenic distillation. The separation by pressure swing adsorption has been studied as an alternative. A fixed-bed pressure swing adsorption yields the heavy component as a pure product. The product recovery and the productivity are not high. In a moving-bed process, because of the counter-current solid-gas contact, the separation achieved is similar to that of the fractionation by distillation. Although the moving-bed operation offers the upper limit for the performance of a cyclic adsorptive process, due to mechanical complexities in the handling of solids the 'simulated' moving-bed is preferred. By moving the inlet and outlet ports of streams located along the length of the bed, a moving-bed process can be realized in a fixed bed. We describe here a 'moving-port' system which permits injection or withdrawal of the fluid along the axial direction in a fixed bed. A fixed bed embedded with the moving-port systems emulates a simulated moving-bed adsorber. The proposed adsorber can fractionate a binary gas mixture into two product streams with high purities. It is similar to the Sorbex process of UOP but does not have the eluent as an additional separating agent. A parametric study indicates that high purity products and a higher productivity by an order of magnitude can be achieved with simulated moving-beds compared to the fixed beds. PMID:15844493

  20. Interface-Induced Ordering of Gas Molecules Confined in a Small Space

    PubMed Central

    Lu, Yi-Hsien; Yang, Chih-Wen; Fang, Chung-Kai; Ko, Hsien-Chen; Hwang, Ing-Shouh

    2014-01-01

    The thermodynamic properties of gases have been understood primarily through phase diagrams of bulk gases. However, observations of gases confined in a nanometer space have posed a challenge to the principles of classical thermodynamics. Here, we investigated interfacial structures comprising either O2 or N2 between water and a hydrophobic solid surface by using advanced atomic force microscopy techniques. Ordered epitaxial layers and cap-shaped nanostructures were observed. In addition, pancake-shaped disordered layers that had grown on top of the epitaxial base layers were observed in oxygen-supersaturated water. We propose that hydrophobic solid surfaces provide low-chemical-potential sites at which gas molecules dissolved in water can be adsorbed. The structures are further stabilized by interfacial water. Here we show that gas molecules can agglomerate into a condensed form when confined in a sufficiently small space under ambient conditions. The crystalline solid surface may even induce a solid-gas state when the gas-substrate interaction is significantly stronger than the gas-gas interaction. The ordering and thermodynamic properties of the confined gases are determined primarily according to interfacial interactions. PMID:25424443

  1. Switching orientation of adsorbed molecules: Reverse domino on a metal surface

    NASA Astrophysics Data System (ADS)

    Braatz, C. R.; Esat, T.; Wagner, C.; Temirov, R.; Tautz, F. S.; Jakob, P.

    2016-01-01

    A thus far unknown phase of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111), characterized by an all perpendicular orientation of the planar molecules and bound to the Ag substrate through the carboxyl oxygen atoms has been identified using infrared absorption spectroscopy and scanning tunneling microscopy. Its formation process requires second layer NTCDA to squeeze into empty spaces between relaxed monolayer NTCDA molecules. Remarkably, this process causes initially parallel oriented NTCDA to likewise adopt the new, highly inclined adsorption geometry. According to our SPA-LEED and STM findings, the new phase displays a distinct long range order and shows a pronounced tendency to form 1D rows or narrow islands. We suggest that extra NTCDA preferentially transforms into the upright configuration close to existing islands and attaches to them, i.e. the transformation process proceeds in a directed and recurrent manner (reverse domino scenario). Identical processing starting with a compressed NTCDA/Ag(111) monolayer leads to a purely parallel oriented bilayer, that is, the NTCDA monolayer phase is retained and merely acts as a passive template for bilayer NTCDA. The new vertical NTCDA phase represents an unusual molecular system with π-orbitals oriented parallel to a metal surface. A substantially reduced coupling of these orbitals to Ag(111) electronic levels is conjectured, which will have a major impact on intermolecular couplings and electronically excited state lifetimes.

  2. Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

    NASA Astrophysics Data System (ADS)

    He, Xin; Barthel, Anthony J.; Kim, Seong H.

    2016-06-01

    The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

  3. A quantum gas of polar molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    Moses, Steven A.

    Ultracold polar molecules, because of their long-range, spatially anisotropic interactions, are a new quantum system in which to study novel many-body phenomena. In our lab, we have produced the first quantum gas of 40K 87Rb polar molecules. These molecules were found to undergo exothermic chemical reactions, and this led to interesting studies of chemistry near absolute zero. By creating the molecules at individual sites of a 3D optical lattice, we completely suppress these chemical reactions, and the polar molecule gas becomes stable and lives for tens of seconds. This thesis documents our efforts to explore coherent, many-body phenomena resulting from long-range dipolar interactions in the lattice. By encoding a spin-1/2 system in the rotational states of the molecules, we were able to realize spin-exchange interactions based on a spin Hamiltonian, which is one of the first steps in studying quantum magnetism with polar molecules. While this study was the first realization of such coherent dipolar interactions with polar molecules in a lattice, its full potential was limited by the low lattice filling fractions. Using our ability to exquisitely control the initial atomic gas mixture, we loaded a Mott insulator of Rb and a band insulator of K into the lattice. This quantum synthesis approach led to significantly higher molecular filling fractions and represents the first fully connected system of polar molecules in an optical lattice. This low-entropy quantum gas of polar molecules opens the door to interesting quantum simulations, which should be attainable in the next generation of the experiment.

  4. Hydrogen storage on high-surface-area carbon monoliths for Adsorb hydrogen Gas Vehicle

    NASA Astrophysics Data System (ADS)

    Soo, Yuchoong; Pfeifer, Peter

    2014-03-01

    Carbon briquetting can increase hydrogen volumetric storage capacity by reducing the useless void volume resulting in a better packing density. It is a robust and efficient space-filling form for an adsorbed hydrogen gas vehicle storage tank. To optimize hydrogen storage capacity, we studied three fabrication process parameters: carbon-to-binder ratio, compaction temperature, and pyrolysis atmosphere. We found that carbon-to-binder ratio and pyrolysis atmosphere have influences on gravimetric excess adsorption. Compaction temperature has large influences on gravimetric and volumetric storage capacity. We have been able to optimize these parameters for high hydrogen storage. All monolith uptakes (up to 260 bar) were measured by a custom-built, volumetric, reservoir-type instrument.

  5. Measurement of Fatigue Crack Growth Relationships in Hydrogen Gas for Pressure Swing Adsorber Vessel Steels

    SciTech Connect

    Somerday, Brian P.; Barney, Monica

    2014-12-04

    We measured the hydrogen-assisted fatigue crack growth rates (da/dN) for SA516 Grade 70 steel as a function of stress-intensity factor range (ΔK) and load-cycle frequency to provide life-prediction data relevant to pressure swing adsorber (PSA) vessels. For ΔK values up to 18.5 MPa m1/2, the baseline da/dN versus ΔK relationship measured at 1Hz in 2.8 MPa hydrogen gas represents an upper bound with respect to crack growth rates measured at lower frequency. However, at higher ΔK values, we found that the baseline da/dN data had to be corrected to account for modestly higher crack growth rates at the lower frequencies relevant to PSA vessel operation.

  6. Measurement of Fatigue Crack Growth Relationships in Hydrogen Gas for Pressure Swing Adsorber Vessel Steels

    DOE PAGESBeta

    Somerday, Brian P.; Barney, Monica

    2014-12-04

    We measured the hydrogen-assisted fatigue crack growth rates (da/dN) for SA516 Grade 70 steel as a function of stress-intensity factor range (ΔK) and load-cycle frequency to provide life-prediction data relevant to pressure swing adsorber (PSA) vessels. For ΔK values up to 18.5 MPa m1/2, the baseline da/dN versus ΔK relationship measured at 1Hz in 2.8 MPa hydrogen gas represents an upper bound with respect to crack growth rates measured at lower frequency. However, at higher ΔK values, we found that the baseline da/dN data had to be corrected to account for modestly higher crack growth rates at the lower frequenciesmore » relevant to PSA vessel operation.« less

  7. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons.

    PubMed

    Chou, L-C; Jang, C-Y; Wu, Y-H; Tsai, W-C; Wang, S-K; Chen, J; Chang, S-C; Liu, C-C; Shai, Y; Wen, C-R

    2008-12-01

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F(+) and F(-) PSD ion yields were measured from CF(3)Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF(3)Cl dose=0.3x10(15) molecules/cm(2), approximately 0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF(3)Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F(+) ion desorption is associated with the bond breaking of the surface CF(3)Cl, CF(2)Cl, CFCl, and SiF species. (c) the F(-) yield is mainly due to DA and DD of the adsorbed CF(3)Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F(+), or F(-) ion produced by scission of C-F bond of CF(3)Cl, CF(2)Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF(3)Cl-covered surface. Based on this model and the variation rates of the F(+)F(-) signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV [near the F(1s) edge], the photolysis cross section was deduced as a function of energy. PMID:19063541

  8. Line broadening of confined CO gas: from molecule-wall to molecule-molecule collisions with pressure.

    PubMed

    Hartmann, J-M; Boulet, C; Auwera, J Vander; El Hamzaoui, H; Capoen, B; Bouazaoui, M

    2014-02-14

    The infrared absorption in the fundamental band of CO gas confined in porous silica xerogel has been recorded at room temperature for pressures between about 5 and 920 hPa using a high resolution Fourier transform spectrometer. The widths of individual lines are determined from fits of measured spectra and compared with ab initio predictions obtained from requantized classical molecular dynamics simulations. Good agreement is obtained from the low pressure regime where the line shapes are governed by molecule-wall collisions to high pressures where the influence of molecule-molecule interactions dominates. These results, together with those obtained with a simple analytical model, indicate that both mechanisms contribute in a practically additive way to the observed linewidths. They also confirm that a single collision of a molecule with a wall changes its rotational state. These results are of interest for the determination of some characteristics of the opened porosity of porous materials through optical soundings. PMID:24527910

  9. Development of Novel CO2 Adsorbents for Capture of CO2 from Flue Gas

    SciTech Connect

    Fauth, D.J.; Filburn, T.P.; Gray, M.L.; Hedges, S.W.; Hoffman, J.; Pennline, H.W.; Filburn, T.

    2007-06-01

    Capturing CO2 emissions generated from fossil fuel-based power plants has received widespread attention and is considered a vital course of action for CO2 emission abatement. Efforts are underway at the Department of Energy’s National Energy Technology Laboratory to develop viable energy technologies enabling the CO2 capture from large stationary point sources. Solid, immobilized amine sorbents (IAS) formulated by impregnation of liquid amines within porous substrates are reactive towards CO2 and offer an alternative means for cyclic capture of CO2 eliminating, to some degree, inadequacies related to chemical absorption by aqueous alkanolamine solutions. This paper describes synthesis, characterization, and CO2 adsorption properties for IAS materials previously tested to bind and release CO2 and water vapor in a closed loop life support system. Tetraethylenepentamine (TEPA), acrylonitrile-modified tetraethylenepentamine (TEPAN), and a single formulation consisting of TEPAN and N, N’-bis(2-hydroxyethyl)ethylenediamine (BED) were individually supported on a poly (methyl methacrylate) (PMMA) substrate and examined. CO2 adsorption profiles leading to reversible CO2 adsorption capacities were obtained using thermogravimetry. Under 10% CO2 in nitrogen at 25°C and 1 atm, TEPA supported on PMMA over 60 minutes adsorbed ~3.2 mmol/g{sorbent} whereas, TEPAN supported on PMMA along with TEPAN and BED supported on PMMA adsorbed ~1.7 mmol/g{sorbent} and ~2.3 mmol/g{sorbent} respectively. Cyclic experiments with a 1:1 weight ratio of TEPAN and BED supported on poly (methyl methacrylate) beads utilizing a fixed-bed flow system with 9% CO2, 3.5% O2, nitrogen balance with trace gas constituents were studied. CO2 adsorption capacity was ~ 3 mmols CO2/g{sorbent} at 40°C and 1.4 atm. No beneficial effect on IAS performance was found using a moisture-laden flue gas mixture. Tests with 750 ppmv NO in a humidified gas stream revealed negligible NO sorption onto the IAS. A high SO2

  10. Two-dimensional electron gas formed on the indium-adsorbed Si(111)3×3-Au surface

    NASA Astrophysics Data System (ADS)

    Kim, J. K.; Kim, K. S.; McChesney, J. L.; Rotenberg, E.; Hwang, H. N.; Hwang, C. C.; Yeom, H. W.

    2009-08-01

    Electronic structure of the In-adsorbed Si(111)3×3-Au surface was investigated by core-level and angle-resolved photoelectron spectroscopy. On the Si(111)3×3-Au surface, In adsorbates were reported to remove the characteristic domain-wall network and produce a very well-ordered 3×3 surface phase. Detailed band dispersions and Fermi surfaces were mapped for the pristine and In-dosed Si(111)3×3-Au surfaces. After the In adsorption, the surface bands shift toward a higher binding energy, increasing substantially the electron filling of the metallic band along with a significant sharpening of the spectral features. The resulting Fermi surface indicates the formation of a perfect isotropic two-dimensional electron-gas system filled with 0.3 electrons. This band structure agrees well with that expected, in a recent density-functional theory calculation, for the conjugate-honeycomb trimer model of the pristine Si(111)3×3-Au surface. Core-level spectra indicate that In adsorbates interact mostly with Si surface atoms. The possible origins of the electronic structure modification by In adsorbates are discussed. The importance of the domain wall and the indirect role of In adsorbates are emphasized. This system provides an interesting playground for the study of two-dimensional electron gas on solid surfaces.

  11. Adsorbed sulfur-gas methods for both near-surface exploration and downhole logging

    SciTech Connect

    Farwell, S.O.; Barinaga, C.J.; Dolenc, M.R.; Farwell, G.H.

    1986-08-01

    The use of sulfur-containing gases in petroleum exploration is supported by (1) the idea that sulfur may play a role in petroleum genesis, (2) the corresponding existence of sulfur-containing compounds in petroleum and the potential for vertical migration of the low-molecular-weight sulfur species from these reservoirs, (3) the production of H/sub 2/S by anaerobic microorganism populations that develop in the subsurface areas overlying petroleum reservoirs due to the concomitant supply of hydrocarbon nutrients, (4) the recent discovery of near-surface accumulations of pyrite and marcasite as the source of induction potential anomalies over certain fields, and (5) the strong adsorptive affinities of sulfur gases to solid surfaces, which enhance both the concentration and localization of such sulfur-expressed anomalies. During the past 3 years, numerous near-surface soil samples and well cuttings from the Utah-Wyoming Overthrust belt have been analyzed for adsorbed sulfur-gas content by two novel analytical techniques: thermal desorption/metal foil collection/flash desorption/sulfur-selective detection (TD/MFC/FD/SSD) and thermal desorption/cryogenic preconcentration/high-resolution-gas chromatography/optimized-flame photometry (TD/CP/HRGC/OFP).

  12. Porous materials as high performance adsorbents for CO2 capture, gas separation and purification

    NASA Astrophysics Data System (ADS)

    Wang, Jun

    Global warming resulted from greenhouse gases emission has received a widespread attention. Among the greenhouse gases, CO2 contributes more than 60% to global warming due to its huge emission amount. The flue gas contains about 15% CO2 with N2 as the balance. If CO2 can be separated from flue gas, the benefit is not only reducing the global warming effect, but also producing pure CO2 as a very useful industry raw material. Substantial progress is urgent to be achieved in an industrial process. Moreover, energy crisis is one of the biggest challenges for all countries due to the short life of fossil fuels, such as, petroleum will run out in 50 years and coal will run out in 150 years according to today's speed. Moreover, the severe pollution to the environment caused by burning fossil fuels requires us to explore sustainable, environment-friendly, and facile energy sources. Among several alternative energy sources, natural gas is one of the most promising alternative energy sources due to its huge productivity, abundant feed stock, and ease of generation. In order to realize a substantial adsorption process in industry, synthesis of new adsorbents or modification of existing adsorbent with improved properties has become the most critical issue. This dissertation reports systemic characterization and development of five serials of novel adsorbents with advanced adsorption properties. In chapter 2, nitrogen-doped Hypercross-linking Polymers (HCPs) have been synthesized successfully with non-carcinogenic chloromethyl methyl ether (CME) as the cross-linking agent within a single step. Texture properties, surface morphology, CO2/N2 selectivity, and adsorption heat have been presented and demonstrated properly. A comprehensive discussion on factors that affect the CO2 adsorption and CO2/N 2 separation has also been presented. It was found that high micropore proportion and N-content could effectively enhance CO2 uptake and CO2/N2 separation selectivity. In chapter 3, a

  13. Porous materials as high performance adsorbents for CO2 capture, gas separation and purification

    NASA Astrophysics Data System (ADS)

    Wang, Jun

    Global warming resulted from greenhouse gases emission has received a widespread attention. Among the greenhouse gases, CO2 contributes more than 60% to global warming due to its huge emission amount. The flue gas contains about 15% CO2 with N2 as the balance. If CO2 can be separated from flue gas, the benefit is not only reducing the global warming effect, but also producing pure CO2 as a very useful industry raw material. Substantial progress is urgent to be achieved in an industrial process. Moreover, energy crisis is one of the biggest challenges for all countries due to the short life of fossil fuels, such as, petroleum will run out in 50 years and coal will run out in 150 years according to today's speed. Moreover, the severe pollution to the environment caused by burning fossil fuels requires us to explore sustainable, environment-friendly, and facile energy sources. Among several alternative energy sources, natural gas is one of the most promising alternative energy sources due to its huge productivity, abundant feed stock, and ease of generation. In order to realize a substantial adsorption process in industry, synthesis of new adsorbents or modification of existing adsorbent with improved properties has become the most critical issue. This dissertation reports systemic characterization and development of five serials of novel adsorbents with advanced adsorption properties. In chapter 2, nitrogen-doped Hypercross-linking Polymers (HCPs) have been synthesized successfully with non-carcinogenic chloromethyl methyl ether (CME) as the cross-linking agent within a single step. Texture properties, surface morphology, CO2/N2 selectivity, and adsorption heat have been presented and demonstrated properly. A comprehensive discussion on factors that affect the CO2 adsorption and CO2/N 2 separation has also been presented. It was found that high micropore proportion and N-content could effectively enhance CO2 uptake and CO2/N2 separation selectivity. In chapter 3, a

  14. Ion-Molecule Reactions in Gas Phase Radiation Chemistry.

    ERIC Educational Resources Information Center

    Willis, Clive

    1981-01-01

    Discusses some aspects of the radiation chemistry of gases, focusing on the ion-molecule and charge neutralization reactions which set study of the gas phase apart. Uses three examples that illustrate radiolysis, describing the radiolysis of (1) oxygen, (2) carbon dioxide, and (3) acetylene. (CS)

  15. The prebiotic molecules observed in the interstellar gas

    PubMed Central

    Thaddeus, P

    2006-01-01

    Over 130 molecules have been identified in the interstellar gas and circumstellar shells, the largest among them is a carbon chain with 13 atoms and molecular weight of 147 (twice that of the simplest amino acid glycine). The high reliability of astronomical identifications, as well as the fairly accurate quantitative analysis which can often be achieved, is emphasized. Glycine itself has been claimed, but a recent analysis indicates that few, if any, of the astronomical radio lines attributed to glycine are actually from that molecule. Polycyclic aromatic hydrocarbons (PAHs) have long been proposed as the source of the unidentified infrared bands between 3 and 16 μm, but no single PAH has been identified in space, partly because PAHs generally have weak or non-existent radio spectra. A remarkable exception is the non-planar corannulene molecule (C20H10) that has a strong radio spectrum; in the rich molecular cloud TMC-1, it is found that less than 10−5 of the carbon is contained in this molecule, suggesting that PAHs are not the dominant large molecules in the interstellar gas, as has been claimed. Owing to inherent spectroscopic limitations, determining the structures of the large molecules in space may require capture of the dust grains, which are continually entering the outer Solar System. PMID:17008209

  16. The prebiotic molecules observed in the interstellar gas.

    PubMed

    Thaddeus, P

    2006-10-29

    Over 130 molecules have been identified in the interstellar gas and circumstellar shells, the largest among them is a carbon chain with 13 atoms and molecular weight of 147 (twice that of the simplest amino acid glycine). The high reliability of astronomical identifications, as well as the fairly accurate quantitative analysis which can often be achieved, is emphasized. Glycine itself has been claimed, but a recent analysis indicates that few, if any, of the astronomical radio lines attributed to glycine are actually from that molecule. Polycyclic aromatic hydrocarbons (PAHs) have long been proposed as the source of the unidentified infrared bands between 3 and 16 microm, but no single PAH has been identified in space, partly because PAHs generally have weak or non-existent radio spectra. A remarkable exception is the non-planar corannulene molecule (C20H10) that has a strong radio spectrum; in the rich molecular cloud TMC-1, it is found that less than 10-5 of the carbon is contained in this molecule, suggesting that PAHs are not the dominant large molecules in the interstellar gas, as has been claimed. Owing to inherent spectroscopic limitations, determining the structures of the large molecules in space may require capture of the dust grains, which are continually entering the outer Solar System. PMID:17008209

  17. Charged supramolecular assemblies of surfactant molecules in gas phase.

    PubMed

    Bongiorno, David; Ceraulo, Leopoldo; Indelicato, Sergio; Turco Liveri, Vincenzo; Indelicato, Serena

    2016-01-01

    The aim of this review is to critically analyze recent literature on charged supramolecular assemblies formed by surfactant molecules in gas phase. Apart our specific interest on this research area, the stimuli to undertake the task arise from the widespread theoretical and applicative benefits emerging from a comprehensive view of this topic. In fact, the study of the formation, stability, and physicochemical peculiarities of non-covalent assemblies of surfactant molecules in gas phase allows to unveil interesting aspects such as the role of attractive, repulsive, and steric intermolecular interactions as driving force of supramolecular organization in absence of interactions with surrounding medium and the size and charge state dependence of aggregate structural and dynamical properties. Other interesting aspects worth to be investigated are joined to the ability of these assemblies to incorporate selected solubilizates molecules as well as to give rise to chemical reactions within a single organized structure. In particular, the incorporation of large molecules such as proteins has been of recent interest with the objective to protect their structure and functionality during the transition from solution to gas phase. Exciting fall-out of the study of gas phase surfactant aggregates includes mass and energy transport in the atmosphere, origin of life and simulation of supramolecular aggregation in the interstellar space. Moreover, supramolecular assemblies of amphiphilic molecules in gas phase could find remarkable applications as atmospheric cleaning agents, nanosolvents and nanoreactors for specialized chemical processes in confined space. Mass spectrometry techniques have proven to be particularly suitable to generate these assemblies and to furnish useful information on their size, size polydispersity, stability, and structural organization. On the other hand molecular dynamics simulations have been very useful to rationalize many experimental findings and to

  18. Research on the theory and application of adsorbed natural gas used in new energy vehicles: A review

    NASA Astrophysics Data System (ADS)

    Nie, Zhengwei; Lin, Yuyi; Jin, Xiaoyi

    2016-05-01

    Natural gas, whose primary constituent is methane, has been considered a convincing alternative for the growth of the energy supply worldwide. Adsorbed natural gas (ANG), the most promising methane storage method, has been an active field of study in the past two decades. ANG constitutes a safe and low-cost way to store methane for natural gas vehicles at an acceptable energy density while working at substantially low pressures (3.5-4.0 MPa), allowing for conformable store tank. This work serves to review the state-of-the-art development reported in the scientific literature on adsorbents, adsorption theories, ANG conformable tanks, and related technologies on ANG vehicles. Patent literature has also been searched and discussed. The review aims at illustrating both achievements and problems of the ANG technologies- based vehicles, as well as forecasting the development trends and critical issues to be resolved of these technologies.

  19. Markedly different adsorption behaviors of gas molecules on defective monolayer MoS2: a first-principles study.

    PubMed

    Li, Hongxing; Huang, Min; Cao, Gengyu

    2016-06-01

    Sulfur vacancy (SV) is one of the most typical defects in two-dimensional monolayer MoS2, leading to reactive sites. We presented a systematic study of the adsorption behaviors of gas molecules, CO2, N2, H2O, CO, NH3, NO, O2, H2 and NO2, on monolayer MoS2 with single SV by first-principles calculations. It was found that CO2, N2 and H2O molecules physisorbed at the proximity of single SV. Our adsorption energy calculations and charge transfer analysis showed that the interactions between CO2, N2 and H2O molecules and defective MoS2 are stronger than the cases of CO2, N2 and H2O molecules adsorbed on pristine MoS2, respectively. The defective MoS2 based gas sensors may be more sensitive to CO2, N2 and H2O molecules than pristine MoS2 based ones. CO, NO, O2 and NH3 molecules were found to chemisorb at the S vacancy site and thus modify the electronic properties of defective monolayer MoS2. Magnetism was induced upon adsorption of NO molecules and the defective states induced by S vacancy can be completely removed upon adsorption of O2 molecules, which may provide some helpful information for designing new MoS2 based nanoelectronic devices in future. The H2 and NO2 molecules were found to dissociate at S vacancy. The dissociation of NO2 molecules resulted in O atoms located at the S vacancy site and NO molecules physisorbed on O-doped MoS2. The calculated results showed that NO2 molecules can help heal the S vacancy of the MoS2 monolayer. PMID:27198064

  20. Sensing gas molecules using graphitic nanoribbon films and networks

    NASA Astrophysics Data System (ADS)

    An, Yanbin; Johnson, Jason L.; Behnam, Ashkan; Pearton, S. J.; Ural, Ant

    2011-03-01

    We fabricate and study the gas sensing properties of graphitic nanoribbon (GNR) films and networks consisting of multi-layer graphene nanoribbons with an average width of 7 nm. We experimentally demonstrate the high sensitivity of these films and networks for sensing gas molecules at the parts-per-million (ppm) level, in particular hydrogen and ammonia. The sensing response exhibits excellent repeatability and full recovery in air. Furthermore, our results show that functionalization by metal nanoparticles could significantly improve the sensitivity. We characterize the sensing response at various temperatures, gas concentrations, recovery ambients, and film thicknesses. We find that the relative resistance response of the GNR films shows a power-law dependence on the gas concentration, which can be explained by the Freundlich isotherm. The activation energy obtained from the sensing experiments is consistent with the theoretical calculations of the adsorption energies of gas molecules on graphene sheets and nanoribbons. Their simple and low-cost fabrication process and good sensing response open up the possibility of using graphitic nanoribbon films and networks for large-scale sensing applications.

  1. Using Coupled Harmonic Oscillators to Model Some Greenhouse Gas Molecules

    SciTech Connect

    Go, Clark Kendrick C.; Maquiling, Joel T.

    2010-07-28

    Common greenhouse gas molecules SF{sub 6}, NO{sub 2}, CH{sub 4}, and CO{sub 2} are modeled as harmonic oscillators whose potential and kinetic energies are derived. Using the Euler-Lagrange equation, their equations of motion are derived and their phase portraits are plotted. The authors use these data to attempt to explain the lifespan of these gases in the atmosphere.

  2. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons

    SciTech Connect

    Chou, L.-C.; Jang, C.-Y.; Wu, Y.-H.; Tsai, W.-C.; Wang, S.-K.; Chen, J.; Chang, S.-C.; Liu, C.-C.; Shai, Y.; Wen, C.-R.

    2008-12-07

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F{sup +} and F{sup -} PSD ion yields were measured from CF{sub 3}Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF{sub 3}Cl dose=0.3x10{sup 15} molecules/cm{sup 2}, {approx}0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF{sub 3}Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F{sup +} ion desorption is associated with the bond breaking of the surface CF{sub 3}Cl, CF{sub 2}Cl, CFCl, and SiF species. (c) the F{sup -} yield is mainly due to DA and DD of the adsorbed CF{sub 3}Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F{sup +}, or F{sup -} ion produced by scission of C-F bond of CF{sub 3}Cl, CF{sub 2}Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF{sub 3}Cl-covered surface. Based on this model and the variation rates of the F{sup +}/F{sup -} signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV[near the F(1s) edge], the photolysis cross section was deduced as a function of energy.

  3. Continuous-time core-level photon-stimulated desorption spectroscopy for monitoring soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface

    SciTech Connect

    Chou, L.-C.; Wen, C.-R.

    2006-05-15

    Continuous-time core-level photon-stimulated desorption (PSD) spectroscopy was proposed for monitoring the soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface. Monochromatic synchrotron radiation was used as a soft x-ray light source in the photon-induced reactions of CF{sub 3}Cl adsorbed on a Si(111)-7x7 surface at 30 K and also as a probe for studying the produced fluorination states of the bonding surface Si atom in the positive-ion PSD spectroscopy. The F{sup +} PSD spectrum was obtained by monitoring the F{sup +} signal as a function of incident photon energy near the Si(2p) edge (98-110 eV). Sequential F{sup +} PSD spectra were measured as a function of photon exposure at four adsorbate coverages (the first dose=0.3x10{sup 15} molecules/cm{sup 2}, the second dose=0.8x10{sup 15} molecules/cm{sup 2}, the third dose=2.2x10{sup 15} molecules/cm{sup 2}, and the fourth dose=3.2x10{sup 15} molecules/cm{sup 2}). For the first and second CF{sub 3}Cl-dosed surfaces, the sequential F{sup +} PSD spectra show the variation of their shapes with photon exposure and indicate the formation of surface SiF species. The sequential F{sup +} PSD spectra for the third and fourth CF{sub 3}Cl-dosed surfaces also show the variation of their shapes with photon exposure and depict the production of surface SiF and SiF{sub 3} species.

  4. Infrared Spectroscopy and Catalysis Research: Infrared spectra of adsorbed molecules provide important information in the study of catalysis.

    PubMed

    Eischens, R P

    1964-10-23

    The examples discussed here represent only a small part of the published work relating to infrared spectra of adsorbed molecules. The publications in this field indicate that infrared spectroscopy is being used for surface chemistry research in about 50 laboratories throughout the world. This effort is mainly devoted to problems related to catalysis, and in this field infrared spectroscopy is the most widely used physical tool for surface chemistry studies. The general acceptance of infrared spectroscopy is primarily due to the fact that it provides information which is pertinent to the understanding of surface reactions on an atomic scale. During the last decade significant progress has also been made in the classical chemical techniques of catalysis study and in utilization of physical tools which depend on phenomena of magnetism, conductivity, low-energy electron diffraction, and electron emission. Probably the most important progress has been in the field of inorganic chemistry, where dramatic advances have been made in knowledge of metal coordination compounds. Such knowledge is vital to the understanding of catalysis on metal surfaces. I believe this progress has produced an attitude of sophisticated optimism among catalysis researchers with regard to eventual understanding of heterogeneous catalysis. This attitude is closely related to the realization that there is no "secret of catalysis" which places catalytic action beyond the limits of ordinary chemical knowledge (22). This view implies that the chemical aspects of heterogeneous catalysis are not unique and that the use of solid catalysts merely provides a highly effective exposure of catalytic atoms and facilitates separation of the products from the catalyst. Many capable catalysis researchers believe that studies of homogeneous catalysis provide the most direct route for the study of heterogeneous catalysis. Obviously homogeneous reactions catalyzed by compounds containing only one or two metal atoms

  5. Molecule formation in quasar broad-line cloud gas

    SciTech Connect

    Kallman, T.; Lepp, S.; Giovannoni, P.

    1987-10-01

    Models for the broad-line emitting clouds of quasars typically assume that the clouds have column densities of at most 10 to the 23rd/sq cm. The consequences of relaxing this assumption are examined, and it is shown that: (1) at slightly larger column densities the gas may cool to about 1000 K as a result of molecule formation; (2) in much of the molecule-forming region the temperature may have either of two values, about 1000 K or 6000-8000 K; (3) the strengths of most observable optical lines, including C II semiforbidden 2326-A lines and Fe II lines, are unaffected by such large column densities; and (4) lines from low-ionization species such as Na I are readily formed at large column densities. Observations of such lines provide evidence for large cloud column densities. 47 references.

  6. Optics of a gas of coherently spinning molecules.

    PubMed

    Steinitz, Uri; Prior, Yehiam; Averbukh, Ilya Sh

    2014-01-10

    We consider the optical properties of a gas of molecules that are brought to fast unidirectional spinning by a pulsed laser field. It is shown that a circularly polarized probe light passing through the medium inverts its polarization handedness and experiences a frequency shift controllable by the sense and the rate of molecular rotation. Our analysis is supported by two recent experiments on the laser-induced rotational Doppler effect in molecular gases and provides a good qualitative and quantitative description of the experimental observations. PMID:24483895

  7. Polarity of an MCM-41 adsorbent surface modified with methyl and phenyl groups based on data from gas chromatography

    NASA Astrophysics Data System (ADS)

    Sukhareva, D. A.; Gus'kov, V. Yu.; Karpov, S. I.; Kudasheva, F. Kh.; Roessner, F.; Borodina, E. V.

    2016-02-01

    The polarity of an MCM-41 adsorbent surface and organosilylated composites based on it with grafted trimethylsilane and dimethylphenylsilane groups is studied via inverse gas chromatography at infinite dilution. The dispersion and specific components of the value proportional to the Helmholtz adsorption energy are calculated, and a comparative analysis of the surface polarity of MCM-41 and its modified analogs relative to the commercially available C-120 silica gel is performed. The electrostatic and donor-acceptor components of the specific Helmholtz adsorption energy are calculated through linear decomposition of the adsorption energy. It is established that MCM-41 is less polar than C-120. The modification of the initial adsorbent surface leads to a reduction in polarity, due mainly to the weakening of induction and orientation interactions. It is concluded that the surfaces of the modified samples retain the ability to form hydrogen bonds.

  8. First-principles investigation of armchair boron nitride nanoribbons for sensing PH3 gas molecules

    NASA Astrophysics Data System (ADS)

    Srivastava, Pankaj; Jaiswal, Neeraj K.; Sharma, Varun

    2014-09-01

    The present work exhibits density functional theory (DFT) based first-principles calculations to explore the sensing properties of bare armchair boron nitride nanoribbons (ABNNR) for PH3 gas molecules. Edges of the ribbon were considered as the sites of possible adsorption with two different configurations i.e. adsorption at one edge and adsorption at both edges of the ribbon. It is revealed that B atoms of the ribbons are more energetically favorable sites for the adsorption of PH3 molecules as compared with N atoms. The adsorption of PH3 affects the electronic properties of nanoribbons. One edge PH3 adsorbed ribbons are metallic whereas in both edges PH3 adsorption, the band gap is decreased than that of bare ribbon. The changes in electronic properties caused by PH3 adsorption are further supported by the current-voltage (I-V) characteristics of the considered configurations. The results show that ABNNR can serve as a potential candidate for PH3 sensing applications.

  9. Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces

    NASA Astrophysics Data System (ADS)

    Dey, S.; Banik, M.; Hulkko, E.; Rodriguez, K.; Apkarian, V. A.; Galperin, M.; Nitzan, A.

    2016-01-01

    Surface-enhanced Raman scattering (SERS) from bipyridyl ethylene adsorbed on gold dumbbells shows Fano-like spectra at high incident light intensity. This is accompanied by an increased electronic temperature, while no vibrational anti-Stokes scattering is observed. Theory indicates that interference between vibrational and electronic Raman scattering can yield such asymmetric scattering lineshapes. The best fit to observations is however obtained by disregarding this coupling and accounting for the detailed lineshape of the continuous electronic component of the SERS.

  10. Novel synthesis of bismuth-based adsorbents for the removal of 129I in off-gas

    NASA Astrophysics Data System (ADS)

    Yang, Jae Hwan; Shin, Jin Myeong; Park, Jang Jin; Park, Geun Il; Yim, Man Sung

    2015-02-01

    New adsorbents based on bismuth were investigated for the capture of iodine-129 (129I) in off-gas produced from spent fuel reprocessing. Porous bulky materials were synthesized with polyvinyl alcohol (PVA) as a sacrificial template. Our findings showed that the iodine trapping capacity of as-synthesized samples could reach 1.9-fold that of commercial silver-exchanged zeolite (AgX). The thermodynamic stability of the reaction products explains the high removal efficiency of iodine. We also found that the pore volume of each sample was closely related to the ratio of the reaction products.

  11. Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?

    PubMed

    Aleksandrov, Hristiyan A; Neyman, Konstantin M; Hadjiivanov, Konstantin I; Vayssilov, Georgi N

    2016-08-10

    The paper addresses possible ambiguities in the determination of the state of platinum species by the stretching frequency of a CO probe, which is a common technique for characterization of platinum-containing catalytic systems. We present a comprehensive comparison of the available experimental data with our theoretical modeling (density functional) results of pertinent systems - platinum surfaces, nanoparticles and clusters as well as reduced or oxidized platinum moieties on a ceria support. Our results for CO adsorbed on-top on metallic Pt(0), with C-O vibrational frequencies in the region 2018-2077 cm(-1), suggest that a decrease of the coordination number of the platinum atom, to which CO is bound, by one lowers the CO frequency by about 7 cm(-1). This trend corroborates the Kappers-van der Maas correlation derived from the analysis of the experimental stretching frequency of CO adsorbed on platinum-containing samples on different supports. We also analyzed the effect of the charge of platinum species on the CO frequency. Based on the calculated vibrational frequencies of CO in various model systems, we concluded that the actual state of the platinum species may be mistaken based only on the measured value of the C-O vibrational frequency due to overlapping regions of frequencies corresponding to different types of species. In order to identify the actual state of platinum species one has to combine this powerful technique with other approaches. PMID:27444400

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

    SciTech Connect

    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.

  13. Adsorption of two gas molecules at a single metal site in a metal-organic framework.

    PubMed

    Runčevski, Tomče; Kapelewski, Matthew T; Torres-Gavosto, Rodolfo M; Tarver, Jacob D; Brown, Craig M; Long, Jeffrey R

    2016-07-01

    One strategy to markedly increase the gas storage capacity of metal-organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules-specifically hydrogen, methane, or carbon dioxide. PMID:27284590

  14. Adsorption of two gas molecules at a single metal site in a metal–organic framework

    SciTech Connect

    Runčevski, Tomče; Kapelewski, Matthew T.; Torres-Gavosto, Rodolfo M.; Tarver, Jacob D.; Brown, Craig M.; Long, Jeffrey R.

    2016-01-01

    One strategy to markedly increase the gas storage capacity of metal-organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules--specifically hydrogen, methane, or carbon dioxide.

  15. Conformations of polyaniline molecules adsorbed on Au(111) probed by in situ STM and ex situ XPS and NEXAFS.

    PubMed

    Lee, YiHui; Chang, ChinZen; Yau, ShuehLin; Fan, LiangJen; Yang, YawWen; Yang, LiangYueh Ou; Itaya, Kingo

    2009-05-13

    In situ scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) have been used to examine the conformation of a monolayer of polyaniline (PAN) molecules produced on a Au(111) single-crystal electrode by anodization at 1.0 V [vs reversible hydrogen electrode (RHE)] in 0.10 M H(2)SO(4) containing 0.030 M aniline. The as-produced PAN molecules took on a well-defined linear conformation stretching for 500 A or more, as shown by in situ and ex situ STM. The XPS and NEXAFS results indicated that the linear PAN seen at 1.0 V assumed the form of an emeraldine salt made of PAN chains and (bi)sulfate anions. Shifting the potential from 1.0 to 0.7 V altered the shape of the PAN molecules from straight to crooked, which was ascribed to restructuring of the Au(111) electrified interface on the basis of voltammetric and XPS results. In situ STM showed that further decreasing the potential to 0.5 V transformed the crooked PAN threads into a mostly linear form again, with preferential alignment and formation of some locally ordered structures. PAN molecules could be reduced from emeraldine to leucoemeraldine as the potential was decreased to 0.2 V or less. In situ STM showed that the fully reduced PAN molecules were straight but mysteriously shortened to approximately 50 A in length. The conformation of PAN did not recuperate when the potential was shifted positively to 1.0 V. PMID:19361217

  16. Adsorption of CO2 from flue gas streams by a highly efficient and stable aminosilica adsorbent.

    PubMed

    Liu, Shou-Heng; Lin, Yuan-Chung; Chien, Yi-Chi; Hyu, Han-Ren

    2011-02-01

    Three ordered mesoporous silicas (OMSs) with different pore sizes and pore architectures were prepared and modified with amine functional groups by a postgrafting method. The carbon dioxide (CO2) adsorption on these amine-modified OMSs was measured by using microbalances at 348 K, and their adsorption capacities were found to be 0.2-1.4 mmol g(-1) under ambient pressure using dry 15% CO2. It was found experimentally that the CO2 adsorption capacity and adsorption rate were attributed to the density of amine groups and pore volume, respectively. A simple method is described for the production of densely anchored amine groups on a solid adsorbent invoking direct incorporation of tetraethylenepentamine onto the as-synthesized OMSs. Unlike conventional amine-modified OMSs, which typically show CO2 adsorption capacity less than 2 mmol g(-1), such organic template occluded amine-OMS composites possessed remarkably high CO2 uptake of approximately 4.6 mmol g(-1) at 348 K and 1 atm for a dry 15% CO2/nitrogen feed mixture. The enhancement of 8% in CO2 adsorption capacity was also observed in the presence of 10.6% water vapor. Durability tests done by cyclic adsorption-desorption revealed that these adsorbents also possess excellent stability. PMID:21387939

  17. David Adler Lectureship Award Talk: Friction and energy dissipation mechanisms in adsorbed molecules and molecularly thin films

    NASA Astrophysics Data System (ADS)

    Krim, Jacqueline

    2015-03-01

    Studies of the fundamental origins of friction have undergone rapid progress in recent years, with the development of new experimental and computational techniques for measuring and simulating friction at atomic length and time scales. The increased interest has sparked a variety of discussions and debates concerning the nature of the atomic-scale and quantum mechanisms that dominate the dissipative process by which mechanical energy is transformed into heat. Measurements of the sliding friction of physisorbed monolayers and bilayers can provide information on the relative contributions of these various dissipative mechanisms. Adsorbed films, whether intentionally applied or present as trace levels of physisorbed contaminants, moreover are ubiquitous at virtually all surfaces. As such, they impact a wide range of applications whose progress depends on precise control and/or knowledge of surface diffusion processes. Examples include nanoscale assembly, directed transport of Brownian particles, material flow through restricted geometries such as graphene membranes and molecular sieves, passivation and edge effects in carbon-based lubricants, and the stability of granular materials associated with frictional and frictionless contacts. Work supported by NSFDMR1310456.

  18. Conductivity Measurements of Pyrrole Molecules Incorporated into Chemically Adsorbed Monolayer by Conducting Probe Technique in Atomic Force Microscope

    NASA Astrophysics Data System (ADS)

    Yamamoto, Shin‑ichi; Ogawa, Kazufumi

    2006-03-01

    A monomolecular layer containing pyrrolyl groups at the surface was prepared between two parallel Pt electrodes on a glass substrate by a chemical adsorption technique using N-[11-(trichlorosilyl)undecyl] pyrrole (PNN). Then, the pyrrolyl was polymerized with pure water by applying a DC voltage of 10 V between the two Pt electrodes. It was confirmed using an optical microscope that many electric paths were formed between the two Pt electrodes by a decoration technique using electrochemical polymerization in an aqueous medium containing pyrrole after the polymerization. Next, a conductive probe of an atomic force microscope (AFM) was used to examine an electrical polymerized path through the surface of the polypyrrolyl group in a chemically adsorbed monomolecular layer. The resistance of one electric path in the monomolecular layer was measured using an AFM with an attached Au-covered tip at room temperature. With a measurement volume of about 0.2 nm (the thickness of the electric path in the monomolecular layer) × 200 μm (the average width of the electric path) × 100 μm (the distance between the Pt electrode and the Au-covered AFM tip), the resistance at room temperature of one electric path was 4 k Ω under ambient conditions. From the results in the atmosphere, the conductivity of a super long conjugated polypyrrolyl group without any dopant in a lateral direction was ohmically estimated to be at least 6.0 × 105 S/m.

  19. On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

    NASA Astrophysics Data System (ADS)

    Gao, Yi; Galperin, Michael; Nitzan, Abraham

    2016-06-01

    Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases when the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.

  20. Orbital tomography: Molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules

    PubMed Central

    Offenbacher, Hannes; Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Puschnig, Peter; Ramsey, Michael G.

    2015-01-01

    The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be presented. From the band maps it will be concluded that the molecule is planarised and adopts a tilted geometry. Finally the momentum maps down to HOMO-11 will be analysed and real space orbitals reconstructed. PMID:26752804

  1. Comparison of nutshell granular activated carbons to commercial adsorbents for the purge-and-trap gas chromatographic analysis of volatile organic compounds.

    PubMed

    Wartelle, L H; Marshall, W E; Toles, C A; Johns, M M

    2000-05-26

    Granular activated carbons (GACs) made from agricultural by-products were investigated as adsorbents for short path thermal desorption gas chromatographic analysis of selected polar and nonpolar organic compounds. GACs made from macadamia nut, black walnut and hazelnut shells were compared to four commercially available adsorbents, namely, Tenax TA, Carboxen 569, Carbosieve SIII and coconut charcoal for their properties in purge-and-trap analysis. Adsorption values and breakthrough volumes were calculated for compounds from C3 and C6-C10. GACs derived from macadamia nut shells were found to adsorb and desorb between 80% (benzene) and 277% (ethylbenzene) more acetone (C3), benzene (C6), toluene (C7), ethyl- (C8), n-propyl- (C9), or sec.-butylbenzenes (C10) purged from water at the 100 ppb level than the commercial adsorbents tested. PMID:10893033

  2. Evaluation and Application of a Solid Adsorbent Method for Monitoring Exposure to Volatile Organic Compounds from Oil and Gas Operations.

    NASA Astrophysics Data System (ADS)

    Smith, K. R.; Helmig, D.; Thompson, C. R.; Wang, W.; Terrell, R. M.; Lewis, A. C.

    2014-12-01

    Residential communities are being increasingly impacted by emissions from oil and gas development and this has driven the need for simple, effective, and low-cost methods for air quality monitoring. Primary emissions from oil and gas production consist of volatile organic compounds (VOCs) ranging from the short chain alkanes and alkenes to aromatic and semi-volatile species; many of these are a concern from both an air quality and public health viewpoint, as they can lead to local ozone pollution and increased risk of cancer or respiratory illness. The fate of hydrocarbons once in the atmosphere is ultimately oxidation through to CO2 and water, adding to the greenhouse gas burden. Measurement techniques that are capable of identifying and quantifying the full range of primary emissions of concern are required to assess community exposure to air toxics and to better inform residents, as well as local and state legislators. Here, we present evaluation of a low-cost air monitoring technique using stainless steel diffusion cartridges containing multiple solid adsorbents. Over the course of a three-month period in summer of 2014, cartridges were deployed at five monitoring sites located around Boulder County in the Northern Colorado Front Range, and exposed to ambient air for periods of up to four days along with concurrent sampling using stainless steel SUMMA canisters. Samples collected with both methods were subsequently analyzed for VOCs by GC-FID and the results were compared to determine the accuracy and precision of the diffusion cartridge method. Results of this evaluation show that the diffusion cartridge method has the potential to be a simple and low-cost solution for widespread exposure monitoring in communities near oil and gas development regions. Such measurements may also provide supporting evidence on wider effects on greenhouse gas emissions from oil and gas development operations.

  3. Optical and electronic properties of SO2 molecule adsorbed on Si-doped (8, 0) boron nitride nanotube

    NASA Astrophysics Data System (ADS)

    Guo, Shuang-Shuang; Wei, Xiu-Mei; Zhang, Jian-Min; Zhu, Gang-Qiang; Guo, Wan-Jin

    2016-09-01

    The study of the optical properties of pristine BNNT, Si-doped BNNTs and SO2 molecule adsorption on Si-doped BNNTs is that, to our knowledge, few relevant research have ever been found. In this paper, the adsorption behaviors of Sulfur dioxide (SO2) molecule on Si-doped Boron nitride nanotubes (BNNTs) are investigated applying the first-principles calculations. The main contribution of this paper is that the foremost investigation for the optical properties of the pristine BNNT, Si-doped BNNTs and SO2 adsorption on Si-doped BNNTs. Additionally, the electronic properties and the structural properties are also presented. In our calculations of optical properties, the dielectric constant, the refractive index and the absorption coefficient are obtained. Comparing the pristine BNNT, our results indicate that, the blue-shifts (in the main peaks of the dielectric constant of SiB -BNNT and SO2-SiB -BNNT), and the red-shifts (in the main peaks of the refractive index of SiN -BNNT and SO2-SiN -BNNT) are appeared. Under these conditions, Si-doped BNNT and Si-doped BNNT with SO2 adsorption, the gaps are reduced both for the speculated optical band gaps and the electronic structure band gaps.

  4. Analysis of the Molecules Structure and Vertical Electron Affinity of Organic Gas Impact on Electric Strength

    NASA Astrophysics Data System (ADS)

    Jiao, Juntao; Xiao, Dengming; Zhao, Xiaoling; Deng, Yunkun

    2016-05-01

    It is necessary to find an efficient selection method to pre-analyze the gas electric strength from the perspective of molecule structure and the properties for finding the alternative gases to sulphur hexafluoride (SF6). As the properties of gas are determined by the gas molecule structure, the research on the relationship between the gas molecule structure and the electric strength can contribute to the gas pre-screening and new gas development. In this paper, we calculated the vertical electron affinity, molecule orbits distribution and orbits energy of gas molecules by the means of density functional theory (DFT) for the typical structures of organic gases and compared their electric strengths. By this method, we find part of the key properties of the molecule which are related to the electric strength, including the vertical electron affinity, the lowest unoccupied molecule orbit (LUMO) energy, molecule orbits distribution and negative-ion system energy. We also listed some molecule groups such as unsaturated carbons double bonds (C=C) and carbonitrile bonds (C≡N) which have high electric strength theoretically by this method. supported by National Natural Science Foundation of China (Nos. 51177101 and 51337006)

  5. Henry`s law gas-solid chromatography and correlations of virial coefficients for hydrocarbons, chlorofluorocarbons, ethers, and sulfur hexafluoride adsorbed onto carbon

    SciTech Connect

    Rybolt, T.R.; Epperson, M.T.; Weaver, H.W.; Thomas, H.E.; Clare, S.E.; Manning, B.M.; McClung, J.T.

    1995-07-01

    Gas-solid chromatography was used to determine the Henry`s law second gas-solid virial coefficients within the temperature range of 314--615 K for ethane, propane, butane, isobutane, pentane, hexane, heptane, chloromethane, dichloromethane, trichloromethane, tetrachloromethane, trichlorofluoromethane (Freon 11), chlorodifluoromethane (Freon 22), dichlorodifluoromethane (Freon 12), methyl ether, ethyl ether, and sulfur hexafluoride with Carbopack B, a microporous carbon adsorbent. The temperature dependence of the second gas-solid virial coefficients of these adsorbates was used in conjunction with analyses based on a graphical method, a single-surface numeric integration method, a single-surface analytic expression method, and a two-surface analytic expression method to determine the gas-solid interaction energies and other parameters. The interaction energies were correlated with a ratio of the critical temperature divided by the square root of the critical pressure. The four methods were compared in their abilities to successfully calculate second gas-solid virial coefficient values.

  6. THE APPLICATION OF HIGH RESOLUTION ELECTRON ENERGY LOSS SPECTROSCOPY TO THE CHARACTERIZATION OF ADSORBED MOLECULES ON RHODIUM SINGLE CRYSTAL SURFACES

    SciTech Connect

    Dubois, L.H.; Somorjai, G.A.

    1980-01-01

    The scattering of low energy electrons by metal surfaces has been studied for many years now. The electron's ease of generation and detection and high surface sensitivity (low penetration depth) make it an ideal probe for surface scientists. The impinging electron can interact with the surface in basically two ways: it can either elastically reflect (or diffract) from the surface without losing energy or lose a portion of it's incident energy and inelastically scatter. In this paper we will be concerned with only one of many possible inelastic scattering processes: the loss of the electron's energy to the vibrational modes of atoms and molecules chemisorbed on the surface. This technique is known as high resolution electron energy loss spectroscopy (or ELS, EELS, HRELS, HREELS, etc.).

  7. Collision cross section calculations for polyatomic ions considering rotating diatomic/linear gas molecules

    SciTech Connect

    Larriba-Andaluz, Carlos Hogan, Christopher J.

    2014-11-21

    Structural characterization of ions in the gas phase is facilitated by measurement of ion collision cross sections (CCS) using techniques such as ion mobility spectrometry. Further information is gained from CCS measurement when comparison is made between measurements and accurately predicted CCSs for model ion structures and the gas in which measurements are made. While diatomic gases, namely molecular nitrogen and air, are being used in CCS measurement with increasingly prevalency, the majority of studies in which measurements are compared to predictions use models in which gas molecules are spherical or non-rotating, which is not necessarily appropriate for diatomic gases. Here, we adapt a momentum transfer based CCS calculation approach to consider rotating, diatomic gas molecule collisions with polyatomic ions, and compare CCS predictions with a diatomic gas molecule to those made with a spherical gas molecular for model spherical ions, tetra-alkylammonium ions, and multiply charged polyethylene glycol ions. CCS calculations are performed using both specular-elastic and diffuse-inelastic collisions rules, which mimic negligible internal energy exchange and complete thermal accommodation, respectively, between gas molecule and ion. The influence of the long range ion-induced dipole potential on calculations is also examined with both gas molecule models. In large part we find that CCSs calculated with specular-elastic collision rules decrease, while they increase with diffuse-inelastic collision rules when using diatomic gas molecules. Results clearly show the structural model of both the ion and gas molecule, the potential energy field between ion and gas molecule, and finally the modeled degree of kinetic energy exchange between ion and gas molecule internal energy are coupled to one another in CCS calculations, and must be considered carefully to obtain results which agree with measurements.

  8. Collision cross section calculations for polyatomic ions considering rotating diatomic/linear gas molecules.

    PubMed

    Larriba-Andaluz, Carlos; Hogan, Christopher J

    2014-11-21

    Structural characterization of ions in the gas phase is facilitated by measurement of ion collision cross sections (CCS) using techniques such as ion mobility spectrometry. Further information is gained from CCS measurement when comparison is made between measurements and accurately predicted CCSs for model ion structures and the gas in which measurements are made. While diatomic gases, namely molecular nitrogen and air, are being used in CCS measurement with increasingly prevalency, the majority of studies in which measurements are compared to predictions use models in which gas molecules are spherical or non-rotating, which is not necessarily appropriate for diatomic gases. Here, we adapt a momentum transfer based CCS calculation approach to consider rotating, diatomic gas molecule collisions with polyatomic ions, and compare CCS predictions with a diatomic gas molecule to those made with a spherical gas molecular for model spherical ions, tetra-alkylammonium ions, and multiply charged polyethylene glycol ions. CCS calculations are performed using both specular-elastic and diffuse-inelastic collisions rules, which mimic negligible internal energy exchange and complete thermal accommodation, respectively, between gas molecule and ion. The influence of the long range ion-induced dipole potential on calculations is also examined with both gas molecule models. In large part we find that CCSs calculated with specular-elastic collision rules decrease, while they increase with diffuse-inelastic collision rules when using diatomic gas molecules. Results clearly show the structural model of both the ion and gas molecule, the potential energy field between ion and gas molecule, and finally the modeled degree of kinetic energy exchange between ion and gas molecule internal energy are coupled to one another in CCS calculations, and must be considered carefully to obtain results which agree with measurements. PMID:25416874

  9. Scrutinizing individual CoTPP molecule adsorbed on coinage metal surfaces from the interplay of STM experiment and theory

    NASA Astrophysics Data System (ADS)

    Houwaart, Torsten; Le Bahers, Tangui; Sautet, Philippe; Auwärter, Willi; Seufert, Knud; Barth, Johannes V.; Bocquet, Marie-Laure

    2015-05-01

    The cobalt tetraphenyl porphyrin (CoTPP) molecule and its adsorption on clean Cu and Ag surfaces are comparatively analyzed within the Density Functional Theory (DFT) framework. Different sets of exchange-correlation functionals - the Local Density Approximation (LDA) and the Gradient Generalized Approximation (along with the PBE functional and the semi-empirical Grimme's corrections of dispersion) - are compared. Two prominent structural adsorption properties are disclosed in all sets of calculations: an asymmetric saddle deformation of CoTPP with an enhanced tilting of the upwards bent pyrroles and a single adsorption site where the Co center occupies a bridge position and one molecular axis (along the direction of the lowered pair of opposite pyrroles) is aligned with the dense-packed < 1 1 bar 0 > substrate direction. The similarities between Cu(111) and Ag(111) surfaces extend to the interfacial electronic structure with similar electronic redistribution and molecular charging. However subtle differences between the two substrates are revealed with bias-dependent STM simulations, especially in the low-bias imaging range. The STM calculations underline the difficulty for the commonly used GGA + D2 DFT framework to quantitatively predict the energy positions of the frontier molecular orbitals (MOs).

  10. Heating of interstellar gas by large molecules or small grains

    SciTech Connect

    Lepp, S.; Dalgarno, A.

    1988-12-01

    The heating of the interstellar medium by photoelectric emission from large molecules or small grains is explored. Photodetachment of large negative ions may be a significant heat source in diffuse clouds. For an abundance of large molecules relative to hydrogen greater than 2 x 10 to the -7th, the heating rate from the photoelectrons produced in the photoionization of large molecules and the photodetachment of large molecular negative ions exceeds the standard grain-heating rate. Theoretical models have been used to infer the abundances of large molecules from the C(+)/C abundance ratios in the interstellar clouds toward Zeta Oph and Zeta Per. 33 references.

  11. Pyrolysis of blended animal manures to produce combustible gas and value-added charcoal adsorbent

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Blended swine solids, chicken litter, and rye grass were pyrolyzed using a skid-mounted sytem. Produced gas composition was analyzed for major hydrocarbons and S-containing compounds. Charcoal was analyzed for its surface functional groups, contact angles, HHV, and total element contents. Some of th...

  12. Adsorption of two gas molecules at a single metal site in a metal–organic framework

    SciTech Connect

    Runčevski, Tomče; Kapelewski, Matthew T.; Torres-Gavosto, Rodolfo M.; Tarver, Jacob D.; Brown, Craig M.; Long, Jeffrey R.

    2016-01-01

    One strategy to markedly increase the gas storage capacity of metal–organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules—specifically hydrogen, methane, or carbon dioxide.

  13. Dependence of Rare-Gas Adsorbate Dipole Moment on Substrate Work Function

    NASA Astrophysics Data System (ADS)

    Chen, Yen-Ching

    The distinctly different behaviors of rare gas adsorded on various metals has been a puzzle for more than two decades. On refractory metals, the deduction of the metal work functions is unexpectedly large, while on simple metals, the effect is nearly undetectably small. The "switching" theory proposed by Flynn and Chen explains the general trend of the substrate dependent work function change reasonably well and also produces the observed linear dependence of the induced dipole moment on the heat of adsorption. The present research is to provide further experimental evidence for the theory and mainly focuses on the simple metals to supplement the paucity of data in this area. The Kelvin method is adopted for the relative work function measurements on freshly evaporated samples: Al, Mg, and alkali metals. Samples were held at about 15(DEGREES)K inside a liquid He cooled shielding can. Belljar pressures rose typically into the 10('-9) Torr range during metal evaporation and fell back into the 10('-10) Torr range afterwards. The effective pressure around the samples was certainly much lower. Rare gas dopant, Xe, Kr or Ar, was successively added to one face of the Kelvin electrodes from a calibrated molecular beam, with intervening measurements. The other face was left intact as reference which was driven by a bimorph at a frequency near 145 Hz. The electronic sensitivity for the measurements is better than 0.2 meV at a response time of a few seconds. The coverage dependence of work function changes was measured and the Topping model was employed to deduce the effective polarizabilities and the initial dipole moments. The data obtained in this work as well as those reported recently in the literature provides further support to the proposed "switching" theory in explaining the work function change due to the rare gas absorption.

  14. Adsorbents for capturing mercury in coal-fired boiler flue gas.

    PubMed

    Yang, Hongqun; Xu, Zhenghe; Fan, Maohong; Bland, Alan E; Judkins, Roddie R

    2007-07-19

    This paper reviews recent advances in the research and development of sorbents used to capture mercury from coal-fired utility boiler flue gas. Mercury emissions are the source of serious health concerns. Worldwide mercury emissions from human activities are estimated to be 1000 to 6000 t/annum. Mercury emissions from coal-fired power plants are believed to be the largest source of anthropogenic mercury emissions. Mercury emissions from coal-fired utility boilers vary in total amount and speciation, depending on coal types, boiler operating conditions, and configurations of air pollution control devices (APCDs). The APCDs, such as fabric filter (FF) bag house, electrostatic precipitator (ESP), and wet flue gas desulfurization (FGD), can remove some particulate-bound and oxidized forms of mercury. Elemental mercury often escapes from these devices. Activated carbon injection upstream of a particulate control device has been shown to have the best potential to remove both elemental and oxidized mercury from the flue gas. For this paper, NORIT FGD activated carbon was extensively studied for its mercury adsorption behavior. Results from bench-, pilot- and field-scale studies, mercury adsorption by coal chars, and a case of lignite-burned mercury control were reviewed. Studies of brominated carbon, sulfur-impregnated carbon and chloride-impregnated carbon were also reviewed. Carbon substitutes, such as calcium sorbents, petroleum coke, zeolites and fly ash were analyzed for their mercury-adsorption performance. At this time, brominated activated carbon appears to be the best-performing mercury sorbent. A non-injection regenerable sorbent technology is briefly introduced herein, and the issue of mercury leachability is briefly covered. Future research directions are suggested. PMID:17544578

  15. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  16. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    SciTech Connect

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-28

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  17. Orientation Difference of Chemically Immobilized and Physically Adsorbed Biological Molecules on Polymers Detected at the Solid/Liquid Interfaces in Situ

    PubMed Central

    Ye, Shuji; Nguyen, Khoi Tan; Boughton, Andrew P.; Mello, Charlene M.; Chen, Zhan

    2009-01-01

    A surface sensitive second order nonlinear optical technique, sum frequency generation (SFG) vibrational spectroscopy, was applied to study peptide orientation on polymer surfaces, supplemented by a linear vibrational spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Using the antimicrobial peptide Cecropin P1 as a model system, we have quantitatively demonstrated that chemically immobilized peptides on polymers adopt a more ordered orientation than less tightly bound physically adsorbed peptides. These differences were also observed in different chemical environments, e.g., air versus water. Although numerous studies have reported a direct correlation between the choice of immobilization method and the performance of an attached biological molecule, the lack of direct biomolecular structure and orientation data has made it difficult to elucidate the relationship between structure, orientation and function at a surface. In this work, we directly studied the effect of chemical immobilization method on biomolecular orientation/ordering, an important step for future studies of biomolecular activity. The methods for orientation analysis described within are also of relevance to understanding biosensors, biocompatibility, marine-antifouling, membrane protein functions, and antimicrobial peptide activities. PMID:19961170

  18. Infrared Spectroscopy of Molecules in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Zhang, Keqing

    Fourier transform infrared spectroscopy is applied to the studies of several very different molecular systems. The spectra of the diatomic molecules BF, AlF, and MgF were recorded and analyzed. Dunham coefficients were obtained. The data of two isotopomers, 11BF and 10BF, were used to determine the mass-reduced Dunham coefficients, along with Born-Oppenheimer breakdown constants. Parameterized potential energy functions of BF and AlF were determined by fitting the available data using the solutions of the radial Schrodinger equation. Two vibrational modes of the short-lived and reactive BrCNO molecule were recorded at high resolution. Rotation-vibration transitions of the fundamental bands of both isotopomers 79BrCNO and 81BrCNO were assigned and analyzed. From the rotational constants, it was found that the Br-C bond length in BrCNO anomalously short when a linear geometry was assumed. This may indicate that BrCNO is quasi-linear, simulating the parent HCNO molecule. The emission spectra of the gaseous polycyclic aromatic hydrocarbon (PAH) molecules naphthalene, anthracene, pyrene, and chrysene were recorded in the far-infrared and mid-infrared regions. The assignments of fundamental modes and some combination modes were made. The vibrational bands that lie in the far-infrared are unique for different PAHs and allow discrimination among the four PAH molecules. The far-infrared PAH spectra, therefore, may prove useful in the assignments of unidentified spectral features from astronomical objects.

  19. Direct Observation of a Gas Molecule (H2, Ar) Swallowed by C60

    SciTech Connect

    Sawa, H.; Kakiuchi, T.; Wakabayashi, Y.; Murata, Y.; Murata, M.; Komatsu, K.; Yakigaya, K.; Takagi, H.; Dragoe, N.

    2007-01-19

    Various types of endohedral fullerene complexes are known to date. The well known metallofullerenes are generally produced by arc-discharge method, but the use of such extremely drastic conditions is apparently not suitable for encapsulation of unstable molecules or gases. We recently succeeded in incorporation of a H2 molecule or an Ar atom in 100% into a C60. In order to observe the endohedral gas molecule directly, the X-ray diffraction analysis using synchrotron radiation were carried out. We observed a gas molecule encapsulated in each fullerene cage using structure analysis and the maximum entropy method. These gas molecules are floating inside of the hollow cavities and are completely isolated from the outside.

  20. Carbon-supported ionic liquids as innovative adsorbents for CO₂ separation from synthetic flue-gas.

    PubMed

    Erto, Alessandro; Silvestre-Albero, Ana; Silvestre-Albero, Joaquín; Rodríguez-Reinoso, Francisco; Balsamo, Marco; Lancia, Amedeo; Montagnaro, Fabio

    2015-06-15

    Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization. PMID:25710387

  1. Separation and analysis of trace volatile formaldehyde in aquatic products by a MoO₃/polypyrrole intercalative sampling adsorbent with thermal desorption gas chromatography and mass spectrometry.

    PubMed

    Ma, Yunjian; Zhao, Cheng; Zhan, Yisen; Li, Jianbin; Zhang, Zhuomin; Li, Gongke

    2015-05-01

    An in situ embedded synthesis strategy was developed for the preparation of a MoO3 /polypyrrole intercalative sampling adsorbent for the separation and analysis of trace volatile formaldehyde in aquatic products. Structural and morphological characteristics of the MoO3 /polypyrrole intercalative adsorbent were investigated by a series of characterization methods. The MoO3 /polypyrrole sampling adsorbent possessed a higher sampling capacity and selectivity for polar formaldehyde than commonly used commercial adsorbent Tenax TA. Finally, the MoO3 /polypyrrole adsorbent was packed in the thermal desorption tube that was directly coupled to gas chromatography with mass spectrometry for the analysis of trace volatile formaldehyde in aquatic products. Trace volatile formaldehyde from real aquatic products could be selectively sampled and quantified to be 0.43-6.6 mg/kg. The detection limit was achieved as 0.004 μg/L by this method. Good recoveries for spiked aquatic products were achieved in range of 75.0-108% with relative standard deviations of 1.2-9.0%. PMID:25677048

  2. Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's “A” and Herzberg-Teller contributions in the SERS spectra

    NASA Astrophysics Data System (ADS)

    Chowdhury, Joydeep; Chandra, Subhendu; Ghosh, Manash

    2015-01-01

    The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution.

  3. Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's "A" and Herzberg-Teller contributions in the SERS spectra.

    PubMed

    Chowdhury, Joydeep; Chandra, Subhendu; Ghosh, Manash

    2015-01-25

    The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution. PMID:25168230

  4. Adsorbed natural gas storage with activated carbons made from Illinois coals and scrap tires

    USGS Publications Warehouse

    Sun, Jielun; Brady, T.A.; Rood, M.J.; Lehmann, C.M.; Rostam-Abadi, M.; Lizzio, A.A.

    1997-01-01

    Activated carbons for natural gas storage were produced from Illinois bituminous coals (IBC-102 and IBC-106) and scrap tires by physical activation with steam or CO2 and by chemical activation with KOH, H3PO4, or ZnCl2. The products were characterized for N2-BET area, micropore volume, bulk density, pore size distribution, and volumetric methane storage capacity (Vm/Vs). Vm/Vs values for Illinois coal-derived carbons ranged from 54 to 83 cm3/cm3, which are 35-55% of a target value of 150 cm3/cm3. Both granular and pelletized carbons made with preoxidized Illinois coal gave higher micropore volumes and larger Vm/Vs values than those made without preoxidation. This confirmed that preoxidation is a desirable step in the production of carbons from caking materials. Pelletization of preoxidized IBC-106 coal, followed by steam activation, resulted in the highest Vm/Vs value. With roughly the same micropore volume, pelletization alone increased Vm/Vs of coal carbon by 10%. Tire-derived carbons had Vm/Vs values ranging from 44 to 53 cm3/cm3, lower than those of coal carbons due to their lower bulk densities. Pelletization of the tire carbons increased bulk density up to 160%. However, this increase was offset by a decrease in micropore volume of the pelletized materials, presumably due to the pellet binder. As a result, Vm/Vs values were about the same for granular and pelletized tire carbons. Compared with coal carbons, tire carbons had a higher percentage of mesopores and macropores.

  5. Chemical Potential of Triethylene Glycol Adsorbed on Surfaces Relevant to Gas Transport and Processing - Studies Using Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Kvamme, B.; Olsen, R.; Sjöblom, S.; Leirvik, K. N.; Kuznetsova, T.

    2014-12-01

    Natural gas will inevitably contain trace amounts of water and other impurities during different stages of processing and transport. Glycols, such as triethylene glycol (TEG), will in many cases follow the water. The glycol contents of the gas can originate from preceding glycol-drying units or it can be a residue from the direct injection of glycols used to prevent hydrate formation. Thus, it is important to know how glycol contents will affect the different paths leading to hydrate formation. Glycols may in some cases dominate the condensed water phase. If this occurs, it will lead to the well-documented shift in the hydrate stability curve, due to the altered activity of the water. A great deal of information on the molecular path of a glycol through the system can be obtained from calculating the chemical potential. Due to difficulties in measuring interfacial chemical potentials, these often need to be estimated using theoretical tools. We used molecular dynamics (MD) to study how TEG behaves in the vicinity of mineral surfaces such as calcite and hematite. Many methods exist for estimating chemical potentials based on MD trajectories. These include techniques such as free energy perturbation theory (FEP) and thermodynamic integration (TI). Such methods require sufficient sampling of configurations where free energy is to be estimated. Thus, it can be difficult to estimate chemical potentials on surfaces. There are several methods to circumvent this problem, such as blue moon sampling and umbrella sampling. These have been considered and the most important have been used to estimate chemical potentials of TEG adsorbed on the mineral surfaces. The resulting chemical potentials were compared to the chemical potential of TEG in bulk water, which was estimated using temperature thermodynamic integration.

  6. Interaction of various gas molecules with paddle-wheel-type open metal sites of porous coordination polymers: theoretical investigation.

    PubMed

    Hijikata, Yuh; Sakaki, Shigeyoshi

    2014-03-01

    We theoretically evaluated binding energies (Eb's) between various gas molecules and the Cu center open metal site (Cu-OMS) of Cu paddle-wheel units, [Cu2(O2CR)4] (R = H, Me, or Ph) using density functional theory (DFT) and MP2-MP4. The optimized geometry of the model system [Cu2(O2CPh)4] agrees with the experimental structure. The Eb of CO with [Cu2(O2CH)4] is only slightly different between the open-shell singlet and triplet states. The calculated Eb decreases in the order MeNC > H2O > MeCN > C2H4 > C2H2 > CO > CO2 > N2 > CH4 > H2. The trend is discussed in terms of the electrostatic interaction energy (ES), exchange repulsion energy (EX), and charge-transfer (CT) + polarization (Pol) interaction energy at the Hartree-Fock level and the electron correlation effect. The ES increases linearly with an increase in Eb, while the EX decreases linearly with an increase in Eb. These relationships indicate that the ES compensates for the EX. In other words, the Eb does not depend on the sum of ES and EX, which corresponds to the static energy. The electron correlation effect contributes little to the above-mentioned decreasing order of Eb. The total Eb roughly increases with an increase in the CT+Pol term, suggesting that the CT+Pol term plays important roles in determining the trend of Eb. The shift of the stretching frequency of adsorbed gas molecules on the Cu-OMS is reproduced well by the DFT calculation with the model system [Cu2(O2CH)4(L)2] (L = gas molecule). We found that the positive charge on the Cu significantly contributes to the shift in the end-on coordination gas molecules such as CO, MeNC, MeCN, and N2. Although the shift has been generally discussed in terms of donation and back-donation, the present result indicates that the electrostatic potential field in the porous coordination polymer should be considered in the discussion of the frequency shift. PMID:24512503

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

    PubMed

    Mychaskiw, George

    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

  8. 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

  9. Understanding and controlling laser-matter interactions: From solvated dye molecules to polyatomic molecules in gas phase

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha

    The goal of my research is to obtain a better understanding of the various processes that occur during and following laser-matter interactions from both the physical and chemical point of view. In particular I focused my research on understanding two very important aspects of laser-matter interaction; 1) Intense laser-matter interactions for polyatomic molecules in the gas phase in order to determine to what extent processes like excitation, ionization and fragmentation can be controlled by modifying the phase and amplitude of the laser field according to the timescales for electronic, vibrational and rotational energy transfer. 2) Developing pulse shaping based single beam methods aimed at studying solvated molecules in order to elucidate processes like inhomogeneous broadening, solvatochromic shift and to determine the electronic coherence lifetimes of solvated molecules. The effect of the chirped femtosecond pulses on fluorescence and stimulated emission from solvated dye molecules was studied and it was observed that the overall effect depends quadratically on pulse energy, even where excitation probabilities range from 0.02 to 5%, in the so-called "linear excitation regime". The shape of the chirp dependence is found to be independent of the energy of the pulse. It was found that the chirp dependence reveals dynamics related to solvent rearrangement following excitation and also depends on electronic relaxation of the chromophore. Furthermore, the chirped pulses were found to be extremely sensitive to solvent environment and that the complementary phases having the opposite sign provide information about the electronic coherence lifetimes. Similar to chirped pulses, the effects of a phase step on the excitation spectrum and the corresponding changes to the stimulated emission spectrum were also studied and it was found that the coherent feature on the spectrum is sensitive to the dephasing time of the system. Therefore a single phase scanning method can

  10. Organic molecules in the gas phase of dense interstellar clouds.

    PubMed

    Irvine, W M

    1995-03-01

    Since a previous COSPAR review on this subject, the number of molecular species identified by astronomers in dense interstellar clouds or in the envelopes expelled by evolved stars has grown from about eighty to approximately one hundred. Recent detections in stellar envelopes include the radical CP, the second phosphorus-containing astronomical molecule; SiN, the first astronomical molecule with a Si-N bond; and the HCCN radical. In the dense interstellar clouds recent detections or verifications of previous possible identifications include the H3O+ ion, which is a critical intermediary in the production of H2O and O2; the CCO radical, which is isoelectronic with HCCN; the SO+ ion, which appears to be diagnostic of shock chemistry; two new isomers of cyanoacetylene, HCCNC and CCCNH; and the two cumulenes H2C3 and H2C4. Some recent work is also described on the mapping of interstellar clouds in multiple molecular transitions in order to separate variations in chemical abundance from gradients in physical parameters. PMID:11539249

  11. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  12. GAS-PHASE MOLECULAR DYNAMICS: VIBRATIONAL DYNAMICS OF POLYATOMIC MOLECULES

    SciTech Connect

    MUCKERMAN,J.T.

    1999-06-09

    The goal of this research is the understanding of elementary chemical and physical processes important in the combustion of fossil fuels. Interest centers on reactions and properties of short-lived chemical intermediates. High-resolution, high-sensitivity, laser absorption methods are augmented by high-temperature, flow-tube reaction kinetics studies with mass-spectrometric sampling. These experiments provide information on the energy levels, structures and reactivity of molecular free radical species and, in turn, provide new tools for the study of energy flow and chemical bond cleavage in radicals involved in chemical systems. The experimental work is supported by theoretical studies using time-dependent quantum wavepacket calculations, which provide insight into energy flow among the vibrational modes of polyatomic molecules and interference effects in multiple-surface dynamics.

  13. Gas-Phase Molecular Dynamics: Vibrational Dynamics of Polyatomic Molecules

    SciTech Connect

    Muckerman, J.T.

    1999-05-21

    The goal of this research is the understanding of elementary chemical and physical processes important in the combustion of fossil fuels. Interest centers on reactions and properties of short-lived chemical intermediates. High-resolution, high-sensitivity, laser absorption methods are augmented by high- temperature, flow-tube reaction kinetics studies with mass-spectrometic sampling. These experiments provide information on the energy levels, structures and reactivity of molecular free radical species and in turn, provide new tools for the study of energy flow and chemical bond cleavage in the radicals involved in chemical systems. The experimental work is supported by theoretical studies using time-dependent quantum wavepacket calculations, which provide insight into energy flow among the vibrational modes of polyatomic molecules and interference effects in multiple-surface dynamics.

  14. Adsorption and Gas Separation of Molecules by Carbon Nanohorns.

    PubMed

    Gatica, Silvina M; Nekhai, Anton; Scrivener, Adam

    2016-01-01

    In this paper, we report the results of Monte Carlo simulations of the adsorption of neon, argon, methane and carbon dioxide in carbon nanohorns. We model the nanohorns as an array of carbon cones and obtained adsorption isotherms and isosteric heats. The main sites of adsorption are inside the cones and in the interstices between three cones. We also calculated the selectivity of carbon dioxide/methane, finding that nanohorns are a suitable substrate for gas separation. Our simulations are compared to available experimental data. PMID:27213313

  15. Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

    SciTech Connect

    Ogletree, D.F.

    1986-11-01

    LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2..sqrt..3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (..sqrt..3 x ..sqrt..3) reconstruction on the (111) face of the ..cap alpha..-CuAl alloy has been determined.

  16. Creation of a low-entropy quantum gas of polar molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    Moses, Steven A.; Covey, Jacob P.; Miecnikowski, Matthew T.; Yan, Bo; Gadway, Bryce; Ye, Jun; Jin, Deborah S.

    2015-11-01

    Ultracold polar molecules, with their long-range electric dipolar interactions, offer a unique platform for studying correlated quantum many-body phenomena. However, realizing a highly degenerate quantum gas of molecules with a low entropy per particle is challenging. We report the synthesis of a low-entropy quantum gas of potassium-rubidium molecules (KRb) in a three-dimensional optical lattice. We simultaneously load into the optical lattice a Mott insulator of bosonic Rb atoms and a single-band insulator of fermionic K atoms. Then, using magnetoassociation and optical state transfer, we efficiently produce ground-state molecules in the lattice at those sites that contain one Rb and one K atom. The achieved filling fraction of 25% should enable future studies of transport and entanglement propagation in a many-body system with long-range dipolar interactions.

  17. Creation of a low-entropy quantum gas of polar molecules in an optical lattice.

    PubMed

    Moses, Steven A; Covey, Jacob P; Miecnikowski, Matthew T; Yan, Bo; Gadway, Bryce; Ye, Jun; Jin, Deborah S

    2015-11-01

    Ultracold polar molecules, with their long-range electric dipolar interactions, offer a unique platform for studying correlated quantum many-body phenomena. However, realizing a highly degenerate quantum gas of molecules with a low entropy per particle is challenging. We report the synthesis of a low-entropy quantum gas of potassium-rubidium molecules (KRb) in a three-dimensional optical lattice. We simultaneously load into the optical lattice a Mott insulator of bosonic Rb atoms and a single-band insulator of fermionic K atoms. Then, using magnetoassociation and optical state transfer, we efficiently produce ground-state molecules in the lattice at those sites that contain one Rb and one K atom. The achieved filling fraction of 25% should enable future studies of transport and entanglement propagation in a many-body system with long-range dipolar interactions. PMID:26542566

  18. Superhard Coatings Synthesis Assisted by Pulsed Beams of High-Energy Gas Molecules

    NASA Astrophysics Data System (ADS)

    Metel, Alexander; Bolbukov, Vasily; Volosova, Marina; Grigoriev, Sergei; Melnik, Yury; Department of high-efficiency machining technologies Team

    2015-09-01

    For production of nanocomposite superhard (HV 5000) and fracture-tough coatings on dielectric substrates a source of metal atoms accompanied by pulsed beams of 30-keV neutral molecules was used. The source is equipped with two parallel equipotential grids placed between a magnetron target and a substrate. Negative high-voltage pulses applied to the high-transparency grids accelerate from the magnetron plasma ions, which are transformed into high-energy neutral molecules due to charge-exchange collisions with gas molecules between the grids. Mixing of the substrate and coating materials through bombardment by high-energy gas molecules results in an adequate compressive stress of the coating and interface width exceeding 1 μm, which allows deposition of 100- μm-thick coatings with a perfect adhesion. The work was supported by the Grant No. 14-29-00297 of the Russian Science Foundation.

  19. Formation of van der Waals molecules in buffer-gas-cooled magnetic traps [corrected].

    PubMed

    Brahms, N; Tscherbul, T V; Zhang, P; Kłos, J; Sadeghpour, H R; Dalgarno, A; Doyle, J M; Walker, T G

    2010-07-16

    We predict that a large class of helium-containing cold polar molecules form readily in a cryogenic buffer gas, achieving densities as high as 10(12)  cm(-3). We explore the spin relaxation of these molecules in buffer-gas-loaded magnetic traps and identify a loss mechanism based on Landau-Zener transitions arising from the anisotropic hyperfine interaction. Our results show that the recently observed strong T(-6) thermal dependence of the spin-change rate of silver (Ag) trapped in dense (3)He is accounted for by the formation and spin change of Ag(3)He van der Waals molecules, thus providing indirect evidence for molecular formation in a buffer-gas trap. PMID:20867761

  20. Nonequilibrium vibrational excitation of molecules behind a shock front in a gas mixture

    NASA Astrophysics Data System (ADS)

    Dobkin, S. V.; Son, E. E.

    1981-10-01

    It is shown that when a shock wave propagates in a light gas with a small admixture of heavy gas, the nonequilibrium vibrational excitation of molecules of the heavy gas can occur. In this case, the vibrational temperature can increase to values exceeding the gas temperature behind the shock wave, in contrast to the equilibrium case. Vibrational energy in a shock wave in a mixture of helium and uranium hexafluoride is calculated as an example. The possibility of experimentally observing this effect is discussed.

  1. Momentum resolved electron stimulated desorption ion angular distribution, a new technique, probing the low frequency motion of adsorbed molecules on single crystal surfaces

    SciTech Connect

    Ahner, J.; Mocuta, D.; Yates, J.T. Jr.

    1999-07-01

    A new technique, momentum resolved electron stimulated desorption ion angular distribution (ESDIAD), provides a method for taking snapshots of the zero-point position and lateral momentum of particles adsorbed on crystalline surfaces. By employing state-of-the-art electronics and computer technology it is possible to record for each desorbing particle the desorption direction together with the flight time. High momentum and directional resolved images are obtained, with time-of-flight resolution in the picosecond range and data acquisition rates up to 100 kHz. This enables us to deconvolute spatial and momentum contributions to the ESDIAD pattern and to map the low frequency motion of the adsorbed particles. These maps reflect the adsorbate interactions with the substrate and with neighboring species on the substrate. For selected examples it is demonstrated that by measuring the three dimensional momentum vector for each desorbing particle it is possible to probe the lowest energy states of adsorbed species, as well as to measure the momentum distribution when the adsorbed species gains thermal energy. Such information can be used as a basis for thinking about anisotropies in lateral motion of particles on surfaces. One major opportunity involves the study of dissimilar chemisorbed species which, when imaged together in momentum and real space, give new insights into the first stages of interaction between the species, leading ultimately to a chemical reaction. {copyright} {ital 1999 American Vacuum Society.}

  2. Footprint organization of chiral molecules on metallic surfaces

    NASA Astrophysics Data System (ADS)

    Uñac, R. O.; Rabaza, A. V. Gil; Vidales, A. M.; Zgrablich, G.

    2007-10-01

    We study the behavior of chiral molecules adsorbed on clean metallic surfaces using a lattice-gas model and Monte Carlo simulation. The aim is to model and simulate the structure (footprints and organization) formed by molecules on the surface as they adsorb. The model, which is applicable to chiral species like S- and R-alanine, or similar, discloses the conditions to generate different ordered phases that have been observed in experiments by other authors. In our model, each enantiomer may adsorb in two different configurations (species) and several effects are taken into account: inhibition, blockage of neighboring adsorptive sites (steric effects) and promotion of sites representing, in some sense, modifications in the surface properties due to molecule-surface interactions. These adsorption rules are inspired by the enantiomeric character of adsorbed species. We perform a systematic study of the different phases formed in order to qualitatively understand the mechanism for the formation of adsorbate structures experimentally found by other authors.

  3. PAHs molecules and heating of the interstellar gas

    NASA Technical Reports Server (NTRS)

    Verstraete, Laurent; Leger, Alain; Dhendecourt, Louis B.; Dutuit, O.; Defourneau, D.

    1989-01-01

    Until now it has remained difficult to account for the rather high temperatures seen in many diffuse interstellar clouds. Various heating mechanisms have been considered: photoionization of minor species, ionization of H by cosmic rays, and photoelectric effect on small grains. Yet all these processes are either too weak or efficient under too restricting conditions to balance the observed cooling rates. A major heat source is thus still missing in the thermal balance of the diffuse gas. Using photoionization cross sections measured in the lab, it was shown that in order to balance the observed cooling rates in cold diffuse clouds (T approx. 80 K) the PAHs would have to contain 15 percent of the cosmic abundance of carbon. This value does not contradict the former estimation of 6 percent deduced from the IR emission bands since this latter is to be taken as a lower limit. Further, it was estimated that the contribution to the heating rate due to PAH's in a warm HI cloud, assuming the same PAH abundance as for a cold HI cloud, would represent a significant fraction of the value required to keep the medium in thermal balance. Thus, photoionization of PAHs might well be a major heat source for the cold and warm HI media.

  4. Composite thermochemistry of gas phase U(VI)-containing molecules

    SciTech Connect

    Bross, David H.; Peterson, Kirk A.

    2014-12-28

    Reaction energies have been calculated for a series of reactions involving UF{sub 6}, UO{sub 3}, UO{sub 2}(OH){sub 2}, and UO{sub 2}F{sub 2} using coupled cluster singles and doubles with perturbative triples, CCSD(T), with a series of correlation consistent basis sets, including newly developed pseudopotential (PP)- and all-electron (AE) Douglas-Kroll-Hess-based sets for the U atom. The energies were calculated using a Feller-Peterson-Dixon composite approach in which CCSD(T) complete basis set (CBS) limits were combined with a series of additive contributions for spin-orbit coupling, outer-core correlation, and quantum electrodynamics effects. The calculated reaction enthalpies (both PP and AE) were combined with the accurately known heat of formation of UF{sub 6} to determine the enthalpies of formation of UO{sub 3}, UO{sub 2}(OH){sub 2}, and UO{sub 2}F{sub 2}. The contribution to the reaction enthalpies due to correlation of the 5s5p5d electrons of U was observed to be very slowly convergent with basis set and at the CBS limit their impact on the final enthalpies was on the order of 1 kcal/mol or less. For these closed shell molecules, spin-orbit effects contributed about 1 kcal/mol to the final enthalpies. Interestingly, the PP and AE approaches yielded quite different spin-orbit contributions (similar magnitude but opposite in sign), but the total scalar plus spin-orbit results from the two approaches agreed to within ∼1 kcal/mol of each other. The final composite heat of formation for UO{sub 2}F{sub 2} was in excellent agreement with experiment, while the two results obtained for UO{sub 3} were just outside the ±2.4 kcal/mol error bars of the currently recommended experimental value. An improved enthalpy of formation (298 K) for UO{sub 2}(OH){sub 2} is predicted from this work to be −288.7 ± 3 kcal/mol, compared to the currently accepted experimental value of −292.7 ± 6 kcal/mol.

  5. Composite thermochemistry of gas phase U(VI)-containing molecules.

    PubMed

    Bross, David H; Peterson, Kirk A

    2014-12-28

    Reaction energies have been calculated for a series of reactions involving UF6, UO3, UO2(OH)2, and UO2F2 using coupled cluster singles and doubles with perturbative triples, CCSD(T), with a series of correlation consistent basis sets, including newly developed pseudopotential (PP)- and all-electron (AE) Douglas-Kroll-Hess-based sets for the U atom. The energies were calculated using a Feller-Peterson-Dixon composite approach in which CCSD(T) complete basis set (CBS) limits were combined with a series of additive contributions for spin-orbit coupling, outer-core correlation, and quantum electrodynamics effects. The calculated reaction enthalpies (both PP and AE) were combined with the accurately known heat of formation of UF6 to determine the enthalpies of formation of UO3, UO2(OH)2, and UO2F2. The contribution to the reaction enthalpies due to correlation of the 5s5p5d electrons of U was observed to be very slowly convergent with basis set and at the CBS limit their impact on the final enthalpies was on the order of 1 kcal/mol or less. For these closed shell molecules, spin-orbit effects contributed about 1 kcal/mol to the final enthalpies. Interestingly, the PP and AE approaches yielded quite different spin-orbit contributions (similar magnitude but opposite in sign), but the total scalar plus spin-orbit results from the two approaches agreed to within ∼1 kcal/mol of each other. The final composite heat of formation for UO2F2 was in excellent agreement with experiment, while the two results obtained for UO3 were just outside the ±2.4 kcal/mol error bars of the currently recommended experimental value. An improved enthalpy of formation (298 K) for UO2(OH)2 is predicted from this work to be -288.7 ± 3 kcal/mol, compared to the currently accepted experimental value of -292.7 ± 6 kcal/mol. PMID:25554152

  6. Site-selective patterning of organic luminescent molecules via gas phase deposition.

    PubMed

    Hao, Juanyuan; Lu, Nan; Wu, Qiong; Hu, Wei; Chen, Xiaodong; Zhang, Hongyu; Wu, Ying; Wang, Yue; Chi, Lifeng

    2008-05-20

    In this paper, we present a bottom-up approach to pattern organic luminescent molecules with a feature size down to sub-100 nm over wafer-sized areas. This method is based on the selective gas deposition of organic molecules on self-organized patterned structures, which consist of an organic monolayer with two different phases rather than different materials. The site selectivity is controllable by deposition rate and the pattern features. The reason for the site selectivity may be due to the nucleation and diffusion behaviors of the deposited organic molecules on different monolayer phases. PMID:18370416

  7. Creating a quantum degenerate gas of stable molecules via weak photoassociation

    NASA Astrophysics Data System (ADS)

    Mackie, Matt; Phou, Pierre

    2010-07-01

    Quantum degenerate molecules represent a new paradigm for fundamental studies and practical applications. Association of already quantum degenerate atoms into molecules provides a crucial shortcut around the difficulty of cooling molecules to ultracold temperatures. Whereas association can be induced with either laser or magnetic fields, photoassociation requires impractical laser intensity to overcome poor overlap between the atom pair and molecular wave functions, and experiments are currently restricted to magnetoassociation. Here we model realistic production of a quantum degenerate gas of stable molecules via two-photon photoassociation of Bose-condensed atoms. An adiabatic change of the laser frequency converts the initial atomic condensate almost entirely into stable molecular condensate, even for low-intensity lasers. Results for dipolar LiNa provide an upper bound on the necessary photoassociation laser intensity for alkali-metal atoms ~30 W/cm2, indicating a feasible path to quantum degenerate molecules beyond magnetoassociation.

  8. Volume shrinkage of a metal-organic framework host induced by the dispersive attraction of guest gas molecules.

    PubMed

    Joo, Jaeyong; Kim, Hyungjun; Han, Sang Soo

    2013-11-21

    Using a density functional theory calculation including van der Waals (vdW) corrections, we report that H2 adsorption in a cubic-crystalline microporous metal-organic framework (MOF-5) leads to volume shrinkage, which is in contrast to the intuition that gas adsorption in a confined system (e.g., pores in a material) increases the internal pressure and then leads to volumetric expansion. This extraordinary phenomenon is closely related to the vdW interactions between MOF and H2 along with the H2-H2 interaction, rather than the Madelung-type electrostatic interaction. At low temperatures, H2 molecules adsorbed in the MOF-5 form highly symmetrical interlinked nanocages that change from a cube-like shape to a sphere-like shape with H2 loading, helping to exert centrosymmetric forces and hydrostatic (volumetric) stresses from the collection of dispersive interactions. The generated internal negative stress is sufficient to overcome the stiffness of the MOF-5 which is a soft material with a low bulk modulus (15.54 GPa). PMID:24072185

  9. Screening Metal-Organic Frameworks by Analysis of Transient Breakthrough of Gas Mixtures in a Fixed Bed Adsorber

    SciTech Connect

    Krishna, Rajamani; Long, Jeffrey R.

    2011-07-07

    Metal–organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO₂ capture and H₂ purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing screening and ranking MOFs with regard to their anticipated performance in pressure swing adsorption (PSA) units. For this purpose, the most commonly used metrics are the adsorption selectivity and the working capacity. Here, we suggest an additional metric for comparing MOFs that is based on the analysis of the transient response of an adsorber to a step input of a gaseous mixture. For a chosen purity of the gaseous mixture exiting from the adsorber, a dimensionless breakthrough time τ{sub break} can be defined and determined; this metric determines the frequency of required regeneration and influences the productivity of a PSA unit. The values of τ{sub break} are dictated both by selectivity and by capacity metrics .By performing transient adsorber calculations for separation of CO₂/H₂, CO₂/CH₄, CH₄/H₂, and CO₂/CH₄/H₂ mixtures, we compare the values of τbreak to highlight some important advantages of MOFs over conventionally used adsorbents such as zeolite NaX. For a given separation duty, such comparisons provide a more realistic ranking of MOFs than afforded by either selectivity or capacity metrics alone. We conclude that breakthrough calculations can provide an essential tool for screening MOFs.

  10. Analyte induced water adsorbability in gas phase biosensors: the influence of ethinylestradiol on the water binding protein capacity.

    PubMed

    Snopok, Borys; Kruglenko, Ivanna

    2015-05-01

    An ultra-sensitive gas phase biosensor/tracer/bio-sniffer is an emerging technology platform designed to provide real-time information on air-borne analytes, or those in liquids, through classical headspace analysis. The desired bio-sniffer measures gaseous 17α- ethinylestradiol (ETED) as frequency changes on a quartz crystal microbalance (QCM), which is a result of the interactions of liquid sample components in the headspace (ETED and water) with a biorecognition layer. The latter was constructed by immobilization of polyclonal antiserum against a phenolic A-ring of estrogenic receptors through protein A. The QCM response exhibited stretched exponential kinetics of negative frequency shifts with reversible and "irreversible" components of mass uptake onto the sensor surface in static headspace conditions when exposed to water solutions of ETED over the sensor working range, from 10(-10) to 10(-17) g L(-1). It was shown that the variations in the QCM response characteristics are due to the change of the water-binding capacity of the sensing layer induced by protein transformations initiated by the binding of ETED molecules. This result is well correlated with the natural physiological function of estrogens in controlling the homeostasis of body fluids in living beings. PMID:25763411

  11. Quasiparticle excitations of adsorbates on doped graphene

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Wickenburg, Sebastian; Wong, Dillon; Karrasch, Christoph; Wang, Yang; Lu, Jiong; Omrani, Arash A.; Brar, Victor; Tsai, Hsin-Zon; Wu, Qiong; Corsetti, Fabiano; Mostofi, Arash; Kawakami, Roland K.; Moore, Joel; Zettl, Alex; Louie, Steven G.; Crommie, Mike

    Adsorbed atoms and molecules can modify the electronic structure of graphene, but in turn it is also possible to control the properties of adsorbates via the graphene substrate. In my talk, I will discuss the electronic structure of F4-TCNQ molecules on doped graphene and present a first-principles based theory of quasiparticle excitations that captures the interplay of doping-dependent image charge interactions between substrate and adsorbate and electron-electron interaction effects on the molecule. The resulting doping-dependent quasiparticle energies will be compared to experimental scanning tunnelling spectra. Finally, I will also discuss the effects of charged adsorbates on the electronic structure of doped graphene.

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

    NASA Astrophysics Data System (ADS)

    Adams, N. G.; Fondren, L. D.; McLain, J. L.; Jackson, D. M.

    Several ring compounds have been detected in interstellar gas clouds, ISC, including the aromatic, benzene. Polycyclic aromatic hydrocarbons, PAH's, have been implicated as carriers of diffuse interstellar bands (DIB's) 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 (C_5H_5N, C_4H_4N_2, C_5H_{11}N and C_4H_8O_2) has been tested in the laboratory using charge transfer excitation in ion-molecule reactions. The fragmentation paths, including production of C_4H_4^+, C_3H_3N^+ and HCN, suggest reverse routes to the parent molecules, which are presently under laboratory investigation as production sources.

  13. 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.

  14. A quantum gas of ground state molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    Danzl, Johann; Mark, Manfred; Haller, Elmar; Gustavsson, Mattias; Hart, Russell; Nägerl, Hanns-Christoph

    2009-05-01

    Ultracold samples of molecules are ideally suited for fundamental studies in physics and chemistry. For many of the proposed experiments full molecular state control and high phase space densities are needed. We create a dense quantum gas of ground state Cs2 molecules trapped at the wells of a 3D optical lattice, i.e. a molecular Mott-insulator-like state with ground state molecules with vibrational quantum number v = 0. We first efficiently produce weakly bound molecules with v 155 on a Feshbach resonance out of an atomic Mott-insulator state that is obtained from a Bose-Einstein condensate (BEC) of Cs atoms. These molecules are then (coherently) transferred to the ground state by two sequential two-photon STIRAP processes via the intermediate vibrational level v 73 ^1. The molecule production efficiency and the single-step STIRAP transfer efficiency reach 50% and 80%, respectively. We discuss the stability of the system and our progress towards the creation of a BEC of ground state molecules, which is expected to form when the molecular Mott-like state is ``melted'' upon lowering the lattice depth and releasing the molecules from the wells into a large volume trap. ^1J. G. Danzl, E. Haller, M. Gustavsson, M. Mark, R. Hart, N. Bouloufa, O. Dulieu, H. Ritsch, H.-C. Nägerl, Science 321, 1062 (2008).

  15. 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

  16. Bombardment of gas molecules on single graphene layer at high temperature

    NASA Astrophysics Data System (ADS)

    Murugesan, Ramki; Park, Jae Hyun; Ha, Dong Sung

    2014-12-01

    Graphite is widely used as a material for rocket-nozzle inserts due to its excellent thermo-physical properties as well as low density. During the operation of rockets, the surface of the graphite nozzle is subjected to very high heat fluxes and the undesirable erosion of the surface occurs due to the bombardment of gas molecules with high kinetic energy, which causes a significant reduction of nozzle performance. However, the understanding and quantification of such bombardment is not satisfactory due to its complexity: The bond breaking-forming happens simultaneously for the carbon atoms of graphene, some gas molecules penetrate through the surface, some of them are reflected from the surface, etc. In the present study, we perform extensive molecular dynamics (MD) simulations to examine the bombardment phenomena in high temperature environment (several thousand Kelvin). Advanced from the previous studies that have focused on the bombardment by light molecules (e.g., H2), we will concentrate on the impact by realistic molecules (e.g., CO2 and H2O ). LAMMPS is employed for the MD simulations with NVE ensemble and AIREBO potential for graphene. The molecular understanding of the interaction between graphene and highly energetic gas molecules will enable us to design an efficient thermo-mechanical protection system.

  17. Bombardment of gas molecules on single graphene layer at high temperature

    SciTech Connect

    Murugesan, Ramki; Park, Jae Hyun; Ha, Dong Sung

    2014-12-09

    Graphite is widely used as a material for rocket-nozzle inserts due to its excellent thermo-physical properties as well as low density. During the operation of rockets, the surface of the graphite nozzle is subjected to very high heat fluxes and the undesirable erosion of the surface occurs due to the bombardment of gas molecules with high kinetic energy, which causes a significant reduction of nozzle performance. However, the understanding and quantification of such bombardment is not satisfactory due to its complexity: The bond breaking-forming happens simultaneously for the carbon atoms of graphene, some gas molecules penetrate through the surface, some of them are reflected from the surface, etc. In the present study, we perform extensive molecular dynamics (MD) simulations to examine the bombardment phenomena in high temperature environment (several thousand Kelvin). Advanced from the previous studies that have focused on the bombardment by light molecules (e.g., H{sub 2}), we will concentrate on the impact by realistic molecules (e.g., CO{sub 2} and H{sub 2}O). LAMMPS is employed for the MD simulations with NVE ensemble and AIREBO potential for graphene. The molecular understanding of the interaction between graphene and highly energetic gas molecules will enable us to design an efficient thermo-mechanical protection system.

  18. A Gas Chromatography Experiment for Proving the Application of Quantum Symmetry Restrictions in Homonuclear Diatomic Molecules.

    ERIC Educational Resources Information Center

    Dosiere, M.

    1985-01-01

    Background information, procedures used, and typical results obtained are provided for an experiment in which gas chromatography is used to prove the application of quantum symmetry restrictions in homonuclear diatomic molecules. Comparisons between experimental results and theoretical computed values show good agreement, within one to two…

  19. Ground state of a hydrogen ion molecule immersed in an inhomogeneous electron gas

    NASA Astrophysics Data System (ADS)

    Diaz-Valdes, J.; Gutierrez, F. A.; Matamala, A. R.; Denton, C. D.; Vargas, P.; Valdes, J. E.

    2007-01-01

    In this work we have calculated the ground state energy of the hydrogen molecule, H2+, immersed in the highly inhomogeneous electron gas around a metallic surface within the local density approximation. The molecule is perturbed by the electron density of a crystalline surface of Au <1 0 0> with the internuclear axis parallel to the surface. The surface spatial electron density is calculated through a linearized band structure method (LMTO-DFT). The ground state of the molecule-ion was calculated using the Born-Oppenheimer approximation for a fixed-ion while the screening effects of the inhomogeneous electron gas are depicted by a Thomas-Fermi like electrostatic potential. We found that within our model the molecular ion dissociates at the critical distance of 2.35 a.u. from the first atomic layer of the solid.

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

    SciTech Connect

    White, Mark D.; Lee, Won Suk

    2014-05-14

    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 rapid 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

  1. Quantum mechanical computations and spectroscopy: from small rigid molecules in the gas phase to large flexible molecules in solution.

    PubMed

    Barone, Vincenzo; Improta, Roberto; Rega, Nadia

    2008-05-01

    Interpretation of structural properties and dynamic behavior of molecules in solution is of fundamental importance to understand their stability, chemical reactivity, and catalytic action. While information can be gained, in principle, by a variety of spectroscopic techniques, the interpretation of the rich indirect information that can be inferred from the analysis of experimental spectra is seldom straightforward because of the subtle interplay of several different effects, whose specific role is not easy to separate and evaluate. In such a complex scenario, theoretical studies can be very helpful at two different levels: (i) supporting and complementing experimental results to determine the structure of the target molecule starting from its spectral properties; (ii) dissecting and evaluating the role of different effects in determining the observed spectroscopic properties. This is the reason why computational spectroscopy is rapidly evolving from a highly specialized research field into a versatile and widespread tool for the assignment of experimental spectra and their interpretation in terms of chemical physical effects. In such a situation, it becomes important that both computationally and experimentally oriented chemists are aware that new methodological advances and integrated computational strategies are available, providing reliable estimates of fundamental spectral parameters not only for relatively small molecules in the gas phase but also for large and flexible molecules in condensed phases. In this Account, we review the most significant methodological contributions from our research group in this field, and by exploiting some recent results of their application to the computation of IR, UV-vis, NMR, and EPR spectral parameters, we discuss the microscopic mechanisms underlying solvent and vibrational effects on the spectral parameters. After reporting some recent achievements for the study of excited states by first principle quantum mechanical

  2. Enhancement of Sublimation of Single Graphene Layer by Interacting with Gas Molecules in Rarefied Environment

    NASA Astrophysics Data System (ADS)

    Murugesan, Ramki; Park, Jae Hyun

    2014-11-01

    Graphene has excellent mechanical properties. One of them is the resistance to high temperature environment. Since the sublimation temperature of graphene is over 4500 K, it has been used for diverse high temperature applications in order to protect the system. In this study, using extensive molecular dynamics simulations, we show that the sublimation of graphene could be enhanced (occurs at the lower temperature) by interacting with the gas molecules. With increase in temperature, the bonds in graphene becomes so sensitive to interact with the incoming gas molecules. When the temperature is low, the graphene is stable to the impingement of gas molecules: The light H2 gases are stick to the graphene surface and remains being attached while the heavy CO2 and H2O are bounced back from the surface. However, at high temperature H2 gases are absorbed on the graphene and destroy the C -C bonds by forming C -H bonds. The local breakage of bond at the impingement spot spreads the entire graphene soon, causing a complete sublimation. Even though the heavy CO2 and H2O molecules also break the C -C bonds at high temperature,but their impingement effect is localized and the breakage does not propagate over the entire surface. This research was supported by Agency for Defence Development (ADD).

  3. Organic molecules in ices and their release into the gas phase

    NASA Astrophysics Data System (ADS)

    Fayolle, Edith; Oberg, Karin I.; Garrod, Robin; van Dishoeck, Ewine; Rajappan, Mahesh; Bertin, Mathieu; Romanzin, Claire; Michaut, Xavier; Fillion, Jean-Hugues

    2015-08-01

    Organic molecules in the early stages of star formation are mainly produced in icy mantles surrounding interstellar dust grains. Identifying these complex organics and quantifying their abundance during the evolution of young stellar objects is of importance to understand the emergence of life. Simple molecules in ices, up to methanol in size, have been identified in the interstellar medium through their mid-IR vibrations, but band confusion prevents detections of more complex and less abundant organic molecules in interstellar ices. The presence of complex organics on grains can instead be indirectly inferred from observations of their rotational lines in the gas phase following ice sublimation.Thermal sublimation of protostellar ices occurs when icy grains flow toward a central protostar, resulting in the formation of a hot-core or a hot-corinos. The high degree of chemical complexity observed in these dense and warm regions can be the results of i) direct synthesis on the grains followed by desorption, but also to ii) the desorption of precursors from the ice followed by gas-phase chemistry. I will show how spatially resolved millimetric observations of hot cores and cooler protostellar environments, coupled to ice observations can help us pinpoint the ice or gas-phase origin of these organic species.Organic molecules have also recently been observed in cold environments where thermal desorption can be neglected. The presence of these cold molecules in the gas phase is most likely due to non-thermal desorption processes induced by, for e.g., photon-, electron-, cosmic-ray-irradiation, shock, exothermic reactions... I will present laboratory and observational efforts that push our current understanding of these non-thermal desorption processes and how they could be use to quantify the amount of organics in ices.

  4. Site-Specific Fragmentation of Polystyrene Molecule Using Size-Selected Ar Gas Cluster Ion Beam

    NASA Astrophysics Data System (ADS)

    Moritani, Kousuke; Mukai, Gen; Hashinokuchi, Michihiro; Mochiji, Kozo

    2009-04-01

    The secondary ion mass spectrum (SIMS) of a polystyrene thin film was investigated using a size-selected Ar gas cluster ion beam (GCIB). The fragmentation in the SIM spectrum varied by kinetic energy per atom (Eatom); the Eatom dependence of the secondary ion intensity of the fragment species of polystyrene can be essentially classified into three types based on the relationship between Eatom and the dissociation energy of a specific bonding site in the molecule. These results indicate that adjusting Eatom of size-selected GCIB may realize site-specific bond breaking within a molecule.

  5. Quantum Phase Transition Between a Luttinger Liquid and a Gas of Cold Molecules

    SciTech Connect

    Law, K. T.; Feldman, D. E.

    2008-08-29

    We consider cold polar molecules confined in a helical optical lattice similar to those used in holographic microfabrication. An external electric field polarizes molecules along the axis of the helix. The large-distance intermolecular dipolar interaction is attractive but the short-scale interaction is repulsive due to geometric constraints and thus prevents collapse. The interaction strength depends on the electric field. We show that a zero-temperature second-order liquid-gas transition occurs at a critical field. It can be observed under experimentally accessible conditions.

  6. Natural gas cleanup: Evaluation of a molecular sieve carbon as a pressure swing adsorbent for the separation of methane/nitrogen mixtures

    SciTech Connect

    Grimes, R.W.

    1994-06-01

    This report describes the results of a preliminary evaluation to determine the technical feasibility of using a molecular sieve carbon manufactured by the Takeda Chemical Company of Japan in a pressure owing adsorption cycle for upgrading natural gas (methane) contaminated with nitrogen. Adsorption tests were conducted using this adsorbent in two, four, and five-step adsorption cycles. Separation performance was evaluated in terms of product purity, product recovery, and sorbent productivity for all tests. The tests were conducted in a small, single-column adsorption apparatus that held 120 grams of the adsorbent. Test variables included adsorption pressure, pressurization rate, purge rate and volume, feed rate, and flow direction in the steps from which the product was collected. Sorbent regeneration was accomplished by purging the column with the feed gas mixture for all but one test series where a pure methane purge was used. The ratio between the volumes of the pressurization gas and the purge gas streams was found to be an important factor in determining separation performance. Flow rates in the various cycle steps had no significant effect. Countercurrent flow in the blow-down and purge steps improved separation performance. Separation performance appears to improve with increasing adsorption pressure, but because there are a number of interrelated variables that are also effected by pressure, further testing will be needed to verify this. The work demonstrates that a molecular sieve carbon can be used to separate a mixture of methane and nitrogen when used in a pressure swing cycle with regeneration by purge. Further work is needed to increase product purity and product recovery.

  7. Stability of metal organic frameworks and interaction of small gas molecules in these materials

    NASA Astrophysics Data System (ADS)

    Tan, Kui

    The work in this dissertation combines spectroscopy ( in-situ infrared absorption and Raman), powder X-ray diffraction and DFT calculations to study the stability of metal organic frameworks materials (MOFs) in the presence of water vapor and other corrosive gases (e.g., SO 2, NO2 NO), and the interaction and competitive co-adsorption of several gases within MOFs by considering two types of prototypical MOFs: 1) a MOF with saturated metal centers based on paddlewheel secondary building units: M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co, bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine], and 2) a MOF with unsaturated metal centers: M2(dobdc) [M=Mg2+, Zn2+, Ni2+, Co2+ and dobdc = 2,5-dihydroxybenzenedicarboxylate]. We find that the stability of MOFs to water vapor critically depends on their structure and the specific metal cation in the building units. For M(bdc)(ted)0.5, the metal-bdc bond is the most vulnerable for Cu(bdc)(ted)0.5, while the metal-ted bond is first attacked for the Zn and Co analogs. In contrast, Ni(bdc)(ted)0.5 remains stable under the same conditions. For M2(dobdc), or MOF-74, the weak link is the dobdc-metal bond. The water molecule is dissociatively adsorbed at the metal-oxygen group with OH adsorption directly on the metal center and H adsorption on the bridging O of the phenolate group in the dobdc linker. Other technologically important molecules besides water, such as NO, NO2, SO2, tend to poison M2(dobdc) through dissociative or molecular adsorption onto the open metal sites. A high uptake SO2 capacity was measured in M(bdc)(ted)0.5, attributed to multipoint interactions between the guest SO2 molecule and the MOF host. In the case of competitive co-adsorption between CO2 and other small molecules, we find that binding energy alone is not a good indicator of molecular site occupation within the MOF (i.e., it cannot successfully predict and evaluate the displacement of CO2 by other molecules). Instead, we show that the kinetic barrier for the

  8. Direct visual evidence for chemical mechanism of SERRS of the S-complex of pyrimidine molecule adsorbed on silver nanoparticle via charge transfer.

    PubMed

    Zhang, Xin; Wang, Peijie; Sheng, Shaoxiang; Zhang, Lisheng; Fang, Yan

    2014-01-01

    In this paper, the S-complex of pyrimidine molecule absorbed on silver clusters was employed as a model molecule to study the enhancement mechanism in surface-enhanced resonance Raman scattering (SERRS). We described the chemical enhancement of SERRS through charge transfer (CT) from Ag20 to pyrimidine on resonance excitation, and electromagnetic enhancement through intracluster charge redistribution (CR) on the electronic intracluster collective oscillation excitation. It is shown that SERRS process of the pyrimidine molecule absorbed on silver clusters with different incident wavelength are dominated by different enhancement mechanisms. Both experimental and theoretical works have been performed to understand the CT process in SERRS. PMID:24287052

  9. Intermediate energy proton stopping power for hydrogen molecules and monoatomic helium gas

    NASA Technical Reports Server (NTRS)

    Xu, Y. J.; Khandelwal, G. S.; Wilson, J. W.

    1984-01-01

    Stopping power in the intermediate energy region (100 keV to 1 MeV) was investigated, based on the work of Lindhard and Winther, and on the local plasma model. The theory is applied to calculate stopping power of hydrogen molecules and helium gas for protons of energy ranging from 100 keV to 2.5 MeV. Agreement with the experimental data is found to be within 10 percent.

  10. Chemically accurate energy barriers of small gas molecules moving through hexagonal water rings.

    PubMed

    Hjertenæs, Eirik; Trinh, Thuat T; Koch, Henrik

    2016-07-21

    We present chemically accurate potential energy curves of CH4, CO2 and H2 moving through hexagonal water rings, calculated by CCSD(T)/aug-cc-pVTZ with counterpoise correction. The barriers are extracted from a potential energy surface obtained by allowing the water ring to expand while the gas molecule diffuses through. State-of-the-art XC-functionals are evaluated against the CCSD(T) potential energy surface. PMID:27345929

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

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2016-05-01

    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.

  12. 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.

  13. Small hydrocarbon molecules in cloud-forming brown dwarf and giant gas planet atmospheres

    NASA Astrophysics Data System (ADS)

    Bilger, C.; Rimmer, P.; Helling, Ch.

    2013-11-01

    We study the abundances of complex carbon-bearing molecules in the oxygen-rich dust-forming atmospheres of brown dwarfs and giant gas planets. The inner atmospheric regions that form the inner boundary for thermochemical gas-phase models are investigated. Results from DRIFT-PHOENIX atmosphere simulations, which include the feedback of phase-non-equilibrium dust cloud formation on the atmospheric structure and the gas-phase abundances, are utilized. The resulting element depletion leads to a shift in the carbon-to-oxygen ratio such that several hydrocarbon molecules and cyanopolyyne molecules can be present. An increase in surface gravity and/or a decrease in metallicity support the increase in the partial pressures of these species. CO, CO2, CH4 and HCN contain the largest fraction of carbon. In the upper atmosphere of low-metallicity objects, more carbon is contained in C4H than in CO, and also CH3 and C2H2 play an increasingly important role as carbon sink. We determine chemical relaxation time-scales to evaluate if hydrocarbon molecules can be affected by transport-induced quenching. Our results suggest that a considerable amount of C2H6 and C2H2 could be expected in the upper atmospheres not only of giant gas planets, but also of brown dwarfs. However, the exact quenching height strongly depends on the data source used. These results will have an impact on future thermokinetic studies, as they change the inner boundary condition for those simulations.

  14. Gas phase reactions of CH(3)(+) with a series of homo- and heterocyclic molecules.

    PubMed

    Fondren, L Dalila; Adams, Nigel G; Stavish, Leah

    2009-01-22

    In gas phase ion chemistry, the growth of larger molecules is known to occur through association of ions and neutrals. Where the ion attaches to the neutral is important because it can influence the possibility of additional associations, effectively enabling or terminating further molecular growth. This was investigated by using a Selected Ion Flow Tube (SIFT) at 300 K to study the reactions of CH(3)(+) with the following series of single-ring homocyclic and heterocyclic molecules: benzene (C(6)H(6)), cyclohexane (C(6)H(12)), pyridine (C(5)H(5)N), pyrimidine (C(4)H(4)N(2)), piperidine (C(5)H(11)N), 1,4-dioxane (C(4)H(8)O(2)), furan (C(4)H(4)O), pyrrole (C(4)H(5)N), and pyrrolidine (C(4)H(9)N). Most of the reactions, except for 1,4-dioxane, pyrrole, and pyrrolidine, proceed at the gas kinetic rate. In the ion product distributions, charge transfer, hydride ion abstraction, proton transfer, fragmentation, and association were observed. In particular, proton transfer is seen to be small in all cases even though these channels are energetically favorable. Association is appreciable when the molecules are aromatic (except for furan) and nonexistent when there are no pi electrons in the ring. CH(3)(+) ions are an important intermediate in molecular synthesis in interstellar clouds and in the Titan ionosphere and ring molecules have also been detected in these media. The significance of the studied reactions to these media is discussed. PMID:19090756

  15. Targeted adsorption of molecules in the colon with the novel adsorbent-based medicinal product, DAV132: A proof of concept study in healthy subjects.

    PubMed

    de Gunzburg, Jean; Ducher, Annie; Modess, Christiane; Wegner, Danilo; Oswald, Stefan; Dressman, Jennifer; Augustin, Violaine; Feger, Céline; Andremont, Antoine; Weitschies, Werner; Siegmund, Werner

    2015-01-01

    During antibiotic treatments, active residuals reaching the colon profoundly affect the bacterial flora resulting in the emergence of resistance. To prevent these effects, we developed an enteric-coated formulated activated-charcoal based product, DAV132, meant to deliver its adsorbent to the ileum and neutralize antibiotic residues in the proximal colon. In a randomized, control, crossover study, the plasma pharmacokinetics of the probe drugs amoxicillin (500 mg) absorbed in the proximal intestine, and sulfapyridine (25 mg) metabolized from sulfasalazine in the cecum and rapidly absorbed, were compared after a single administration in 18 healthy subjects who had received DAV132, uncoated formulated activated charcoal (FAC) or water 16 and 8 hours before, concomitantly with the probe drugs, and 8 hours thereafter. The AUC0-96 h of amoxicillin was reduced by more than 70% when it was taken with FAC, but bioequivalent when it was taken with water or DAV132. By contrast, the AUC0-96 h of sulfapyridine was reduced by more than 90% when administered with either FAC or DAV132 in comparison with water. The results show that DAV132 can selectively adsorb drug compounds in the proximal colon, without interfering with drug absorption in the proximal small intestine, thereby constituting a proof of concept that DAV132 actually functions in humans. PMID:25042595

  16. 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.

  17. [Analysis of organochlorine pesticides and pyrethroid pesticides in vegetables by gas chromatography-electron capture detection coupled with solid-phase extraction using multiwalled carbon nanotubes as adsorbent].

    PubMed

    Zhao, Haixiang; Jia, Yanxia; Ding, Mingyu; Sun, Dajiang; Zhao, Mengbin

    2011-05-01

    A multi-residue analytical method based on solid-phase extraction (SPE) with multiwalled carbon nanotubes (MWCNTs) as adsorbent was developed. The determination of 6 organochlorine pesticides and 7 pyrethroid pesticides in vegetables (including cucumber, cherry tomato, cabbage, lettuce, purple cabbage, leek, shallot and onion) was carried out by gas chromatography-electron capture detection (GC-ECD). The GC-ECD method used two columns (HP-50 and HP-1) and two ECD detectors. The HP-50 column was used for the analysis and the HP-1 column for validation. The clean-up conditions were optimized. The analytes were extracted by acetonitrile, and the extract was cleaned up by the MWCNTs SPE cartridge. The extract was re-dissolved by hexane, eluted with acetone-hexane (7:3, v/v) from the columns. The recoveries were over 70% for the 11 pesticides in the 13 pesticides. The results indicated that the MWCNTs SPE cartridge was efficient for 8 vegetable samples, because it reduced the contamination of the coloring materials to GC-ECD. The experimental results showed the MWCNTs SPE cartridge can adsorb the coloring materials and the eluant was nearly colorless. PMID:21847981

  18. Adsorptive removal of methylene blue by CuO-acid modified sepiolite as effective adsorbent and its regeneration with high-temperature gas stream.

    PubMed

    Su, Chengyuan; Wang, Liang; Chen, Menglin; Huang, Zhi; Lin, Xiangfeng

    2016-01-01

    In this study, the dynamic adsorption of methylene blue dye onto CuO-acid modified sepiolite was investigated. Meanwhile, the equilibrium and kinetic data of the adsorption process were studied to understand the adsorption mechanism. Furthermore, a high-temperature gas stream was applied to regenerate the adsorbent. The results showed that the Langmuir isotherm model was applied to describe the adsorption process. The positive value of enthalpy change indicated that the adsorption process was endothermic in nature. In the dynamic adsorption process, the best adsorption performance was achieved when the ratio of column height to diameter was 2.56 and the treatment capacity was 6 BV/h. The optimal scenario for regeneration experiments was the regeneration temperature of 550-650 °C, the space velocity of 100 min(-1) and the regeneration time of 10 min. The effective adsorption of CuO-acid modified sepiolite was kept for 12 cycles of adsorption and regeneration. PMID:27533859

  19. Ultrafast electron diffraction from laser-aligned molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Yang, Jie

    Ultrafast electron diffraction has emerged since the end of last century, and has become an increasingly important tool for revealing great details of molecular dynamics. In comparison to spectroscopic techniques, ultrafast electron diffraction directly probes time-resolved structure of target molecules, and therefore can potentially provide "molecular movies" of the reactions being studied. These molecular movies are critical for understanding and ultimately controlling the energy conversion pathways and efficiencies of photochemical processes. In this dissertation, I have focused on ultrafast electron diffraction from gas-phase molecules, and have investigated several long-standing challenges that have been preventing researchers from being able to achieve 3-D molecular movies of photochemical reactions. The first challenge is to resolve the full 3-D structure for molecules in the gas phase. The random orientation of molecules in the gas phase smears out the diffraction signal, which results in only 1-D structural information being accessible. The second challenge lies in temporal resolution. In order to resolve coherent nuclear motions on their natural time scale, a temporal resolution of ˜200 femtosecond or better is required. However, due to experimental limitations the shortest temporal resolution that had been achieved was only a few picoseconds in early 2000, by Zewail group from Caltech. The first challenge is tackled by laser-alignment. In the first half of the dissertation, I approach this method both theoretically and experimentally, and demonstrate that by using a short laser pulse to transiently align target molecules in space, 3-D molecular structure can be reconstructed ab-initio from diffraction patterns. The second half of the dissertation presents two experiments, both of which are important steps toward imaging coherent nuclear motions in real time during photochemical reactions. The first experiment simultaneously resolves molecular alignment

  20. Production of a Quantum Gas of Rovibronic Ground-State Molecules in AN Optical Lattice

    NASA Astrophysics Data System (ADS)

    Danzl, Johann G.; Mark, Manfred J.; Haller, Elmar; Gustavsson, Mattias; Hart, Russell; Nägerl, Hanns-Christoph

    2010-02-01

    Recent years have seen tremendous progress in the field of cold and ultracold molecules. A central goal in the field is currently the realization of stable rovibronic ground-state molecular samples in the regime of quantum degeneracy, e.g. in the form of molecular Bose-Einstein condensates, molecular degenerate Fermi gases, or, when an optical lattice is present, molecular Mott-insulator phases. However, molecular samples are not readily cooled to the extremely low temperatures at which quantum degeneracy occurs. In particular, laser cooling, the 'workhorse' for the field of atomic quantum gases, is generally not applicable to molecular samples. Here we take an important step beyond previous work1 and provide details on the realization of an ultracold quantum gas of ground-state dimer molecules trapped in an optical lattice as recently reported in Ref. 2. We demonstrate full control over all internal and external quantum degrees of freedom for the ground-state molecules by deterministically preparing the molecules in a single quantum state, i.e. in a specific hyperfine sublevel of the rovibronic ground state, while the molecules are trapped in the motional ground state of the individual lattice wells. We circumvent the problem of cooling by associating weakly-bound molecules out of a zero-temperature atomic Mott-insulator state and by transferring these to the absolute ground state in a four-photon STIRAP process. Our preparation procedure directly leads to a long-lived, lattice-trapped molecular many-body state, which we expect to form the platform for many of the envisioned future experiments with molecular quantum gases, e.g. on precision molecular spectroscopy, quantum information science, and dipolar quantum systems.

  1. Reactions of metal cluster anions with inorganic and organic molecules in the gas phase.

    PubMed

    Zhao, Yan-Xia; Liu, Qing-Yu; Zhang, Mei-Qi; He, Sheng-Gui

    2016-07-28

    The study of gas phase ion-molecule reactions by state-of-the-art mass spectrometric experiments in conjunction with quantum chemistry calculations offers an opportunity to clarify the elementary steps and mechanistic details of bond activation and conversion processes. In the past few decades, a considerable number of publications have been devoted to the ion-molecule reactions of metal clusters, the experimentally and theoretically tractable models for the active phase of condensed phase systems. The focus of this perspective concerns progress on activation and transformation of important inorganic and organic molecules by negatively charged metal clusters. The metal cluster anions cover bare metal clusters as well as ligated systems with oxygen, carbon, and nitrogen, among others. The following important issues have been summarized and discussed: (i) dependence of chemical reactivity and selectivity on cluster structures and sizes, metals and metal oxidation states, odd-even electron numbers, etc. and (ii) effects of doping, ligation, and pre-adsorption on the reactivity of metal clusters toward rather inert molecules. PMID:27346242

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

    DOE PAGESBeta

    Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; Lu, Zhengliang; Chen, Banglin; Dai, Sheng; Yue, Yanfeng; Rabone, Jeremy A.; Liu, Hongjun; Wang, Jihang; et al

    2015-04-13

    A flexible metal–organic framework (MOF) of [Zn3(btca)2(OH)2]·(guest)n (H2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N2, 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 highly selective adsorption of CO2/N2, CO2/Ar, andmore » CO2/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

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

    SciTech Connect

    Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; Lu, Zhengliang; Chen, Banglin; Dai, Sheng; Yue, Yanfeng; Rabone, Jeremy A.; Liu, Hongjun; Wang, Jihang; Fang, Youxing

    2015-04-13

    A flexible metal–organic framework (MOF) of [Zn3(btca)2(OH)2]·(guest)n (H2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N2, 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 highly selective adsorption of CO2/N2, CO2/Ar, and CO2/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.

  4. Accurate proton affinity and gas-phase basicity values for molecules important in biocatalysis

    PubMed Central

    Moser, Adam; Range, Kevin; York, Darrin M.

    2010-01-01

    Benchmark quantum calculations of proton affinities and gas phase basicities of molecules relevant to biochemical processes, particulsarly acid/base catalysis, are presented and compared for a variety of multi-level and density-functional quantum models. Included are nucleic acid bases in both keto and enol tautomeric forms, ribose in B-form and A-form sugar pucker conformations, amino acid side chains and backbone molecules, and various phosphates and phosphoranes including thio substitutions. This work presents a high-level thermodynamic characterization of biologically relevant protonation states, and provides a benchmark database for development of next-generation semiempirical and approximate density-functional quantum models, and parameterization of methods to predict pKa values and relative solvation energies. PMID:20942500

  5. Polaron-molecule transitions in a two-dimensional Fermi gas

    SciTech Connect

    Parish, Meera M.

    2011-05-15

    We address the problem of a single 'spin-down' impurity atom interacting attractively with a spin-up Fermi gas in two dimensions (2D). We consider the case where the mass of the impurity is greater than or equal to the mass of a spin-up fermion. Using a variational approach, we resolve the questions raised by previous studies and show that there is, in fact, a transition between polaron and molecule (dimer) ground states in 2D. For the molecule state, we use a variational wave function with a single particle-hole excitation on the Fermi sea and we find that its energy matches that of the exact solution in the limit of infinite impurity mass. Thus, we expect the variational approach to provide a reliable tool for investigating 2D systems.

  6. 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.

  7. Enhanced Raman spectroscopy of molecules adsorbed on carbon-doped TiO₂ obtained from titanium carbide: a visible-light-assisted renewable substrate.

    PubMed

    Kiran, Vankayala; Sampath, Srinivasan

    2012-08-01

    Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO(2) (C-TiO(2)) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO(2) substrates are synthesized by varying experimental conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction, and X-ray photoelectron spectroscopic techniques. C-TiO(2) in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO(2), improves the intensities of Raman signals, compared to undoped TiO(2). Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO(2) is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn, triggers charge transfer between TiO(2) and analyte. The C-TiO(2) substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h. PMID:22738214

  8. Intermediate energy proton stopping power for hydrogen molecules and monoatomic helium gas

    NASA Technical Reports Server (NTRS)

    Xu, Y. J.; Khandelwal, G. S.; Wilson, J. W.

    1984-01-01

    Stopping power in the intermediate energy region (100 keV to 1 MeV) was investigated, based on the work of Lindhard and Winther, and on the local plasma model. The theory is applied to calculate stopping power of hydrogen molecules and helium gas for protons of energy ranging from 100 keV to 2.5 MeV. Agreement with the experimental data is found to be within 10 percent. Previously announced in STAR as N84-16955

  9. Rationally designed micropores within a metal-organic framework for selective sorption of gas molecules.

    PubMed

    Chen, Banglin; Ma, Shengqian; Zapata, Fatima; Fronczek, Frank R; Lobkovsky, Emil B; Zhou, Hong-Cai

    2007-02-19

    A microporous metal-organic framework, MOF, Cu(FMA)(4,4'-Bpe)0.5 (3a, FMA = fumarate; 4,4'-Bpe = 4,4'-Bpe = trans-bis(4-pyridyl)ethylene) was rationally designed from a primitive cubic net whose pores are tuned by double framework interpenetration. With pore cavities of about 3.6 A, which are interconnected by pore windows of 2.0 x 3.2 A, 3a shows highly selective sorption behaviors of gas molecules. PMID:17291116

  10. 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.

  11. Laser-driven rotational dynamics of gas-phase molecules: Control and applications

    NASA Astrophysics Data System (ADS)

    Ren, Xiaoming

    In this thesis, our work on developing new techniques to measure and enhance field-free molecular alignment and orientation is described. Non-resonant femtosecond laser pulses are used to align and orient rotationally-cold gas-phase molecules. The time-dependent Schrodinger equation is solved to simulate the experimental results. A single-shot kHz velocity map imaging (VMI) spectrometer is developed for characterizing 1D and 3D alignment. Stimulated by a novel metric for 3D alignment proposed by Makhija et al. [Phys. Rev. A 85,033425 (2012)], a multi-pulse scheme to improve 3D alignment is demonstrated experimentally on difluoro-iodobenzene molecules and the best field-free 3D alignment is achieved. A degenerate four wave mixing probe is developed to overcome limitations in VMI measurement; experiments on different types of molecules show good agreement with computational results. Highly aligned linear molecules are used for high harmonic generation experiments. Due to the high degree of alignment, fractional revivals, variation of revival structure with harmonic order and the shape resonance and Cooper minimum in the photoionization cross section of molecular nitrogen are all observed directly in experiment for the first time. Enhanced orientation from rotationally cold heteronuclear molecules is also demonstrated. We follow the theory developed by Zhang et al. [Phys. Rev. A 83, 043410 (2011)] and demonstrate experimentally for the first time that for rotationally cold carbon monoxide an aligning laser pulse followed by a two-color laser pulse can increase field-free orientation level by almost a factor of three compared to using just the two-color pulse.

  12. Properties of clusters in the gas phase. V - Complexes of neutral molecules onto negative ions

    NASA Technical Reports Server (NTRS)

    Keesee, R. G.; Lee, N.; Castleman, A. W., Jr.

    1980-01-01

    Ion-molecules association reactions of the form A(-)(B)n-1 + B = A(-)(B)n were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl(-), I(-), and NO2(-) with n ranging from one to three or four, and onto SO2(-) and SO3(-) with n equal to one; and (2) carbon dioxide onto Cl(-), I(-), NO2(-), CO3(-), and SO3(-) with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions.

  13. [Simultaneous determination of 16 organophosphorous pesticides in vegetables, fruits and tea by gas chromatography coupled with clean-up by mesoporous alumina as solid-phase extraction adsorbent].

    PubMed

    Hu, Yeqin; Xi, Cunxian; Cao, Shurui; Wang, Guomin; Li, Xianliang; Zhang, Lei; Zhang, Yunhuai

    2014-07-01

    A gas chromatographic method based on solid-phase extraction was developed for the simultaneous determination of 16 organophosphorous pesticides in vegetables, fruits and tea, including cabbage, lettuce, pumpkin, onion, tomato, turnip, apple, pear and tea. The samples were extracted with ethyl acetate, and clean-up with mesoporous alumina as solid-phase extraction adsorbent. The separation of target compounds was performed on a DB-1701 capillary column, and the quantitative analysis of the organophosphorous pesticides was carried out by gas chromatography with flame photometric detection. The results showed that the calibration curves of the 16 organophosphorous pesticides were linear in the range of 10-2 000 microg/L with good correlation coefficients (R2 > 0.997). The recoveries of the pesticides in different samples at three spiked levels ranged from 83.2% to 103.8% with the relative standard deviations of 2.0%-9.9%. This method has high sensitivity, high accuracy and good repeatability, and can be applied to the determination of the organophosphorus pesticide residues in vegetables, fruits and tea. PMID:25255574

  14. Adsorption and desorption of sulfur dioxide on novel adsorbents for flue gas desulfurization. Final report, September 1, 1994--February 29, 1996

    SciTech Connect

    Lin, Y.S.; Deng, S.G.

    1996-08-05

    A sol-gel granulation method was developed to prepare spherical {gamma}-alumina granular supports and supported CuO granular sorbents for flue gas desulfurization. The prepared {gamma}-alumina supported CuO sorbents exhibit desirable pore structure and excellent mechanical properties. The sorbents contain higher loading (30-40 wt. %) of CuO dispersed in the monolayer or sub-monolayer form, giving rise to a larger SO{sub 2} sorption capacity ({gt}20 wt.%) and a faster sorption rate as compared to similar sorbents reported in the literature. With these excellent sulfation and mechanical properties, the sol-gel derived {gamma}-alumina supported CuO granular sorbents offer great potential for use in the dry, regenerative flue gas desulfurization process. Research efforts were also made to prepare DAY zeolite supported sorbents with various CuO contents by the microwave and conventional thermal dispersion methods at different conditions. Monolayer or sub-monolayer coating of Cu(NO{sub 3})sub 2 or CuO was achieved on several DAY supported sorbents by the microwave heating method but not by the conventional thermal dispersion method. The DAY zeolite supported CuO sorbents prepared by the microwave heating method can adsorb up to 15 wt.% of SO{sub 2}. The results obtained have demonstrated the feasibility of effective preparation of zeolite supported CuO sorbents by the microwave heating method.

  15. [Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

    PubMed

    Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

    2010-05-01

    The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively. PMID:20623845

  16. 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.

  17. The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

    NASA Technical Reports Server (NTRS)

    Nordine, Paul C.; Fujimoto, Gordon T.; Greene, Frank T.

    1987-01-01

    The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

  18. Gas-phase ion/molecule reactions of corannulene, a fullerene subunit

    SciTech Connect

    Becker, H.; Schwarz, H. ); Javahery, G.; Petrie, S.; Bohme, D.K. ); Cheng, P.C.; Scott, L.T. )

    1993-12-01

    Corannulene is intriguing, not only because of its highly-strained bowl-like structure, but also as a subunit of C[sub 60] and other fullerenes. The carbon skeleton of corannulene appears several times in C[sub 60], and its curvature mimics the curvature of C[sub 60]. Inspired by this curiosity, and having previously investigated ion/molecule reactions of C[sub 60] cations, we began an unprecedented experimental investigation of ion/molecule reactions of corannulene. Here we report the first observations of gas-phase ion/molecule reactions with corannulene: reactions of the corannulene cation (cor[sup [sm bullet]+]) with C[sub 60] and of neutral corannulene with Ar[sup [sm bullet]+], cor[sup [sm bullet]+], C[sub 60][sup [sm bullet]+], C[sub 60][sup 2+], and C[sub 60][sup [sm bullet]3+]. Both electronic and topographical features are expected to be of consequence in many of these reactions. 22 refs., 1 tab.

  19. 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.

  20. Influence of the presence of small gas molecules in the structure of comblike polyacrylates: a Monte Carlo study.

    PubMed

    León, Salvador; Zanuy, David; Alemán, Carlos

    2002-05-01

    A theoretical strategy has been developed to study the motion of small molecules through ordered polymeric systems. The strategy, which has been incorporated into a computer program denoted MCDP/2, is especially useful to study comblike polymers organized in biphasic arrangements. This is because it is based on a configurational bias Monte Carlo algorithm, which is more efficient than conventional methods to study dense systems. The MCDP/2 program has been used to investigate the influence of CH(4) and CO(2) gas molecules in the structure of isotactic poly(octadecyl acrylate), a typical comblike polymer. For this purpose, the pure polymer and different molecular systems constituted by several gas molecules dissolved in the polymer matrix have been simulated. Results indicated that the structural relaxation of the polymer is not coupled to the motion of gas molecules. The importance of these results in the field of molecular modeling of transport properties in comblike polymers is discussed. PMID:11948586

  1. Fluorescence dynamics of microsphere-adsorbed sunscreens

    NASA Astrophysics Data System (ADS)

    Krishnan, R.

    2005-03-01

    Sunscreens are generally oily substances which are prepared in organic solvents, emulsions or dispersions with micro- or nanoparticles. These molecules adsorb to and integrate into skin cells. In order to understand the photophysical properties of the sunscreen, we compare steady-state and time-resolved fluorescence in organic solvent of varying dielectric constant ɛ and adsorbed to polystyrene microspheres and dispersed in water. Steady-state fluorescence is highest and average fluorescence lifetime longest in toluene, the solvent of lowest ɛ. However, there is no uniform dependence on ɛ. Sunscreens PABA and padimate-O show complex emission spectra. Microsphere-adsorbed sunscreens exhibit highly non-exponential decay, illustrative of multiple environments of the adsorbed molecule. The heterogeneous fluorescence dynamics likely characterizes sunscreen adsorbed to cells.

  2. Biomass-based palm shell activated carbon and palm shell carbon molecular sieve as gas separation adsorbents.

    PubMed

    Sethupathi, Sumathi; Bashir, Mohammed Jk; Akbar, Zinatizadeh Ali; Mohamed, Abdul Rahman

    2015-04-01

    Lignocellulosic biomass has been widely recognised as a potential low-cost source for the production of high added value materials and proved to be a good precursor for the production of activated carbons. One of such valuable biomasses used for the production of activated carbons is palm shell. Palm shell (endocarp) is an abundant by-product produced from the palm oil industries throughout tropical countries. Palm shell activated carbon and palm shell carbon molecular sieve has been widely applied in various environmental pollution control technologies, mainly owing to its high adsorption performance, well-developed porosity and low cost, leading to potential applications in gas-phase separation using adsorption processes. This mini-review represents a comprehensive overview of the palm shell activated carbon and palm shell carbon molecular sieve preparation method, physicochemical properties and feasibility of palm shell activated carbon and palm shell carbon molecular sieve in gas separation processes. Some of the limitations are outlined and suggestions for future improvements are pointed out. PMID:25804669

  3. Resolution of D- and L-glucoses by chiral N-octyl-beta-D-glycoside-Cu(II) complex adsorbed at the gas/liquid interface of small bubbles.

    PubMed

    Sakai, M; Miyazawa, K; Jitsumatsu, H; Kamio, K; Mitsuiki, S; Toh, N; Sugihara, G; Norde, W

    2010-10-15

    A new technique of the jet drop method (JDM) was applied to a chiral molecular discrimination of optically active D- or L-glucose (guest) by chiral N-octyl-beta-D-glycoside (ObetaDG)-Cu(II) complex (host) at the gas/liquid interface of small bubbles. The discrimination of glucoses as the guests is possible using ObetaDG adsorbed at the gas/liquid interface of bubbles where it acts as the host, either in the presence or the absence of Cu(II) ions. In order to make clear the host-guest interaction at the gas/liquid interface, the composition of 5000 top jet drops periodically collected onto a slide glass receiver was analyzed. The relative concentration (eta(i)-1) and the surface excess amount, Gamma(i)(0) of species i such as D- and L-glucoses, and ObetaDG were determined as a function of bubble size, d(b) and bulk concentration C(b). The partition coefficient, Pi(i)=Gamma(i)(0)/C(b) was also evaluated for each component. The adsorption of these materials either in the presence or absence of Cu(II) ions, was assigned to the Freundlich type, and the discrimination of D- and L-glucoses with ObetaDG was evaluated in terms of the Freundlich constant, k(i) and 1/n. The discrimination ability of ObetaDG was also evaluated by determining the equilibrium constants, K(c) of complex formations for the respective glucoses in the presence and absence of Cu(II) ions. It was found that L-glucose can form a more stable complex with ObetaDG-Cu(II). PMID:20634045

  4. Interaction of gas molecules with crystalline polymer separation membranes: Atomic-scale modeling and first-principles calculations

    SciTech Connect

    Sergey N. Rashkeev; Eric S. Peterson

    2011-11-01

    Carbon dioxide (CO2)-induced plasticization can significantly decrease the gas separation performance of membranes in high-temperature or high pressure conditions, such as industrial methane (CH4) separations. In this paper, we investigated the crystalline phase of three polymers (polybenzimidazole (PBI), Bis(isobutylcarboxy)polybenzimidazole (PBI-Butyl), and KaptonTM) and interactions between gas molecules (CO2 and N2) and these polymers. A novel, molecular dynamics (MD) based, computational technique was employed to find unknown crystalline structures of these polymer materials. The interaction of CO2 and N2 gases with these crystals was studied by first-principles calculations and by classical MD simulations. The results showed that the packing structure and the interlayer coupling in polymer crystals determine the permeability and diffusivity of gas molecules. This methodology also allows prediction of plastic swelling in these materials caused by gas molecules absorbed in the polymer matrix.

  5. Gas molecule scattering & ion mobility measurements for organic macro-ions in He versus N2 environments.

    PubMed

    Larriba-Andaluz, Carlos; Fernández-García, Juan; Ewing, Michael A; Hogan, Christopher J; Clemmer, David E

    2015-06-14

    A pending issue in linking ion mobility measurements to ion structures is that the collisional cross section (CCS, the measured structural parameter in ion mobility spectrometry) of an ion is strongly dependent upon the manner in which gas molecules effectively impinge on and are reemitted from ion surfaces (when modeling ions as fixed structures). To directly examine the gas molecule impingement and reemission processes and their influence, we measured the CCSs of positively charged ions of room temperature ionic liquids 1-ethyl-3-methylimidazolium dicyanamide (EMIM-N(CN)2) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) in N2 using a differential mobility analyzer-mass spectrometer (DMA-MS) and in He using a drift tube mobility spectrometer-mass spectrometer (DT-MS). Cluster ions, generated via electrosprays, took the form (AB)N(A)z, spanning up to z = 20 and with masses greater than 100 kDa. As confirmed by molecular dynamics simulations, at the measurement temperature (∼300 K), such cluster ions took on globular conformations in the gas phase. Based upon their attained charge levels, in neither He nor N2 did the ion-induced dipole potential significantly influence gas molecule-ion collisions. Therefore, differences in the CCSs measured for ions in the two different gases could be primarily attributed to differences in gas molecule behavior upon collision with ions. Overwhelmingly, by comparison of predicted CCSs with selected input impingement-reemission laws to measurements, we find that in N2, gas molecules collide with ions diffusely--they are reemitted at random angles relative to the gas molecule incoming angle--and inelastically. Meanwhile, in He, gas molecules collide specularly and elastically and are emitted from ion surfaces at determined angles. The results can be rationalized on the basis of the momentum transferred per collision; in the case of He, individual gas molecule collisions minimally perturb the atoms within a cluster ion

  6. Gas-chromatographic studies of the sorption thermodynamics of adamantanes on a carbon adsorbent modified with polyethylene glycol with β-cyclodextrin additives

    NASA Astrophysics Data System (ADS)

    Yashkin, S. N.; Ageeva, Yu. A.

    2013-11-01

    The thermodynamic characteristics of sorption of adamantane and its derivatives on a mixed stationary phase consisting of a graphite-like solid substrate, polyethylene glycol, and β-cyclodextrin (βCD) were determined by gas chromatography. The introduction of β-CD additives to a polar polymer matrix was shown to considerably decrease the chromatographic retention of the sorbates, which is evidence of the macrocyclic effect. The presence of β-CD molecules was found to increase the selective properties of the mixed sorbent with respect to the structural isomers of adamantanes.

  7. Kinetics of disilane molecule decomposition on the growth surface of silicon in vacuum gas-phase epitaxy reactors

    NASA Astrophysics Data System (ADS)

    Orlov, L. K.; Smyslova, T. N.

    2012-11-01

    The range of the characteristic decomposition rates of dihydride molecule radicals adsorbed by the silicon surface in the temperature interval 450-700°C is experimentally found for a number of kinetic models. A relationship between the rate of silicon atom incorporation into a growing crystal and the characteristic rate of disilane molecule pyrolysis on the silicon surface is found. The temperature dependence of the rate of disilane fragment decomposition on the silicon surface is nonmonotonic, and its run depends on temperature conditions. It is shown that the temperature dependence of the molecular decomposition rate on the growth surface is described by a superposition of two activation curves with various activation energies. The activation energies depend on the peculiarity of interaction between the molecular beam and the silicon surface when the filling of surface states with hydrogen is low and high.

  8. The physical basis for absorption of light. [effects on wave functions of gas molecules and atoms

    NASA Technical Reports Server (NTRS)

    Pickett, H. M.

    1979-01-01

    The effects of light absorption on the wave functions of gas-phase molecules and atoms are investigated by high resolution spectral measurements of radiation emerging from a sample. A Stark-modulated sample of methyl fluoride was irradiated at the 102 GHz rotational transition and the emergent radiation was resolved by means of a spectrum analyzer. For signal oscillator frequencies below or above the molecular resonance by one modulation frequency, the amplitudes of the upper and lower modulation sidebands are found to be of nonuniform intensity, which is inconsistent with amplitude modulation. Emission due to polarization is, however, calculated to be consistent with the results observed, indicating that light absorption should be considered as a subtractive stimulated emission.

  9. NMR dynamics of quantum discord for spin-carrying gas molecules in a closed nanopore

    SciTech Connect

    Yurishchev, M. A.

    2014-11-15

    A local orthogonal transformation that transforms any centrosymmetric density matrix of a two-qubit system to the X form has been found. A piecewise-analytic-numerical formula Q = min(Q{sub π/2}, Q{sub θ}, Q{sub 0}), where Q{sub π/2} and Q{sub 0} are analytical expressions and the branch Q{sub 0θ} can be obtained only by numerically searching for the optimal measurement angle θ ∈ (0, π/2), is proposed to calculate the quantum discord Q of a general X state. The developed approaches have been applied for a quantitative description of the recently predicted flickering (periodic disappearance and reappearance) of the quantum-information pair correlation between nuclear 1/2 spins of atoms or molecules of a gas (for example, {sup 129}Xe) in a bounded volume in the presence of a strong magnetic field.

  10. Generation, Detection and characterization of Gas-Phase Transition Metal containing Molecules

    SciTech Connect

    Steimle, Timothy

    2015-12-15

    The objective of this project was to generate, detect, and characterize small, gas-phase, metal containing molecules. In addition to being relevant to high temperature chemical environments (e.g. plasmas and combustion), gas-phase experiments on metal containing molecules serve as the most direct link to a molecular-level theoretical model for catalysis. Catalysis (i.e. the addition of a small about of recoverable material to control the rate and direction of a chemical reaction) is critical to the petroleum and pharmaceutical industries as well as environmental remediation. Currently, the majority of catalytic materials are based on very expensive metals such as platinum (Pt), palladium (Pd), iridium (Ir,) rhenium (Re), and rhodium (Rh). For example, the catalyst used for converting linear hydrocarbon molecules (e.g. hexane) to cyclic molecules (e.g. cyclohexane) is a mixture of Pt and Re suspended on alumina. It enables straight chain alkanes to be converted into branched-chain alkanes, cyclohexanes and aromatic hydrocarbons which are used, amongst other things, to enhance the octane number of petrol. A second example is the heterogeneous catalysis used in automobile exhaust systems to: a) decrease nitrogen oxide; b) reduce carbon monoxide; and c) oxidize unburned hydrocarbons. The exhaust is vented through a high-surface area chamber lined with Pt, Pd, and Rh. For example, the carbon monoxide is catalytically converted to carbon dioxide by reaction with oxygen. The research results from this work have been published in readily accessible journals1-28. The ground and excited electronic state properties of small metal containing molecules that we determine were: a) electronic state distributions and lifetimes, b) vibrational frequencies, c) bond lengths and angles, d) hyperfine interactions, e) permanent electric dipole moments, mel, and f) magnetic dipoles, μm. In general terms, μel, gives insight into the charge distribution and mm into

  11. Pillared Interlayered Clays as Adsorbents of Gases and Vapors

    NASA Astrophysics Data System (ADS)

    Pires, J.; Pinto, M. L.

    This chapter reviews recent works where porous materials prepared from clays, particularly pillared interlayered clays (PILCs), were studied as gas phase adsorbents. It also includes the cases which used the adsorption of gases and vapors for the nanotextural characterization of the materials, other than the usual low temperature nitrogen adsorption. This is, for instance, the case of the adsorption of molecules of volatile organic compounds (VOCs), with various dimensions and shapes, which can be used as probe molecules for the characterization of the porosity or concerning the topic of the VOCs abatement. A similar situation occurs with water adsorption, whose results can be informative not only on the desiccant properties of the materials but also on their surface chemistry. A more recent line of studies of adsorption by materials prepared from clays, namely, the hydrocarbon purification from natural gas or biogas, was also addressed.

  12. Photodecomposition of chloromethanes adsorbed on silica surfaces

    NASA Technical Reports Server (NTRS)

    Ausloos, P.; Rebbert, R. E.; Glasgow, L.

    1977-01-01

    Irradiation of CCl4, CFCl3, and CF2Cl2 in the presence of C2H6 in vessels containing silica sand or fused quartz tubing results in the formation of chlorine-containing products. The formation of these compounds occurs at wavelengths extending up to approximately 400 nm, that is, at wavelengths well beyond the absorption threshold of the chloromethanes in the gas phase. It is suggested that CCl4 adsorbed on silica surfaces photodissociates to yield CCl3 and CCl2 species. The poor material balance obtained in these experiments indicates that several of the chlorine-containing fragments are strongly adsorbed on the surface. At a CCl4 pressure of 13 Pa (0.1 torr), photolysis with 366 nm light in the presence of sand results in the decomposition of one molecule for every 10,000 photons striking the surface. Under otherwise identical conditions, the photon-induced breadkdown of CFCl3 and CF2Cl2 is respectively only 10% or 3% as efficient.

  13. Adsorption of gas molecules on transition metal embedded graphene: a search for high-performance graphene-based catalysts and gas sensors

    NASA Astrophysics Data System (ADS)

    Zhou, Miao; Lu, Yun-Hao; Cai, Yong-Qing; Zhang, Chun; Feng, Yuan-Ping

    2011-09-01

    We report an investigation on the adsorption of small gas molecules (O2, CO, NO2 and NH3) on pristine and various transition metal embedded graphene samples using a first-principles approach based on density-functional theory (DFT). The most stable adsorption geometry, energy, charge transfer, and magnetic moment of these molecules on graphene embedded with different transition metal elements are thoroughly discussed. Our calculations found that embedded transition metal elements in general can significantly enhance the interactions between gas molecules and graphene, and for applications of graphene-based catalysis, Ti and Au may be the best choices among all transition metal elements. We also expect a detailed analysis of the electronic structures and magnetic properties of these systems to shed light on future applications of graphene-based gas sensing and spintronics.

  14. Detection of the Elusive Triazane Molecule (N3 H5 ) in the Gas Phase.

    PubMed

    Förstel, Marko; Maksyutenko, Pavlo; Jones, Brant M; Sun, Bing-Jian; Chen, Shih-Hua; Chang, Agnes H-H; Kaiser, Ralf I

    2015-10-26

    We report the detection of triazane (N3 H5 ) in the gas phase. Triazane is a higher order nitrogen hydride of ammonia (NH3 ) and hydrazine (N2 H4 ) of fundamental importance for the understanding of the stability of single-bonded chains of nitrogen atoms and a potential key intermediate in hydrogen-nitrogen chemistry. The experimental results along with electronic-structure calculations reveal that triazane presents a stable molecule with a nitrogen-nitrogen bond length that is a few picometers shorter than that of hydrazine and has a lifetime exceeding 6±2 μs at a sublimation temperature of 170 K. Triazane was synthesized through irradiation of ammonia ice with energetic electrons and was detected in the gas phase upon sublimation of the ice through soft vacuum ultraviolet (VUV) photoionization coupled with a reflectron-time-of-flight mass spectrometer. Isotopic substitution experiments exploiting [D3 ]-ammonia ice confirmed the identification through the detection of its fully deuterated counterpart [D5 ]-triazane (N3 D5 ). PMID:26331382

  15. Efficiency of excimer molecule formation in plasma jets of inert gas mixtures with SF6 and CCl4

    NASA Astrophysics Data System (ADS)

    Rogulich, V. S.; Starodub, V. P.; Shevera, V. S.

    1988-10-01

    The formation of krypton and xenon monofluorides and monochlorides in continuous plasma jets of inert gas mixtures with SF6 and CCl4 molecules is investigated experimentally. Absolute concentrations of KrF, XeF, KrCl, and XeCl excimer molecules in the jet are determined. The energy efficiency of specific input power conversion to the spontaneous B-X emission in the KrF band is estimated at 2-4 percent. Ways of increasing the concentration of excimer molecules in the plasma jet are analyzed.

  16. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  17. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  18. Adsorbed Water Illustration

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe on NASA's Phoenix Mars Lander detected small and variable amounts of water in the Martian soil.

    In this schematic illustration, water molecules are represented in red and white; soil minerals are represented in green and blue. The water, neither liquid, vapor, nor solid, adheres in very thin films of molecules to the surfaces of soil minerals. The left half illustrates an interpretation of less water being adsorbed onto the soil-particle surface during a period when the tilt, or obliquity, of Mars' rotation axis is small, as it is in the present. The right half illustrates a thicker film of water during a time when the obliquity is greater, as it is during cycles on time scales of hundreds of thousands of years. As the humidity of the atmosphere increases, more water accumulates on mineral surfaces. Thicker films behave increasingly like liquid water.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  19. Adsorption and desorption of sulfur dioxide on novel adsorbents for flue gas desulfurization. Final report, September 1, 1993--August 31, 1994

    SciTech Connect

    Lin, Y.S.

    1995-02-01

    Dry regenerative sorption processes have recently attracted increasing attention in flue gas desulfurization (FGD) because of their several advantages over the conventional wet-scrubbing processes. Dry sorbents are usually made by coating a transition or alkaline earth metal precursor on the surface of a porous support. Major disadvantages of these sorbents prepared by the conventional methods include relatively poor attrition resistance and low SO{sub 2} sorption capacity. The physical and especially chemical attrition (associated with the sulphation-oxidation-reduction cycles in the process) deteriorates the performance of the sorbents. The low SO{sub 2} sorption capacity is primarily due to the small surface area of the support. Materials with a high surface area are not used as the supports for FGD sorbents because these materials usually are not thermally stable at high temperatures. In the past year, the research supported by Ohio Coal Development Office was focused on synthesis and properties of sol-gel derived alumina and zeolite sorbents with improved properties for FGD. The sol-gel derived alumina has large surface area, mesopore size and excellent mechanical strength. Some alumina-free zeolites not only posses the basic properties required as a sorbent for FGD (hydrophobicity, thermal and chemical stability, mechanical strength) but also have extremely large surface area and selective surface chemistry. The major objectives of this research program were to synthesize the sol-gel derived sorbents and to explore the use of the zeolites either directly as adsorbents or as sorbent support for FGD. The research was aimed at developing novel FGD sorbents possessing better sorption equilibrium and kinetic properties and improved physical and chemical attrition resistance.

  20. Metastable BrO2+ and NBr2+ molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Aoto, Yuri Alexandre; de Oliveira-Filho, Antonio Gustavo S.; Franzreb, Klaus; Ornellas, Fernando R.

    2011-03-01

    The doubly positively charged gas-phase molecules BrO2+ and NBr2+ have been produced by prolonged high-current energetic oxygen (17 keV 16O-) ion surface bombardment (ion beam sputtering) of rubidium bromide (RbBr) and of ammonium bromide (NH4Br) powdered ionic salt samples, respectively, pressed into indium foil. These novel species were observed at half-integer m/z values in positive ion mass spectra for ion flight times of roughly ˜12 μs through a magnetic-sector secondary ion mass spectrometer. Here we present these experimental results and combine them with a detailed theoretical investigation using high level ab initio calculations of the ground states of BrO2+ and NBr2+, and a manifold of excited electronic states. NBr2+ and BrO2+, in their ground states, are long-lived metastable gas-phase molecules with well depths of 2.73 × 104 cm-1 (3.38 eV) and 1.62 × 104 cm-1 (2.01 eV); their fragmentation channels into two monocations lie 2.31 × 103 cm-1 (0.29 eV) and 2.14 × 104 cm-1 (2.65 eV) below the ground state minimum. The calculated lifetimes for NBr2+ (v″ < 35) and BrO2+ (v″ < 18) are large enough to be considered stable against tunneling. For NBr2+, we predicted Re = 3.051 a0 and ωe = 984 cm-1; for BrO2+, we obtained 3.033 a0 and 916 cm-1, respectively. The adiabatic double ionization energies of BrO and NBr to form metastable BrO2+ and NBr2+ are calculated to be 30.73 and 29.08 eV, respectively. The effect of spin-orbit interactions on the low-lying (Λ + S) states is also discussed.

  1. 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.

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

    SciTech Connect

    Kompanets, V O; Laptev, Vladimir B; Makarov, Aleksandr A; Pigulskii, S V; Ryabov, Evgenii A; Chekalin, Sergei V

    2013-04-30

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

  3. Role of interspecies interactions in the preparation of a low-entropy gas of polar molecules in a lattice

    NASA Astrophysics Data System (ADS)

    Safavi-Naini, A.; Wall, M. L.; Rey, A. M.

    2015-12-01

    The preparation of a quantum degenerate gas of heteronuclear molecules has been an outstanding challenge. We use path-integral quantum Monte Carlo simulations to understand the role of interactions and finite temperature effects in the protocol currently employed to adiabatically prepare a low-entropy gas of polar molecules in a lattice starting from an ultracold Bose-Fermi mixture. We find that interspecies interactions affect the final temperature of the mixture after the adiabatic loading procedure and detrimentally limit the molecular peak filling. Our conclusions are in agreement with recent experimental measurements [Moses et al., Science 350, 659 (2015), 10.1126/science.aac6400] and therefore are of immediate relevance for the myriad experiments that aim to form molecules from dual-species atomic gases.

  4. 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.

  5. Collision lifetimes of polyatomic molecules at low temperatures: Benzene–benzene vs benzene–rare gas atom collisions

    SciTech Connect

    Cui, Jie; Krems, Roman V.; Li, Zhiying

    2014-10-28

    We use classical trajectory calculations to study the effects of the interaction strength and the geometry of rigid polyatomic molecules on the formation of long-lived collision complexes at low collision energies. We first compare the results of the calculations for collisions of benzene molecules with rare gas atoms He, Ne, Ar, Kr, and Xe. The comparison illustrates that the mean lifetimes of the collision complexes increase monotonically with the strength of the atom–molecule interaction. We then compare the results of the atom–benzene calculations with those for benzene–benzene collisions. The comparison illustrates that the mean lifetimes of the benzene–benzene collision complexes are significantly reduced due to non-ergodic effects prohibiting the molecules from sampling the entire configuration space. We find that the thermally averaged lifetimes of the benzene–benzene collisions are much shorter than those for Xe with benzene and similar to those for Ne with benzene.

  6. Tracking all-vapor instant gas-hydrate formation and guest molecule populations: a possible probe for molecules trapped in water nanodroplets.

    PubMed

    Uras-Aytemiz, Nevin; Cwiklik, Lukasz; Paul Devlin, J

    2012-11-28

    Quantitative Fourier-transform infrared spectra for low-temperature (160-200 K) aerosols of clathrate-hydrate nanoparticles that contain large-cage catalysts and small-cage nonpolar guests have been extended to a broad range of vapor compositions and sampling conditions. The data better reveal the stages by which room-temperature vapor mixtures, when cooled below ∼220 K, instantly generate aerosols with particles composed exclusively of the corresponding clathrate hydrates. In particular the quantitative data help relate the nature of the hydrates that form to the composition of the aqueous nanodroplets of the first stages of the rapid transition from the all-vapor mixture. The overall transition from an all-vapor mixture to "gas"-hydrate nanocrystals is a multistage one that has been characterized as homogeneous nucleation and growth of solution nanodroplets (∼240 K) followed by nucleation and growth of the gas-hydrate particles (∼220 K); all occurring within a subsecond that follows pulsing of the warm vapor into a sampling cold chamber. This may serve well as a general description of the instantaneous generation of the gas-hydrate aerosols, but closer consideration of the nature of the sampling method, in context with recent computation-based insights to (a) gas-hydrate nucleation stages∕rates and (b) the lifetimes of trapped small nonpolar molecules in cold aqueous nanodroplets, suggests a more complex multistage transition. The simulated lifetimes and extensive new quantitative infrared data significantly broaden the knowledge base in which the instantaneous transition from vapor to crystalline hydrate particles is viewed. The apparent need for a high occupancy of large-cage catalytic guest molecules currently limits the practical value of the all-vapor method. Only through greater clarity in the molecular-level description of the transition will the ultimate limits be defined. PMID:23206013

  7. Tracking all-vapor instant gas-hydrate formation and guest molecule populations: A possible probe for molecules trapped in water nanodroplets

    NASA Astrophysics Data System (ADS)

    Uras-Aytemiz, Nevin; Cwiklik, Lukasz; Paul Devlin, J.

    2012-11-01

    Quantitative Fourier-transform infrared spectra for low-temperature (160-200 K) aerosols of clathrate-hydrate nanoparticles that contain large-cage catalysts and small-cage nonpolar guests have been extended to a broad range of vapor compositions and sampling conditions. The data better reveal the stages by which room-temperature vapor mixtures, when cooled below ˜220 K, instantly generate aerosols with particles composed exclusively of the corresponding clathrate hydrates. In particular the quantitative data help relate the nature of the hydrates that form to the composition of the aqueous nanodroplets of the first stages of the rapid transition from the all-vapor mixture. The overall transition from an all-vapor mixture to "gas"-hydrate nanocrystals is a multistage one that has been characterized as homogeneous nucleation and growth of solution nanodroplets (˜240 K) followed by nucleation and growth of the gas-hydrate particles (˜220 K); all occurring within a subsecond that follows pulsing of the warm vapor into a sampling cold chamber. This may serve well as a general description of the instantaneous generation of the gas-hydrate aerosols, but closer consideration of the nature of the sampling method, in context with recent computation-based insights to (a) gas-hydrate nucleation stages/rates and (b) the lifetimes of trapped small nonpolar molecules in cold aqueous nanodroplets, suggests a more complex multistage transition. The simulated lifetimes and extensive new quantitative infrared data significantly broaden the knowledge base in which the instantaneous transition from vapor to crystalline hydrate particles is viewed. The apparent need for a high occupancy of large-cage catalytic guest molecules currently limits the practical value of the all-vapor method. Only through greater clarity in the molecular-level description of the transition will the ultimate limits be defined.

  8. Absolute configuration assignment of a chiral molecule in the gas phase using foil-induced Coulomb explosion imaging

    NASA Astrophysics Data System (ADS)

    Herwig, Philipp; Zawatzky, Kerstin; Schwalm, Dirk; Grieser, Manfred; Heber, Oded; Jordon-Thaden, Brandon; Krantz, Claude; Novotný, Oldřich; Repnow, Roland; Schurig, Volker; Vager, Zeev; Wolf, Andreas; Trapp, Oliver; Kreckel, Holger

    2014-11-01

    Chiral molecules exist in two configurations that are nonsuperposable mirror images of one another. The underlying molecular structure is referred to as the absolute configuration. In chiral environments, the handedness of molecules influences their chemical characteristics dramatically, and therefore the determination of absolute configurations is of fundamental interest in organic chemistry and biology. Commonly applied techniques to assign absolute configuration are anomalous single-crystal x-ray diffraction and vibrational circular dichroism. However, these techniques become increasingly more challenging when applied to molecules that are made out of light atoms exclusively. Furthermore, there is no established method to determine the absolute handedness of gas-phase molecules that are not optically active. In this work, we apply the foil-induced Coulomb explosion imaging technique to determine directly the absolute configuration of the chiral molecule trans-2,3-dideuterooxirane (C2OD2H2) in the gas phase. The experiment leads to the definitive assignment of the (R ,R ) configuration to an enantio-selected dideuterooxirane sample with a statistical confidence of 5 σ . As the handedness of trans-2,3-dideuterooxirane is unambiguously linked by chemical synthesis to the stereochemical key reference glyceraldehyde, our results provide an independent verification of the absolute configuration of the stereochemical reference standard.

  9. 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

    2012-10-01

    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. PMID:22958218

  10. Diffusion, thermalization, and optical pumping of YbF molecules in a cold buffer-gas cell

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

    We produce YbF molecules with a density of 1018 m-3 using laser ablation inside a cryogenically cooled cell filled with a helium buffer gas. Using absorption imaging and absorption spectroscopy we study the formation, diffusion, thermalization, and optical pumping of the molecules. The absorption images show an initial rapid expansion of molecules away from the ablation target followed by a much slower diffusion to the cell walls. We study how the time constant for diffusion depends on the helium density and temperature and obtain values for the YbF-He diffusion cross section at two different temperatures. We measure the translational and rotational temperatures of the molecules as a function of time since formation, obtain the characteristic time constant for the molecules to thermalize with the cell walls, and elucidate the process responsible for limiting this thermalization rate. Finally, we make a detailed study of how the absorption of the probe laser saturates as its intensity increases, showing that the saturation intensity is proportional to the helium density. We use this to estimate collision rates and the density of molecules in the cell.

  11. Spectral Luminescent Properties of the Glycine Molecule in a Gas Discharge

    NASA Astrophysics Data System (ADS)

    General, A. A.; Migovich, M. I.; Kelman, V. A.; Zhmenyak, Yu. V.; Zvenigorodsky, V. V.

    2016-01-01

    We have experimentally studied the luminescence spectra of glycine powder in the plasma of a repetitively pulsed longitudinal discharge in argon-glycine and helium-glycine mixtures. We have identified the main fragments of the glycine molecule emitting in the 200-1000 nm region. The emitting molecules due to fragmentation of glycine and dissociation of the carboxyl (-COOH) and amino (-NH2) groups are nitrogen, carbon monoxide, and cyanogen molecules.

  12. Calculation of Ground State Rotational Populations for Kinetic Gas Homonuclear Diatomic Molecules including Electron-Impact Excitation and Wall Collisions

    SciTech Connect

    David R. Farley

    2010-08-19

    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 non-equilibrating 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.

  13. Separation of the attractive and repulsive contributions to the adsorbate-adsorbate interactions of polar adsorbates on Si(100)

    NASA Astrophysics Data System (ADS)

    Lin, Ying-Hsiu; Jeng, Horng-Tay; Lin, Deng-Sung

    2015-11-01

    Dissociative adsorption of H2O, NH3, CH3OH and CH3NH2 polar molecules on the Si(100) surface results in a 1:1 mixture of two adsorbates (H and multi-atomic fragment A = OH, NH2, CH3O, CH3NH, respectively) on the surface. By using density functional theory (DFT) calculations, the adsorption geometry, the total energies and the charge densities for various possible ordered structures of the mixed adsorbate layer have been found. Analyzing the systematic trends in the total energies unveils concurrently the nearest-neighbor interactions ENN and the next nearest-neighbor interactions ENNN between two polar adsorbates A. In going from small to large polar adsorbates, ENN's exhibit an attractive-to-repulsive crossover behavior, indicating that they include competing attractive and repulsive contributions. Exploration of the charge density distributions allows the estimation of the degree of charge overlapping between immediately neighboring A's, the resulting contribution of the steric repulsions, and that of the attractive interactions to the corresponding ENN's. The attractive contributions to nearest neighboring adsorbate-adsorbate interactions between the polar adsorbates under study are shown to result from hydrogen bonds or dipole-dipole interactions.

  14. Hot-Wire Chemical Vapor Deposition Of Polycrystalline Silicon : From Gas Molecule To Solar Cell

    NASA Astrophysics Data System (ADS)

    van Veenendaal, P. A. T. T.

    2002-10-01

    Although the effort to investigate the use of renewable energy sources, such as wind and solar energy, has increased, their contribution to the total energy consumption remains insignificant. The conversion of solar energy into electricity through solar cells is one of the most promising techniques, but the use of these cells is limited by the high cost of electricity. The major contributions to these costs are the material and manufacturing costs. Over the past decades, the development of silicon based thin film solar cells has received much attention, because the fabrication costs are low. A promising material for use in thin film solar cells is polycrystalline silicon (poly-Si:H). A relatively new technique to deposit poly-Si:H is Hot-Wire Chemical Vapor Deposition (Hot-Wire CVD), in which the reactant gases are catalytically decomposed at the surface of a hot filament, mainly tungsten and tantalum. The main advantages of Hot-Wire CVD over PE-CVD are absence of ion bombardment, high deposition rate, low equipment cost and high gas utilization. This thesis deals with the full spectrum of deposition, characterization and application of poly-Si:H thin films, i.e. from gas molecule to solar cell. Studies on the decomposition of silane on the filament showed that the process is catalytic of nature and that silane is decomposed into Si and 4H. The dominant gas phase reaction is the reaction of Si and H with silane, resulting in SiH3, Si2H6, Si3H6 and H2SiSiH2. The film growth precursors are Si, SiH3 and Si2H4. Also, XPS results on used tantalum and tungsten filaments are discussed. The position dependent measurements show larger silicon contents at the ends of the tungsten filament, as compared to the middle, due to a lower filament temperature. This effect is insignificant for a tantalum filament. Deposition time dependent measurements show an increase in silicon content of the tungsten filament with time, while the silicon content on the tantalum filament saturates

  15. Mesoporous Silica: A Suitable Adsorbent for Amines

    PubMed Central

    2009-01-01

    Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices. PMID:20628459

  16. Magnetic-field-induced quadrupole coupling in the nuclear magnetic resonance of noble-gas atoms and molecules

    SciTech Connect

    Manninen, Pekka; Vaara, Juha; Pyykkoe, Pekka

    2004-10-01

    An analytic response theory formulation for the leading-order magnetic field-induced and field-dependent quadrupole splitting in nuclear magnetic resonance spectra is presented and demonstrated with first-principles calculations for {sup 21}Ne, {sup 36}Ar, and {sup 83}Kr in noble gas atoms. The case of molecules was studied for {sup 33}S in the sulphur hexafluoride molecule, as well as for {sup 47/49}Ti, {sup 91}Zr, and {sup 177,179}Hf in group(IV) tetrahalides. According to our calculations, the hitherto experimentally unknown field-induced quadrupole splitting in molecules rises to 10{sup 2} Hz for {sup 177,179}Hf nuclei in HfF{sub 4} and 10{sup 1} Hz for {sup 47/49}Ti in TiCl{sub 4}, and is hence of observable magnitude.

  17. Examining Adsorbed Polymer Conformations with Fluorescence Imaging

    NASA Astrophysics Data System (ADS)

    Parkes, Maria; Chennaoui, Mourad; Wong, Janet; Tribology Group, Dept. of Mechanical Engineering Team

    2011-03-01

    The conformation of adsorbed polymers can have significant impact on their properties such as dynamics and elasticity as well as their ability to take part in reactions with other molecules. Experimental research to determine adsorbed polymer conformation has relied mainly on atomic force microscopy (AFM) studies. During an AFM scan, the contact between the scanning probe and the polymer could affect the polymer conformation, particularly where parts of the polymer might have formed projected loops and tails. In this work, conformations of model polymers are examined with total internal reflection fluorescence microscopy (TIRFM). The advantage of TIRFM over AFM is that TIRFM is a non contact technique. Lambda DNA labelled along its length with fluorescent probes was adsorbed in a projected 2D -- 3D state. With TIRFM, the relationship between intensity and depth was used as a basis to determine how the conformation of the adsorbed polymers evolved with time using our custom algorithm.

  18. Cooperative Reformable Channel System with Unique Recognition of Small Gas Molecules in a two-dimensional ZIF-membrane

    NASA Astrophysics Data System (ADS)

    Motevalli, Benyamin; Taherifar, Neda; Liu, Zhe

    We report a cooperative reformable channel system in a coordination porous polymer, named as ZIF-L. Three types of local flexible ligands coexist in the crystal structure of this polymer, resulting in ultra-flexibility. The reformable channel is able to regulate permeation of a nonspherical guest molecule, such as N2 or CO2, based on its longer molecular dimension, which is in a striking contrast to conventional molecular sieves that regulate the shorter cross-sectional dimension of the guest molecules. Our density functional theory (DFT) calculations reveal that the guest molecule induces dynamic motion of the flexible ligands, leading to the channel reformation, and then the guest molecule reorientates itself to fit in the reformed channel. Such a unique ``induced fit-in'' mechanism causes the gas molecule to pass through 6 membered-ring windows in the c- crystal direction of ZIF-L with its longer axis parallel to the window plane. Our experimental permeance of N2 through the ZIF-L membranes is about three times greater than that of CO2, supporting the DFT simulation predictions.

  19. Optically pumped gas laser using electronic transitions in the NaRb molecule

    SciTech Connect

    Kaslin, V.M.; Yakushev, O.F.

    1983-12-01

    Laser superradiance was achieved for the first time as a result of an electronic transition in a diatomic heteronuclear molecule as a result of direct optical pumping. This superradiance was observed in the region of 670 nm due to a transition to the ground state X/sup 1/..sigma../sup +/ of the intermetallic alkali molecule NaRb pumped by radiation from a pulsed copper vapor laser (lambda = 510.6 nm).

  20. A quantum gas of polar KRb molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    Covey, Jacob; Miecnikowski, Matthew; Moses, Steven; Fu, Zhengkun; Jin, Deborah; Ye, Jun

    2016-05-01

    Ultracold polar molecules provide new opportunities for investigation of strongly correlated many-body spin systems such as many-body localization and quantum magnetism. In an effort to access such phenomena, we load polar KRb molecules into a three-dimensional optical lattice. In this system, we observed many-body spin dynamics between molecules pinned in a deep lattice, even though the filling fraction of the molecules was only 5%. We have recently performed a thorough investigation of the molecule creation process in an optical lattice, and consequently improved our filling fraction to 30% by preparing and overlapping Mott and band insulators of the initial atomic gases. More recently, we switched to a second generation KRb apparatus that will allow application of large, stable electric fields as well as high-resolution addressing and detection of polar molecules in optical lattices. We plan to use these capabilities to study non-equilibrium spin dynamics in an optical lattice with nearly single site resolution. I will present the status and direction of the second generation apparatus.

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

    SciTech Connect

    Yang, Ji-Min; Liu, Qing; Sun, Wei-Yin

    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 size 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.

  2. Formation of Complex Organics by Gas Phase and Intracluster Ion-Molecule Reactions Involving Acetylene and Hydrogen Cyanide

    NASA Astrophysics Data System (ADS)

    El-Shall, S.; Hamed, A.; Soliman, A. R.; Momoh, P. O.

    2011-05-01

    Many complex organics including polycyclic aromatic hydrocarbons are present in flames and combustion processes as well as in interstellar clouds and solar nebulae. Here, we present evidence for the formation of complex covalent organics by gas phase and intracluster reactions of the benzene, phenylium, pyridine, pyrimidine, phenylacetylene and benzonitrile cations with acetylene and hydrogen cyanide molecules. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. Measurements of collision cross sections in helium provide structural information on the adducts and allow probing structural changes at different temperatures (isomerization). We observed multiple additions of five acetylene molecules on the pyridine cation at room temperature. This is a remarkable result considering that only two acetylene molecules were added to the phenyl cation and no addition was observed on the benzene cation at room temperature. The experimental results are in full agreement with the ab initio calculations which predict that the first and second acetylenes add to the pyridine ion in barrierless, highly exothermic reactions. Similar reactions have been observed for the pyrimidine radical cation although the extent of the addition reactions is limited to only two acetylene molecules at room temperature. The results provide the first evidence for the incorporation of nitrogen in the formation cyclic hydrocarbons via the gas phase reactions of pyridine and pyrimidine ions with acetylene molecules. In addition, the formation of covalent adducts in the ionized acetylene/HCN system will be reported for the first time. Sequential reactions leading to the formation of pyridine and pyrimidine radical cations and higher adducts are observed over a wide range of temperature and pressure. The formation of these covalent adducts may represent a general class of addition reactions that can form complex

  3. Photochemistry of Nitrate Adsorbed on Mineral Dust

    NASA Astrophysics Data System (ADS)

    Gankanda, A.; Grassian, V. H.

    2013-12-01

    Mineral dust particles in the atmosphere are often associated with adsorbed nitrate from heterogeneous reactions with nitrogen oxides including HNO3 and NO2. Although nitrate ion is a well-studied chromophore in natural waters, the photochemistry of adsorbed nitrate on mineral dust particles is yet to be fully explored. In this study, wavelength dependence of the photochemistry of adsorbed nitrate on different model components of mineral dust aerosol has been investigated using transmission FTIR spectroscopy. Al2O3, TiO2 and NaY zeolite were used as model systems to represent non-photoactive oxides, photoactive semiconductor oxides and porous materials respectively, present in mineral dust aerosol. In this study, adsorbed nitrate is irradiated with 254 nm, 310 nm and 350 nm narrow band light. In the irradiation with narrow band light, NO2 is the only detectable gas-phase product formed from nitrate adsorbed on Al2O3 and TiO2. The NO2 yield is highest at 310 nm for both Al2O3 and TiO2. Unlike Al2O3 and TiO2, in zeolite, adsorbed nitrate photolysis to nitrite is observed only at 310 nm during narrow band irradiation. Moreover gas phase products were not detected during nitrate photolysis in zeolite at all three wavelengths. The significance of these differences as related to nitrate photochemistry on different mineral dust components will be highlighted.

  4. Creation of an Ultracold Gas of Ground-State Dipolar 23Na 87 Molecules

    NASA Astrophysics Data System (ADS)

    Guo, Mingyang; Zhu, Bing; Lu, Bo; Ye, Xin; Wang, Fudong; Vexiau, Romain; Bouloufa-Maafa, Nadia; Quéméner, Goulven; Dulieu, Olivier; Wang, Dajun

    2016-05-01

    We report the successful production of an ultracold sample of absolute ground-state 23Na 87Rb molecules. Starting from weakly bound Feshbach molecules formed via magnetoassociation, the lowest rovibrational and hyperfine level of the electronic ground state is populated following a high-efficiency and high-resolution two-photon Raman process. The high-purity absolute ground-state samples have up to 8000 molecules and densities of over 1011 cm-3 . By measuring the Stark shifts induced by external electric fields, we determined the permanent electric dipole moment of the absolute ground-state 23Na 87Rb and demonstrated the capability of inducing an effective dipole moment over 1 D. Bimolecular reaction between ground-state 23Na 87Rb molecules is endothermic, but we still observed a rather fast decay of the molecular sample. Our results pave the way toward investigation of ultracold molecular collisions in a fully controlled manner and possibly to quantum gases of ultracold bosonic molecules with strong dipolar interactions.

  5. Polarized fluorescence of polyatomic fragments produced through photodissociation of polyatomic molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Blokhin, A. P.; Gelin, M. F.; Kalosha, I. I.; Polubisok, S. A.; Tolkachev, V. A.

    1999-01-01

    A combined theoretical and experimental study is carried of the polarized emission of polyatomic products produced through photodissociation of polyatomic molecules. A general approach, based on the formalism of dissociation kernels and orientational correlation functions, is developed to predict anisotropy of the fluorescence of photoproducts. We consider the most general case of asymmetric top parent and product molecules. The rotational predissociation effect is taken into account. Various kinds of photoreactions are studied: those when fragments after dissociation are in the electronically excited states and those when fragments are in the ground electronic states so that additional laser pulse is necessary to excite their fluorescence. Particular attention is concentrated on those practically important extreme cases, when predissociation times and lifetimes of the electronically excited states of photoproducts are short or long as compared to the averaged period of free rotation. The steady state polarized fluorescence of radicals produced through dissociation of several disulfides into two identical radicals is measured. The results are interpreted in the framework of the free recoil model (FRM). In this model, photoproducts are assumed to experience no torque and fly apart freely, so that the only origin of the fragment rotation is rotation of the parent molecule. Predictions of the impulsive model (IM), in which fragments are supposed to suffer instantaneous torque due to the rupture of the chemical bonds of the parent molecule, are demonstrated to disagree strongly with our experimental data. This gives an additional confirmation of the validity of the FRM in describing dissociation of polyatomic molecules into polyatomic fragments. The FRM can therefore be invoked to estimate interrelation between the characteristic times, governing the processes of dissociation and emission, and the averaged period of free molecular rotation. Also, the FRM can be used

  6. Amine-pillared Nanosheet Adsorbents for CO2 Capture Applications

    NASA Astrophysics Data System (ADS)

    Jiang, Hui

    Amine-functionalized solid adsorbents have gained attention within the last decade for their application in carbon dioxide capture, due to their many advantages such as low energy cost for regeneration, tunable structure, elimination of corrosion problems, and additional advantages. However, one of the challenges facing this technology is to accomplish both high CO 2 capture capacity along with high CO2 diffusion rates concurrently. Current amine-based solid sorbents such as porous materials similar to SBA-15 have large pores diffusion entering molecules; however, the pores become clogged upon amine inclusion. To meet this challenge, our group's solution involves the creation of a new type of material which we are calling-amino-pillared nanosheet (APN) adsorbents which are generated from layered nanosheet precursors. These materials are being proposed because of their unique lamellar structure which exhibits ability to be modified by organic or inorganic pillars through consecutive swelling and pillaring steps to form large mesoporous interlayer spaces. After the expansion of the layer space through swelling and pillaring, the large pore space can be functionalized with amine groups. This selective functionalization is possible by the choice of amine group introduced. Our choice, large amine molecules, do not access the micropore within each layer; however, either physically or chemically immobilized onto the surface of the mesoporous interlayer space between each layer. The final goal of the research is to investigate the ability to prepare APN adsorbents from a model nanoporous layered materials including nanosheets precursor material MCM-22(P) and nanoporous layered silicate material AMH-3. MCM-22(P) contains 2-dimensional porous channels, 6 membered rings (MB) openings perpendicular to the layers and 10 MB channels in the plane of the layers. However, the transport limiting openings (6 MB) to the layers is smaller than CO2 gas molecules. In contrast, AMH-3 has

  7. Electron swarm parameters in SiH sub 4 -rare gas mixtures and collision cross sections for monosilane molecules

    SciTech Connect

    Kurachi, M.; Nakamura, Y. . Faculty of Science and Technology)

    1991-04-01

    Previously measured drift velocity and longitudinal diffusion coefficient in SiH{sub 4}-Ar mixtures were re-analyzed, and the new vibrational excitation cross sections for monosilane molecules were obtained. Not only were the new cross sections consistent with swarm parameters, but also the ratio of their magnitudes at the resonance peak agreed with recent measurements of the electron beam experiment. Having known the vibrational excitation cross sections, the analysis of the primary ionization coefficient measured in SiH{sub 4}-Kr mixtures led to a consistent inelastic cross section, which possibly corresponds to the total cross section for neutral dissociations for the molecule. In this paper it was confirmed that the derived set of the cross sections also gave good agreement with the electron swarm parameters measured in pure monosilane gas.

  8. Molecule-modulated photoconductivity and gain-amplified selective gas sensing in polar GaN nanowires

    NASA Astrophysics Data System (ADS)

    Chen, R. S.; Lu, C. Y.; Chen, K. H.; Chen, L. C.

    2009-12-01

    We report the strong molecular effects on the surface-dominant photoconductivity with high-gain transport in the polar GaN nanowires. Both the transient and steady-state photocurrents are sensitive and selective to the adsorptions of oxygen and hydrogen. The surface band bending of GaN nanowires is proposed to be effectively reduced or enhanced by oxygen or hydrogen, respectively, as a donorlike or acceptorlike surface state. The molecular effect, corroborated with the high-gain photoresponse nature of GaN nanowires is found to amplify the molecule-selective photocurrent signal by near three orders of magnitude higher than its counterpart in dark current. The molecule-tunable photoconductivity, as demonstrated here, would benefit a variety of applications, ranging from the high-gain optoelectronic devices, photoelectric energy transducer, as well as gas and chemical sensors.

  9. The role of multiparticle correlations and Cooper pairing in the formation of molecules in an ultracold gas of Fermi atoms with a negative scattering length

    SciTech Connect

    Babichenko, V. S. Kagan, Yu.

    2012-11-15

    The influence of multiparticle correlation effects and Cooper pairing in an ultracold Fermi gas with a negative scattering length on the formation rate of molecules is investigated. Cooper pairing is shown to cause the formation rate of molecules to increase, as distinct from the influence of Bose-Einstein condensation in a Bose gas on this rate. This trend is retained in the entire range of temperatures below the critical one.

  10. Is there a Difference in Van Der Waals Interactions between Rare Gas Atoms Adsorbed on Metallic and Semiconducting Single-Walled Carbon Nanotubes?

    SciTech Connect

    Chen, De-Li; Mandeltort, Lynn; Saidi, Wissam A.; Yates, John T.; Cole, Milton W.; Johnson, J. Karl

    2013-03-01

    Differences in polarizabilities of metallic (M) and semiconducting (S) single-walled carbon nanotubes (SWNTs) might give rise to differences in adsorption potentials. We show from experiments and van der Waals-corrected density functional theory (DFT) that binding energies of Xe adsorbed on M- and S-SWNTs are nearly identical. Temperature programmed desorption of Xe on purified M- and S-SWNTs give similar peak temperatures, indicating that desorption kinetics and binding energies are independent of the type of SWNT. Binding energies computed from vdW-corrected DFT are in good agreement with experiments.

  11. Oxygen K-edge absorption spectra of small molecules in the gas phase

    SciTech Connect

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O/sub 2/, CO, CO/sub 2/ and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs.

  12. Measuring the internal energy content of molecules transported across the liquid-gas interface

    NASA Astrophysics Data System (ADS)

    Maselli, Olivia J.; Gascooke, Jason R.; Lawrance, Warren D.; Buntine, Mark A.

    2009-09-01

    Many details concerning the mechanism associated with the liberation of molecules from a liquid surface remain to be elucidated. We use the liquid microjet technique coupled with laser spectroscopy to measure the rotational and vibrational energy content of benzene spontaneously evaporating from a water-ethanol solution. These measurements provide molecular level insight into the mass and energy transfer processes associated with evaporation.

  13. Creation of a strongly dipolar gas of ultracold ground-state 23 Na87 Rb molecules

    NASA Astrophysics Data System (ADS)

    Guo, Mingyang; Zhu, Bing; Lu, Bo; Ye, Xin; Wang, Fudong; Wang, Dajun; Vexiau, Romain; Bouloufa-Maafa, Nadia; Quéméner, Goulven; Dulieu, Olivier

    2016-05-01

    We report on successful creation of an ultracold sample of ground-state 23 Na87 Rb molecules with a large effective electric dipole moment. Through a carefully designed two-photon Raman process, we have successfully transferred the magneto-associated Feshbach molecules to the singlet ground state with high efficiency, obtaining up to 8000 23 Na87 Rb molecules with peak number density over 1011 cm-3 in their absolute ground-state level. With an external electric field, we have induced an effective dipole moment over 1 Debye, making 23 Na87 Rb the most dipolar ultracold particle ever achieved. Contrary to the expectation, we observed a rather fast population loss even for 23 Na87 Rb in the absolute ground state with the bi-molecular exchange reaction energetically forbidden. The origin for the short lifetime and possible ways of mitigating it are currently under investigation. Our achievements pave the way toward investigation of ultracold bosonic molecules with strong dipolar interactions. This work is supported by the Hong Kong RGC CUHK404712 and the ANR/RGC Joint Research Scheme ACUHK403/13.

  14. Structure analysis and photochemistry of adsorbates on platinum and palladium surfaces. [1,2-dichloroethene

    SciTech Connect

    Grassian, V.H.

    1987-05-01

    The vibrational spectra of benzene and toluene adsorbed on Pd(111) indicates at 180K these molecules weakly bond to the surface. The adsorption of benzene and toluene on Pt(111) is much stronger as indicated by large frequency shifts from gas phase values. Pyridine adsorption on both Pt(111) and Pd(111) was studied as a function of temperature. At room temperature pyridine decomposes on the surface to form an ..cap alpha..-pyridyl fragment (NC/sub 5/H/sub 4/) on Pt(111), whereas the molecule remains intact on Pd(111). The electron energy loss spectra of pyridine adsorbed on these surfaces is compared to the ir spectra of two osmium cluster compounds: Os/sub 3/(CO)/sub 11/(NC/sub 5/H/sub 5/), a pyridine complex, and HOs/sub 3/(CO)/sub 10/(NC/sub 5/H/sub 4/), a pyridyl complex. The stronger interaction of these molecules to the platinum surface is a consequence of the stronger bonding of the 5d orbitals as compared to the 4d orbitals. The uv photochemistry of 2-butene and 1,2-dichloroethene when adsorbed on Pt and Pd surfaces was also studied.

  15. Measurement of breakthrough volumes of volatile chemical warfare agents on a poly(2,6-diphenylphenylene oxide)-based adsorbent and application to thermal desorption-gas chromatography/mass spectrometric analysis.

    PubMed

    Kanamori-Kataoka, Mieko; Seto, Yasuo

    2015-09-01

    To establish adequate on-site solvent trapping of volatile chemical warfare agents (CWAs) from air samples, we measured the breakthrough volumes of CWAs on three adsorbent resins by an elution technique using direct electron ionization mass spectrometry. The trapping characteristics of Tenax(®) TA were better than those of Tenax(®) GR and Carboxen(®) 1016. The latter two adsorbents showed non-reproducible breakthrough behavior and low VX recovery. The specific breakthrough values were more than 44 (sarin) L/g Tenax(®) TA resin at 20°C. Logarithmic values of specific breakthrough volume for four nerve agents (sarin, soman, tabun, and VX) showed a nearly linear correlation with the reciprocals of their boiling points, but the data point of sulfur mustard deviated from this linear curve. Next, we developed a method to determine volatile CWAs in ambient air by thermal desorption-gas chromatography (TD-GC/MS). CWA solutions that were spiked into the Tenax TA(®) adsorbent tubes were analyzed by a two-stage TD-GC/MS using a Tenax(®) TA-packed cold trap tube. Linear calibration curves for CWAs retained in the resin tubes were obtained in the range between 0.2pL and 100pL for sarin, soman, tabun, cyclohexylsarin, and sulfur mustard; and between 2pL and 100pL for VX and Russian VX. We also examined the stability of CWAs in Tenax(®) TA tubes purged with either dry or 50% relative humidity air under storage conditions at room temperature or 4°C. More than 80% sarin, soman, tabun, cyclohexylsarin, and sulfur mustard were recovered from the tubes within 2 weeks. In contrast, the recoveries of VX and Russian VX drastically reduced with storage time at room temperature, resulting in a drop to 10-30% after 2 weeks. Moreover, we examined the trapping efficiency of Tenax TA(®) adsorbent tubes for vaporized CWA samples (100mL) prepared in a 500mL gas sampling cylinder. In the concentration range of 0.2-2.5mg/m(3), >50% of sarin, soman, tabun, cyclohexylsarin, and HD were

  16. Drag force and transport property of a small cylinder in free molecule flow: A gas-kinetic theory analysis.

    PubMed

    Liu, Changran; Li, Zhigang; Wang, Hai

    2016-08-01

    Analytical expressions are derived for aerodynamic drag force on small cylinders in the free molecule flow using the gas-kinetic theory. The derivation considers the effect of intermolecular interactions between the cylinder and gas media. Two limiting collision models, specular and diffuse scattering, are investigated in two limiting cylinder orientations with respect to the drift velocity. The earlier solution of Dahneke [B. E. Dahneke, J. Aerosol Sci. 4, 147 (1973)10.1016/0021-8502(73)90066-9] is shown to be a special case of the current expressions in the rigid-body limit of collision. Drag force expressions are obtained for cylinders that undergo Brownian rotation and for those that align with the drift velocity. The validity of the theoretical expressions is tested against experimental mobility data available for carbon nanotubes. PMID:27627388

  17. Drag force and transport property of a small cylinder in free molecule flow: A gas-kinetic theory analysis

    NASA Astrophysics Data System (ADS)

    Liu, Changran; Li, Zhigang; Wang, Hai

    2016-08-01

    Analytical expressions are derived for aerodynamic drag force on small cylinders in the free molecule flow using the gas-kinetic theory. The derivation considers the effect of intermolecular interactions between the cylinder and gas media. Two limiting collision models, specular and diffuse scattering, are investigated in two limiting cylinder orientations with respect to the drift velocity. The earlier solution of Dahneke [B. E. Dahneke, J. Aerosol Sci. 4, 147 (1973), 10.1016/0021-8502(73)90066-9] is shown to be a special case of the current expressions in the rigid-body limit of collision. Drag force expressions are obtained for cylinders that undergo Brownian rotation and for those that align with the drift velocity. The validity of the theoretical expressions is tested against experimental mobility data available for carbon nanotubes.

  18. Molecular Adsorber Coating

    NASA Technical Reports Server (NTRS)

    Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

    2011-01-01

    A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

  19. Structure and properties of water film adsorbed on mica surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Gutian; Tan, Qiyan; Xiang, Li; Cai, Di; Zeng, Hongbo; Yi, Hong; Ni, Zhonghua; Chen, Yunfei

    2015-09-01

    The structure profiles and physical properties of the adsorbed water film on a mica surface under conditions with different degrees of relative humidity are investigated by a surface force apparatus. The first layer of the adsorbed water film shows ice-like properties, including a lattice constant similar with ice crystal, a high bearing capacity that can support normal pressure as high as 4 MPa, a creep behavior under the action of even a small normal load, and a character of hydrogen bond. Adjacent to the first layer of the adsorbed water film, the water molecules in the outer layer are liquid-like that can flow freely under the action of external loads. Experimental results demonstrate that the adsorbed water layer makes the mica surface change from hydrophilic to weak hydrophobic. The weak hydrophobic surface may induce the latter adsorbed water molecules to form water islands on a mica sheet.

  20. Half-quantum vortex molecules in a binary dipolar Bose gas.

    PubMed

    Shirley, Wilbur E; Anderson, Brandon M; Clark, Charles W; Wilson, Ryan M

    2014-10-17

    We study the ground state phases of a rotating two-component, or binary, Bose-Einstein condensate, wherein one component possesses a large permanent magnetic dipole moment. A variety of nontrivial phases emerge in this system, including a half-quantum vortex (HQV) chain phase and a HQV molecule phase, where HQVs bind at short distances. We attribute these phases to the development of a minimum in the HQV interaction potential, which emerges without coherent coupling or attractive interactions between the components. Thus, we show that the presence of dipolar interactions in this system provides a unique mechanism for the formation of HQV molecules and results in a rich ground state phase diagram. PMID:25361261

  1. Rotational excitation of hydrogen molecules by collisions with hydrogen atoms. [interstellar gas energetics

    NASA Technical Reports Server (NTRS)

    Green, S.; Truhlar, D. G.

    1979-01-01

    Rate constants for rotational excitation of hydrogen molecules by collisions with hydrogen atoms have been obtained from quantum-mechanical calculations for kinetic temperatures between 100 and 5000 K. These calculations involve the rigid-rotator approximation, but other possible sources of error should be small. The calculations indicate that the early values of Nishimura are larger than accurate rigid-rotator values by about a factor of 20 or more.

  2. Mössbauer spectroscopy of trimethyl tin halide molecules matrix-isolated in solid rare gas

    NASA Astrophysics Data System (ADS)

    Bukshpan, S.

    1991-02-01

    The study of matrix-isolated (CH 3) 3SnCl, (CH 3) 3SnBr and (CH 3) 3SnI reveals a tetrahedral molecular structure similar to the corresponding phenyl molecules. The results confirm that in the crystalline state of these compounds the tin atom is five-coordinated while in the matrix-isolated state the coordination number is four.

  3. Strongly aligned gas-phase molecules at free-electron lasers

    DOE PAGESBeta

    Kierspel, Thomas; Wiese, Joss; Mullins, Terry; Robinson, Joseph; Aquila, Andy; Barty, Anton; Bean, Richard; Boll, Rebecca; Boutet, Sebastien; Bucksbaum, Philip; et al

    2015-09-16

    Here, we demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the linac coherent light source. Chirped laser pulses, i.e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2, 5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment ofmore » $$\\langle {\\mathrm{cos}}^{2}{\\theta }_{2{\\rm{D}}}\\rangle =0.85$$ was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses.« less

  4. Strongly aligned gas-phase molecules at free-electron lasers

    SciTech Connect

    Kierspel, Thomas; Wiese, Joss; Mullins, Terry; Robinson, Joseph; Aquila, Andy; Barty, Anton; Bean, Richard; Boll, Rebecca; Boutet, Sebastien; Bucksbaum, Philip; Chapman, Henry N.; Christensen, Lauge; Fry, Alan; Hunter, Mark; Koglin, Jason E.; Liang, Mengning; Mariani, Valerio; Morgan, Andrew; Natan, Adi; Petrovic, Vladimir; Rolles, Daniel; Rudenko, Artem; Schnorr, Kirsten; Stapelfeldt, Henrik; Stern, Stephan; Thogersen, Jan; Yoon, Chun Hong; Wang, Fenglin; Trippel, Sebastian; Kupper, Jochen

    2015-09-16

    Here, we demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the linac coherent light source. Chirped laser pulses, i.e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2, 5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment of $\\langle {\\mathrm{cos}}^{2}{\\theta }_{2{\\rm{D}}}\\rangle =0.85$ was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses.

  5. Dipolar Effects in an Ultracold Gas of LiCs Molecules

    NASA Astrophysics Data System (ADS)

    Weidemueller, Matthias

    2011-05-01

    Recently, there has been important progress in the investigation of ultracold polar molecules in the absolute ground state, thus opening intriguing perspectives for strongly correlated quantum systems under the influence of long-range dipolar forces. We have studied the formation of LiCs molecules via photoassociation (PA) in a double-species magneto-optical trap. The LiCs dimer is a particularly promising candidate for observing dipolar effects, as it possesses the largest dipole moment of all alkali dimers (5.5 Debye in the ground state). Ultracold LiCs molecules in the absolute rovibrational ground state are formed by a single photo-association step. The dipole moment of ground state levels is determined by Stark spectroscopy and was found to be in excellent agreement with the theoretical predictions. Vibrational redistribution due to spontaneous emission and blackbody radiation is observed and compared a rate-equation model.In collaboration with Johannes Deiglmayr, Marc Repp, University of Heidelberg; Roland Wester, University of Innsbruck; and Olivier Dulieu, Laboratoire Aime Cotton. Work was supported by DFG and ESF in the framework of the Eurocores EuroQUAM as well as the Heidelberg Center for Quantum Dynamics.

  6. SCC-DFTB calculation of the static first hyperpolarizability: From gas phase molecules to functionalized surfaces

    NASA Astrophysics Data System (ADS)

    Nénon, Sébastien; Champagne, Benoît

    2013-05-01

    The performance of the self-consistent charge density functional tight binding (SCC-DFTB) method for calculating the first hyperpolarizability of π-conjugated compounds has been assessed with respect to results obtained with high-level ab initio methods and density functional theory (DFT). The SCC-DFTB method performs similarly or better than DFT with the PBE XC functional. Thus, if for small π-conjugated linkers SCC-DFTB can reproduce trends, for longer chains the first hyperpolarizabilities are overestimated. In the case of push-pull thiophenes, the β values are strongly overestimated, as it is also the case with the B3LYP and PBE XC functionals. On the other hand, the SCC-DFTB method closely reproduces the evolution of β in p-disubstituted benzenes as a function of the donor and acceptor groups, as estimated at the MP2 level. The reliability of SCC-DFTB to determine the bond length alternation and the dihedral angles between the aromatic rings has also been tackled, demonstrating that both are underestimated. Overall, the SCC-DFTB calculations are of the same quality as those performed with the conventional PBE XC functional on which the method was parameterized but the SCC-DFTB calculations are computationally very little demanding, and it can therefore be adopted for very large systems for screening nonlinear optical materials as well as for assessing structure-property relationships. This is illustrated with an application on the first hyperpolarizability of an indolino-oxazolidine molecular switch grafted on a SiO2 surface. This has enabled to pinpoint (i) the effect of the surface on the donor/acceptor character of the linking substituent, (ii) the impact of molecular orientation, (iii) the role of a spacer between the π-conjugated switch and the surface, (iv) the global effect of the surface on the β contrast, and also (v) the fact that the molecular switches can maintain this contrast when adsorbed.

  7. Preparation of Surface Adsorbed and Impregnated Multi-walled Carbon Nanotube/Nylon-6 Nanofiber Composites and Investigation of their Gas Sensing Ability

    PubMed Central

    Lala, Neeta L.; Thavasi, Velmurugan; Ramakrishna, Seeram

    2009-01-01

    We have prepared electrospun Nylon-6 nanofibers via electrospinning, and adsorbed multi-walled carbon nanotubes (MWCNTs) onto the surface of Nylon-6 fibers using Triton® X-100 to form a MWCNTs/Nylon-6 nanofiber composite. The dispersed MWCNTs have been found to be stable in hexafluoroisopropanol for several months without precipitation. A MWCNTs/Nylon-6 nanofiber composite based chemical sensor has demonstrated its responsiveness towards a wide range of solvent vapours at room temperature and only mg quantities of MWCNTs were expended. The large surface area and porous nature of the electrospun Nylon-6/MWCNT nanofibers facilitates greater analyte permeability. The experimental analysis has indicated that the dipole moment, functional group and vapour pressure of the analytes determine the magnitude of the responsiveness. PMID:22389589

  8. Standoff Spectroscopy of Surface Adsorbed Chemicals

    SciTech Connect

    Van Neste, Charles W; Senesac, Larry R; Thundat, Thomas George

    2009-01-01

    Despite its immediate applications, selective detection of trace quantities of surface adsorbed chemicals, such as explosives, without physically collecting the sample molecules is a challenging task. Standoff spectroscopic techniques offer an ideal method of detecting chemicals without using a sample collection step. Though standoff spectroscopic techniques are capable of providing high selectivity, their demonstrated sensitivities are poor. Here we describe standoff detection of trace quantities of surface adsorbed chemicals using two quantum cascade lasers operated simultaneously, with tunable wavelength windows that match with absorption peaks of the analytes. This standoff method is a variation of photoacoustic spectroscopy, where scattered light from the sample surface is used for exciting acoustic resonance of the detector. We demonstrate a sensitivity of 100 ng/cm{sup 2} and a standoff detection distance of 20 m for surface adsorbed analytes such as explosives and tributyl phosphate.

  9. A triply interpenetrated microporous metal-organic framework for selective sorption of gas molecules.

    PubMed

    Chen, Banglin; Ma, Shengqian; Hurtado, Eric J; Lobkovsky, Emil B; Zhou, Hong-Cai

    2007-10-15

    A microporous metal-organic framework Zn(ADC)(4,4'-Bpe)(0.5).xG [1; ADC = 4,4'-azobenzenedicarboxylate, 4,4'-Bpe = trans-bis(4-pyridyl)ethylene, G = guest molecules] with a triply interpenetrative primitive cubic net was synthesized and characterized. With pores of about 3.4 x 3.4 A, the activated 1a exhibits highly selective sorption behavior toward H(2)/N(2), H(2)/CO, and CO(2)/CH(4). PMID:17854181

  10. Experimental and Numerical Investigation of Guest Molecule Exchange Kinetics based on the 2012 Ignik Sikumi Gas Hydrate Field Trial

    NASA Astrophysics Data System (ADS)

    Ruprecht Yonkofski, C. M.; Horner, J.; White, M. D.

    2015-12-01

    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 a thorough quality check. The Ignik Sikumi #1 data set is extensive, but contains no direct evidence of the guest-molecule exchange process. This study uses numerical simulation to provide an interpretation of the CH4/CO2/N2 guest molecule exchange process that occurred at Ignik Sikumi #1. Simulations were further informed by experimental observations. The goal of the scoping experiments was to understand kinetic exchange rates and develop parameters for use in Iġnik Sikumi history match simulations. The experimental procedure involves two main stages: 1) the formation of CH4 hydrate in a consolidated sand column at 750 psi and 2°C and 2) flow-through of a 77.5/22.5 N2/CO2 molar ratio gas mixture across the column. Experiments were run both above and below the hydrate stability zone in order to observe exchange behavior across varying conditions. The numerical simulator, STOMP-HYDT-KE, was then used to match experimental results, specifically fitting kinetic behavior. Once this behavior is understood, it can be applied to field scale models based on Ignik Sikumi #1.

  11. Molecular Frame Photoemission: Probe of the Photoionization Dynamics for Molecules in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Dowek, D.; Picard, Y. J.; Billaud, P.; Elkharrat, C.; Houver, J. C.

    2009-04-01

    Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the I(χ, θe, varphie) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, varphie) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hν = 19 eV, where direct PI is the only channel opened, and hν = 32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.

  12. Turing Patterning Using Gene Circuits with Gas-Induced Degradation of Quorum Sensing Molecules

    PubMed Central

    Hasty, Jeff; Tsimring, Lev

    2016-01-01

    The Turing instability was proposed more than six decades ago as a mechanism leading to spatial patterning, but it has yet to be exploited in a synthetic biology setting. Here we characterize the Turing instability in a specific gene circuit that can be implemented in vitro or in populations of clonal cells producing short-range activator N-Acyl homoserine lactone (AHL) and long-range inhibitor hydrogen peroxide (H2O2) gas. Slowing the production rate of the AHL-degrading enzyme, AiiA, generates stable fixed states, limit cycle oscillations and Turing patterns. Further tuning of signaling parameters determines local robustness and controls the range of unstable wavenumbers in the patterning regime. These findings provide a roadmap for optimizing spatial patterns of gene expression based on familiar quorum and gas sensitive E. coli promoters. The circuit design and predictions may be useful for (re)programming spatial dynamics in synthetic and natural gene expression systems. PMID:27148743

  13. Greenhouse Gas Molecule CO2 Detection Using a Capacitive Micromachined Ultrasound Transducer.

    PubMed

    Barauskas, Dovydas; Pelenis, Donatas; Virzonis, Darius; Baltrus, John P; Baltrusaitis, Jonas

    2016-07-01

    We manufactured and tested a capacitive micromachined ultrasound transducer (CMUT)-based sensor for CO2 detection at environmentally relevant concentrations using polyethylenimine as a CO2 binding material. The assembly of a sensing chip was 10 × 20 mm, and up to 5 gases can potentially be detected simultaneously using a masking technique and different sensing materials. The limit of detection was calculated to be 0.033 CO2 vol % while the limit of quantification was calculated to be 0.102%. The sensor exhibited a linear response between 0.06% and 0.30% CO2 while concentrations close to those in flue gas can also be measured using dilution with inert gas. PMID:27321769

  14. Black Molecular Adsorber Coatings for Spaceflight Applications

    NASA Technical Reports Server (NTRS)

    Abraham, Nithin Susan; Hasegawa, Mark Makoto; Straka, Sharon A.

    2014-01-01

    The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

  15. Three-dimensional graphene aerogel-supported iron oxide nanoparticles as an efficient adsorbent for magnetic solid phase extraction of organophosphorus pesticide residues in fruit juices followed by gas chromatographic determination.

    PubMed

    Mahpishanian, Shokouh; Sereshti, Hassan

    2016-04-22

    In this research, a magnetic three dimensional-graphene nanocomposite (3D-G-Fe3O4) was prepared, characterized and used as an effective nanoadsorbent in magnetic solid-phase extraction (MSPE) of eight organophosphorus pesticides (OPPs) from juice samples prior to gas chromatography-nitrogen phosphorous detection (GC-NPD). The properties and morphology of 3D-G-Fe3O4 were characterized by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR) and vibrating sample magnetometry (VSM). The main experimental parameters affecting extraction recoveries including extraction time, amount of adsorbent, pH of sample solution, salt concentration and desorption conditions were carefully studied and optimized. The results showed wide linear concentration ranges with determination coefficients between 0.9973 and 0.9999. The limits of detection (S/N=3) of the method and limits of quantification (S/N=10) were from 1.2 to 5.1 ng L(-1) and 3.4-17.0 ng L(-1), respectively. The intra-day and inter-day RSDs were 2.6-5.1% and 3.5-6.9%, respectively. The method was successfully applied to the analysis of OPPs in fruit juices (apple, orange, grape, sour-cherry and apricot) with recoveries in range of 86.6-107.5%. The GC-NPD results were confirmed by gas chromatography-mass spectrometry (GC-MS). The results demonstrated that with combination of highly interconnected 3D network structure and magnetism property of adsorbent, 3D-G-Fe3O4 aerogel exhibited exceptional extraction ability towards the OPPs. PMID:27018186

  16. Regenerative adsorbent heat pump

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative adsorbent heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system and at least a portion of the heat of adsorption. A series of at least four compressors containing an adsorbent is provided. A large amount of heat is transferred from compressor to compressor so that heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  17. Structural investigations of adsorbed films of Methyl Halides on Boron Nitride

    NASA Astrophysics Data System (ADS)

    Sprung, Michael; Freitag, Andrea; Hanson, Jonathan; Larese, John

    2000-03-01

    The Methyl Halides are a group of molecules whose properties of thin adsorbed films on Graphite have been well characterized. Boron Nitride forms a hexagonal structure with a slightly larger (about 2% ) unit cell than Graphite. The study of thin films of Methyl Halides (CH_3R, R=Cl, Br and I) on Boron Nitride is motivated by the hope to gain a better understanding of adsorbate-substrate interaction. High resolution adsorption isotherms and x-ray powder diffraction have been used to investigate the monolayer structures of CH_3R adsorbed on Boron Nitride. The experiments were carried out at the Beamline X7B of the NSLS. The gases were dosed onto the sample with an automated gas handling system, and a Mar345 image plate detector was used to collect the data. The measurements were performed in a temperature range between 50 and 175 K. All three adsorbates form a solid monolayer structure on Boron Nitride at low temperature. The structure of Methyl Chloride and Methyl Bromide is very similar to the high-density structure of CH_3Cl on Graphite. This is surprising for CH_3Br because it forms a different structure on Graphite. Methyl Iodide forms similar structures on both substrates.

  18. Chemical reactions between cold trapped Ba+ ions and neutral molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Roth, B.; Offenberg, D.; Zhang, C. B.; Schiller, S.

    2008-10-01

    Using a laser-cooled ion trapping apparatus, we have investigated laser-induced chemical reactions between cold trapped Ba+ ions and several neutral molecular gases at room temperature, O2 , CO2 , and N2O , leading to the production of cold trapped (≈20mK) BaO+ ions. The BaO+ ions were converted back to Ba+ ions via reaction with room-temperature CO. Reaction rates were determined by employing molecular dynamics simulations. The cold mixed-species ion ensembles produced were used for studying the efficiency of sympathetic cooling, by variation of the ratio of laser-cooled to sympathetically cooled ion numbers. In one extreme case, 20 laser-cooled Ba+138 ions were capable of maintaining the translational temperature of 120 sympathetically cooled barium isotopes (Ba+135-137) and 430 Ba16138O+ molecules at approximately 25mK .

  19. Linear tension of two-dimensional drops on planar adsorbent faces

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.; Zaytseva, E. S.; Rabinovich, A. B.

    2016-06-01

    The size dependence of the linear tension of round two-dimensional equilibrium drops in the vapor phase on a homogeneous surface of an adsorbent is studied at the pressure of saturated two-dimensional vapor. The calculations are based on the lattice gas model in a quasi-chemical approximation with allowance for the correlation effects of the nearest interacting molecules. Methods for calculating linear tension using the equimolecular reference line are considered. Temperature dependences of the linear tension are studied for metastable and equilibrium drops. It is found that the differences between the thermodynamic properties of two types of drops are slight over a wide range of variation in drop radii.

  20. An index of the literature for bimolecular gas phase cation-molecule reaction kinetics

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.

    2003-01-01

    This is an index to the literature for gas phase bimolecular positive ionmolecule reactions. Over 2300 references are cited. Reaction rate coefficients and product distributions of the reactions are abstracted out of the original citations where available. This index is intended to cover the literature from 1936 to 2003. This is a continuation of several surveys: the original (Huntress Astrophys. J. Suppl. Ser., 33, 495 (1977)), an expansion (Anicich and Huntress, Astrophys. J. Suppl. Ser. 62, 553 (1986)), a supplement (Anicich, Astrophys. J. Suppl. Ser. 84, 215 (1993)), and an evaluation (Anicich, V. G. J. Phys. Chem. Ref. Data 22,1469 (1993b). The Table of reactions is listed by reactant ion.

  1. Computer simulations of adsorbed liquid crystal films

    NASA Astrophysics Data System (ADS)

    Wall, Greg D.; Cleaver, Douglas J.

    2003-01-01

    The structures adopted by adsorbed thin films of Gay-Berne particles in the presence of a coexisting vapour phase are investigated by molecular dynamics simulation. The films are adsorbed at a flat substrate which favours planar anchoring, whereas the nematic-vapour interface favours normal alignment. On cooling, a system with a high molecule-substrate interaction strength exhibits substrate-induced planar orientational ordering and considerable stratification is observed in the density profiles. In contrast, a system with weak molecule-substrate coupling adopts a director orientation orthogonal to the substrate plane, owing to the increased influence of the nematic-vapour interface. There are significant differences between the structures adopted at the two interfaces, in contrast with the predictions of density functional treatments of such systems.

  2. Post-translational modification in the gas phase: mechanism of cysteine S-nitrosylation via ion-molecule reactions

    PubMed Central

    Osburn, Sandra; O'Hair, Richard A.J.; Black, Stephen M.; Ryzhov, Victor

    2013-01-01

    The gas-phase mechanism of S-nitrosylation of thiols was studied in a quadrupole ion trap mass spectrometer. This was done via ion-molecule reactions of protonated cysteine and many of its derivatives and other thiol ions with neutral tert-butyl nitrite or nitrous acid. Our results showed that the presence of the carboxylic acid functional group, –COOH, in the vicinity of the thiol group is essential for the gas-phase nitrosylation of thiols. When the carboxyl proton is replaced by a methyl group (cysteine methyl ester) no nitrosylation was observed. Other thiols lacking a carboxylic acid functional group displayed no S-nitrosylation, strongly suggesting that the carboxyl hydrogen plays a key role in the nitrosylation process. These results are in excellent agreement with a solution-phase mechanism proposed by Stamler et al. (J. S. Stamler, E. J. Toone, S. A. Lipton, N. J. Sucher. Neuron 1997, 18, 691–696) who suggested a catalytic role for the carboxylic acid group adjacent to cysteine residues and with later additions by Ascenzi et al. (P. Ascenzi, M. Colasanti, T. Persichini, M. Muolo, F. Polticelli, G. Venturini, D. Bordo, M. Bolognesi. Biol. Chem. 2000, 381, 623–627) who postulated that the presence of the carboxyl in the cysteine microenvironment in proteins is crucial for S-nitrosylation. A concerted mechanism for the gas-phase S-nitrosylation was proposed based on our results and was further studied using theoretical calculations. Our calculations showed that this proposed pathway is exothermic by 44.0 kJ mol−1. This is one of the few recent examples when a gas-phase mechanism matches one in solution. PMID:22006383

  3. Post-translational modification in the gas phase: mechanism of cysteine S-nitrosylation via ion-molecule reactions.

    PubMed

    Osburn, Sandra; O'Hair, Richard A J; Black, Stephen M; Ryzhov, Victor

    2011-11-15

    The gas-phase mechanism of S-nitrosylation of thiols was studied in a quadrupole ion trap mass spectrometer. This was done via ion-molecule reactions of protonated cysteine and many of its derivatives and other thiol ions with neutral tert-butyl nitrite or nitrous acid. Our results showed that the presence of the carboxylic acid functional group, -COOH, in the vicinity of the thiol group is essential for the gas-phase nitrosylation of thiols. When the carboxyl proton is replaced by a methyl group (cysteine methyl ester) no nitrosylation was observed. Other thiols lacking a carboxylic acid functional group displayed no S-nitrosylation, strongly suggesting that the carboxyl hydrogen plays a key role in the nitrosylation process. These results are in excellent agreement with a solution-phase mechanism proposed by Stamler et al. (J. S. Stamler, E. J. Toone, S. A. Lipton, N. J. Sucher. Neuron 1997, 18, 691-696) who suggested a catalytic role for the carboxylic acid group adjacent to cysteine residues and with later additions by Ascenzi et al. (P. Ascenzi, M. Colasanti, T. Persichini, M. Muolo, F. Polticelli, G. Venturini, D. Bordo, M. Bolognesi. Biol. Chem. 2000, 381, 623-627) who postulated that the presence of the carboxyl in the cysteine microenvironment in proteins is crucial for S-nitrosylation. A concerted mechanism for the gas-phase S-nitrosylation was proposed based on our results and was further studied using theoretical calculations. Our calculations showed that this proposed pathway is exothermic by 44.0 kJ mol(-1). This is one of the few recent examples when a gas-phase mechanism matches one in solution. PMID:22006383

  4. Dissociation degree of nitrogen molecule in low-pressure microwave-discharge nitrogen plasma with various rare-gas admixtures

    NASA Astrophysics Data System (ADS)

    Kuwano, Kei; Nezu, Atsushi; Matsuura, Haruaki; Akatsuka, Hiroshi

    2016-08-01

    The dissociation degree of nitrogen molecules is examined in a microwave discharge nitrogen–rare gas mixture plasma with a total discharge pressure of 1 Torr, by actinometry measurement. Although the spectral line from the excited nitrogen atoms is overlapped by the band spectrum of the N2 first positive system (1PS), the subtraction of the 1PS spectrum fitted theoretically can successfully extract the atomic nitrogen line, which enables actinometry measurement. The nitrogen dissociation degree decreases with increasing mixture ratio of Ar to Kr, whereas it increases with He, which is attributed to the variations in the electron temperature and density. When we dilute the nitrogen with neon, however, we find an anomalous increase in the nitrogen dissociation degree by several orders of magnitude even at a downstream region in the discharge tube. The reason for the dissociation enhancement upon adding neon is discussed in terms of atomic and molecular processes in the plasma.

  5. Nuclear dynamics and spectator effects in resonant inelastic soft x-ray scattering of gas-phase water molecules

    SciTech Connect

    Weinhardt, Lothar; Benkert, Andreas; Meyer, Frank; Blum, Monika; Wilks, Regan G.; Yang, Wanli; Baer, Marcus; Reinert, Friedrich; and others

    2012-04-14

    The electronic structure of gas-phase H{sub 2}O and D{sub 2}O molecules has been investigated using resonant inelastic soft x-ray scattering (RIXS). We observe spectator shifts for all valence orbitals when exciting into the lowest three absorption resonances. Strong changes of the relative valence orbital emission intensities are found when exciting into the different absorption resonances, which can be related to the angular anisotropy of the RIXS process. Furthermore, excitation into the 4a{sub 1} resonance leads to nuclear dynamics on the time scale of the RIXS process; we find evidence for vibrational coupling and molecular dissociation in both, the spectator and the participant emission.

  6. Fabrication of zeolitic imidazolate framework-8-methacrylate monolith composite capillary columns for fast gas chromatographic separation of small molecules.

    PubMed

    Yusuf, Kareem; Badjah-Hadj-Ahmed, Ahmed Yacine; Aqel, Ahmad; ALOthman, Zeid Abdullah

    2015-08-01

    A composite zeolitic imidazolate framework-8 (ZIF-8) with a butyl methacrylate-co-ethylene dimethacrylate (BuMA-co-EDMA) monolithic capillary column (33.5cm long×250μm i.d.) was fabricated to enhance the separation efficiency of methacrylate monoliths toward small molecules using conventional low-pressure gas chromatography in comparison with a neat butyl methacrylate-co-ethylene dimethacrylate (BuMA-co-EDMA) monolithic capillary column (33.5cm long×250μm i.d.). The addition of 10mgmL(-1) ZIF-8 micro-particles increased the BET surface area of BuMA-co-EDMA by 3.4-fold. A fast separation of five linear alkanes in 36s with high resolution (Rs≥1.3) was performed using temperature program. Isothermal separation of the same sample also showed a high efficiency (3315platesm(-1) for octane) at 0.89min. Moreover, the column was able to separate skeletal isomers, such as iso-octane/octane and 2-methyl octane/nonane. In addition, an iso-butane/iso-butylene gas mixture was separated at ambient temperature. Comparison with an open tubular TR-5MS column (30m long×250μm i.d.) revealed the superiority of the composite column in separating the five-membered linear alkane mixture with 4-5 times increase in efficiency and a total separation time of 0.89min instead of 4.67min. A paint thinner sample was fully separated using the composite column in 2.43min with a good resolution (Rs≥0.89). The perfect combination between the polymeric monolith, with its high permeability, and ZIF-8, with its high surface area and flexible 0.34nm pore openings, led to the fast separation of small molecules with high efficiency and opened a new horizon in GC applications. PMID:26141277

  7. Kohn-Sham approach to Fermi gas superfluidity: The bilayer of fermionic polar molecules

    NASA Astrophysics Data System (ADS)

    Ancilotto, Francesco

    2016-05-01

    By using a well-established "ab initio" theoretical approach developed in the past to quantitatively study the superconductivity of condensed matter systems, based on the Kohn-Sham density functional theory, I study the superfluid properties and the BCS-BEC crossover of two parallel bi-dimensional layers of fermionic dipolar molecules, where the pairing mechanism leading to superfluidity is provided by the interlayer coupling between dipoles. The finite temperature superfluid properties of both the homogeneous system and one where the fermions in each layer are confined by a square optical lattice are studied at half filling conditions, and for different values of the strength of the confining optical potential. The T = 0 results for the homogeneous system are found to be in excellent agreement with diffusion Monte Carlo results. The superfluid transition temperature in the BCS region is found to increase, for a given interlayer coupling, with the strength of the confining optical potential. A transition occurs at sufficiently small interlayer distances, where the fermions becomes localized within the optical lattice sites in a square geometry with an increased effective lattice constant, forming a system of localized composite bosons. This transition should be signaled by a sudden drop in the superfluid fraction of the system.

  8. GAS-PHASE REACTIONS OF POLYCYCLIC AROMATIC HYDROCARBON ANIONS WITH MOLECULES OF INTERSTELLAR RELEVANCE

    SciTech Connect

    Demarais, Nicholas J.; Yang Zhibo; Martinez, Oscar; Wehres, Nadine; Bierbaum, Veronica M.; Snow, Theodore P. E-mail: Zhibo.Yang@Colorado.edu E-mail: Nadine.Wehres@Colorado.edu E-mail: Theodore.Snow@Colorado.edu

    2012-02-10

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C{sub 6}H{sup -}{sub 5}), naphthalenide (C{sub 10}H{sup -}{sub 7}), and anthracenide (C{sub 14}H{sup -}{sub 9}) with atomic H, H{sub 2}, and D{sub 2} using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O{sub 2}, CO{sub 2}, N{sub 2}O, C{sub 2}H{sub 2}, CH{sub 3}OH, CH{sub 3}CN, (CH{sub 3}){sub 2}CO, CH{sub 3}CHO, CH{sub 3}Cl, and (CH{sub 3}CH{sub 2}){sub 2}O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  9. Gas-phase ion-molecule reactions of small nitroalkanes and their deprotonated anions.

    PubMed

    Kato, Shuji; Carrigan, Kathleen E; DePuy, Charles H; Bierbaum, Veronica M

    2004-01-01

    Gas-phase reactions of nitromethane (1), nitroethane (2), 2-nitropropane (3), 2-methyl-2-nitropropane (4) and nitrocyclopropane (5) were studied at 300 K using the flowing afterglow technique. These nitroalkanes react with gas-phase bases HO(-), CH(3)O(-) and HOO(-) very rapidly with rate coefficients of (2.5-4.3) x 10(-9) cm(3) s(-1) and reaction efficiencies of 60-100%, for example, k = 3.2 x 10(-9) cm(3) s(-1) (86%) for 5 reacting with hydroperoxide anion. Proton transfer (PT) is the only reaction observed for 1 while elimination (E2) is the exclusive pathway for 4 yielding isobutene and NO(2)(-). Both PT and E2 reactions are observed for 2, 3 and 5, the former being the major pathway. Deprotonated anions of 1, 2, 3 and 5 were subjected to reactivity studies with CH(3)I, CO(2), CS(2) and SO(2). Nucleophilic substitution (S(N)2) reaction occurs with CH(3)I while characteristic products CS(2)O(-) and SO(3)(-) are formed from CS(2) and SO(2), respectively, along with competing adduct formation. The SN(2) rate is greater, whereas the reactivities with the triatomic reagents are smaller for deprotonated nitrocyclopropane than for the other acyclic anions. These observations strongly suggest that the reactions of nitroalkane [M - H](-) anions occur through initial attack from the terminal oxygen; the nitrocyclopropane carbanion is more strained and, thus, less stabilized by resonance [R(2)C(-) - NO2 <--> R(2)=NO(2)(-)] resulting in the greater basicity/nucleophilicy and the less negative charge on the oxygen site. PMID:15103100

  10. Adsorbent and adsorbent bed for materials capture and separation processes

    SciTech Connect

    Liu, Wei

    2011-01-25

    A method device and material for performing adsorption wherein a fluid mixture is passed through a channel in a structured adsorbent bed having a solid adsorbent comprised of adsorbent particles having a general diameter less than 100 um, loaded in a porous support matrix defining at least one straight flow channel. The adsorbent bed is configured to allow passage of a fluid through said channel and diffusion of a target material into said adsorbent under a pressure gradient driving force. The targeted molecular species in the fluid mixture diffuses across the porous support retaining layer, contacts the adsorbent, and adsorbs on the adsorbent, while the remaining species in the fluid mixture flows out of the channel.

  11. First-principles study of Au-Cu alloy surface changes induced by gas adsorption of CO, NO, or O2.

    PubMed

    Dhifallah, Marwa; Dhouib, Adnene; Aldulaijan, Sarah; D I Renzo, Francesco; Guesmi, Hazar

    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 O2 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 the (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. PMID:27421421

  12. H-bonding of an NH3 gas molecule to H2O/Pt(111) — A barrier-free path

    NASA Astrophysics Data System (ADS)

    Henkelman, Graeme; Feibelman, Peter J.

    2016-02-01

    Does an OH-flipping barrier hinder H-bond formation between a gas phase molecule and a water monolayer whose free OH ligands point toward a substrate? According to density functional theory calculations for water on Pt(111) the answer is yes, when the molecule is CO or N2, but no when it is NH3. The difference is the relatively strong attraction of the NH3 lone pair to free OH ligands.

  13. Methane Recovery from Gaseous Mixtures Using Carbonaceous Adsorbents

    NASA Astrophysics Data System (ADS)

    Buczek, Bronisław

    2016-06-01

    Methane recovery from gaseous mixtures has both economical and ecological aspect. Methane from different waste gases like mine gases, nitrogenated natural gases and biogases can be treated as local source for production electric and heat energy. Also occurs the problem of atmosphere pollution with methane that shows over 20 times more harmful environmental effect in comparison to carbon dioxide. One of the ways utilisation such gases is enrichment of methane in the PSA technique, which requires appropriate adsorbents. Active carbons and carbon molecular sieve produced by industry and obtained in laboratory scale were examined as adsorbent for methane recuperation. Porous structure of adsorbents was investigated using densimetry measurements and adsorption of argon at 77.5K. On the basis of adsorption data, the Dubinin-Radushkevich equation parameters, micropore volume (Wo) and characteristics of energy adsorption (Eo) as well as area micropores (Smi) and BET area (SBET) were determined. The usability of adsorbents in enrichment of the methane was evaluated in the test, which simulate the basic stages of PSA process: a) adsorbent degassing, b) pressure raise in column by feed gas, c) cocurrent desorption with analysis of out flowing gas. The composition of gas phase was accepted as the criterion of the suitability of adsorbent for methane separation from gaseous mixtures. The relationship between methane recovery from gas mixture and texture parameters of adsorbents was found.

  14. Interaction energy and itinerant ferromagnetism in a strongly interacting Fermi gas in the absence of molecule formation

    SciTech Connect

    He, Lianyi

    2014-11-26

    In this study, we investigate the interaction energy and the possibility of itinerant ferromagnetism in a strongly interacting Fermi gas at zero temperature in the absence of molecule formation. The interaction energy is obtained by summing the perturbative contributions of Galitskii-Feynman type to all orders in the gas parameter. It can be expressed by a simple phase-space integral of an in-medium scattering phase shift. In both three and two dimensions (3D and 2D), the interaction energy shows a maximum before reaching the resonance from the Bose-Einstein condensate side, which provides a possible explanation of the experimental measurements of the interaction energy. This phenomenon can be theoretically explained by the qualitative change of the nature of the binary interaction in the medium. The appearance of an energy maximum has significant effects on the itinerant ferromagnetism. In 3D, the ferromagnetic transition is reentrant and itinerant ferromagnetism exists in a narrow window around the energy maximum. In 2D, the present theoretical approach suggests that itinerant ferromagnetism does not exist, which reflects the fact that the energy maximum becomes much lower than the energy of the fully polarized state.

  15. Interaction energy and itinerant ferromagnetism in a strongly interacting Fermi gas in the absence of molecule formation

    DOE PAGESBeta

    He, Lianyi

    2014-11-26

    In this study, we investigate the interaction energy and the possibility of itinerant ferromagnetism in a strongly interacting Fermi gas at zero temperature in the absence of molecule formation. The interaction energy is obtained by summing the perturbative contributions of Galitskii-Feynman type to all orders in the gas parameter. It can be expressed by a simple phase-space integral of an in-medium scattering phase shift. In both three and two dimensions (3D and 2D), the interaction energy shows a maximum before reaching the resonance from the Bose-Einstein condensate side, which provides a possible explanation of the experimental measurements of the interactionmore » energy. This phenomenon can be theoretically explained by the qualitative change of the nature of the binary interaction in the medium. The appearance of an energy maximum has significant effects on the itinerant ferromagnetism. In 3D, the ferromagnetic transition is reentrant and itinerant ferromagnetism exists in a narrow window around the energy maximum. In 2D, the present theoretical approach suggests that itinerant ferromagnetism does not exist, which reflects the fact that the energy maximum becomes much lower than the energy of the fully polarized state.« less

  16. Evaluation of Chemical Interactions between Small Molecules in the Gas Phase Using Chemical Force Microscopy

    PubMed Central

    Lee, Jieun; Ju, Soomi; Kim, In Tae; Jung, Sun-Hwa; Min, Sun-Joon; Kim, Chulki; Sim, Sang Jun; Kim, Sang Kyung

    2015-01-01

    Chemical force microscopy analyzes the interactions between various chemical/biochemical moieties in situ. In this work we examined force-distance curves and lateral force to measure the interaction between modified AFM tips and differently functionalized molecular monolayers. Especially for the measurements in gas phase, we investigated the effect of humidity on the analysis of force-distance curves and the images in lateral force mode. Flat chemical patterns composed of different functional groups were made through micro-contact printing and lateral force mode provided more resolved analysis of the chemical patterns. From the images of 1-octadecanethiol/11-mercapto-1-undecanoic acid patterns, the amine group functionalized tip brought out higher contrast of the patterns than an intact silicon nitride tip owing to the additional chemical interaction between carboxyl and amine groups. For more complex chemical interactions, relative chemical affinities toward specific peptides were assessed on the pattern of 1-octadecanethiol/phenyl-terminated alkanethiol. The lateral image of chemical force microscopy reflected specific preference of a peptide to phenyl group as well as the hydrophobic interaction. PMID:26690165

  17. Mechanisms of laser interaction with metal carbonyls adsorbed on Si(111)7 × 7: Thermal vs photoelectronic effects

    NASA Astrophysics Data System (ADS)

    Gluck, N. S.; Ying, Z.; Bartosch, C. E.; Ho, W.

    1987-05-01

    Ultrahigh vacuum studies of the interaction of 514 nm radiation from a cw Ar ion laser and its second harmonic at 257 nm with mono- and multilayer coverages of Mo(CO)6, W(CO)6, and Fe(CO)5 adsorbed on Si(111)7×7 at 90 K using thermal desorption spectroscopy (TDS), laser induced desorption spectroscopy, high resolution electron energy loss spectroscopy (HREELS), and Auger electron spectroscopy were performed. A model for the temperature rise of the sample due to cw laser heating is developed. By directly measuring the substrate temperature, these experiments were able to distinguish between photoelectronic and thermal effects active in the decomposition and desorption mechanisms of the adsorbed carbonyls. Results from TDS and HREELS show that Mo(CO)6 and W(CO)6 are molecularly adsorbed, while Fe(CO)5 partially dissociates upon adsorption. The decomposition of adsorbed Mo(CO)6 is caused by electronic excitation due to direct absorption of the 257 nm radiation. Irradiation with 514 nm radiation results in no photochemistry. The same mechanism is dominant for adsorbed W(CO)6 and Fe(CO)5; however, new excitation mechanisms are available to these molecules that lead to bonding changes in W(CO)6 and Fe(CO)5 with 514 nm irradiation. The photodecomposition products of the adsorbed carbonyls are found to be different from the gas-phase decomposition products. The surface stabilizes the adsorbed carbonyls, preventing complete removal of all the CO ligands. Desorption of CO due to photoelectronic excitation is found to occur via sequential single photon absorption and extraction of CO ligands. Evidence of clustering of carbonyl fragments was observed after 257 nm irradiation.

  18. [Determination of six phthalate acid esters in camellia oil by gas chromatography-mass spectrometry coupled with solid-phase extraction using single-walled carbon nanotubes as adsorbent].

    PubMed

    Zhang, Fan; Li, Zhonghai; Zhang, Ying; Huang, Zhiqiang; Wang, Xiaosong

    2014-07-01

    An analytical method based on solid-phase extraction with single-walled carbon nanotubes (SWCNTs) as adsorbent was developed for the simultaneous determination of six phthalate acid esters (PAEs) in camellia oil by gas chromatography-mass spectrometry (GC-MS). The samples were diluted by hexane and then cleaned up with a glass SWCNTs solid phase extraction (SPE) column. The PAEs were measured by GC-MS in selected ion monitoring (SIM) mode, using external standard method for quantitative analysis. The important factors affecting extraction efficiency, such as the dilution volume of hexane, the type of adsorbent material, the dosage of SWCNTs, the volume of wash solution, the type and volume of elution solution were optimized. The optimal conditions were as follows: the dilution volume of hexane was 5 mL, the dosage of SWCNTs was 0.6 g, the wash solution was 20 mL hexane, and the elution solution was 5 mL toluene. The six PAEs had a good linear range from 0.05 mg/L to 1.0 mg/L, with the correlation coefficients (r) all above 0.999 9. The average recoveries of the six targets in spiked camellia oil (from 0.05 mg/kg to 1.0 mg/kg) ranged from 86.4% to 111.7% with the relative standard deviations (RSDs) from 4.2% to 10.4%. The developed method is accurate, quick and suitable for the determination of the six PAEs in camellia oil. PMID:25255566

  19. Electronic structure of benzene adsorbed on Ni and Cu surfaces

    SciTech Connect

    Weinelt, M.; Nilsson, A.; Wassdahl, N.

    1997-04-01

    Benzene has for a long time served as a prototype adsorption system of large molecules. It adsorbs with the molecular plane parallel to the surface. The bonding of benzene to a transition metal is typically viewed to involve the {pi} system. Benzene adsorbs weakly on Cu and strongly on Ni. It is interesting to study how the adsorption strength is reflected in the electronic structure of the adsorbate-substrate complex. The authors have used X-ray Emission (XE) and X-ray Absorption (XA) spectroscopies to selectively study the electronic states localized on the adsorbed benzene molecule. Using XES the occupied states can be studies and with XAS the unoccupied states. The authors have used beamline 8.0 and the Swedish endstation equipped with a grazing incidence x-ray spectrometer and a partial yield absorption detector. The resolution in the XES and XAS were 0.5 eV and 0.05 eV, respectively.

  20. New insights into perfluorinated adsorbents for analytical and bioanalytical applications.

    PubMed

    Marchetti, Nicola; Guzzinati, Roberta; Catani, Martina; Massi, Alessandro; Pasti, Luisa; Cavazzini, Alberto

    2015-01-01

    Perfluorinated (F-) adsorbents are generally prepared by bonding perfluoro-functionalized silanes to silica gels. They have been employed for a long time essentially as media for solid-phase extraction of F-molecules or F-tagged molecules in organic chemistry and heterogeneous catalysis. More recently, this approach has been extended to proteomics and metabolomics. Owing to their unique physicochemical properties, namely fluorophilicity and proteinophilicity, and a better understanding of some fundamental aspects of their behavior, new applications of F-adsorbents in the field of environmental science and bio-affinity studies can be envisaged. In this article, we revisit the most important features of F-adsorbents by focusing, in particular, on some basic information that has been recently obtained through (nonlinear) chromatographic studies. Finally, we try to envisage new applications and possibilities that F-adsorbents will allow in the near future. PMID:25358910

  1. Ion Molecule Reactions of Gas-Phase Chromium Oxyanions:CrxOyHz- + O2

    SciTech Connect

    Anita K. Gianotto; Brittany D. M. Hodges; Peter de B. Harrington; Anthony Appelhans; John E. Olson; Gary S. Groenewold

    2003-10-01

    Chromium oxyanions, CrxOyHz-, were generated in the gas-phase using a quadrupole ion trap secondary ion mass spectrometer (IT-SIMS), where they were reacted with O2. Only CrO2- of the Cr1OyHz- envelope was observed to react with oxygen, producing primarily CrO3-. The rate constant for the reaction of CrO2- with O2 was 38% of the Langevin collision constant at 310 K. CrO3-, CrO4-, and CrO4H- were unreactive with O2 in the ion trap. In contrast, Cr2O4- was observed to react with O2 producing CrO3- + CrO3 via oxidative degradation at a rate that was 15% efficient. The presence of background water facilitated the reaction of Cr2O4- + H2O to form Cr2O5H2-; the hydrated product ion Cr2O5H2- reacted with O2 to form Cr2O6- (with concurrent elimination of H2O) at a rate that was 6% efficient. Cr2O5- also reacted with O2 to form Cr2O7- (4% efficient) and Cr2O6- + O (2% efficient); these reactions proceeded in parallel. By comparison, Cr2O6- was unreactive with O2, and in fact, no further O2 addition could be observed for any of the Cr2O6Hz- anions. Generalizing, CrxOyHz- species that have low coordinate, low oxidation state metal centers are susceptible to O2 oxidation. However, when the metal coordination is >3, or when the formal oxidation state is =5, reactivity stops.

  2. 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 ...

  3. Interstellar molecules

    NASA Astrophysics Data System (ADS)

    Smith, D.

    1987-09-01

    Some 70 different molecular species have so far been detected variously in diffuse interstellar clouds, dense interstellar clouds, and circumstellar shells. Only simple (diatomic and triatomic) species exist in diffuse clouds because of the penetration of destructive UV radiations, whereas more complex (polyatomic) molecules survive in dense clouds as a result of the shielding against this UV radiation provided by dust grains. A current list of interstellar molecules is given together with a few other molecular species that have so far been detected only in circumstellar shells. Also listed are those interstellar species that contain rare isotopes of several elements. The gas phase ion chemistry is outlined via which the observed molecules are synthesized, and the process by which enrichment of the rare isotopes occurs in some interstellar molecules is described.

  4. Detecting the mass and position of an adsorbate on a drum resonator

    PubMed Central

    Zhang, Y.; Zhao, Y. P.

    2014-01-01

    The resonant frequency shifts of a circular membrane caused by an adsorbate are the sensing mechanism for a drum resonator. The adsorbate mass and position are the two major (unknown) parameters determining the resonant frequency shifts. There are infinite combinations of mass and position which can cause the same shift of one resonant frequency. Finding the mass and position of an adsorbate from the experimentally measured resonant frequencies forms an inverse problem. This study presents a straightforward method to determine the adsorbate mass and position by using the changes of two resonant frequencies. Because detecting the position of an adsorbate can be extremely difficult, especially when the adsorbate is as small as an atom or a molecule, this new inverse problem-solving method should be of some help to the mass resonator sensor application of detecting a single adsorbate. How to apply this method to the case of multiple adsorbates is also discussed. PMID:25294971

  5. Orbital tomography for highly symmetric adsorbate systems

    NASA Astrophysics Data System (ADS)

    Stadtmüller, B.; Willenbockel, M.; Reinisch, E. M.; Ules, T.; Bocquet, F. C.; Soubatch, S.; Puschnig, P.; Koller, G.; Ramsey, M. G.; Tautz, F. S.; Kumpf, C.

    2012-10-01

    Orbital tomography is a new and very powerful tool to analyze the angular distribution of a photoemission spectroscopy experiment. It was successfully used for organic adsorbate systems to identify (and consequently deconvolute) the contributions of specific molecular orbitals to the photoemission data. The technique was so far limited to surfaces with low symmetry like fcc(110) oriented surfaces, owing to the small number of rotational domains that occur on such surfaces. In this letter we overcome this limitation and present an orbital tomography study of a 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) monolayer film adsorbed on Ag(111). Although this system exhibits twelve differently oriented molecules, the angular resolved photoemission data still allow a meaningful analysis of the different local density of states and reveal different electronic structures for symmetrically inequivalent molecules. We also discuss the precision of the orbital tomography technique in terms of counting statistics and linear regression fitting algorithm. Our results demonstrate that orbital tomography is not limited to low-symmetry surfaces, a finding which makes a broad field of complex adsorbate systems accessible to this powerful technique.

  6. Radial diffusion and penetration of gas molecules and aerosol particles through laminar flow reactors, denuders, and sampling tubes.

    PubMed

    Knopf, Daniel A; Pöschl, Ulrich; Shiraiwa, Manabu

    2015-04-01

    Flow reactors, denuders, and sampling tubes are essential tools for many applications in analytical and physical chemistry and engineering. We derive a new method for determining radial diffusion effects and the penetration or transmission of gas molecules and aerosol particles through cylindrical tubes under laminar flow conditions using explicit analytical equations. In contrast to the traditional Brown method [Brown, R. L. J. Res. Natl. Bur. Stand. (U. S.) 1978, 83, 1-8] and CKD method (Cooney, D. O.; Kim, S. S.; Davis, E. J. Chem. Eng. Sci. 1974, 29, 1731-1738), the new approximation developed in this study (known as the KPS method) does not require interpolation or numerical techniques. The KPS method agrees well with the CKD method under all experimental conditions and also with the Brown method at low Sherwood numbers. At high Sherwood numbers corresponding to high uptake on the wall, flow entry effects become relevant and are considered in the KPS and CKD methods but not in the Brown method. The practical applicability of the KPS method is demonstrated by analysis of measurement data from experimental studies of rapid OH, intermediate NO3, and slow O3 uptake on various organic substrates. The KPS method also allows determination of the penetration of aerosol particles through a tube, using a single equation to cover both the limiting cases of high and low deposition described by Gormley and Kennedy (Proc. R. Ir. Acad., Sect. A. 1949, 52A, 163-169). We demonstrate that the treatment of gas and particle diffusion converges in the KPS method, thus facilitating prediction of diffusional loss and penetration of gases and particles, analysis of chemical kinetics data, and design of fluid reactors, denuders, and sampling lines. PMID:25744622

  7. Surface-enhanced fluorescence and surface-enhanced Raman scattering of push-pull molecules: sulfur-functionalized 4-amino-7-nitrobenzofurazan adsorbed on Ag and Au nanostructured substrates.

    PubMed

    Muniz-Miranda, Maurizio; Del Rosso, Tommaso; Giorgetti, Emilia; Margheri, Giancarlo; Ghini, Giacomo; Cicchi, Stefano

    2011-04-01

    We investigated the chemisorption of self-assembled monolayers of sulfur-functionalized 4-amino-7-nitrobenzofurazan on gold and silver nanoisland films (NIFs) by means of surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS). The ligand is a push-pull molecule, where an intramolecular charge transfer occurs between an electron-donor and an electron-acceptor group, thus exhibiting nonlinear optical properties that are related to both SERS and SEF effects. The presence of different heteroatoms in the molecule ensures the possibility of chemical interaction with both silver and gold substrates. The SERS spectra suggest that furazan is bound to silver via lone pairs of the nitrogen atoms, whereas the ligand is linked to gold via a sulfur atom. Silver NIFs provide more efficient enhancement of both fluorescence and Raman scattering in comparison with gold NIFs. The present SEF and SERS investigation could provide useful information for foreseeing changes in the nonlinear responses of this push-pull molecule. PMID:21331491

  8. Equilibrium molecular theory of two-dimensional adsorbate drops on surfaces of heterogeneous adsorbents

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2016-08-01

    A molecular statistical theory for calculating the linear tension of small multicomponent droplets in two-dimensional adsorption systems is developed. The theory describes discrete distributions of molecules in space (on a scale comparable to molecular size) and continuous distributions of molecules (at short distances inside cells) in their translational and vibrational motions. Pair intermolecular interaction potentials (the Mie type potential) in several coordination spheres are considered. For simplicity, it is assumed that distinctions in the sizes of mixture components are slight and comparable to the sizes of adsorbent adsorption centers. Expressions for the pressure tensor components inside small droplets on the heterogeneous surface of an adsorbent are obtained, allowing calculations of the thermodynamic characteristics of a vapor-fluid interface, including linear tension. Problems in refining the molecular theory are discussed: describing the properties of small droplets using a coordination model of their structure, considering the effect an adsorbate has on the state of a near-surface adsorbent region, and the surface heterogeneity factor in the conditions for the formation of droplets.

  9. Role of molecular orientational anisotropy in the chiral resolution of enantiomers in adsorbed overlayers.

    PubMed

    Szabelski, Paweł; Woszczyk, Aleksandra

    2012-07-31

    Separation of chiral molecules using achiral inputs is an interesting alternative to traditional techniques based on the chiral recognition mechanism. In this article we propose a lattice gas Monte Carlo model of two-dimensional chiral segregation induced by breaking of molecular orientational symmetry. Simulations were performed on a square lattice for rigid chain molecules composed of four and five identical segments. Mirror-image flat chain conformations resulting in different enantiomeric pairs were considered for each probe molecule. The enantiomers were assumed to interact via short-ranged segment-segment interaction potential limited to nearest neighbors on the lattice. We considered two qualitatively different situations in which (1) the molecules were allowed to rotate on the surface and adopt any of the four planar orientations and (2) the rotation was blocked, so that only one planar orientation was possible. The results obtained for the racemic overlayers showed clearly that the orientational symmetry breaking can induce spontaneous segregation of the enantiomers into large enantiopure domains. However, this effect was observed only for molecules with sufficiently long linear fragment. In the case of kinked bulky molecules a mixed assembly was formed, demonstrating the role of molecular shape in the orientationally biased segregation of enantiomers in adsorbed films. The insights from this study can be useful in developing strategies for 2D chiral separations in which external directional fields are used. PMID:22747234

  10. The gas phase ion/molecule chemistry of four carbanions generated from vinylene carbonate and its methyl and dimethyl derivatives

    NASA Astrophysics Data System (ADS)

    Robinson, Marin S.; Breitbeil, Fred W.

    1992-09-01

    The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HC[triple bond; length as m-dash]C---O-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2=CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3C[triple bond; length as m-dash]C---O- and CH2=CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HC[triple bond; length as m-dash]C---S- and CH3C=C---S-. The ions CH2=CC(O)CH3 and CH2=CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.

  11. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    PubMed Central

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-01-01

    The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis. PMID:25960309

  12. Anomalous EPR intensity distribution of the methyl radical quartet adsorbed on the surface of porous materials. Comparison with solid gas matrix isolation.

    PubMed

    Benetis, Nikolas P; Dmitriev, Yurij

    2013-05-23

    The two inner lines of the EPR quartet of methyl radicals trapped in cryogenic gas matrices are superpositions of the inner transitions of an A-proton-spin quartet and an E-proton-spin doublet. Their intensity relative to the outer lines provides information on the population of the methyl-rotation quantum states. The above intensity ratio for the CH3 in solids is a challenging problem of the quantum dynamics and statistical thermodynamics. The influence of the quantum-mechanical/inertial rotation on the intensity distribution of the hf components of methyl radical on the surface of porous materials, e.g., silica gel, is investigated by EPR line shape simulations and compared with spectra of the radical isolated in the bulk of solid gas samples. The experimental part of this study includes the first in literature EPR observation of methyl radical in the bulk of N2O solid and provides new essential information on CH3 in CO2 and Ar matrices, thus, covering both strongly hindered and almost free rotation of the radical. We verify the observation of nonrotating methyl radicals in a N2O matrix, discovered earlier in cold CO2, give a thorough account of their EPR characteristics, and explore their formation at the inner surface of porous materials. Combination of a classical spin-Hamiltonian with employment of quantum effects due to nuclear spin-rotation coupling and the radical symmetry were used to interpret the experimental spectral observations. The cause of experimentally found unexpected contribution of the excited degenerate E-doublets to the EPR spectrum down to 4.2 K and A/E transition amplitude ratios sometimes as high as ca. 1:8 at liquid-N2 temperature is sought. The validity of Bose-Einstein quantum (BEq-) statistics of the spin rotation states in addition to the classical Maxwell-Boltzmann (Boltzmann) statistics was also assessed against experimental population A/E-ratio data. The BEq-statistics were not previously applied to similar systems. Furthermore

  13. [Magnetic multi-walled carbon nanotubes as a solid phase extraction adsorbent for the determination of 13 phthalate acid esters in water samples by gas chromatography-mass spectrometry].

    PubMed

    Fu, Shanliang; Ding, Li; Zhu, Shaohua; Jiao, Yanna; Gong, Qiang; Chen, Jitao; Wang, Libing

    2011-08-01

    A method based on solid phase extraction (SPE) with magnetic multi-walled carbon nanotubes (MWCNTs) as adsorbent was developed for the determination of 13 phthalate acid esters (PAEs) in water samples by gas chromatography-mass spectrometry (GC-MS). The factors affecting the extraction efficiency, such as extraction time, pH of water sample, desorption solvent, and desorption time, were carefully investigated. The optimized conditions were as follows: extraction time, 10 min; pH of water samples, 5 - 7; desorption solvent, 2 mL acetone; desorption time, 5 min. The extraction efficiencies were 89.7% - 100.5% under the optimized conditions. The method was sensitive with the detection limits (S/N = 3) between 0.08 -0.47 microg/L for the 13 PAEs. The developed method was successfully applied for the analysis of tap water, bottle drinking water and lake water, and none of the 13 PAEs was detected. The recoveries ranged from 84.5% to 107.5% for the 3 real spiked samples, and the relative standard deviations were between 1.9% and 12.8%. The developed method has proved convenient, time-saving, accurate, sensitive, and environmental-friendly, and can be used for the determination of PAEs in water samples. PMID:22128736

  14. Surface Ionization Gas Detection at SnO2 Surfaces

    NASA Astrophysics Data System (ADS)

    Krenkow, A.; Oberhüttinger, C.; Habauzit, A.; Kessler, M.; Göbel, J.; Müller, G.

    2009-05-01

    In surface ionization (SI) gas detection adsorbed analyte molecules are converted into ionic species at a heated solid surface and extracted into free space by an oppositely biased counter electrode. In the present work we consider the formation of positive and negative analyte gas ions at SnO2 surfaces. We find that SI leads to positive ion formation only, with the SI efficiency scaling with the ionization energy of the analyte gas molecules. Aromatic and aliphatic hydrocarbons with amine functional groups exhibit particularly high SI efficiencies.

  15. Mercury adsorption properties of sulfur-impregnated adsorbents

    USGS Publications Warehouse

    Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2002-01-01

    Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

  16. Method of recovering adsorbed liquid compounds from molecular sieve columns

    DOEpatents

    Burkholder, Harvey R.; Fanslow, Glenn E.

    1983-01-01

    Molecularly adsorbed volatile liquid compounds are recovered from molecular sieve adsorbent columns by directionally applying microwave energy to the bed of the adsorbent to produce a mixed liquid-gas effluent. The gas portion of the effluent generates pressure within the bed to promote the discharge of the effluent from the column bottoms. Preferably the discharged liquid-gas effluent is collected in two to three separate fractions, the second or intermediate fraction having a substantially higher concentration of the desorbed compound than the first or third fractions. The desorption does not need to be assisted by passing a carrier gas through the bed or by applying reduced pressure to the outlet from the bed.

  17. Method of recovering adsorbed liquid compounds from molecular sieve columns

    DOEpatents

    Burkholder, H.R.; Fanslow, G.E.

    1983-12-20

    Molecularly adsorbed volatile liquid compounds are recovered from molecular sieve adsorbent columns by directionally applying microwave energy to the bed of the adsorbent to produce a mixed liquid-gas effluent. The gas portion of the effluent generates pressure within the bed to promote the discharge of the effluent from the column bottoms. Preferably the discharged liquid-gas effluent is collected in two to three separate fractions, the second or intermediate fraction having a substantially higher concentration of the desorbed compound than the first or third fractions. The desorption does not need to be assisted by passing a carrier gas through the bed or by applying reduced pressure to the outlet from the bed. 8 figs.

  18. 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

  19. 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.

  20. 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

    2016-01-01

    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

  1. Selective detection of toxic cyanogen gas in the presence of O2, and H2O molecules using a AlN nanocluster

    NASA Astrophysics Data System (ADS)

    Solimannejad, Mohammad; Kamalinahad, Saeedeh; Shakerzadeh, Ehsan

    2016-08-01

    The interaction of cyanogen molecule with Al12N12 nanocage has been studied using density functional theory (DFT) at CAM-B3LYP/6-31+G(d) level. Geometric, electronic structure and natural bond orbitals (NBO) analysis display that adsorption of cyanogen onto exterior surface of Al12N12 is physisorption with adsorption energy (Eads) equal to -55.36 kJ/mol. UV-vis study shows a high intensity peak in 388.9 nm due to interaction of gas with nanocage. It is expected that Al12N12 will be used in designing novel materials for potential applications to detect toxic cyanogen molecule.

  2. Gas-phase ion-molecule reactions for resolution of atomic isobars: AMS and ICP-MS perspectives

    NASA Astrophysics Data System (ADS)

    Bandura, Dmitry R.; Baranov, Vladimir I.; Litherland, A. E.; Tanner, Scott D.

    2006-09-01

    Ion-molecule reactions that can be used for resolution of spectral overlaps of long-lived or stable (T1/2 > 100 years) atomic isobars on the long-lived radio-isotopes (100 < T1/2 < 1012 years) in mass spectrometry are considered. Results for the separations of isobaric overlaps via cation reactions with NO, N2O, O2, CO2, C2H2, CH3F studied with the Inductively Coupled Plasma Dynamic Reaction Cell(TM) Mass Spectrometer (ICP-DRC(TM)-MS) with use of stable isotopes are presented. Overview of potential and reported reactions for separation of 35 isobars is given. Potential for the following isobaric pairs separation is shown (reaction gas and the extent of separation achieved to date in parenthesis): 32Si+/32S+(NO, 5 x 104), 40K+/40Ar+(N2O, 1.9 x 103), 40K+/40Ca+(N2O, 50), 59Ni+/59Co+(N2O, 6), 79Se+/79Br+(O2, 7.2 x 103), 81Kr+/81Br+(C2H2, 1.5 x 104), 93Mo+/93Nb+(N2O, 100), 93Mo+/93Zr+(N2O, 150), 135Cs+/135Ba+(N2O, 8 x 104), 137,138La+/137,138Ba+(O2, 40), 146Sm+/146Nd+(CO2, 1.5 x 105), 176Lu+/176Hf+(NO, 2.8 x 103), 187Re+/187Os+(N2O, 2.8 x 104). Effect of instrumental parameters on reactivity is discussed. The relevance of this work to accelerator mass spectrometry is discussed briefly.

  3. Adsorption kinetics of diatomic molecules.

    PubMed

    Burde, Jared T; Calbi, M Mercedes

    2014-05-01

    The adsorption dynamics of diatomic molecules on solid surfaces is examined by using a Kinetic Monte Carlo algorithm. Equilibration times at increasing loadings are obtained, and explained based on the elementary processes that lead to the formation of the adsorbed film. The ability of the molecules to change their orientation accelerates the overall uptake and leads to competitive kinetic behaviour between the different orientations. The dependence of the equilibration time on coverage follows the same decreasing trend obtained experimentally for ethane adsorption on closed-end carbon nanotube bundles. The exploration of molecule-molecule interaction effects on this trend provides relevant insights to understand the kinetic behaviour of other species, from simpler molecules to larger polyatomic molecules, adsorbing on surfaces with different binding strength. PMID:24654004

  4. 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…

  5. Natural gas conversion process

    SciTech Connect

    Gondouin, M.

    1991-01-01

    Work continued on Task No. 3. Particular attention was given to the back pressure control at the two gaseous effluent outlets and to the incineration of these effluents prior to their disposal. Temperature of the riser/regenerator and steam requirements were predicted from the gasification kinetics of coke and of coal char experimentally determined at atmospheric pressure, but at somewhat lower temperatures by H. Heinemann. The results of interactions of CH4 molecules with a Hydrogen Plasma in the adsorbed layer at the surface of refractory oxides were compared with those in the gas phase in order to select the optimum temperature range in the Cyclone reactor.

  6. Synthesis of Pure and N-substituted Cyclic Hydrocarbons (e.g. Pyrimidine) via Gas-Phase Ion-Molecule Reactions

    NASA Astrophysics Data System (ADS)

    Bera, Partha P.; Peverati, Roberto; Head-Gordon, Martin; Lee, Timothy J.

    2015-08-01

    Large polyatomic carbonaceous molecules, known as polycyclic aromatic hydrocarbons, are known to exist in the outflows of carbon stars. How these large polyatomic molecules are synthesized in such exotic conditions is, thus far, unknown. Molecular ions, including positive and negative ions, are in relative abundance in the high radiation fields present under such conditions. Hence, barrierless ion-molecule interactions may play a major role in guiding molecules towards each other and initiating reactions. We study these condensation pathways to determine whether they are a viable means of forming large pure hydrocarbon molecules, and nitrogen-containing carbonaceous chains, stacks, and even cyclic compounds. By employing accurate quantum chemical methods we have investigated the processes of growth, structures, nature of bonding, mechanisms, and spectroscopic properties of the ensuing ionic products after pairing small carbon, hydrogen, and nitrogen-containing molecules. We have also studied the ion-neutral association pathways involving pure-carbon molecules e.g. acetylene, ethylene and other hydrocarbons, and their dissociation fragments in a plasma discharge as well as how nitrogen atoms are incorporated into the carbon ring during growth. Specifically, we explored the mechanisms by which the synthesis of pyrimidine will be feasible in the gas phase in conjunction with ion-mobility experiments. We have used accurate ab initio coupled cluster theory, Møller-Plesset and Z-averaged perturbation theories, density functional theory, and coupled cluster theory quantum chemical methods together with large correlation consistent basis sets in these investigations. We found that a series of hydrocarbons with a specific stoichiometric composition prefers cyclic molecule formation rather than chains. Some of the association products we investigated have large oscillator strengths for charge-transfer type electronic excitations in the near infrared and visible regions of

  7. A fragment method for systematic improvement of anharmonic adsorbate vibrational frequencies: Acetylene on Cu(001)

    SciTech Connect

    Chulkov, Sergey K. Benoit, David M.

    2013-12-07

    We suggest a novel method for systematic improvement of anharmonic adsorbate frequencies based on a fragment approach. The calculations are carried out by considering the adsorbed molecule separately and computing an energy correction using high-level ab initio method in addition to a standard calculation of the whole adsorbed system using quantum mechanical techniques with periodic boundary conditions. We demonstrate its reliability for a C{sub 2}H{sub 2} molecule chemisorbed on a Cu(001) surface. We also show that the accuracy of the presented approach with a suitable description of the periodic surface depends mainly on the accuracy of the high-level ab initio method used to describe the adsorbate molecule. Moreover, our technique potentially allows to predict adsorbate vibrational spectra with spectroscopic accuracy.

  8. Effect of the internal motions of an adsorbate on the characteristics of adsorption for structurally heterogenous surfaces of slit-like pores

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.; Zaitseva, E. S.; Rabinovich, A. B.

    2016-01-01

    The effect of internal motions of an adsorbate on the local characteristics of adsorption and layering phase diagrams are studied for structurally heterogeneous surfaces of slit-like pores. A molecular model describing adsorbate distributions inside slit-like pores, which is based on discrete distribution functions (lattice gas model), is used for the calculation. Molecular distributions are calculated by the Lennard-Jones potential (12-6) in a quasi-chemical approximation reflecting the effects of direct correlations of interacting particles and for the combined interaction of an adsorbate with walls in the average potential approximation (9-3) and the short-range Lennard-Jones potential for structurally heterogeneous surface areas. The conclusion is made that internal motions reflect the vibrational motion of molecules within a modified quasi-dimer model and a displacement of the adsorbate during its translational motion inside cells. It was found that the taking into account of internal motions decreases the critical temperature of adsorbate layering in slit-like pores.

  9. Halide anion effect on surface enhanced Raman scattering of 2-amino,5-nitropyridine adsorbed on silver sols

    NASA Astrophysics Data System (ADS)

    Muniz-Miranda, Maurizio; Neto, Natale; Sbrana, Giuseppe

    1995-03-01

    2-Amino,5-nitropiridine (ANP) can be adsorbed on silver sols as neutral molecule or ANP- anion, as detected by SERS. The adsorption of the ANP- is related to the presence of hydroxide ions on the metal surface. Strongly adsorbed halide anions are able to remove hydroxide ions from the silver surface, inducing the adsorption of ANP as neutral molecule.

  10. Gas adsorption and accumulation on hydrophobic surfaces: Molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Luo, Qing-Qun; Yang, Jie-Ming

    2015-09-01

    Molecular dynamics simulations show that the gas dissolved in water can be adsorbed at a hydrophobic interface and accumulates thereon. Initially, a water depletion layer appears on the hydrophobic interface. Gas molecules then enter the depletion layer and form a high-density gas-enriched layer. Finally, the gas-enriched layer accumulates to form a nanobubble. The radian of the nanobubble increases with time until equilibrium is reached. The equilibrium state arises through a Brenner-Lohse dynamic equilibrium mechanism, whereby the diffusive outflux is compensated by an influx near the contact line. Additionally, supersaturated gas also accumulates unsteadily in bulk water, since it can diffuse back into the water and is gradually adsorbed by a solid substrate. Project supported by the National Natural Science Foundation of China (Grant No. 21376161).

  11. Ion-Molecule Reaction of Gas-Phase Chromium Oxyanions: CrxOyHz- + H2O

    SciTech Connect

    Gianotto, Anita Kay; Hodges, Brittany DM; Benson, Michael Timothy; Harrington, Peter Boves; Appelhans, Anthony David; Olson, John Eric; Groenewold, Gary Steven

    2003-08-01

    Chromium oxyanions having the general formula CrxOyHz- play a key role in many industrial, environmental, and analytical processes, which motivated investigations of their intrinsic reactivity. Reactions with water are perhaps the most significant, and were studied by generating CrxOyHz- in the gas phase using a quadrupole ion trap secondary ion mass spectrometer. Of the ions in the Cr1OyHz envelope (y = 2, 3, 4; z = 0, 1), only CrO2- was observed to react with H2O, producing the hydrated CrO3H2- at a slow rate (~0.07% of the ion-molecule collision constant at 310 K). CrO3-, CrO4-, and CrO4H- were unreactive. In contrast, Cr2O4-, Cr2O5-, and Cr2O5H2- displayed a considerable tendency to react with H2O. Cr2O4- underwent sequential reactions with H2O, initially producing Cr2O5H2- at a rate that was ~7% efficient. Cr2O5H2- then reacted with a second H2O by addition to form Cr2O6H4- (1.8% efficient) and by OH abstraction to form Cr2O6H3- (0.6% efficient). The reactions of Cr2O5- were similar to those of Cr2O5H2-: Cr2O5- underwent addition to form Cr2O6H2- (3% efficient) and OH abstraction to form Cr2O6H- (<1% efficient). By comparison, Cr2O6- was unreactive with H2O, and in fact, no further H2O addition could be observed for any of the Cr2O6Hz- anions. Hartree-Fock ab initio calculations showed that reactive CrxOyHz- species underwent nucleophilic attack by the incoming H2O molecules, which produced an initially formed adduct in which the water O was bound to a Cr center. The experimental and computational studies suggested that Cr2OyHz- species that have bi- or tricoordinated Cr centers are susceptible to attack by H2O; however, when the metal becomes tetracoordinate, reactivity stops. For the Cr2OyHz- anions the lowest energy structures all contained rhombic Cr2O2 rings with pendant O atoms and/or OH groups. The initially formed [Cr2Oy- + H2O] adducts underwent H rearrangement to a gem O atom to produce stable dihydroxy structures. The calculations indicated that

  12. Relationship between surface viscosity and surface composition of adsorbed surfactant films

    SciTech Connect

    Djabbarah, N.F.; Wasan, D.T.

    1982-02-01

    The single-bubble foaming technique was used to determine the surface excess concentrations of aqueous solutions of sodium lauryl sulfate (SLS) and lauryl alcohol (LOH). The excess concentrations of sodium lauryl sulfate-lauryl alcohol showed that lauryl alcohol is preferentially adsorbed at the surface, but only partially displaces sodium lauryl sulfate. This causes a higher total surface concentration and, consequently, a closer packing of surfactant molecules. The total surface excess concentration increases with an increase in the bulk concentration of the 2 surfactants until the critical micelle concentration (CMC) is reached. At concentrations exceeding the CMC, the surface excess concentration of LOH remains virtually constant, while that of SLS declines. This is due to the formation of SLS micelles. The surface excess concentration data have been used to estimate the extent of molecular packing at the gas/liquid interface and to assess interactions among surfactant molecules in order to explain trends in surface viscosity of a mixed surfactant system adsorbed from an aqueous solution. 30 references.

  13. Boron nitride as a selective gas adsorbent

    SciTech Connect

    Janik, J.F.; Ackerman, W.C.; Paine, R.T.; Hua, D.W.; Maskara, A.; Smith, D.M. )

    1994-02-01

    A series of eight porous boron nitride materials with nitrogen/BET surface areas of 437-712 m[sup 2]/g have been produced using polymeric precursors varied by systematic synthesis modifications. All samples exhibit type I isotherms indicating that a majority of the porosity occurs in pores with radius less than 1.0 nm. Carbon dioxide adsorption at 273 K was analyzed using the Dubinin-Radushkevich (D-R) and Dubinin-Astakov (D-A) equations. Significant differences between BET/N[sub 2] and D-R/CO[sub 2] surface areas are observed. Adsorption of carbon dioxide and methane is measured at 273 K over the pressure range of 0-800 Torr, and significant differences in adsorption selectivity are observed. Although all eight samples have similar BET surface areas, the carbon dioxide uptake at 273 K and 800 Torr varies from 9.5 to 125 cm[sup 3]/g. Differences in the chemical and physical structure of the samples are probed with Fourier transform IR, X-ray diffraction, and small angle X-ray scattering measurements. CH[sub 4]/CO[sub 2] selectivity correlates with both the radius of gyration obtained from SAXS and the D-A coefficient from CO[sub 2] adsorption. 16 refs., 9 figs., 1 tab.

  14. Application of Silver Impregnated Iodine Adsorbent to Nuclear Facilities

    NASA Astrophysics Data System (ADS)

    Fukasawa, Tetsuo; Nakamura, Tomotaka; Kondo, Yoshikazu; Funabashi, Kiyomi

    Radioactive iodine is one of the most important nuclides to be prevented for release from nuclear facilities and many facilities have off-gas treatment systems to minimize the volatile nuclides dispersion to the environment. Silver impregnated inorganic adsorbents were known as inflammable and stable fixing materials for iodine and the authors started to develop 25 years ago a kind of inorganic adsorbent that has better capability compared with conventional ones. Aluminum oxide (Alumina) was selected as a carrier material and silver nitrate as an impregnated one. Pore diameters were optimized to avoid the influence of impurities such as humidity in the off-gas stream at lower temperatures. Experiments and improvements were alternately conducted for the new adsorbent. The tests were carried out in various conditions to confirm the performance of the developed adsorbent, which clarified its good ability to remove iodine. Silver nitrate impregnated alumina adsorbent (AgA) has about twice the capacity for iodine adsorption and higher iodine removal efficiency at relatively high humidity than conventional ones. The AgA chemically and stably fixes radioactive iodine and fits the storage and disposal of used adsorbent. AgA is now and will be applied to nuclear power plants, reprocessing plants, and research facilities.

  15. Cryogenic adsorber design in a helium refrigeration system

    NASA Astrophysics Data System (ADS)

    Hu, Zhongjun; Zhang, Ning; Li, Zhengyu; Li, Q.

    2012-06-01

    The cryogenic adsorber is specially designed to eliminate impurities in gaseous helium such as O2, and N2 which is normally difficult to remove, based on the reversible cryotrapping of impurities on an activated carbon bed. The coconut shell activated carbon is adopted because of its developed micropore structure and specific surface area. This activated carbon adsorption is mostly determined by the micropore structure, and the adsorption rate of impurities is inversely proportional to the square of the particle sizes. The active carbon absorber's maximum permissible flow velocity is 0.25 m/s. When the gas flow velocity increases, the adsorption diffusion rate of the adsorbent is reduced, because an increase in the magnitude of the velocity resulted in a reduced amount of heat transfer to a unit volume of impure gas. According to the numerical simulation of N2 adsorption dynamics, the appropriate void tower link speed and the saturated adsorption capacity are determined. Then the diameter and height of the adsorber are designed. The mass transfer length should be taken into account in the adsorber height design. The pressure decrease is also calculated. The important factors that influence the adsorber pressure decrease are the void tower speed, the adsorbed layer height, and the active carbon particle shape and size.

  16. Control of acid gases using a fluidized bed adsorber.

    PubMed

    Chiang, Bo-Chin; Wey, Ming-Yen; Yeh, Chia-Lin

    2003-08-01

    During incineration, secondary pollutants such as acid gases, organic compounds, heavy metals and particulates are generated. Among these pollutants, the acid gases, including sulfur oxides (SO(x)) and hydrogen chloride (HCl), can cause corrosion of the incinerator piping and can generate acid rain after being emitted to the atmosphere. To address this problem, the present study used a novel combination of air pollution control devices (APCDs), composed of a fluidized bed adsorber integrated with a fabric filter. The major objective of the work is to demonstrate the performance of a fluidized bed adsorber for removal of acid gases from flue gas of an incinerator. The adsorbents added in the fluidized bed adsorber were mainly granular activated carbon (AC; with or without chemical treatment) and with calcium oxide used as an additive. The advantages of a fluidized bed reactor for high mass transfer and high gas-solid contact can enhance the removal of acid gases when using a dry method. On the other hand, because the fluidized bed can filter particles, fine particles prior to and after passing through the fluidized bed adsorber were investigated. The competing adsorption on activated carbon between different characteristics of pollutants was also given preliminary discussion. The results indicate that the removal efficiencies of the investigated acid gases, SO(2) and HCl, are higher than 94 and 87%, respectively. Thus, a fluidized bed adsorber integrated with a fabric filter has the potential to replace conventional APCDs, even when there are other pollutants at the same time. PMID:12935758

  17. Neutral gas temperature measurements of high-power-density fluorocarbon plasmas by fitting swan bands of C{sub 2} molecules

    SciTech Connect

    Bai Bo; Sawin, Herbert H.; Cruden, Brett A.

    2006-01-01

    The neutral gas temperature of fluorocarbon plasmas in a remote toroidal transformer-coupled source was measured to be greater than 5000 K, under the conditions of a power density greater than 15 W/cm{sup 3} and pressures above 2 torr. The rovibrational bands of C{sub 2} molecules (swan bands, d {sup 3}{pi}{sub g}{yields}a {sup 3}{pi}{sub u}) were fitted to obtain the rotational temperature that was assumed to equal the translational temperature. This rotational-translational temperature equilibrium assumption was supported by the comparison with the rotational temperature of second positive system of added N{sub 2}. For the same gas mixture, the neutral gas temperature is nearly a linear function of plasma power, since the conduction to chamber wall and convection are the major energy-loss processes, and they are both proportional to neutral gas temperature. The dependence of the neutral gas temperature on O{sub 2} flow rate and pressure can be well represented through the power dependence, under the condition of constant current operation. An Arrhenius type of dependence between the etching rate of oxide film and the neutral gas temperature is observed, maybe indicating the importance of the pyrolytic dissociation in the plasma formation process when the temperature is above 5000 K.

  18. Nitrogen Molecule Adsorption on Cationic Tantalum Clusters and Rhodium Clusters and Desorption from Their Nitride Clusters Studied by Thermal Desorption Spectrometry.

    PubMed

    Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

    2016-06-23

    Adsorption and desorption of N2 molecules onto cationic Ta and Rh clusters in the gas phase were investigated in the temperature range of 300-1000 K by using thermal desorption spectrometry in combination with density functional theory (DFT) calculations. For Ta6(+), the first N2 molecule was found to adsorb dissociatively, and it remained adsorbed when Ta6(+)N2 was heated to 1000 K. In contrast, the second and the subsequent N2 molecules adsorbed weakly as a molecular form and were released into the gas phase when heated to 600 K. The difference can be explained in terms of the activation barrier between the molecular and dissociative forms. On the other hand, when Ta clusters were generated in the presence of N2 gas by the laser ablation of a Ta rod, isomeric clusters, TanNm(+), having heat resistivity were formed. For Rh6(+), N2 adsorbed molecularly at 300 K and desorbed totally at 450 K. These results were consistent with the DFT calculations, indicating that the dissociative adsorption of N2 is endothermic. PMID:27276438

  19. Leonardite char adsorbents

    SciTech Connect

    Knudson, Curtis L.

    1993-01-01

    A process of preparing lignite (low rank) coal filter material, suitable for use in lieu of more expensive activated carbon filter materials, is disclosed. The process comprises size reducing Leonardite coal material to a suitable filtering effective size, and thereafter heating the size reduced Leonardite preferably to at least 750.degree. C. in the presence of a flow of an inert gas.

  20. Leonardite char adsorbents

    DOEpatents

    Knudson, C.L.

    1993-10-19

    A process of preparing lignite (low rank) coal filter material, suitable for use in lieu of more expensive activated carbon filter materials, is disclosed. The process comprises size reducing Leonardite coal material to a suitable filtering effective size, and thereafter heating the size reduced Leonardite preferably to at least 750 C in the presence of a flow of an inert gas. 1 figure.

  1. Adsorbed water and CO on Pt electrode modified with Ru

    NASA Astrophysics Data System (ADS)

    Futamata, Masayuki; Luo, Liqiang

    Highly sensitive ATR-SEIRA spectroscopy was exploited to elucidate water, CO and electrolyte anions adsorbed on the Ru modified Pt film electrode. CO on Ru domains was oxidized below ca. +0.3 V, followed by pronounced water adsorption. Since the oxidation potential of CO on Pt domain was significantly reduced compared to bare Pt, these water molecules on Ru obviously prompt CO oxidation on adjacent Pt surface as consistent with the bifunctional mechanism. Diffusion of adsorbate from Ru to Pt surfaces was indicated in dilute CH 3OH solution by spectral changes with potential.

  2. The electronic spectrum of CUONg4 (Ng = Ne, Ar, Kr, Xe): New insights in the interaction of the CUO molecule with noble gas matrices

    NASA Astrophysics Data System (ADS)

    Tecmer, Paweł; van Lingen, Henk; Gomes, André Severo Pereira; Visscher, Lucas

    2012-08-01

    The electronic spectrum of the CUO molecule was investigated with the IHFSCC-SD (intermediate Hamiltonian Fock-space coupled cluster with singles and doubles) method and with TD-DFT (time-dependent density functional theory) employing the PBE and PBE0 exchange-correlation functionals. The importance of both spin-orbit coupling and correlation effects on the low-lying excited-states of this molecule are analyzed and discussed. Noble gas matrix effects on the energy ordering and vibrational frequencies of the lowest electronic states of the CUO molecule were investigated with density functional theory (DFT) and TD-DFT in a supermolecular as well as a frozen density embedding (FDE) subsystem approach. This data is used to test the suitability of the FDE approach to model the influence of different matrices on the vertical electronic transitions of this molecule. The most suitable potential was chosen to perform relativistic wave function theory in density functional theory calculations to study the vertical electronic spectra of the CUO and CUONg4 with the IHFSCC-SD method.

  3. Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

    PubMed

    Biswas, Biswajit; Singh, Prashant Chandra

    2015-11-11

    The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes. PMID:26523809

  4. Recovery of nitrogen and light hydrocarbons from polyalkene purge gas

    DOEpatents

    Zwilling, Daniel Patrick; Golden, Timothy Christoph; Weist, Jr., Edward Landis; Ludwig, Keith Alan

    2003-06-10

    A method for the separation of a gas mixture comprises (a) obtaining a feed gas mixture comprising nitrogen and at least one hydrocarbon having two to six carbon atoms; (b) introducing the feed gas mixture at a temperature of about 60.degree. F. to about 105.degree. F. into an adsorbent bed containing adsorbent material which selectively adsorbs the hydrocarbon, and withdrawing from the adsorbent bed an effluent gas enriched in nitrogen; (c) discontinuing the flow of the feed gas mixture into the adsorbent bed and depressurizing the adsorbent bed by withdrawing depressurization gas therefrom; (d) purging the adsorbent bed by introducing a purge gas into the bed and withdrawing therefrom an effluent gas comprising the hydrocarbon, wherein the purge gas contains nitrogen at a concentration higher than that of the nitrogen in the feed gas mixture; (e) pressurizing the adsorbent bed by introducing pressurization gas into the bed; and (f) repeating (b) through (e) in a cyclic manner.

  5. Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Ruiz, Victor G.; Camarillo-Cisneros, Javier; Liu, Wei; Ferri, Nicola; Reuter, Karsten; Tkatchenko, Alexandre

    2016-05-01

    Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdWsurf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdWsurf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

  6. Surface Ionization Gas Detection at SnO{sub 2} Surfaces

    SciTech Connect

    Krenkow, A.; Oberhuettinger, C.; Habauzit, A.; Kessler, M.; Goebel, J.; Mueller, G.

    2009-05-23

    In surface ionization (SI) gas detection adsorbed analyte molecules are converted into ionic species at a heated solid surface and extracted into free space by an oppositely biased counter electrode. In the present work we consider the formation of positive and negative analyte gas ions at SnO{sub 2} surfaces. We find that SI leads to positive ion formation only, with the SI efficiency scaling with the ionization energy of the analyte gas molecules. Aromatic and aliphatic hydrocarbons with amine functional groups exhibit particularly high SI efficiencies.

  7. Pine Pyrolysis Vapor Phase Upgrading Over ZSM-5 Catalyst: Effect of Temperature, Hot Gas Filtration, and Hydrogen Donor Molecule on the Rate of Deactivation of Catalyst

    SciTech Connect

    Mukarakate, C.; Zhang, X.; Nimlos, M.; Robichaud, D.; Donohoe, B.

    2013-01-01

    The conversion of primary vapors from pine pyrolysis over a ZSM-5 catalyst was characterized using a micro-reactor coupled to a molecular beam mass spectrometer (MBMS) to allow on-line measurement of the upgraded vapors. This micro-reacor-MBMS system was used to investigate the effects of hot gas filtration, temperature and hydrogen donor molecules on the rate of deactivation of the UPV2 catalyst. Our results show that the life of catalyst is significantly improved by using better filtration. Temperature had an effect on both product distribution and catalyst deactivation. The hydrogen donor molecules (HDM) used in this study show better reduction in catalyst deactivation rates at high temperatures.

  8. Chemisorption on surfaces — an historical look at a representative adsorbate: carbon monoxide

    NASA Astrophysics Data System (ADS)

    Yates, John T.

    1994-01-01

    The study of the interaction of molecules with clean surfaces extends back to the work of Irving Langmuir. In this historical account, the development of selected experimental methods for the study of molecular adsorption will be discussed. This will be done by historically reviewing research on one of the most well-studied adsorbate molecules, carbon monoxide. Many of the modern surface science techniques have first been used to study chemisorbed carbon monoxide, and the CO molecule is employed even today as a test molecule for currently developing surface measurement instruments such as the low temperature STM. In addition to being a good test molecule for new surface measurement techniques, adsorbed carbon monoxide is one of the centrally important molecules in the field of heterogeneous catalysis where the production of synthetic fuels and useful organic molecules often depends on the catalytic behavior of the adsorbed CO molecule. Interestingly, the carbon monoxide molecule also serves as a bridge between surface chemistry on the transition metals and the field of organometallic chemistry. Concepts about the chemical bonding and the reactive behavior of CO chemisorbed on transition metal surfaces and CO bound in transition metal carbonyls link these two fields together in a significant manner. The carbon monoxide molecule has been the historical focal point of many endeavors in surface chemistry and surface physics, and research on adsorbed carbon monoxide well represents many of the key advances which characterize the first thirty years of the development of surface science.

  9. Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

    NASA Technical Reports Server (NTRS)

    Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

    2006-01-01

    A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides

  10. Ultracold polar KRb molecules

    NASA Astrophysics Data System (ADS)

    Neyenhuis, Brian; Chotia, Amodsen; Moses, Steven; Ye, Jun; Jin, Deborah

    2011-05-01

    Ultracold polar molecules in the quantum degenerate regime open the possibility of realizing quantum gases with long-range, and spatially anisotropic, interparticle interactions. Currently, we can create a gas of ultracold fermionic ground-state KRb molecules in with a peak density of 1012 cm-3 and a temperature just 1.4 times the Fermi temperature. We will report on efforts to further cool this gas of molecules. One possibility is to evaporatively cool a spin-polarized molecular Fermi gas confined in quasi-2D, where we would rely on dipole-dipole interactions for rethermalization. We acknowledge funding from NIST, NSF, and AFOSR-MURI.

  11. 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.

  12. Determination of local concentration of H{sub 2}O molecules and gas temperature in the process of hydrogen - oxygen gas mixture heating by means of linear and nonlinear laser spectroscopy

    SciTech Connect

    Kozlov, D N; Kobtsev, V D; Stel'makh, O M; Smirnov, Valery V; Stepanov, E V

    2013-01-31

    Employing the methods of linear absorption spectroscopy and nonlinear four-wave mixing spectroscopy using laserinduced gratings we have simultaneously measured the local concentrations of H{sub 2}O molecules and the gas temperature in the process of the H{sub 2} - O{sub 2} mixture heating. During the measurements of the deactivation rates of pulsed-laser excited singlet oxygen O{sub 2} (b {sup 1}{Sigma}{sup +}{sub g}) in collisions with H{sub 2} in the range 294 - 850 K, the joint use of the two methods made it possible to determine the degree of hydrogen oxidation at a given temperature. As the mixture is heated, H{sub 2}O molecules are formed by 'dark' reactions of H{sub 2} with O{sub 2} in the ground state. The experiments have shown that the measurements of tunable diode laser radiation absorption along an optical path through the inhomogeneously heated gas mixture in a cell allows high-accuracy determination of the local H{sub 2}O concentration in the O{sub 2} laser excitation volume, if the gas temperature in this volume is known. When studying the collisional deactivation of O{sub 2} (b {sup 1}{Sigma}{sup +}{sub g}) molecules, the necessary measurements of the local temperature can be implemented using laser-induced gratings, arising due to spatially periodic excitation of O{sub 2} (X{sup 3}{Sigma}{sup -}{sub g}) molecules to the b {sup 1}{Sigma}{sup +}{sub g} state by radiation of the pump laser of the four-wave mixing spectrometer. (laser spectroscopy)

  13. Calculation of the Standard Molal Thermodynamic Properties of Crystalline, Liquid, and Gas Organic Molecules at High Temperatures and Pressures

    NASA Astrophysics Data System (ADS)

    Helgeson, Harold C.; Owens, Christine E.; Knox, Annette M.; Richard, Laurent

    1998-03-01

    Calculation of the thermodynamic properties of organic solids, liquids, and gases at high temperatures and pressures is a requisite for characterizing hydrothermal metastable equilibrium states involving these species and quantifying the chemical affinities of irreversible reactions of organic molecules in natural gas, crude oil, kerogen, and coal with minerals and organic, inorganic, and biomolecular aqueous species in interstitial waters in sedimentary basins. To facilitate calculations of this kind, coefficients for the Parameters From Group Contributions (PFGC) equation of state have been compiled for a variety of groups in organic liquids and gases. In addition, molecular weights, critical temperatures and pressures, densities at 25°C and 1 bar, transition, melting, and boiling temperatures ( Tt,Pr, Tm,Pr, and Tv,Pr, respectively) and standard molal enthalpies of transition (Δ H° t,Pr), melting (Δ H° m,Pr), and vaporization (Δ H° v,Pr) of organic species at 1 bar ( Pr) have been tabulated, together with an internally consistent and comprehensive set of standard molal Gibbs free energies and enthalpies of formation from the elements in their stable state at 298.15 K ( Tr) and Pr (Δ G° f and Δ H° f, respectively). The critical compilation also includes standard molal entropies ( S°) and volumes ( V°) at Tr and Pr, and standard molal heat capacity power function coefficients to compute the standard molal thermodynamic properties of organic solids, liquids, and gases as a function of temperature at 1 bar. These properties and coefficients have been tabulated for more than 500 crystalline solids, liquids, and gases, and those for many more can be computed from the equations of state group additivity algorithms. The crystalline species correspond to normal alkanes (C nH 2( n+1) ) with carbon numbers ( n, which is equal to the number of moles of carbon atoms in one mole of the species) ranging from 5 to 100, and 23 amino acids including glycine (C 2H 5NO

  14. Adsorbents and columns in analytical high-performance liquid chromatography: a perspective with regard to development and understanding.

    PubMed

    Unger, Klaus K; Liapis, Athanasios I

    2012-06-01

    A brief historical survey is presented on the evaluation of silica adsorbents in analytical HPLC. The theory of analytical HPLC is mostly still being based on the height equivalent to a theoretical plate concept and the van Deemter equation that was derived from gas phase adsorption involving a linear adsorption isotherm and fast mass transfer kinetics. One can obviously wonder whether the use of the van Deemter equation is relevant and valid for the evaluation of the performance of HPLC systems, where most often the liquid solutes involve charged molecules in electrolytes and in very many cases the adsorbates are macromolecules having diffusion coefficients of small magnitude. Instead of the van Deemter equation, a multi-scale modelling approach that involves microscopic and macroscopic dynamic non-linear mass-transfer-rate models should be employed. Furthermore, advanced experimental methods for the characterisation of porous media and the distribution of the density of immobilised active sites (e.g., ligands) on surfaces as well as microscopic pore-network modelling and molecular dynamics modelling and simulation methods could be used for the design of novel adsorbents whose porous structures and immobilised active sites would provide effective mass transport and adsorption rates for realising efficient separations as well as high dynamic capacities when larger throughputs are required. PMID:22555863

  15. Combining density functional theory (DFT) and collision cross-section (CCS) calculations to analyze the gas-phase behaviour of small molecules and their protonation site isomers.

    PubMed

    Boschmans, Jasper; Jacobs, Sam; Williams, Jonathan P; Palmer, Martin; Richardson, Keith; Giles, Kevin; Lapthorn, Cris; Herrebout, Wouter A; Lemière, Filip; Sobott, Frank

    2016-06-20

    Electrospray ion mobility-mass spectrometry (IM-MS) data show that for some small molecules, two (or even more) ions with identical sum formula and mass, but distinct drift times are observed. In spite of showing their own unique and characteristic fragmentation spectra in MS/MS, no configurational or constitutional isomers are found to be present in solution. Instead the observation and separation of such ions appears to be inherent to their gas-phase behaviour during ion mobility experiments. The origin of multiple drift times is thought to be the result of protonation site isomers ('protomers'). Although some important properties of protomers have been highlighted by other studies, correlating the experimental collision cross-sections (CCSs) with calculated values has proven to be a major difficulty. As a model, this study uses the pharmaceutical compound melphalan and a number of related molecules with alternative (gas-phase) protonation sites. Our study combines density functional theory (DFT) calculations with modified MobCal methods (e.g. nitrogen-based Trajectory Method algorithm) for the calculation of theoretical CCS values. Calculated structures can be linked to experimentally observed signals, and a strong correlation is found between the difference of the calculated dipole moments of the protomer pairs and their experimental CCS separation. PMID:27264846

  16. High capacity cryogel-type adsorbents for protein purification.

    PubMed

    Singh, Naveen Kumar; Dsouza, Roy N; Grasselli, Mariano; Fernández-Lahore, Marcelo

    2014-08-15

    Cryogel bodies were modified to obtain epoxy groups by graft-copolymerization using both chemical and gamma irradiation initiation techniques. The free epoxy adsorbents were reacted further to introduce diethylaminoethanol (DEAE) functionalities. The resulting weak anion-exchange cryogel adsorbents showed dynamic binding capacities of ca. 27±3mg/mL, which was significantly higher than previously reported for this type of adsorbent material. Gamma irradiated grafting initiation showed a 4-fold higher capacity for proteins than chemical grafting initiation procedures. The phosphate capacity for these DEAE cryogels was 119mmol/L and also showed similar column efficiency as compared to commercial adsorbents. The large pores in the cryogel structure ensure convective transport of the molecules to active binding sites located on the polymer-grafted surface of cryogels. However, as cryogels have relatively large pores (10-100μm), the BET area available for surface activation is low, and consequently, the capacity of the cryogels is relatively low for biomolecules, especially when compared to commercial beaded adsorbents. Nevertheless, we have shown that gamma ray mediated surface grafting of cryogel matrices greatly enhance their functional and adsorptive properties. PMID:24980092

  17. Carbon dioxide adsorbent study

    NASA Technical Reports Server (NTRS)

    Onischak, M.; Baker, B. S.

    1973-01-01

    A study was initiated on the feasibility of using the alkali metal carbonate - bi-carbonate solid-gas reaction to remove carbon dioxide from the atmosphere of an EVA life support system. The program successfully demonstrates that carbon dioxide concentrations could be maintained below 0.1 mole per cent using this chemistry. Further a practical method for distributing the carbonates in a coherent sheet form capable of repeated regeneration (50 cycles) at modest temperatures (423 K), without loss in activity was also demonstrated. Sufficiently high reaction rates were shown to be possible with the carbonate - bi-carbonate system such that EVA hardware could be readily designed. Experimental and design data were presented on the basis of which two practical units were designed. In addition to conventional thermally regenerative systems very compact units using ambient temperature cyclic vacuum regeneration may also be feasible. For a one man - 8 hour EVA unit regenerated thermally at the base ship a system volume of 14 liters is estimated.

  18. The density and refractive index of adsorbing protein layers.

    PubMed

    Vörös, Janos

    2004-07-01

    The structure of the adsorbing layers of native and denatured proteins (fibrinogen, gamma-immunoglobulin, albumin, and lysozyme) was studied on hydrophilic TiO(2) and hydrophobic Teflon-AF surfaces using the quartz crystal microbalance with dissipation and optical waveguide lightmode spectroscopy techniques. The density and the refractive index of the adsorbing protein layers could be determined from the complementary information provided by the two in situ instruments. The observed density and refractive index changes during the protein-adsorption process indicated the presence of conformational changes (e.g., partial unfolding) in general, especially upon contact with the hydrophobic surface. The structure of the formed layers was found to depend on the size of the proteins and on the experimental conditions. On the TiO(2) surface smaller proteins formed a denser layer than larger ones and the layer of unfolded proteins was less dense than that adsorbed from the native conformation. The hydrophobic surface induced denaturation and resulted in the formation of thin compact protein films of albumin and lysozyme. A linear correlation was found between the quartz crystal microbalance measured dissipation factor and the total water content of the layer, suggesting the existence of a dissipative process that is related to the solvent molecules present inside the adsorbed protein layer. Our measurements indicated that water and solvent molecules not only influence the 3D structure of proteins in solution but also play a crucial role in their adsorption onto surfaces. PMID:15240488

  19. Carbon adsorbents from products of solid fuel processing

    SciTech Connect

    Pokonova, Yu.V.; Grabovskii, A.I.

    1995-01-10

    Total shale phenols (mixture of alkylresorcinols) or their solution in commercial-grade furfural can be used for forming carbon adsorbents with high mechanical strength (up to 97%), high microporosity (up to 0.41 cm{sup 3}{center_dot}cm{sup -3}), and higher sorption capacity. Samples with medium burnout exhibit higher selectivity (than those molded from conventional wood tar) in the recovery of noble metals from multicomponent metal salt solutions. In these parameters they surpass commercial adsorbents as well. Samples with low burnout exhibit high selectivity and separation ability with respect to gas mixtures.

  20. Interaction of a conjugated polyaromatic molecule with a single dangling bond quantum dot on a hydrogenated semiconductor.

    PubMed

    Godlewski, Szymon; Kolmer, Marek; Engelund, Mads; Kawai, Hiroyo; Zuzak, Rafal; Garcia-Lekue, Aran; Saeys, Mark; Echavarren, Antonio M; Joachim, Christian; Sanchez-Portal, Daniel; Szymonski, Marek

    2016-02-01

    Controlling the strength of the coupling between organic molecules and single atoms provides a powerful tool for tuning electronic properties of single-molecule devices. Here, using scanning tunneling microscopy and spectroscopy (STM/STS) supported by theoretical modeling, we study the interaction of a planar organic molecule (trinaphthylene) with a hydrogen-passivated Ge(001):H substrate and a single dangling bond quantum dot on that surface. The electronic structure of the molecule adsorbed on the hydrogen-passivated surface is similar to the gas phase structure and the measurements show that HOMO and LUMO states contribute to the STM filled and empty state images, respectively. Furthermore, we show that the electronic properties are not significantly affected when the molecule is attached to the single dangling bond, which is in contrast with the strong interaction of the molecule with a dangling bond dimer. Our results show that the dangling bond quantum dots could stabilize organic molecules on a hydrogenated semiconductor without affecting their originally designed gas phase electronic properties. Together with the ability to laterally manipulate the molecules on the surface, this will be advantageous in the construction of single-molecule devices, where the coupling and positioning of the molecules on the substrate could be tuned by a proper design of the surface quantum dot arrays, comprising both single and dimerized dangling bonds. PMID:26766161

  1. Conformational changes of adsorbed proteins

    NASA Astrophysics Data System (ADS)

    Allen, Scott

    2005-03-01

    The adsorption of bovine serum albumin (BSA) and pepsin to gold surfaces has been studied using surface plasmon resonance (SPR). Proteins are adsorbed from solution onto a gold surface and changes in the conformation of the adsorbed proteins are induced by changing the buffer solution. We selected pH and ionic strength values for the buffer solutions that are known from our circular dichroism measurements to cause conformational changes of the proteins in bulk solution. We find that for both BSA and pepsin the changes in conformation are impeded by the interaction of the protein with the gold surface.

  2. Heat capacity of xenon adsorbed on nanobundle grooves

    NASA Astrophysics Data System (ADS)

    Chishko, K. A.; Sokolova, E. S.

    2016-02-01

    A model of a one-dimensional nonideal gas in an external transverse force field is used to interpret the experimentally observed thermodynamic properties of xenon deposited in grooves on the surface of carbon nanobundles. A nonideal gas model with pairwise interactions is not entirely adequate for describing dense adsorbates (at low temperatures), but makes it easy to account for the exchange of particles between the 1D adsorbate and the 3D atmosphere, which is an important factor at intermediate (on the order of 35 K for xenon) and, especially, high (˜100 K) temperatures. In this paper, we examine a 1D real gas taking only the one-dimensional Lennard-Jones interaction into account, but under exact equilibrium with respect to the number of particles between the 1D adsorbate and the 3D atmosphere of the measurement cell. The low-temperature branch of the specific heat is fitted independently by an elastic chain model so as to obtain the best agreement between theory and experiment over the widest possible region, beginning at zero temperature. The gas approximation sets in after temperatures for which the phonon specific heat of the chain essentially transforms to a one-dimensional equipartition law. Here the basic parameters of both models can be chosen so that the heat capacity C(T) of the chain transforms essentially continuously into the corresponding curve for the gas approximation. Thus, it can be expected that an adequate interpretation of the real temperature dependences of the specific heat of low-dimensionality atomic adsorbates can be obtained through a reasonable combination of the phonon and gas approximations. The main parameters of the gas approximation (such as the desorption energy) obtained by fitting the theory to experiments on the specific heat of xenon correlate well with published data.

  3. Laser-induced gas-surface interactions

    NASA Astrophysics Data System (ADS)

    Chuang, T. J.

    Chemical reactions in homogeneous systems activated by laser radiation have been extensively investigated for more than a decade. The applications of lasers to promote gas-surface interactions have just been realized in recent years. The purpose of this paper is to examine the fundamental processes involved in laser-induced gas-surface chemical interactions. Specifically, the photon-enhanced adsorption, adsorbate-adsorbate and adsorbate-solid reactions, product formation and desorption processes are discussed in detail. The dynamic processes involved in photoexcitation of the electronic and vibrational states, the energy transfer and relaxation in competition with chemical interactions are considered. These include both single and multiple photon adsorption, and fundamental and overtone transitions in the excitation process, and inter- and intra-molecular energy transfer, and coupling with phonons, electron-hole pairs and surface plasmons in the energy relaxation process. Many current experimental and theoretical studies on the subject are reviewed and discussed with the goal of clarifying the relative importance of the surface interaction steps and relating the resulting concepts to the experimentally observed phenomena. Among the many gas-solid systems that have been investigated, there has been more extensive use of CO adsorbed on metals, and SF 6 and XeF 2 interactions with silicon as examples to illustrate the many facets of the electronically and vibrationally activated surface processes. Results on IR laser stimulated desorption of C 5H 5N and C 5D 5N molecules from various solid surfaces are also presented. It is clearly shown that rapid intermolecular energy exchange and molecule to surface energy transfer can have important effects on photodesorption cross sections and isotope selectivities. It is concluded that utilization of lasers in gas-surface studies not only can provide fundamental insight into the mechanism and dynamics involved in heterogeneous

  4. Radiolysis of alanine adsorbed in a clay mineral

    NASA Astrophysics Data System (ADS)

    Aguilar-Ovando, Ellen Y.; Negrón-Mendoza, Alicia

    2013-07-01

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically γ-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  5. Radiolysis of alanine adsorbed in a clay mineral

    SciTech Connect

    Aguilar-Ovando, Ellen Y.; Negron-Mendoza, Alicia

    2013-07-03

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically {gamma}-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  6. Molecules between the Stars.

    ERIC Educational Resources Information Center

    Verschuur, Gerrit L.

    1987-01-01

    Provides a listing of molecules discovered to date in the vast interstellar clouds of dust and gas. Emphasizes the recent discoveries of organic molecules. Discusses molecular spectral lines, MASERs (microwave amplification by stimulated emission of radiation), molecular clouds, and star birth. (TW)

  7. Concentration quenching of rhodamine 6G fluorescence in the adsorbed state

    SciTech Connect

    Zemskii, V.I.; Meshkovskii, I.K.; Sokolov, I.A.

    1985-08-01

    Porous glass to which molecules of organic dyes have been added is a promising active solid medium for tunable lasers. The spectroluminescent characteristics of samples of porous glass activated with rhodamine 6G molecules have been studied. It is shown that molecules of rhodamine 6G adsorbed in porus glass retain their capacity for fluorescence with a high quantum yield. Fixation of rhodamine 6G molecules on the pore walls interferes with their association in the concentration range up to 10/sup 19/ cm/sup -3/. Concentration quenching of fluorescence is observed starting with a concentration of dye molecules of 5 x 10/sup 15/ cm/sup -3/; this is explained by inductive-resonance energy transfer between monomeric molecules under conditions of inhomogeneous broadening of the electronic spectra of the adsorbed molecules.

  8. EVALUATION OF SOLID ADSORBENTS FOR THE COLLECTION AND ANALYSES OF AMBIENT BIOGENIC VOLATILE ORGANICS

    EPA Science Inventory

    Micrometeorological flux measurements of biogenic volatile organic compounds (BVOCs) usually require that large volumes of air be collected (whole air samples) or focused during the sampling process (cryogenic trapping or gas-solid partitioning on adsorbents) in order to achiev...

  9. A Robust Highly Interpenetrated Metal−Organic Framework Constructed from Pentanuclear Clusters for Selective Sorption of Gas Molecules

    SciTech Connect

    Zhang, Zhangjing; Xiang, Shengchang; Chen, Yu-Sheng; Ma, Shengqian; Lee, Yongwoo; Phely-Bobin, Thomas; Chen, Banglin

    2010-10-22

    A three-dimensional microporous metal-organic framework, Zn{sub 5}(BTA){sub 6}(TDA){sub 2} {center_dot} 15DMF {center_dot} 8H{sub 2}O (1; HBTA = 1,2,3-benzenetriazole; H{sub 2}TDA = thiophene-2,5-dicarboxylic acid), comprising pentanuclear [Zn{sub 5}] cluster units, was obtained through an one-pot solvothermal reaction of Zn(NO{sub 3}){sub 2}, 1,2,3-benzenetriazole, and thiophene-2,5-dicarboxylate. The activated 1 displays type-I N{sub 2} gas sorption behavior with a Langmuir surface area of 607 m{sup 2} g{sup -1} and exhibits interesting selective gas adsorption for C{sub 2}H{sub 2}/CH{sub 4} and CO{sub 2}/CH{sub 4}.

  10. Gas-phase ion-molecule reactions: a model for the determination of biologically reactive electrophilic contaminants in the environment.

    PubMed

    Freeman, J A; Johnson, J V; Yost, R A; Kuehl, D W

    1994-06-01

    A promising instrumental technique has been investigated to rapidly screen complex environmental samples for chemical contaminants having the propensity to covalently bond to biomacromolecules such as DNA. Radical molecular ions of pyridine, a model compound for nucleophilic bases of DNA, were mass-selected and allowed to react with electrophilic environmental contaminants in the collision cell of a triple quadrupole mass spectrometer. Analytes were introduced into the collision cell via a gas chromatographic column. Reactive chemicals are then characterized by scanning Q3 to identify associative reaction products. A good qualitative correlation was observed for the gas-phase reactivity of a series of electrophilic reagents with both their alkylating reactivity in solution (4-(4-nitrobenzyl)pyridine) and AMES test mutagenicity which had been previously published. Femtomole limits of detection for specific associative reaction products were demonstrated. Gas-phase reactions of ions of environmental contaminants (introduced into the source) with neutral pyridine (in the collision cell) were also investigated. Reactions of the radical molecular ion of the allyl reagents with neutral pyridine were similar to results from the mass-selected reaction of the pyridine radical molecular ion with neutral allylic reagents. PMID:8030792

  11. BRIEF COMMUNICATIONS: Investigation of the vibrational relaxation of CO2 molecules in a heterogeneous gas-cluster system

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Mironov, S. G.; Rebrov, A. K.; Semyachkin, B. E.

    1981-06-01

    An investigation was made of the relaxation of monomers and clusters of carbon dioxide excited in a glow discharge maintained in a condensing supersonic free jet. Measurements were made of the intensity of the output radiation emitted from the 001 vibrational level of the CO2 molecule in a band at 4.3 μ, and also of the intensity and energy of the molecular beam. It was found that the relaxation of the excited monomers as a result of their collisions with clusters occurred at a rate much higher than the rate of VT relaxation in the gaseous phase, and it increased on increase in the average size of the cluster. The clusters which have received the excitation energy directly from the discharge and indirectly from monomers were found to lose this energy with time: in ≲1 msec the excitation was converted into heat and this resulted in partial evaporation of the clusters.

  12. Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-01

    The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

  13. Molecular switches from benzene derivatives adsorbed on metal surfaces

    PubMed Central

    Liu, Wei; Filimonov, Sergey N.; Carrasco, Javier; Tkatchenko, Alexandre

    2013-01-01

    Transient precursor states are often experimentally observed for molecules adsorbing on surfaces. However, such precursor states are typically rather short-lived, quickly yielding to more stable adsorption configurations. Here we employ first-principles calculations to systematically explore the interaction mechanism for benzene derivatives on metal surfaces, enabling us to selectively tune the stability and the barrier between two metastable adsorption states. In particular, in the case of the tetrachloropyrazine molecule, two equally stable adsorption states are identified with a moderate and conceivably reversible barrier between them. We address the feasibility of experimentally detecting the predicted bistable behaviour and discuss its potential usefulness in a molecular switch. PMID:24157660

  14. Temperature programmed desorption of weakly bound adsorbates on Au(111)

    NASA Astrophysics Data System (ADS)

    Engelhart, Daniel P.; Wagner, Roman J. V.; Meling, Artur; Wodtke, Alec M.; Schäfer, Tim

    2016-08-01

    We have performed temperature programmed desorption (TPD) experiments to analyze the desorption kinetics of Ar, Kr, Xe, C2H2, SF6, N2, NO and CO on Au(111). We report desorption activation energies (Edes), which are an excellent proxy for the binding energies. The derived binding energies scale with the polarizability of the molecules, consistent with the conclusion that the surface-adsorbate bonds arise due to dispersion forces. The reported results serve as a benchmark for theories of dispersion force interactions of molecules at metal surfaces.

  15. A DFT study on the adsorption of CO and CO{sub 2} molecules on Pt{sub 4} and Ir{sub 4} clusters

    SciTech Connect

    Munieswaran, P.; Seenithurai, S.; Pandyan, R. Kodi; Kumar, S. Vinodh; Saranya, C.; Mahendran, M.

    2015-06-24

    We analyze the electronic structure and adsorption binding energy of CO and CO{sub 2} molecules adsorbed on Ir{sub 4} and Pt{sub 4} clusters by using Density functional theory (DFT). It is found that the Ir{sub 4} cluster has more adsorption binding energy than Pt{sub 4} cluster. We show that the Ir and Ir - supported materials are good catalytic materials and could be useful for gas sensor applications.

  16. Infrared spectroscopy of HX (X=Br,Cl) adsorbed on LiF(001): Alignment and orientation

    NASA Astrophysics Data System (ADS)

    Blass, P. M.; Jackson, R. C.; Polanyi, J. C.; Weiss, H.

    1991-06-01

    The infrared spectra of HBr and HCl on LiF(001) single crystal surfaces were measured as a function of coverage at temperatures ≤83 K using Fourier-transform infrared (FTIR) spectroscopy. For each hydrogen halide three different spectral features could be distinguished. At low coverages broad absorptions centered at 2265±20 cm-1 (HBr) and at 2515±20 cm-1 (HCl) were observed. These absorptions were attributed to molecules hydrogen-bonded to F- anions of the surface, the angle between the molecular axis and the surface being 21±5° for HBr and 19±5° for HCl as determined from experiments employing polarized infrared radiation. Hydrogen bonding was evidenced by: (i) redshifts with respect to the gas phase (˜300 cm-1), (ii) broad infrared absorption (FWHM: 265±25 cm-1 for HBr, 295±15 cm-1 for HCl), and (iii) enhancement of the infrared absorption intensity compared to the gas phase by more than one order of magnitude for both HBr and HCl. With increasing coverage a second absorption was observed before the first one saturated (HBr:ν=2461±5 cm-1, FWHM=75±10 cm-1; HCl: ν=2763±5 cm-1, FWHM=80±10 cm-1). This absorption was attributed to molecules adsorbed in a second layer. The smaller redshift and spectral width for the second layer were consistent with weaker hydrogen bonding, probably to the halogen of molecules adsorbed in the first layer. Further increase in coverage resulted in the appearance of the well-known doublet absorptions due to formation of solid. Coadsorption of HBr and HCl, as well as experiments under adsorption-desorption equilibrium conditions, confirmed that the first and second layers could coexist. The isotherms could best be understood on the assumption of a repulsive interaction within the first layer.

  17. Mesoporous carbon nanomaterials as environmental adsorbents.

    PubMed

    Tripathi, Pranav K; Gan, Lihua; Liu, Mingxian; Rao, Nageswara N

    2014-02-01

    The transportation and diffusion of the guest objects or molecules in the porous carbon nanomaterials can be facilitated by reducing the pathway and resistance. The reduced pathway depends on the porous nature of carbon nanomaterials. Classification of porous carbon materials by the International Union of Pure and Applied Chemistry (IUPAC) has given a new opportunity to design the pores as per their applicability and to understand the mobility of ions, atoms, and molecules in the porous network of carbon materials and also advanced their countless applicability. However, synthesis of carbon nanomaterials with a desired porous network is still a great challenge. Although, remarkable developments have taken place in the recent years, control over the pores size and/or hierarchical porous architectures, especially in the synthesis of carbon nanospheres (CNSs) and ordered mesoporous carbon (OMCs) is still intriguing. The micro and mesoporous CNSs and OMCs have been prepared by a variety of procedures and over a wide range of compositions using various different surfactant templates and carbon precursors etc. The mechanisms of formation of micromesopore in the CNSs and OMCs are still evolving. On the other hand, the urge for adsorbents with very high adsorption capacities for removing contaminants from water is growing steadily. In this review, we address the state-of-the-art synthesis of micro and mesoporous CNSs and OMCs, giving examples of their applications for adsorptive removals of contaminants including our own research studies. PMID:24749459

  18. The IRAM-30 m line survey of the Horsehead PDR. III. High abundance of complex (iso-)nitrile molecules in UV-illuminated gas

    NASA Astrophysics Data System (ADS)

    Gratier, P.; Pety, J.; Guzmán, V.; Gerin, M.; Goicoechea, J. R.; Roueff, E.; Faure, A.

    2013-09-01

    Context. Complex (iso-)nitrile molecules, such as CH3CN and HC3N, are relatively easily detected in our Galaxy and in other galaxies. Aims: We aim at constraining their chemistry through observations of two positions in the Horsehead edge: the photo-dissociation region (PDR) and the dense, cold, and UV-shielded core just behind it. Methods: We systematically searched for lines of CH3CN, HC3N, C3N, and some of their isomers in our sensitive unbiased line survey at 3, 2, and 1 mm. We stacked the lines of C3N to improve the detectability of this species. We derived column densities and abundances through Bayesian analysis using a large velocity gradient radiative transfer model. Results: We report the first clear detection of CH3NC at millimeter wavelength. We detected 17 lines of CH3CN at the PDR and 6 at the dense core position, and we resolved its hyperfine structure for 3 lines. We detected 4 lines of HC3N, and C3N is clearly detected at the PDR position. We computed new electron collisional rate coefficients for CH3CN, andwe found that including electron excitation reduces the derived column density by 40% at the PDR position, where the electron density is 1-5 cm-3. While CH3CN is 30 times more abundant in the PDR (2.5 × 10-10) than in the dense core (8 × 10-12), HC3N has similar abundance at both positions (8 × 10-12). The isomeric ratio CH3NC/CH3CN is 0.15 ± 0.02. Conclusions: The significant amount of complex (iso-)nitrile molecule in the UV illuminated gas is puzzling as the photodissociation is expected to be efficient. This is all the more surprising in the case of CH3CN, which is 30 times more abundant in the PDR than in the dense core. In this case, pure gas phase chemistry cannot reproduce the amount of CH3CN observed in the UV-illuminated gas. We propose that CH3CN gas phase abundance is enhanced when ice mantles of grains are destroyed through photo-desorption or thermal-evaporation in PDRs, and through sputtering in shocks. Based on observations

  19. Thermodynamic formalism of water uptakes on solid porous adsorbents for adsorption cooling applications

    SciTech Connect

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-19

    This Letter presents a thermodynamic formulation to calculate the amount of water vapor uptakes on various adsorbents such as zeolites, metal organic frameworks, and silica gel for the development of an advanced adsorption chiller. This formalism is developed from the rigor of the partition distribution function of each water vapor adsorptive site on adsorbents and the condensation approximation of adsorptive water molecules and is validated with experimental data. An interesting and useful finding has been established that the proposed model is thermodynamically connected with the pore structures of adsorbent materials, and the water vapor uptake highly depends on the isosteric heat of adsorption at zero surface coverage and the adsorptive sites of the adsorbent materials. Employing the proposed model, the thermodynamic trends of water vapor uptakes on various adsorbents can be estimated.

  20. Photochemistry of adsorbed nitrate on aluminum oxide particle surfaces.

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2009-07-01

    Nitrogen oxides, including nitrogen dioxide and nitric acid, react with mineral dust particles in the atmosphere to yield adsorbed nitrate. Although nitrate ion is a well-known chromophore in natural waters, little is known about the surface photochemistry of nitrate adsorbed on mineral particles. In this study, nitrate adsorbed on aluminum oxide, a model system for mineral dust aerosol, is irradiated with broadband light (lambda > 300 nm) as a function of relative humidity (RH) in the presence of molecular oxygen. Upon irradiation, the nitrate ion readily undergoes photolysis to yield nitrogen-containing gas-phase products including NO(2), NO, and N(2)O, with NO being the major product. The relative ratio and product yields of these gas-phase products change with RH, with N(2)O production being highest at the higher relative humidities. Furthermore, an efficient dark reaction readily converts the major NO product into NO(2) during post-irradiation. Photochemical processes on mineral dust aerosol surfaces have the potential to impact the chemical balance of the atmosphere, yet little is known about these processes. In this study, the impact that adsorbed nitrate photochemistry may have on the renoxification of the atmosphere is discussed. PMID:19534452

  1. Theoretical predictions of the spectroscopic parameters in noble-gas molecules: HXeOH and its complex with water.

    PubMed

    Cukras, Janusz; Sadlej, Joanna

    2011-09-14

    We employ state-of-the-art methods and basis sets to study the effect of inserting the Xe atom into the water molecule and the water dimer on their NMR parameters. Our aim is to obtain predictions for the future experimental investigation of novel xenon complexes by NMR spectroscopy. Properties such as molecular structure and energetics have been studied by supermolecular approaches using HF, MP2, CCSD, CCSD(T) and MP4 methods. The bonding in HXeOH···H(2)O complexes has been analyzed by Symmetry-Adapted Perturbation Theory to provide the intricate insight into the nature of the interaction. We focus on vibrational spectra, NMR shielding and spin-spin coupling constants-experimental signals that reflect the electronic structures of the compounds. The parameters have been calculated at electron-correlated and Dirac-Hartree-Fock relativistic levels. This study has elucidated that the insertion of the Xe atom greatly modifies the NMR properties, including both the electron correlation and relativistic effects, the (129)Xe shielding constants decrease in HXeOH and HXeOH···H(2)O in comparison to Xe atom; the (17)O, as a neighbour of Xe, is deshielded too. The HXeOH···H(2)O complex in its most stable form is stabilized mainly by induction and dispersion energies. PMID:21804992

  2. Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation, Ag{sub 3}{sup +}, with 12-crown-4

    SciTech Connect

    Kumondai, Kousuke; Toyoda, Michisato; Ishihara, Morio; Katakuse, Itsuo; Takeuchi, Takae; Ikeda, Mai; Iwamoto, Kenichi

    2005-07-08

    The reaction mechanisms of silver trimer cation, Ag{sub 3}{sup +}, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag{sub 3}{sup +} with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]{sup +}, [Ag{sub 3}(12C4)]{sup +} and [Ag{sub 3}(12C4){sub 2}]{sup +}, and of [Ag(12C4){sub 2}]{sup +} and [Ag{sub 3}(12C4){sub 3}]{sup +}, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag(12C4)]{sup +} and [Ag(12C4){sub 2}]{sup +} complexes indicated that the neutral dimer (Ag{sub 2}) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag{sub 3}{sup +} through consecutive reactions and that neutral Ag{sub 2} can be easily eliminated from [Ag{sub 3}(12C4)]{sup +}.

  3. Vibrational effects in a weakly-interacting quantum solvent: The CO molecule in 4He gas and in 4He droplets

    NASA Astrophysics Data System (ADS)

    Paesani, F.; Gianturco, F. A.

    2002-06-01

    The coupling between the intermolecular motion and the internal vibrational coordinate in the He-CO system is computed at the post-Hartree-Fock level using the DFT+DISP model already employed by us for similar systems and reviewed here in the main text. The quality of the computation of such weak effects is compared with other, earlier model calculations and then used for the evaluation of the vibrational relaxation cross sections of the CO molecule diluted in 4He gas. A further assessment of the vibrational coupling is carried out by computing, with a stochastic approach that employs the Diffusion Monte Carlo method, the effects on the vibrational frequency of the CO impurity from its immersion in 4He droplets of variable size. Both sets of results are analyzed and discussed to gauge the reliability of the computed coupling vis-a-vis one of those suggested by earlier calculations. This study provides further evidence on the difficulty of quantitatively obtaining from calculations the extremely small effects connected with molecular vibrational features in this system and caused by the weak interaction between the title molecule and a quantum solvent like 4He.

  4. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V.; Ku Kang, Jeung; Yaghi, Omar M.; Terasaki, Osamu

    2015-11-01

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  5. Supercritical fluid regeneration of adsorbents

    NASA Astrophysics Data System (ADS)

    Defilippi, R. P.; Robey, R. J.

    1983-05-01

    The results of a program to perform studies supercritical (fluid) carbon dioxide (SCF CO2) regeneration of adsorbents, using samples of industrial wastewaters from manufacturing pesticides and synthetic solution, and to estimate the economics of the specific wastewater treatment regenerations, based on test data are given. Processing costs for regenerating granular activated carbon GAC) for treating industrial wastewaters depend on stream properties and regeneration throughput.

  6. Collisional properties of cold spin-polarized nitrogen gas: Theory, experiment, and prospects as a sympathetic coolant for trapped atoms and molecules

    SciTech Connect

    Tscherbul, T. V.; Dalgarno, A.; Klos, J.; Zygelman, B.; Pavlovic, Z.; Hummon, M. T.; Lu, H.-I.; Tsikata, E.; Doyle, J. M.

    2010-10-15

    We report a combined experimental and theoretical study of collision-induced dipolar relaxation in a cold spin-polarized gas of atomic nitrogen (N). We use buffer gas cooling to create trapped samples of {sup 14}N and {sup 15}N atoms with densities (5{+-}2)x10{sup 12} cm{sup -3} and measure their magnetic relaxation rates at milli-Kelvin temperatures. These measurements, together with rigorous quantum scattering calculations based on accurate ab initio interaction potentials for the {sup 7}{Sigma}{sub u}{sup +} electronic state of N{sub 2} demonstrate that dipolar relaxation in N+N collisions occurs at a slow rate of {approx}10{sup -13} cm{sup 3}/s over a wide range of temperatures (1 mK to 1 K) and magnetic fields (10 mT to 2 T). The calculated dipolar relaxation rates are insensitive to small variations of the interaction potential and to the magnitude of the spin-exchange interaction, enabling the accurate calibration of the measured N atom density. We find consistency between the calculated and experimentally determined rates. Our results suggest that N atoms are promising candidates for future experiments on sympathetic cooling of molecules.

  7. Calcium decorated and doped phosphorene for gas adsorption

    NASA Astrophysics Data System (ADS)

    Lalitha, Murugan; Nataraj, Yuvarani; Lakshmipathi, Senthilkumar

    2016-07-01

    In this paper, we present the results from first-principles study based on the electronic structure and adsorption characteristics of CH4, CO2, H2 and NH3 adsorbed on Ca decorated/doped phosphorene. Our study finds that phosphorene exhibits n-type behaviour on decorating calcium, and p-type on doping calcium. Gas molecules are physisorbed on both pristine and calcium-mediated phosphorene, visible through their lower binding energy and charge transfer values. Ca decorated phosphorene is suitable for hydrogen storage due to its higher binding energy for H2. Ca doped structures shows increased binding affinity towards CH4 and NH3 in zigzag1 direction and armchair directions respectively. The extracts of our study implies that Ca doped phosphorene possess increased binding affinity towards gas molecules, and the results are highly helpful for gas adsorption and to design gas sensors based on calcium doped or decorated phosphorene.

  8. The detection of optical asymmetry in biogenic molecules by gas chromatography for extraterrestrial space exploration: sample processing studies.

    PubMed

    Pollock, G E; Miyamoto, A K; Oyama, V I

    1970-01-01

    Life detection instrumentation proposed for space missions is necessarily based on fundamental properties of life as we know it. Most biological life detection experiments attempt to elicit biological activity such as metabolism, growth, or reproduction. In addition to these approaches, which could be definitive, it is desirable to attack the problem of life detection as depending on some chemical attribute, since it may be most difficult to elicit a biological response. Fortunately, the property of natural optical activity in organics is synonymous with life, and can be measured by physicochemical methods. The phenomenon of optical activity arising from the selection of one of two possible isomers in living systems has been explained previously. Its detection in extraterrestrial samples would be prima facie evidence for the existence of life. For this reason, among others, gas chromatographic methods for the detection of optical asymmetry have been investigated and developed in recent years. We have preferred the diastereomeric route using (+)-2-butyl derivatives of amino acids and recently we have successfully made and separated derivatives of carbohydrates from glyceraldehyde through some hexoses. A scheme for isolating, purifying and derivatizing amino acids from soils has been devised and applied to rich and poor soils alike. Since the operations involved are simple as shown schematically, the utility of automated wet chemical approaches in space exploration is a distinct possibility. PMID:11826894

  9. Smart Adsorbents with Photoregulated Molecular Gates for Both Selective Adsorption and Efficient Regeneration.

    PubMed

    Cheng, Lei; Jiang, Yao; Yan, Ni; Shan, Shu-Feng; Liu, Xiao-Qin; Sun, Lin-Bing

    2016-09-01

    Selective adsorption and efficient regeneration are two crucial issues for adsorption processes; unfortunately, only one of them instead of both is favored by traditional adsorbents with fixed pore orifices. Herein, we fabricated a new generation of smart adsorbents through grafting photoresponsive molecules, namely, 4-(3-triethoxysilylpropyl-ureido)azobenzene (AB-TPI), onto pore orifices of the support mesoporous silica. The azobenzene (AB) derivatives serve as the molecular gates of mesopores and are reversibly opened and closed upon light irradiation. Irradiation with visible light (450 nm) causes AB molecules to isomerize from cis to trans configuration, and the molecular gates are closed. It is easy for smaller adsorbates to enter while difficult for the larger ones, and the selective adsorption is consequently facilitated. Upon irradiation with UV light (365 nm), the AB molecules are transformed from trans to cis isomers, promoting the desorption of adsorbates due to the opened molecular gates. The present smart adsorbents can consequently benefit not only selective adsorption but also efficient desorption, which are exceedingly desirable for adsorptive separation but impossible for traditional adsorbents with fixed pore orifices. PMID:27559985

  10. Competition between Displacement and Dissociation of a Strong Acid Compared to a Weak Acid Adsorbed on Silica Particle Surfaces: The Role of Adsorbed Water.

    PubMed

    Fang, Yuan; Tang, Mingjin; Grassian, Vicki H

    2016-06-16

    The adsorption of nitric (HNO3) and formic (HCOOH) acids on silica particle surfaces and the effect of adsorbed water have been investigated at 296 K using transmission FTIR spectroscopy. Under dry conditions, both nitric and formic acids adsorb reversibly on silica. Additionally, the FTIR spectra show that both of these molecules remain in the protonated form. At elevated relative humidities (RH), adsorbed water competes both for surface adsorption sites with these acids as well as promotes their dissociation to hydronium ions and the corresponding anions. Compared to HNO3, the extent of dissociation is much smaller for HCOOH, very likely because it is a weaker acid. This study provides valuable insights into the interaction of HNO3 and HCOOH with silica surface on the molecular level and further reveals the complex roles of surface-adsorbed water in atmospheric heterogeneous chemistry of mineral dust particles-many of these containing silica. PMID:27220375

  11. pyIAST: Ideal adsorbed solution theory (IAST) Python package

    NASA Astrophysics Data System (ADS)

    Simon, Cory M.; Smit, Berend; Haranczyk, Maciej

    2016-03-01

    Ideal adsorbed solution theory (IAST) is a widely-used thermodynamic framework to readily predict mixed-gas adsorption isotherms from a set of pure-component adsorption isotherms. We present an open-source, user-friendly Python package, pyIAST, to perform IAST calculations for an arbitrary number of components. pyIAST supports several common analytical models to characterize the pure-component isotherms from experimental or simulated data. Alternatively, pyIAST can use numerical quadrature to compute the spreading pressure for IAST calculations by interpolating the pure-component isotherm data. pyIAST can also perform reverse IAST calculations, where one seeks the required gas phase composition to yield a desired adsorbed phase composition.

  12. Rates and mechanisms of conversion of ice nanocrystals to ether clathrate hydrates: guest-molecule catalytic effects at approximately 120 k.

    PubMed

    Gulluru, Dheeraj B; Devlin, J Paul

    2006-02-01

    A Fourier transform infrared investigation of the rates and energetics of conversion of ice nanocrystals within 3-D arrays to ether clathrate-hydrate (CH) particles at approximately 120 K is reported. After an induction period, apparently necessitated by relatively slow nucleation of the CH phase, the well-established shrinking-core model of particle-adsorbate reaction applies to these conversions in the presence of an abundance of adsorbed ether. This implies that the transport of the ether adsorbate through the product crust encasing a reacting particle core (a necessary aspect of a particle reaction mechanism) is the rate-controlling factor. Diffusion moves adsorbed reactant molecules to the reaction zone at the interface of the ice core with the product (CH) crust. The results indicate that ether hydrate formation rates near 120 K resemble rates for gas hydrates measured near 260 K, implying rates greater by many orders of magnitude for comparable temperatures. A surprising secondary enhancement of ether CH-formation rates by the simultaneous incorporation of simple small gas molecules (N2, CO2, CH4, CO, and N2O) has also been quantified in this study. The rapid CH formation at low temperatures is conjectured to derive from defect-facilitated transport of reactants to an interfacial reaction zone, with the defect populations enhanced through transient H bonding of guest-ether proton-acceptor groups with O-H groups of the hydrate cage walls. PMID:16451023

  13. Method And Apparatus For Regenerating Nox Adsorbers

    DOEpatents

    Driscoll, J. Joshua; Endicott, Dennis L.; Faulkner, Stephen A.; Verkiel, Maarten

    2006-03-28

    Methods and apparatuses for regenerating a NOx adsorber coupled with an exhaust of an engine. An actuator drives a throttle valve to a first position when regeneration of the NOx adsorber is desired. The first position is a position that causes the regeneration of the NOx adsorber. An actuator drives the throttle valve to a second position while regeneration of the NOx adsorber is still desired. The second position being a position that is more open than the first position and operable to regenerate a NOx adsorber.

  14. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    Chmelka, B.F.

    1989-12-01

    Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

  15. Polar vortex dynamics during spring and fall diagnosed using trace gas observations from the Atmospheric Trace Molecule Spectroscopy instrument

    NASA Astrophysics Data System (ADS)

    Manney, G. L.; Michelsen, H. A.; Santee, M. L.; Gunson, M. R.; Irion, F. W.; Roche, A. E.; Livesey, N. J.

    1999-08-01

    Trace gases measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during three Atmospheric Laboratory for Applications and Science (ATLAS) space-shuttle missions, in March/April 1992 (AT-1), April 1993 (AT-2), and November 1994 (AT-3) have been mapped into equivalent latitude/potential temperature (EqL/θ) coordinates. The asymmetry of the spring vortices results in coverage of subtropical to polar EqLs. EqL/θ fields of long-lived tracers in spring in both hemispheres show the net effects of descent at high EqL throughout the winter, reflecting strong descent in the upper stratosphere, decreasing descent at lower altitudes, and evidence of greater descent at the edge of the lower stratospheric vortex than in the vortex center; these results are consistent with trajectory calculations examining the history of the air measured by ATMOS in the month prior to each mission. EqL/θ tracer fields, the derived fields CH4-CH4* (CH4* is the expected CH4 calculated from a prescribed relationship with N2O for fall) and NOy-NOy* (analogous to CH4*), and parcel histories all indicate regions of strong mixing in the 1994 Southern Hemisphere (SH) spring vortex above 500 K, with the strongest mixing confined to the vortex edge region between 500 and 700 K, and mixing throughout the Northern Hemisphere (NH) spring vortex in 1993 below about 850 K. Parcel histories indicate mixing of extravortex air with air near the vortex edge below 500 K in the SH but not with air in the vortex core; they show extravortex air mixing well into the vortex above ˜450 K in the NH and into the vortex edge region below. The effects of severe denitrification are apparent in EqL/θ HNO3 in the SH lower stratospheric spring vortex. The morphology of HNO3 in the Arctic spring lower stratospheric vortex is consistent with the effects of descent. EqL/θ fields of ATMOS NOy-NOy* show decreases consistent with the effects of mixing throughout the NH lower stratospheric vortex. The Eq

  16. 19F Magic angle spinning NMR reporter molecules: empirical measures of surface shielding, polarisability and H-bonding.

    PubMed

    Budarin, Vitaliy L; Clark, James H; Deswarte, Fabien E I; Mueller, Karl T; Tavener, Stewart J

    2007-06-14

    Magic Angle Spinning (MAS) (19)F NMR spectra have been obtained and chemical shifts measured for 37 molecules in the gas phase and adsorbed on the surfaces of six common materials: octadecyl- and octyl-functionalised chromatography silicas, Kieselgel 100 silica, Brockmann neutral alumina, Norit activated charcoal and 3-(1-piperidino)propyl functionalised silica. From these six surfaces, octadecyl-silica is selected as a non-polar reference to which the others are compared. The change in chemical shift of a fluorine nucleus within a molecule on adsorption to a surface from the gas phase, Deltadelta(gas)(surface), is described by the empirical relationship: Deltadelta(gas)(surface) = delta(s) + (alpha(s)+pi(s))/alpha(r) (Deltadelta(gas)(reference) - delta(r)) + delta(HBA) + delta(HBD), where delta(s) and delta(r) are constants that describe the chemical shift induced by the electromagnetic field of the surface under investigation and reference surface, alpha(s) and alpha(r) are the relative surface polarisability for the surface and reference, pi(s) is an additional contribution to the surface polarisabilities due to its ability to interact with aromatic molecules, and delta(HBA) and delta(HBD) are measurements of the hydrogen acceptor and donor properties of the surface. These empirical parameters are measured for the surfaces under study. Silica and alumina are found to undergo specific interactions with aromatic reporter molecules and both accept and donate H-bonds. Activated charcoal was found to have an extreme effect on shielding but no specific interactions with the adsorbed molecules. 3-(1-Piperidino)propyl functionalised silica exhibits H-bond acceptor ability, but does not donate H-bonds. PMID:17487325

  17. Effect of Oxygen Adsorbates on Terahertz Emission Properties of Various Semiconductor Surfaces Covered with Graphene

    NASA Astrophysics Data System (ADS)

    Bagsican, Filchito Renee; Zhang, Xiang; Ma, Lulu; Wang, Minjie; Murakami, Hironaru; Vajtai, Robert; Ajayan, Pulickel M.; Kono, Junichiro; Tonouchi, Masayoshi; Kawayama, Iwao

    2016-07-01

    We have studied coherent terahertz (THz) emission from graphene-coated surfaces of three different semiconductors—InP, GaAs, and InAs—to provide insight into the influence of O2 adsorption on charge states and dynamics at the graphene/semiconductor interface. The amplitude of emitted THz radiation from graphene-coated InP was found to change significantly upon desorption of O2 molecules by thermal annealing, while THz emission from bare InP was nearly uninfluenced by O2 desorption. In contrast, the amount of change in the amplitude of emitted THz radiation due to O2 desorption was essentially the same for graphene-coated GaAs and bare GaAs. However, in InAs, neither graphene coating nor O2 adsorption/desorption affected the properties of its THz emission. These results can be explained in terms of the effects of adsorbed O2 molecules on the different THz generation mechanisms in these semiconductors. Furthermore, these observations suggest that THz emission from graphene-coated semiconductors can be used for probing surface chemical reactions (e.g., oxidation) as well as for developing O2 gas sensor devices.

  18. Adsorbate-induced curvature and stiffening of graphene.

    PubMed

    Svatek, Simon A; Scott, Oliver R; Rivett, Jasmine P H; Wright, Katherine; Baldoni, Matteo; Bichoutskaia, Elena; Taniguchi, Takashi; Watanabe, Kenji; Marsden, Alexander J; Wilson, Neil R; Beton, Peter H

    2015-01-14

    The adsorption of the alkane tetratetracontane (TTC, C44H90) on graphene induces the formation of a curved surface stabilized by a gain in adsorption energy. This effect arises from a curvature-dependent variation of a moiré pattern due to the mismatch of the carbon-carbon separation in the adsorbed molecule and the period of graphene. The effect is observed when graphene is transferred onto a deformable substrate, which in our case is the interface between water layers adsorbed on mica and an organic solvent, but is not observed on more rigid substrates such as boron nitride. Our results show that molecular adsorption can be influenced by substrate curvature, provide an example of two-dimensional molecular self-assembly on a soft, responsive interface, and demonstrate that the mechanical properties of graphene may be modified by molecular adsorption, which is of relevance to nanomechanical systems, electronics, and membrane technology. PMID:25469625

  19. Monte Carlo lattice models for adsorbed polymer conformation

    NASA Technical Reports Server (NTRS)

    Good, B. S.

    1985-01-01

    The adhesion between a polymer film and a metal surface is of great technological interest. However, the prediction of adhesion and wear properties of polymer coated metals is quite difficult because a fundamental understanding of the polymer surface interaction does not yet exist. A computer model for the conformation of a polymer molecule adsorbed on a surface is discussed. The chain conformation is assumed to be described by a partially directed random walk on a three dimensional simple cubic lattice. An attractive surface potential is incorporated into the model through the use of a random walk step probability distribution that is anisotropic in the direction normal to the attractive surface. The effects of variations in potential characteristics are qualitatively included by varying both the degree of anisotropy of the step distribution and the range of the anisotropy. Polymer conformation is characterized by the average end to end distance, average radius of gyration, and average number of chain segments adsorbed on the surface.

  20. Surface Adsorbate Fluctuations and Noise in Nanoelectromechanical Systems

    PubMed Central

    Yang, Y. T.; Callegari, C.; Feng, X. L.; Roukes, M. L.

    2013-01-01

    Physisorption on solid surfaces is important in both fundamental studies and technology. Adsorbates can also be critical for the performance of miniature electromechanical resonators and sensors. Advances in resonant nanoelectromechanical systems (NEMS), particularly mass sensitivity attaining the single-molecule level, make it possible to probe surface physics in a new regime, where a small number of adatoms cause a detectable frequency shift in a high quality factor (Q) NEMS resonator, and adsorbate fluctuations result in resonance frequency noise. Here we report measurements and analysis of the kinetics and fluctuations of physisorbed xenon (Xe) atoms on a high-Q NEMS resonator vibrating at 190.5 MHz. The measured adsorption spectrum and frequency noise, combined with analytic modeling of surface diffusion and adsorption–desorption processes, suggest that diffusion dominates the observed excess noise. This study also reveals new power laws of frequency noise induced by diffusion, which could be important in other low-dimensional nanoscale systems. PMID:21388120

  1. Allantoin as a solid phase adsorbent for removing endotoxins.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

    2013-10-01

    In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance. PMID:24001944

  2. Determining β2-Integrin and Intercellular Adhesion Molecule 1 Binding Kinetics in Tumor Cell Adhesion to Leukocytes and Endothelial Cells by a Gas-driven Micropipette Assay*

    PubMed Central

    Fu, Changliang; Tong, Chunfang; Wang, Manliu; Gao, Yuxin; Zhang, Yan; Lü, Shouqin; Liang, Shile; Dong, Cheng; Long, Mian

    2011-01-01

    Interactions between polymorphonuclear neutrophils (PMNs) and tumor cells have been reported to facilitate the adhesion and subsequent extravasation of tumor cells through the endothelium under blood flow, both of which are mediated by binding β2-integrin to intercellular adhesion molecule 1 (ICAM-1). Here the adhesions between human WM9 metastatic melanoma cells, PMNs, and human pulmonary microvascular endothelial cells (HPMECs) were quantified by a gas-driven micropipette aspiration technique (GDMAT). Our data indicated that the cellular binding affinity of PMN-WM9 pair was 3.9-fold higher than that of the PMN-HPMEC pair. However, the effective binding affinities per molecular pair were comparable between the two cell pairs no matter whether WM9 cells or HPMECs were quiescent or cytokine-activated, indicating that the stronger adhesion between PMN-WM9 pair is mainly attributed to the high expression of ICAM-1 on WM9 cells. These results proposed an alternative mechanism, where WM9 melanoma cells adhere first with PMNs near vessel-wall regions and then bind to endothelial cells via PMNs under blood flow. In contrast, the adhesions between human MDA-MB-231 metastatic breast carcinoma cells and PMNs showed a comparable cellular binding affinity to PMN-HPMEC pair because the ICAM-1 expressions on MDA-MB-231 cells and HPMECs are similar. Furthermore, differences were observed in the intrinsic forward and reverse rates of the β2-integrin-ICAM-1 bond between PMN-TC and PMN-EC pairs. This GDMAT assay enables us to quantify the binding kinetics of cell adhesion molecules physiologically expressed on nucleated cells. The findings also further the understanding of leukocyte-facilitated tumor cell adhesion from the viewpoint of molecular binding kinetics. PMID:21840991

  3. The effect of H2O gas on volatilities of planet-forming major elements. I - Experimental determination of thermodynamic properties of Ca-, Al-, and Si-hydroxide gas molecules and its application to the solar nebula

    NASA Technical Reports Server (NTRS)

    Hashimoto, Akihiko

    1992-01-01

    The vapor pressures of Ca(OH)2(g), Al(OH)3(g), and Si(OH)4(g) molecules in equilibrium with solid calcium-, aluminum, and silicon-oxides, respectively, were determined, and were used to derive the heats of formation and entropies of these species, which are expected to be abundant under the currently postulated physical conditions in the primordial solar nebula. These data, in conjunction with thermodynamic data from literature, were used to calculate the relative abundances of M, MO(x), and M(OH)n gas species and relative volatilities of Fe, Mg, Si, Ca, and Al for ranges of temperature, total pressure, and H/O abundance ratio corresponding to the plausible ranges of physical conditions in the solar nebula. The results are used to explain how Ca and Al could have evaporated from Ca,Al-rich inclusions in carbonaceous chondrites, while Si, Mg, and Fe condensed onto them during the preaccretion alteration of CAIs.

  4. Reconstruction of adsorption potential in Polanyi-based models and application to various adsorbents.

    PubMed

    Pan, Bingjun; Zhang, Huichun

    2014-06-17

    The equilibrium Polanyi adsorption potential was reconstructed as ε = -RT ln(Ca(or H)/δ) to correlate the characteristic energy (E) of Polanyi-based models (qe = f[ε/E]) with the properties or structures of absorbates, where qe is the equilibriumn adsorption capacity, Ca(or H) is the converted concentration from the equilibrium aqueous concentration at the same activity and corresponds to the adsorption from the gas or n-hexadecane (HD) phase by the water-wet adsorbent, and "δ" is an arbitrary divisor to converge the model fitting. Subsequently, the modified Dubinin-Astakhov model based on the reconstructed ε was applied to aqueous adsorption on activated carbon, black carbon, multiwalled carbon nanotubes, and polymeric resin. The fitting results yielded intrinsic characteristic energies Ea, derived from aqueous-to-gas phase conversion, or EH, derived from aqueous-to-HD phase conversion, which reflect the contributions of the overall or specific adsorbate-adsorbent interactions to the adsorption. Effects of the adsorbate and adsorbent properties on Ea or EH then emerge that are unrevealed by the original characteristic energy (Eo), i.e., adsorbates with tendency to form stronger interactions with an adsorbent have larger Ea and EH. Additionally, comparison of Ea and EH allows quantitative analysis of the contributions of nonspecific interactions, that is, a significant relationship was established between the nonspecific interactions and Abraham's descriptors for the adsorption of all 32 solutes on the four different adsorbents: (Ea - EH) = 24.7 × V + 9.7 × S - 19.3 (R(2) = 0.97), where V is McGowan's characteristic volume for adsorbates, and S reflects the adsorbate's polarity/polarizability. PMID:24815932

  5. Graphene-enhanced Raman spectroscopy of thymine adsorbed on single-layer graphene

    NASA Astrophysics Data System (ADS)

    Fesenko, Olena; Dovbeshko, Galyna; Dementjev, Andrej; Karpicz, Renata; Kaplas, Tommi; Svirko, Yuri

    2015-04-01

    Graphene-enhanced Raman scattering (GERS) spectra and coherent anti-Stokes Raman scattering (CARS) of thymine molecules adsorbed on a single-layer graphene were studied. The enhancement factor was shown to depend on the molecular groups of thymine. In the GERS spectra of thymine, the main bands are shifted with respect to those for molecules adsorbed on a glass surface, indicating charge transfer for thymine on graphene. The probable mechanism of the GERS enhancement is discussed. CARS spectra are in accord with the GERS results, which indicates similar benefit from the chemical enhancement.

  6. Molecule nanoweaver

    DOEpatents

    Gerald, II; Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  7. Adsorption and Desorption of Carbon Dioxide and Water Mixtures on Synthetic Hydrophobic Carbonaceous Adsorbents

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    Several synthetic carbonaceous adsorbents produced through pyrolysis of polymeric materials are available commercially. Some appear to have advantages over activated carbon for certain adsorption applications. In particular, they can have tailored hydrophobicities that are significantly greater than that of activated carbon, while moderately high surfaces areas are retained. These sorbents are being investigated for possible use in removing trace contaminants and excess carbon dioxide from air in closed habitats, plant growth chambers, and other applications involving purification of humid gas streams. We have analyzed the characteristics of a few of these adsorbents through adsorption and desorption experiments and standard characterization techniques. This paper presents pure and multicomponent adsorption data collected for carbon dioxide and water on two synthetic carbonaceous adsorbents having different hydrophobicities and capillary condensation characteristics. The observations are interpreted through consideration of the pore structure and surface chemistry of the solids and interactions between adsorbed carbon dioxide, water, and the solvent gas.

  8. Electrosonic spray ionization. A gentle technique for generating folded proteins and protein complexes in the gas phase and for studying ion-molecule reactions at atmospheric pressure.

    PubMed

    Takáts, Zoltán; Wiseman, Justin M; Gologan, Bogdan; Cooks, R Graham

    2004-07-15

    Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization. This ionization method is successfully applied to aqueous solutions of various proteins at neutral pH, and its performance is compared to that of the nanospray and micro ESI techniques. Evidence for efficient desolvation during ESSI is provided by the fact that the peak widths for various multiply charged protein ions are an order of magnitude narrower than those for nanospray. Narrow charge-state distributions compared to other ESI techniques are observed also; for most of the proteins studied, more than 90% of the protein ions can be accumulated in one charge state using ESSI when optimizing conditions. The fact that the abundant charge state is normally as low or lower than that recorded by ESI or nanospray indicates that folded protein ions are generated. The sensitivity of the ionization technique to high salt concentrations is comparable to that of nanospray, but ESSI is considerably less sensitive to high concentrations of organic additives such as glycerol or 2-amino-2-(hydroxymethyl)-1,3-propanediol (Tris base). Noncovalent complexes are observed in the case of myoglobin, protein kinase A/ATP complex, and other proteins. The extent of dissociation of protein ions in ESSI is comparable to or even smaller than that in the case of nanospray, emphasizing the gentle nature of the method. The unique features of ESSI are ascribed to very efficient spraying and the low internal energy supplied to the ions. Evidence is provided that the method is capable of generating fully desolvated protein ions at atmospheric pressure. This allows the technique to be used for the study of ion-molecule reactions at atmospheric

  9. Copper loaded on sol-gel-derived alumina adsorbents for phosphine removal.

    PubMed

    Hsu, Jung-Nan; Bai, Hsunling; Li, Shou-Nan; Tsai, Chuen-Jinn

    2010-05-01

    The hydride gas of phosphine (PH3) is commonly used for semiconductor and optoelectronic industries. The local scrubbers must immediately abate it because of its high toxicity. In this study, copper (Cu) loaded on the sol-gel-derived gamma-alumina (Al2O3) adsorbents are prepared and tested to investigate the possibility of PH3 removal and sorbent regeneration. Test results showed that during the breakthrough time of over 99% PH3 removal efficiency, the maximum adsorption capacity of Cu loaded on the sol-gel-derived gamma-Al2O3 adsorbent is 18 mg-PH3/g-adsorbent. This is much higher than that of Cu loaded on the commercial gamma-Al2O3 adsorbent--8.6 mg-PH3/g-adsorbent. The high specific surface area, narrow pore size distribution, and well dispersion of Cu loaded on the sol-gel-derived gamma-Al2O3 could be the reasons for its high PH3 adsorption capacity. The regeneration test shows that Cu loaded on the sol-gel-derived gamma-Al2O3 adsorbent can be regenerated after a simple air purging procedure. The cumulative adsorption capacity for five regeneration cycles is 65 mg-PH3/g-adsorbent, which is approximately double that of the Cu/zeolite adsorbent demonstrated in the literature. PMID:20480862

  10. Direct Measurement of the Adsorbed Film Volume for Estimating Heats of Adsorption

    NASA Astrophysics Data System (ADS)

    Gillespie, Andrew; Dohnke, Elmar; Rash, Tyler; Stalla, David; Knight, Ernest; Seydel, Florian; Sweany, Mark; Pfeifer, Peter

    Compressed hydrogen and methane require extremely high pressures or low temperatures in order to compete with the energy density of conventional fossil fuels. Adsorbent materials provide a means to increase the energy density of these gasses up to 6 times that of compressed gas at the same temperature and pressure. One major concern in engineering adsorbed gas systems is thermal management during charging and discharging. Adsorption is an exothermic process, releasing heat during charging and absorbing heat during discharging. To estimate the heat of adsorption, it is common to analyze excess adsorption isotherms by converting to absolute adsorption and employ the Clausius Clapeyron relation. However, this method requires an assumed volume of the adsorbed state. It is common for researchers to assume that the adsorbed film occupies the entire pore volume of the adsorbent material. However, the adsorbed film only occupies a fraction of the total pore volume. This yields heats of adsorption that are underestimated by as much as 10kJ/mol at high coverage. In this talk, we present a method to directly measure the adsorbed film volume as a function of temperature and present the resulting heats of adsorption for both methane and hydrogen.

  11. 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

    2016-08-01

    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. PMID:27385527

  12. Dissociation energy of molecules in dense gases

    NASA Technical Reports Server (NTRS)

    Kunc, J. A.

    1992-01-01

    A general approach is presented for calculating the reduction of the dissociation energy of diatomic molecules immersed in a dense (n = less than 10 exp 22/cu cm) gas of molecules and atoms. The dissociation energy of a molecule in a dense gas differs from that of the molecule in vacuum because the intermolecular forces change the intramolecular dynamics of the molecule, and, consequently, the energy of the molecular bond.

  13. Identification and quantification of ozonation products of anthracene and phenanthrene adsorbed on silica particles

    NASA Astrophysics Data System (ADS)

    Perraudin, Emilie; Budzinski, Hélène; Villenave, Eric

    Primary products of the reactions of gas-phase ozone with anthracene and phenanthrene adsorbed on silica model particles have been investigated. Silica was selected as proxy for mineral atmospheric particles. The particles, coated with anthracene or phenanthrene and placed on a filter, were exposed in a reaction cell to a gaseous ozone flow. Ozone concentration was constant ((6.0±0.6)×10 13 molecule cm -3) during the experiments. Anthracene, phenanthrene and their ozonation products were then extracted by focused microwave-assisted extraction or fluid pressurized extraction and analyzed by gas chromatography coupled to mass spectrometry. Anthraquinone and anthrone on the one hand, and 1,1'-biphenyl-2,2'-dicarboxaldehyde on the other hand were identified as the products of anthracene and phenanthrene, respectively and quantified versus time of ozone exposure. This kinetical approach allowed to show that anthraquinone, anthrone and 1,1'-biphenyl-2,2'-dicarboxaldehyde are the primary products of the studied reactions, and to determine their formation yields (respectively, 0.42±0.04, 0.056±0.005 and 1.0±0.4).

  14. Sticking of Molecules on Nonporous Amorphous Water Ice

    NASA Astrophysics Data System (ADS)

    He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

    2016-05-01

    Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

  15. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test

    SciTech Connect

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-15

    Highlights: • Equilibrium test was attempted to evaluate adsorption characteristics of siloxane. • L2 had higher removal efficiency in carbon compared to noncarbon adsorbents. • Total adsorption capacity of siloxane was 300 mg/g by coal activated carbon. • Adsorption characteristics rely on size of siloxane molecule and adsorbent pore. • Conversion of siloxane was caused by adsorption of noncarbon adsorbents. - Abstract: Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

  16. Lyman-α driven molecule formation on SiO2 surfaces-connection to astrochemistry on dust grains in the interstellar medium

    NASA Astrophysics Data System (ADS)

    Rajappan, M.; Yuan, C.; Yates, J. T.

    2011-02-01

    As a model for silicate dust grains in the interstellar medium, we have used high area amorphous SiO2 as a surface on which to carry out Lyman-α (10.2 eV) photodecomposition of adsorbed N2O at 71 K and at a coverage of ~0.3 monolayer. The N2O molecules are adsorbed by hydrogen bonding to surface Si-OH groups. Transmission IR spectroscopy measurements permit the observation of the consumption of adsorbed N2O and the production of various photoproducts. It is observed that in comparison to N2O consumption, the relative rate of formation of the products NO2 and N2O4 made by combination reactions is enhanced significantly on the SiO2 surface. Reactions between photogenerated radicals themselves or between radicals and parent N2O on the SiO2 surface exceed the relative rates observed in the gas phase by factors of up to ~20. As the complexity of the combination product increases, its relative production rate, compared to the gas phase, increases due to the involvement of multiple surface-combination elementary steps. It is proposed that the enhancement of combination reactions on the SiO2 surface is due to the surface's ability to absorb excess energy evolved during the chemical-bond-forming events on the surface. This principle is probably significant on grain surfaces supporting photochemical processes of astrochemical interest, and indeed is expected. The cross section for adsorbed N2O photodecomposition on the porous SiO2 surface is about 7 × 10-20 cm2 and the quantum yield for the adsorbed molecule decomposition is about 0.006, compared to a quantum yield of 1.46 in the gas phase. This decrease in photon efficiency is attributed to absorption and scattering of Lyman-α radiation by the SiO2 particles.

  17. Adsorption of diazinon and hinosan molecules on the iron-doped boron nitride nanotubes surface in gas phase and aqueous solution: A computational study

    NASA Astrophysics Data System (ADS)

    Farmanzadeh, Davood; Rezainejad, Hamid

    2016-02-01

    In this study, the geometric structures and electronic properties of two widely used organophosphorus pesticides, diazinon and hinosan, boron nitride nanotubes (BNNTs) and Fe doped boron nitride nanotubes (FeBNNTs) as adsorbents of these pesticides are studied by density functional theory calculation as well as dispersion correction by Grimme method. The results show that Fe doping in boron nitride nanotubes structures increases the potency of nanotubes to adsorb mentioned pesticides, especially when Fe atom located instead of N atom. Comparing the adsorption energies of diazinon on FeBNNTs with ones for hinosan demonstrate that the adsorption of hinosan is energetically more favorable by FeBNNTs. Assessment of adsorption energies in aqueous solution confirmed significant decrease in their values compared to ones in gaseous phase. However, the adsorption of diazinon and hinosan on both BNNTs and FeBNNTs are exothermic. So, BNNTs and FeBNNTs may be promising candidates as appropriate adsorbents for adsorbing diazinon and hinosan. Also, the results of calculations have revealed that van der Waals interaction energies are remarkably large in adsorption of diazinon and hinosan on all boron nitride nanotubes.

  18. 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

    2015-07-01

    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. PMID:26043808

  19. 40 CFR 65.152 - Carbon adsorbers used as control devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... specified in § 65.63(a)(2), or 40 CFR 60.562-1(a)(1)(i)(A) for process vents, or § 65.83(a)(1) for high... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Carbon adsorbers used as control... Fuel Gas System or a Process § 65.152 Carbon adsorbers used as control devices. (a) Carbon...

  20. 40 CFR 65.152 - Carbon adsorbers used as control devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... specified in § 65.63(a)(2), or 40 CFR 60.562-1(a)(1)(i)(A) for process vents, or § 65.83(a)(1) for high... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Carbon adsorbers used as control... Fuel Gas System or a Process § 65.152 Carbon adsorbers used as control devices. (a) Carbon...

  1. 40 CFR 65.152 - Carbon adsorbers used as control devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... specified in § 65.63(a)(2), or 40 CFR 60.562-1(a)(1)(i)(A) for process vents, or § 65.83(a)(1) for high... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Carbon adsorbers used as control... Fuel Gas System or a Process § 65.152 Carbon adsorbers used as control devices. (a) Carbon...

  2. 40 CFR 65.152 - Carbon adsorbers used as control devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... specified in § 65.63(a)(2), or 40 CFR 60.562-1(a)(1)(i)(A) for process vents, or § 65.83(a)(1) for high... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Carbon adsorbers used as control... Fuel Gas System or a Process § 65.152 Carbon adsorbers used as control devices. (a) Carbon...

  3. 40 CFR 65.152 - Carbon adsorbers used as control devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... specified in § 65.63(a)(2), or 40 CFR 60.562-1(a)(1)(i)(A) for process vents, or § 65.83(a)(1) for high... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Carbon adsorbers used as control... Fuel Gas System or a Process § 65.152 Carbon adsorbers used as control devices. (a) Carbon...

  4. Orientational ordering, site structure, and dynamics for octahedral molecules in low temperature matrices: SF6 and SeF6 in rare gas solidsa)

    NASA Astrophysics Data System (ADS)

    Jones, Llewellyn H.; Swanson, Basil I.

    1983-08-01

    From polarization studies of high resolution IR spectra of SF6 and SeF6 trapped in noble gas solids we show that much of the structure observed for the stretching mode represents site symmetry split components for low symmetry trapping sites, the triply-degenerate ν3 mode being split into a doubly- and singly-degenerate mode. Most of the sites showing polarization are orientationally ordered with the singly-degenerate component perpendicular to the substrate. We attribute the driving force for ordering to guest-host interaction potentials which result in registry between the molecules and the (111) growth plane during deposition. The observed orientational ordering combined with high temperature annealing studies has allowed the identification of the symmetry of certain trapping sites and further analysis of vibrational dephasing dynamics. Several sites with the same nominal symmetry and structure can be tracked through the matrices discussed herein. The implications of the ordering of impurity structure in a host lattice formed by vapor deposition are discussed.

  5. Orientational ordering, site structure, and dynamics for octahedral molecules in low temperature matrices: SF/sub 6/ and SeF/sub 6/ in rare gas solids

    SciTech Connect

    Jones, L.H.; Swanson, B.I.

    1983-08-01

    From polarization studies of high resolution IR spectra of SF/sub 6/ and SeF/sub 6/ trapped in noble gas solids we show that much of the structure observed for the stretching mode represents site symmetry split components for low symmetry trapping sites, the triply-degenerate ..nu../sub 3/ mode being split into a doubly- and singly-degenerate mode. Most of the sites showing polarization are orientationally ordered with the singly-degenerate component perpendicular to the substrate. We attribute the driving force for ordering to guest--host interaction potentials which result in registry between the molecules and the (111) growth plane during deposition. The observed orientational ordering combined with high temperature annealing studies has allowed the identification of the symmetry of certain trapping sites and further analysis of vibrational dephasing dynamics. Several sites with the same nominal symmetry and structure can be tracked through the matrices discussed herein. The implications of the ordering of impurity structure in a host lattice formed by vapor deposition are discussed.

  6. Excitation energy migration in yellow fluorescent protein (citrine) layers adsorbed on modified gold surfaces

    NASA Astrophysics Data System (ADS)

    Yusoff, Hanis Mohd; Rzeźnicka, Izabela I.; Hoshi, Hirotaka; Kajimoto, Shinji; Horimoto, Noriko Nishizawa; Sogawa, Kazuhiro; Fukumura, Hiroshi

    2013-09-01

    The nature of functional proteins adsorbed on solid surfaces is interesting from the perspective of developing of bioelectronics and biomaterials. Here we present evidence that citrine (one of yellow fluorescent protein variants) adsorbed on modified gold surfaces would not undergo denaturation and energy transfer among the adsorbed citrine molecules would occur. Gold substrates were chemically modified with 3-mercaptopropionic acid and tert-butyl mercaptan for the preparation of hydrophilic and hydrophobic surfaces, respectively. A pure solution of citrine was dropped and dried on the modified gold substrates and their surface morphology was studied with scanning tunnelling microscopy (STM). The obtained STM images showed multilayers of citrine adsorbed on the modified surfaces. On hydrophobic surfaces, citrine was adsorbed more randomly, formed various non-uniform aggregates, while on hydrophilic surfaces, citrine appeared more aligned and isolated uniform protein clusters were observed. Fluorescence lifetime and anisotropy decay of these dried citrine layers were also measured using the time correlated single photon counting method. Fluorescence anisotropy of citrine on the hydrophobic surface decayed faster than citrine on the hydrophilic surface. From these results we concluded that fluorescence energy migration occurred faster among citrine molecules which were randomly adsorbed on the hydrophobic surface to compare with the hydrophilic surface.

  7. Photoexcitation of adsorbates on metal surfaces: One-step or three-step

    SciTech Connect

    Petek, Hrvoje

    2012-09-07

    In this essay we discuss the light-matter interactions at molecule-covered metal surfaces that initiate surface photochemistry. The hot-electron mechanism for surface photochemistry, whereby the absorption of light by a metal surface creates an electron-hole pair, and the hot electron scatters through an unoccupied resonance of adsorbate to initiate nuclear dynamics leading to photochemistry, has become widely accepted. Yet, ultrafast spectroscopic measurements of molecule-surface electronic structure and photoexcitation dynamics provide scant support for the hot electron mechanism. Instead, in most cases the adsorbate resonances are excited through photoinduced substrate-to-adsorbate charge transfer. Based on recent studies of the role of coherence in adsorbate photoexcitation, as measured by the optical phase and momentum resolved two-photon photoemission measurements, we examine critically the hot electron mechanism, and propose an alternative description based on direct charge transfer of electrons from the substrate to adsorbate. The advantage of this more quantum mechanically rigorous description is that it informs how material properties of the substrate and adsorbate, as well as their interaction, influence the frequency dependent probability of photoexcitation and ultimately how light can be used to probe and control surface femtochemistry.

  8. 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

    NASA Astrophysics Data System (ADS)

    Makarov, G. N.; Petin, A. N.

    2016-03-01

    We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF6 and CF3I 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 SF6 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 a 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.

  9. Mobility of adsorbed proteins: a Brownian dynamics study.

    PubMed

    Ravichandran, S; Talbot, J

    2000-01-01

    We simulate the adsorption of lysozyme on a solid surface, using Brownian dynamics simulations. A protein molecule is represented as a uniformly charged sphere and interacts with other molecules through screened Coulombic and double-layer forces. The simulation starts from an empty surface and attempts are made to introduce additional proteins at a fixed time interval that is inversely proportional to the bulk protein concentration. We examine the effect of ionic strength and bulk protein concentration on the adsorption kinetics over a range of surface coverages. The structure of the adsorbed layer is examined through snapshots of the configurations and quantitatively with the radial distribution function. We extract the surface diffusion coefficient from the mean square displacement. At high ionic strengths the Coulombic interaction is effectively shielded, leading to increased surface coverage. This effect is quantified with an effective particle radius. Clustering of the adsorbed molecules is promoted by high ionic strength and low bulk concentrations. We find that lateral protein mobility decreases with increasing surface coverage. The observed trends are consistent with previous theoretical and experimental studies. PMID:10620278

  10. A novel fiber-based adsorbent technology

    SciTech Connect

    Reynolds, T.A.

    1997-10-01

    In this Phase I Small Business Innovation Research program, Chemica Technologies, Inc. is developing an economical, robust, fiber-based adsorbent technology for removal of heavy metals from contaminated water. The key innovation is the development of regenerable adsorbent fibers and adsorbent fiber cloths that have high capacity and selectivity for heavy metals and are chemically robust. The process has the potential for widespread use at DOE facilities, mining operations, and the chemical process industry.

  11. Molecular adsorbates as probes of the local properties of doped graphene

    PubMed Central

    Pham, Van Dong; Joucken, Frédéric; Repain, Vincent; Chacon, Cyril; Bellec, Amandine; Girard, Yann; Rousset, Sylvie; Sporken, Robert; Santos, Maria Cristina dos; Lagoute, Jérôme

    2016-01-01

    Graphene-based sensors are among the most promising of graphene’s applications. The ability to signal the presence of molecular species adsorbed on this atomically thin substrate has been explored from electric measurements to light scattering. Here we show that the adsorbed molecules can be used to sense graphene properties. The interaction of porphyrin molecules with nitrogen-doped graphene has been investigated using scanning tunneling microscopy and ab initio calculations. Molecular manipulation was used to reveal the surface below the adsorbed molecules allowing to achieve an atomic-scale measure of the interaction of molecules with doped graphene. The adsorbate’s frontier electronic states are downshifted in energy as the molecule approaches the doping site, with largest effect when the molecule sits over the nitrogen dopant. Theoretical calculations showed that, due to graphene’s high polarizability, the adsorption of porphyrin induces a charge rearrangement on the substrate similar to the image charges on a metal. This charge polarization is enhanced around nitrogen site, leading to an increased interaction of molecules with their image charges on graphene. Consequently, the molecular states are stabilized and shift to lower energies. These findings reveal the local variation of polarizability induced by nitrogen dopant opening new routes towards the electronic tuning of graphene. PMID:27097555

  12. Molecular adsorbates as probes of the local properties of doped graphene

    NASA Astrophysics Data System (ADS)

    Pham, Van Dong; Joucken, Frédéric; Repain, Vincent; Chacon, Cyril; Bellec, Amandine; Girard, Yann; Rousset, Sylvie; Sporken, Robert; Santos, Maria Cristina Dos; Lagoute, Jérôme

    2016-04-01

    Graphene-based sensors are among the most promising of graphene’s applications. The ability to signal the presence of molecular species adsorbed on this atomically thin substrate has been explored from electric measurements to light scattering. Here we show that the adsorbed molecules can be used to sense graphene properties. The interaction of porphyrin molecules with nitrogen-doped graphene has been investigated using scanning tunneling microscopy and ab initio calculations. Molecular manipulation was used to reveal the surface below the adsorbed molecules allowing to achieve an atomic-scale measure of the interaction of molecules with doped graphene. The adsorbate’s frontier electronic states are downshifted in energy as the molecule approaches the doping site, with largest effect when the molecule sits over the nitrogen dopant. Theoretical calculations showed that, due to graphene’s high polarizability, the adsorption of porphyrin induces a charge rearrangement on the substrate similar to the image charges on a metal. This charge polarization is enhanced around nitrogen site, leading to an increased interaction of molecules with their image charges on graphene. Consequently, the molecular states are stabilized and shift to lower energies. These findings reveal the local variation of polarizability induced by nitrogen dopant opening new routes towards the electronic tuning of graphene.

  13. Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

    SciTech Connect

    Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans

    2014-07-28

    Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

  14. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    DOE PAGESBeta

    Gill, Gary A.; Kuo, Li -Jung; Janke, Christopher James; Park, Jiyeon; Jeters, Robert T.; Bonheyo, George T.; Pan, Horng -Bin; Wai, Chien; Khangaonkar, Tarang P.; Bianucci, Laura; et al

    2016-02-07

    The Pacific Northwest National Laboratory's (PNNL) Marine Science Laboratory (MSL) located along the coast of Washington State is evaluating the performance of uranium adsorption materials being developed for seawater extraction under realistic marine conditions with natural seawater. Two types of exposure systems were employed in this program: flow-through columns for testing of fixed beds of individual fibers and pellets and a recirculating water flume for testing of braided adsorbent material. Testing consists of measurements of the adsorption of uranium and other elements from seawater as a function of time, typically 42 to 56 day exposures, to determine the adsorbent capacitymore » and adsorption rate (kinetics). Analysis of uranium and other trace elements collected by the adsorbents was conducted following strong acid digestion of the adsorbent with 50% aqua regia using either Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The ORNL 38H adsorbent had a 56 day adsorption capacity of 3.30 ± 0.68 g U/ kg adsorbent (normalized to a salinity of 35 psu), a saturation adsorption capacity of 4.89 ± 0.83 g U/kg of adsorbent material (normalized to a salinity of 35 psu) and a half-saturation time of 28 10 days. The AF1 adsorbent material had a 56 day adsorption capacity of 3.9 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu), a saturation capacity of 5.4 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu) and a half saturation time of 23 2 days. The ORNL amidoxime-based adsorbent materials are not specific for uranium, but also adsorb other elements from seawater. The major doubly charged cations in seawater (Ca and Mg) account for a majority of the cations adsorbed (61% by mass and 74% by molar percent). For the ORNL AF1 adsorbent material, U is the 4th most abundant element adsorbed by mass and 7th most abundant by molar percentage. Marine testing

  15. The Uranium from Seawater Program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    SciTech Connect

    Gill, Gary; Kuo, Li-Jung; Janke, Christopher James; Park, Jiyeon; Jeters, Robert T; Bonheyo, George; Pan, Horng-Bin; Wai, Chien; Khangaonkar, Tarang P; Bianucci, Laura; Wood, Jordana; Warner, Marvin G; Peterson, Sonja; Abrecht, David; Mayes, Richard T; Tsouris, Costas; Oyola, Yatsandra; Strivens, Jonathan E.; Schlafer, Nicholas; Addleman, Shane R; Chouyyok, Wilaiwan; Das, Sadananda; Kim, Jungseung; Buesseler, Dr. Ken; Breier, Crystalline; D'Alessandro, Dr. Evan

    2016-01-01

    The Pacific Northwest National Laboratory s (PNNL) Marine Science Laboratory (MSL) located along the coast of Washington State is evaluating the performance of uranium adsorption materials being developed for seawater extraction under realistic marine conditions with natural seawater. Two types of exposure systems were employed in this program: flow-through columns for testing of fixed beds of individual fibers and pellets and a recirculating water flume for testing of braided adsorbent material. Testing consists of measurements of the adsorption of uranium and other elements from seawater as a function of time, typically 42 to 56 day exposures, to determine the adsorbent capacity and adsorption rate (kinetics). Analysis of uranium and other trace elements collected by the adsorbents was conducted following strong acid digestion of the adsorbent with 50% aqua regia using either Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The ORNL 38H adsorbent had a 56 day adsorption capacity of 3.30 0.68 g U/ kg adsorbent (normalized to a salinity of 35 psu), a saturation adsorption capacity of 4.89 0.83 g U/kg of adsorbent material (normalized to a salinity of 35 psu) and a half-saturation time of 28 10 days. The AF1 adsorbent material had a 56 day adsorption capacity of 3.9 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu), a saturation capacity of 5.4 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu) and a half saturation time of 23 2 days. The ORNL amidoxime-based adsorbent materials are not specific for uranium, but also adsorb other elements from seawater. The major doubly charged cations in seawater (Ca and Mg) account for a majority of the cations adsorbed (61% by mass and 74% by molar percent). For the ORNL AF1 adsorbent material, U is the 4th most abundant element adsorbed by mass and 7th most abundant by molar percentage. Marine testing at Woods Hole

  16. Heat capacity of quantum adsorbates: Hydrogen and helium on evaporated gold films

    SciTech Connect

    Birmingham, J.T. |

    1996-06-01

    The author has constructed an apparatus to make specific heat measurements of quantum gases adsorbed on metallic films at temperatures between 0.3 and 4 K. He has used this apparatus to study quench-condensed hydrogen films between 4 and 923 layers thick with J = 1 concentrations between 0.28 and 0.75 deposited on an evaporated gold surface. He has observed that the orientational ordering of the J = 1 molecules depends on the substrate temperature during deposition of the hydrogen film. He has inferred that the density of the films condensed at the lowest temperatures is 25% higher than in bulk H{sub 2} crystals and have observed that the structure of those films is affected by annealing at 3.4 K. The author has measured the J = 1 to J = 0 conversion rate to be comparable to that of the bulk for thick films; however, he found evidence that the gold surface catalyzes conversion in the first two to four layers. He has also used this apparatus to study films of {sup 4}He less than one layer thick adsorbed on an evaporated gold surface. He shows that the phase diagram of the system is similar to that for {sup 4}He/graphite although not as rich in structure, and the phase boundaries occur at different coverages and temperatures. At coverages below about half a layer and at sufficiently high temperatures, the {sup 4}He behaves like a two-dimensional noninteracting Bose gas. At lower temperatures and higher coverages, liquidlike and solidlike behavior is observed. The Appendix shows measurements of the far-infrared absorptivity of the high-{Tc} superconductor La{sub 1.87}Sr{sub 0.13}CuO{sub 4}.

  17. Carbon fibers: Thermochemical recovery from advanced composite materials and activation to an adsorbent

    NASA Astrophysics Data System (ADS)

    Staley, Todd Andrew

    This research addresses an expanding waste disposal problem brought about by the increasing use of advanced composite materials, and the lack of technically and environmentally viable recycling methods for these materials. A thermochemical treatment process was developed and optimized for the recycling of advanced composite materials. Counter-current gasification was employed for the treatment of carbon fiber reinforced-epoxy resin composite wastes. These materials were treated, allowing the reclamation of the material's valuable components. As expected in gasification, the organic portion of the waste was thermochemically converted to a combustible gas with small amounts of organic compounds that were identified by GC/MS. These compounds were expected based on data in the literature. The composites contain 70% fiber reinforcement, and gasification yielded approximately 70% recovered fibers, representing nearly complete recovery of fibers from the waste. Through SEM and mechanical testing, the recovered carbon fibers were found to be structurally and mechanically intact, and amenable to re-use in a variety of applications, some of which were identified and tested. In addition, an application was developed for the carbon fiber component of the waste, as an activated carbon fiber adsorbent for the treatment of wastewaters. This novel class of adsorbent was found to have adsorption rates, for various organic molecules, up to a factor of ten times those of commercial granular activated carbon, and adsorption capacities similar to conventional activated carbons. Overall, the research addresses an existing environmental waste problem, employing a thermochemical technique to recycle and reclaim the waste. Components of the reclaimed waste material are then employed, after further modification, to address other existing and potential environmental waste problems.

  18. Complete braided adsorbent for marine testing to demonstrate 3g-U/kg-adsorbent

    SciTech Connect

    Janke, Chris; Yatsandra, Oyola; Mayes, Richard; none,; Gill, Gary; Li-Jung, Kuo; Wood, Jordana; Sadananda, Das

    2014-04-30

    ORNL has manufactured four braided adsorbents that successfully demonstrated uranium adsorption capacities ranging from 3.0-3.6 g-U/kg-adsorbent in marine testing at PNNL. Four new braided and leno woven fabric adsorbents have also been prepared by ORNL and are currently undergoing marine testing at PNNL.

  19. Vibrational lifetimes and friction in adsorbate motion determined from quasi-elastic scattering.

    PubMed

    Lechner, Barbara A J; Hedgeland, Holly; Jardine, Andrew P; Allison, William; Hinch, B J; Ellis, John

    2015-09-14

    The vibrational excitation of molecules adsorbed on a surface is typically probed by spectroscopic techniques such as infrared or Raman spectroscopy. In the present article we demonstrate an alternative method to determine vibrational lifetimes of adsorbate molecules using quasi-elastic helium atom scattering (QHAS). As a probe of diffusive motion of molecules on surfaces QHAS is well established. Here, we demonstrate that QHAS can also be used to probe the vibrational lifetime of a molecule in its adsorption well. Measurements of cyclopentadienyl, C5H5, on Cu(111) allow us to distinguish two substrate phonon modes as well as two molecular vibrational modes, perpendicular and parallel to the surface. We further find that the dephasing of the vibrational motion corresponds to the friction determined in previous diffusion measurements. PMID:26204093

  20. Hemoglobin-mimetic oxygen adsorbent prepared via self-assembly of cysteinyl bolaamphiphiles.

    PubMed

    Lee, Chaemyeong; Kim, Min-Chul; Lee, Sang-Yup

    2016-06-01

    In this study, a novel cysteinyl bolaamphiphilic molecule was synthesized and its self-assembled planar suprastructure was applied as a biomimetic matrix to create a hemoglobin-mimetic oxygen adsorbent that exploits the ability of cysteine thiols to bind hemin. Self-assembly of the cysteinyl bolaamphiphilic molecule exposed cysteine thiols on its surface in the presence of β-mercaptoethanol, known to reduce disulfide bonds, without which, helically coiled structures were generated. The self-assembled planar structure was used as a soft matrix to create a hemoglobin-mimetic oxygen adsorbent. The surface-exposed cysteine thiols were used to attach hemin, producing a hemin-bound, planar structure mimicking hemoglobin. This hemoglobin mimic strongly adsorbed oxygen and remained stable up to 50°C. The cysteinyl bolaamphiphile self-assembled structure provided a biomimetic platform that allowed for the association of biological substances in a manner similar to natural proteins. PMID:26970824

  1. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates.

    PubMed

    Sangodkar, Rahul P; Smith, Benjamin J; Gajan, David; Rossini, Aaron J; Roberts, Lawrence R; Funkhouser, Gary P; Lesage, Anne; Emsley, Lyndon; Chmelka, Bradley F

    2015-07-01

    Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low

  2. Photoinduced surface dynamics of CO adsorbed on a platinum electrode.

    PubMed

    Noguchi, Hidenori; Okada, Tsubasa; Uosaki, Kohei

    2006-08-10

    The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation. PMID:16884215

  3. Energetics of adsorbed CH3 on Pt(111) by calorimetry.

    PubMed

    Karp, Eric M; Silbaugh, Trent L; Campbell, Charles T

    2013-04-01

    The enthalpy and sticking probability for the dissociative adsorption of methyl iodide were measured on Pt(111) at 320 K and at low coverages (up to 0.04 ML, where 1 ML is equal to one adsorbate molecule for every surface Pt atom) using single crystal adsorption calorimetry (SCAC). At this temperature and in this coverage range, methyl iodide produces adsorbed methyl (CH(3,ad)) plus an iodine adatom (I(ad)). Combining the heat of this reaction with reported energetics for Iad gives the standard heat of formation of adsorbed methyl, ΔH(f)(0)(CH3,ad), to be −53 kJ/mol and a Pt(111)–CH3 bond energy of 197 kJ/mol. (The error bar of ±20 kJ/mol for both values is limited by the reported heat of formation of I(ad).) This is the first direct measurement of these values for any alkyl fragment on any surface. PMID:23461481

  4. Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions

    NASA Technical Reports Server (NTRS)

    Shortt, Brian; Chutjian, Ara; Orient, Otto

    2008-01-01

    A method of making more-complex molecules from simpler ones has emerged as a by-product of an experimental study in outer-space atom/surface collision physics. The subject of the study was the formation of CO2 molecules as a result of impingement of O atoms at controlled kinetic energies upon cold surfaces onto which CO molecules had been adsorbed. In this study, the O/CO system served as a laboratory model, not only for the formation of CO2 but also for the formation of other compounds through impingement of rapidly moving atoms upon molecules adsorbed on such cold interstellar surfaces as those of dust grains or comets. By contributing to the formation of increasingly complex molecules, including organic ones, this study and related other studies may eventually contribute to understanding of the origins of life.

  5. Atomic-Scale Control of Electron Transport through Single Molecules

    NASA Astrophysics Data System (ADS)

    Wang, Y. F.; Kröger, J.; Berndt, R.; Vázquez, H.; Brandbyge, M.; Paulsson, M.

    2010-04-01

    Tin-phthalocyanine molecules adsorbed on Ag(111) were contacted with the tip of a cryogenic scanning tunneling microscope. Orders-of-magnitude variations of the single-molecule junction conductance were achieved by controllably dehydrogenating the molecule and by modifying the atomic structure of the surface electrode. Nonequilibrium Green’s function calculations reproduce the trend of the conductance and visualize the current flow through the junction, which is guided through molecule-electrode chemical bonds.

  6. A study of surface enhanced Raman scattering for furfural adsorbed on silver surface

    NASA Astrophysics Data System (ADS)

    Jia, Ting-jian; Li, Peng-wei; Shang, Zhi-guo; Zhang, Ling; He, Ting-chao; Mo, Yu-jun

    2008-02-01

    The normal Raman spectrum (NRS) and the surface enhanced Raman scattering (SERS) spectrum of furfural in silver colloid were recorded and analyzed in this paper. The assignment of these bands to furfural molecules was performed by density functional theory (DFT) calculation. The data of the SERS by comparing with the one of NRS show that furfural molecules are adsorbed on the silver surface via the nonbonding electrons of the carbonyl oxygen.

  7. Modeling adsorption and reactions of organic molecules at metal surfaces.

    PubMed

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  8. Theoretical Investigation of the Reaction Paths of the Aluminum Cluster Cation with Water Molecule in the Gas Phase: A Facile Route for Dihydrogen Release.

    PubMed

    Moc, Jerzy

    2015-08-13

    The gas-phase reaction of the Al6(+) cation with a water molecule is investigated computationally by coupled cluster and density functional theories. Several low-energy paths of the mechanism for dihydrogen production from H2O by the positively charged aluminum cluster are identified. This reaction involves the initial formation of the association complex, exothermic by 25 kcal/mol, followed by the water dissociation and H2 elimination major steps, yielding the Al6O(+) product oxide with either the nonplanar or planar structure. The H2O dissociation on Al6(+) is the rate-determining step. Of the paths probed, the one kinetically most preferred leads from the O-H bond dissociation transition state lying below the separated reactants to the immediate HAl6OH(+) intermediate of the "open" type and involves further the more compact intermediate from which H2 is eliminated. The other reaction paths explored involve the activation enthalpy (at 0 K) for the rate-determining step of less than 2 kcal/mol relative to the Al6(+) + H2O. Natural population analysis based charges indicate that forming of H2 along the elimination coordinate is facilitated by the interaction of the hydridic and protic hydrogens. For the kinetically most favorable route detected, the coupled cluster singles and doubles with perturbative triples (CCSD(T)) relative energies calculated with the unrestricted and restricted HF references are in a good agreement. This investigation is relevant specifically to the recent mass spectrometric study of the reactivity of Aln(+) with water by Arakawa et al., and it provides a mechanistic insight into the formation of the observed AlnO(+) product oxide with n = 6. PMID:26200102

  9. 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

    SciTech Connect

    Chiou, E.W.; Larsen, J.C. ); McCormick, M.P.; McMaster, L.R.; Chu, W.P. ); Rind, D. ); Oltmans, S. )

    1993-03-20

    This paper presents a comparison of the stratospheric water vapor measurements made by the satellite-borne sensors the Stratospheric Aerosol and Gas Experiment II (SAGE II), the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS), and the Spacelab 3 Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment. LIMS obtained data for 7 months between November 1978 and May 1979; ATMOS was carried on Shuttle and observed eight profiles from April 30 to May 6, 1985 at approximately 30[degrees]N and 50[degrees]S; and, SAGE II continues to make measurements since its launch in October 1984. For both 30[degrees]N and 50[degrees]S in May, the comparisons between SAGE II and ATMOS show agreement within the estimated combined uncertainty of the two experiments. Several important features identified by LIMS observations have been confirmed by SAGE II: a well-developed hygropause in the lower stratosphere at low- to mid-latitudes, a poleward latitudinal gradient, increasing water vapor mixing ratios with altitude in the tropics, and the transport of dry lower stratospheric water vapor upward and southward in May, and upward and northward in November. A detailed comparative study also indicates that the two previously suggested corrections for LIMS, a correction in tropical lower stratosphere due to a positive temperature bias and the correction above 28 km based on improved emissivities will bring LIMS measurements much closer to those of SAGE II. The only significant difference occurs at high southern latitudes in May below 18 km, where LIMS measurements are 2-3 ppmv greater. It should be noted that LIMS observations are from 16 to 50 km, ATMOS from 14 to 86 km, and SAGE II from mid-troposphere to 40 km. With multiyear coverage, SAGE II observations should be useful for studying tropospheric-stratospheric exchange, for stratospheric transport, and for preparing water vapor climatologies for the stratosphere and the upper troposphere. 32 refs., 14 figs., 2 tabs.

  10. Properties and potential environmental applications of carbon adsorbents from waste tire rubber

    USGS Publications Warehouse

    Lehmann, C.M.B.; Rameriz, D.; Rood, M.J.; Rostam-Abadi, M.

    2000-01-01

    The properties of tire-derived carbon adsorbents (TDCA) produced from select tire chars were compared with those derived from an Illinois coal and pistachio nut shells. Chemical analyses of the TDCA indicated that these materials contain metallic elements not present in coal-and nut shell-derived carbons. These metals, introduced during the production of tire rubber, potentially catalyze steam gasification reactions of tire char. TDCA carbons contained larger meso-and macopore volumes than their counterparts derived from coal and nut shell (on the moisture-and ash-free-basis). Adsorptive properties of the tire-derived adsorbent carbons for air separation, gas storage, and gas clean up were also evaluated and compared with those of the coal-and nut shell derived carbons as well as a commercial activated carbon. The results revealed that TDCA carbons are suitable adsorbents for removing vapor-phase mercury from combustion flue gases and hazardous organic compounds from industrial gas streams.

  11. NOx adsorber and method of regenerating same

    SciTech Connect

    Endicott, Dennis L.; Verkiel, Maarten; Driscoll, James J.

    2007-01-30

    New technologies, such as NOx adsorber catalytic converters, are being used to meet increasingly stringent regulations on undesirable emissions, including NOx emissions. NOx adsorbers must be periodically regenerated, which requires an increased fuel consumption. The present disclosure includes a method of regenerating a NOx adsorber within a NOx adsorber catalytic converter. At least one sensor positioned downstream from the NOx adsorber senses, in the downstream exhaust, at least one of NOx, nitrous oxide and ammonia concentrations a plurality of times during a regeneration phase. The sensor is in communication with an electronic control module that includes a regeneration monitoring algorithm operable to end the regeneration phase when a time rate of change of the at least one of NOx, nitrous oxide and ammonia concentrations is after an expected plateau region begins.

  12. Pyrolyzed feather fibers for adsorbent and high temperature applications

    NASA Astrophysics Data System (ADS)

    Senoz, Erman

    used in applications such as adsorption, storage, and separation of small gas molecules. The maximum excess H2 storage capacity was 1.5 wt% at 77 K and at pressures below 2 MPa. The notable H2 adsorption of PCFF below 1 MPa can be justified by the abundance of microporosity and the nanopores available for H2 penetration. In the second step of the pyrolysis the protein matrix went through a series of transformations including cyclization and aromatization reactions above the melting point. A partially cyclic carbon-nitrogen framework (carbon/nitrogen ratio=2.38) supported by double and triple bonds and oxygen functionalities is the suggested structural model for the PCFF. The useful fibers and adsorbents produced from CFF in this dissertation can encourage researchers to use high temperature heat treatments on keratin-based fibers. Also, the identified pyrolysis mechanisms can serve as a guide for producing materials with desired properties from protein-based materials, particularly in textile, high performance composite and catalyst industries.

  13. First-principles study of SO2 molecule adsorption on the pristine and Mn-doped boron nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Deng, Zun-Yi; Zhang, Jian-Min; Xu, Ke-Wei

    2015-08-01

    To exploit the potential application of nitride nanotube (BNNT), the adsorption of sulfur dioxide (SO2) on pristine and Mn-doped BNNT was theoretically studied using first-principles approach based on density functional theory (DFT). The most stable adsorption geometry, adsorption energy, magnetic moment, charge transfer and density of states of these systems are discussed. SO2 molecule is weakly adsorbed on the pristine BNNT. The Mn-doped BNNT show high reactivity toward SO2 regardless of the MnB site or MnN site adsorption. The larger formation energies and analysis of density of states show the SO2 molecules are chemically bonded to Mn-doped BNNT and the covalent interaction between the SO2 molecule and Mn atom can be formed. Therefore, the Mn-doped BNNT can be used as SO2 gas sensor manufacturing raw materials, and it may be a potential material for nanodevice applications.

  14. Inorganic chemically active adsorbents (ICAAs)

    SciTech Connect

    Ally, M.R.; Tavlarides, L.

    1997-10-01

    Oak Ridge National Laboratory (ORNL) researchers are developing a technology that combines metal chelation extraction technology and synthesis chemistry. They begin with a ceramic substrate such as alumina, titanium oxide or silica gel because they provide high surface area, high mechanical strength, and radiolytic stability. One preparation method involves silylation to hydrophobize the surface, followed by chemisorption of a suitable chelation agent using vapor deposition. Another route attaches newly designed chelating agents through covalent bonding by the use of coupling agents. These approaches provide stable and selective, inorganic chemically active adsorbents (ICAAs) tailored for removal of metals. The technology has the following advantages over ion exchange: (1) higher mechanical strength, (2) higher resistance to radiation fields, (3) higher selectivity for the desired metal ion, (4) no cation exchange, (5) reduced or no interference from accompanying anions, (6) faster kinetics, and (7) easy and selective regeneration. Target waste streams include metal-containing groundwater/process wastewater at ORNL`s Y-12 Plant (multiple metals), Savannah River Site (SRS), Rocky Flats (multiple metals), and Hanford; aqueous mixed wastes at Idaho National Engineering Laboratory (INEL); and scrubber water generated at SRS and INEL. Focus Areas that will benefit from this research include Mixed Waste, and Subsurface Contaminants.

  15. Enhanced photodegradation of organic dyes adsorbed on a clay.

    PubMed

    Tani, Seiji; Yamaki, Hiroshi; Sumiyoshi, Azumi; Suzuki, Yasutaka; Hasegawa, Shinya; Yamazaki, Suzuko; Kawamata, Jun

    2009-01-01

    The interaction of three photoactive organic dyes, Rhodamine B, Rhodamine 6G and a stilbazolium derivative 4'-dimethylamino-N-methyl-4-stilbazolium with synthetic sodium-saponite has been examined by UV-visible absorption spectroscopy. In all cases, bathochromic shifts and the reduction of peak absorbance for the dyes were observed in the absorption spectra at a low dye concentration (25% adsorption of the cation exchange capacity (CEC) of the clay), although the shape and the width of their absorption bands were similar to those in aqueous solution. This absorption behavior indicates that the organic dye molecules adsorbed onto the surface of the negatively charged clay particles and the adsorbed molecules were well dispersed. The photodegradation of the organic dyes in aqueous solution and in the clay suspension has been also examined by the irradiation of a laser beam at a wavelength of 532 nm. We have found that the hybridization of the organic dyes with the exfoliated clay particles largely enhanced a photodegradation. The clay particles acted as a catalyst even at a high concentration such as approximately 300% of CEC. PMID:19441365

  16. Density-functional investigation of the geometric and electronic structure of ethylene oxide adsorbed on Si(100)

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Li, Qing-Fang; Yang, Cui-Hong; Wei, Yue-Ling; Zhu, Xing-Feng; Rao, Wei-Feng

    2016-05-01

    The geometric and electronic structures of the ethylene oxide (EO) molecule adsorbed on Si(100)-(2 × 1) surface were investigated by using the density-functional theory calculations. All possible adsorbed structures were considered and it was found that only four adsorption structures are stable. The calculations of the formation energy revealed the most stable conformation and demonstrated that the nature of Si-O bond significantly affects the stability of adsorption systems. The analysis of corresponding electronic structures showed that two adsorbed structures are still semiconductor compounds but the other two are not. In particular, the EO after adsorbing was found to be connected via a ring-opening reaction where the molecule forms a five-membered ring together with the surface of dimer silicon atoms, and the produced five-membered ring is almost perpendicular to the silicon surface.

  17. Impact of temperature and electrical potentials on the stability and structure of collagen adsorbed on the gold electrode

    NASA Astrophysics Data System (ADS)

    Meiners, Frank; Ahlers, Michael; Brand, Izabella; Wittstock, Gunther

    2015-01-01

    The morphology and structure of collagen type I adsorbed on gold electrodes were studied as a function of electrode potential and temperature by means of capacitance measurements, polarization modulation infrared reflection-absorption spectroscopy and scanning force microscopy at temperatures of 37 °C, 43 °C and 50 °C. The selected temperatures corresponded to the normal body temperature, temperature of denaturation of collagen molecules and denaturation of collagen fibrils, respectively. Independently of the solution temperature, collagen was adsorbed on gold electrodes in the potential range - 0.7 V < E < 0.4 V vs. Ag/AgCl, where the protein film was very stable. Fragments of collagen molecules made a direct contact to the gold surface and water was present in the film. Protein molecules were oriented preferentially with their long axis towards the gold surface. Collagen molecules in the adsorbed state preserved their native triple helical structure even at temperatures corresponding to collagen denaturation in aqueous solutions. Application of E < - 0.75 V vs. Ag/AgCl leads to the swelling of the protein film by water and desorption from the electrode surface. IR spectra provided no evidence of the thermal denaturation of adsorbed collagen molecules. A temperature increase to 50 °C leads to a distortion of the collagen film. The processes of aggregation and fibrilization were preferred over thermal denaturation for collagen adsorbed on the electrode surface and exposed to changing potentials.

  18. Site blocking effects on adsorbed polyacrylamide conformation

    NASA Astrophysics Data System (ADS)

    Brotherson, Brett A.

    The use of polymers as flocculating additives is a common practice in many manufacturing environments. However, exactly how these polymers interact with surfaces is relatively unknown. One specific topic which is thought to be very important to flocculation is an adsorbed polymer's conformation. Substantial amounts of previous work, mainly using simulations, have been performed to elucidate the theory surrounding adsorbed polymer conformations. Yet, there is little experimental work which directly verifies current theory. In order to optimize the use of polymer flocculants in industrial applications, a better understanding of an adsorbed polymer's conformation on a surface beyond theoretical simulations is necessary. This work looks specifically at site blocking, which has a broad impact on flocculation, adsorption, and surface modification, and investigated its effects on the resulting adsorbed polymer conformation. Experimental methods which would allow direct determination of adsorbed polymer conformational details and be comparable with previous experimental results were first determined or developed. Characterization of an adsorbed polymer's conformation was then evaluated using dynamic light scattering, a currently accepted experimental technique to examine this. This commonly used technique was performed to allow the comparison of this works results with past literature. Next, a new technique using atomic force microscopy was developed, building on previous experimental techniques, to allow the direct determination of an adsorbed polymer's loop lengths. This method also was able to quantify changes in the length of adsorbed polymer tails. Finally, mesoscopic simulation was attempted using dissipative particle dynamics. In order to determine more information about an adsorbed polymer's conformation, three different environmental factors were analyzed: an adsorbed polymer on a surface in water, an adsorbed polymer on a surface in aqueous solutions of varying

  19. Heterogeneous Ozonolysis of Surface Adsorbed Lignin Pyrolysis Products

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.

    2012-12-01

    Biomass combustion releases semi-volatile organic compounds into the troposphere, including many phenols and methoxyphenols as the result of lignin pyrolysis. Given their relatively low vapor pressures, these compounds readily adsorb on inorganic and organic aerosol substrates where they may alter aerosol properties and undergo heterogeneous chemistry. We use infrared spectroscopy (DRIFTS and ATR-FTIR) to monitor the adsorption and subsequent heterogeneous ozonolysis of model lignin pyrolysis products, including catechol, eugenol, and 4-propylguaiacol. Ozonolysis reaction kinetics were compared on various inorganic substrates - such as Al2O3 and NaCl, which serve as mineral and sea salt aerosol substrates, respectively - and as a function of ozone concentration and relative humidity. Following in situ FTIR analysis, the adsorbed organics were extracted and analyzed using gas chromatography-mass spectroscopy to identify reaction products and quantify product branching ratios. Ozonolysis of catechol and 4-propylguaiacol readily resulted in ring cleavage forming dicarboxylic acids (e.g., muconic acid). Eugenol ozonolysis proceeded rapidly at the alkene side chain producing homovanillic acid and homovanillin in an approximate 2:1 branching ratio at 0% RH; ring cleavage was also observed. For all lignin pyrolysis products, heterogeneous ozonolysis was faster on NaCl versus Al2O3. Implications for the atmospheric chemistry of semi-volatile methoxylphenols adsorbed on aerosol substrates will be discussed.

  20. 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)