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Sample records for adsorbed gas molecules

  1. Detection of individual gas molecules adsorbed on graphene.

    PubMed

    Schedin, F; Geim, A K; Morozov, S V; Hill, E W; Blake, P; Katsnelson, M I; Novoselov, K S

    2007-09-01

    The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  4. 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.

  5. A theoretical study of the XP and NEXAFS spectra of alanine: gas phase molecule, crystal, and adsorbate at the ZnO(10 ̅10) surface.

    PubMed

    Gao, You Kun; Traeger, Franziska; Kotsis, Konstantinos; Staemmler, Volker

    2011-06-14

    The adsorption of alanine on the mixed-terminated ZnO(10 ̅10) surface is studied by means of quantum-chemical ab initio calculations. Using a finite cluster model and the adsorption geometry as obtained both by periodic CPMD and embedded cluster calculations, the C1s, N1s and O1s X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra are calculated for single alanine molecules on ZnO(10 ̅10). These spectra are compared with the spectra calculated for alanine in the gas phase and in its crystalline form and with experimental XPS and NEXAFS data for the isolated alanine molecule and for alanine adsorbed on ZnO(10 ̅10) at multilayer and monolayer coverage. The excellent agreement between the experimental and calculated XP and NEXAFS spectra confirms the calculated adsorption geometry: A single alanine molecule is bound to ZnO(10 ̅10) in a dissociated bidentate form with the two O atoms of the acid group bound to two Zn atoms of the surface and the proton transferred to one O atom of the surface. Other possible structures, such as adsorption of alanine in one of its neutral or zwitterionic forms in which the proton of the -COOH group remains at this group or is transferred to the amino group, can be excluded since they would give rise to quite different XP spectra. In the multilayer coverage regime, on the other hand, alanine is in its crystalline form as is also shown by the analysis of the XP spectra.

  6. Imaging the wave functions of adsorbed molecules.

    PubMed

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

    2014-01-14

    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.

  7. 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.

  8. 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.

  9. 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.

  10. Chiral switching by spontaneous conformational change in adsorbed organic molecules.

    PubMed

    Weigelt, Sigrid; Busse, Carsten; Petersen, Lars; Rauls, Eva; Hammer, Bjørk; Gothelf, Kurt V; Besenbacher, Flemming; Linderoth, Trolle R

    2006-02-01

    Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-12-05

    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.

  13. Forces from periodic charging of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Kocić, N.; Decurtins, S.; Liu, S.-X.; Repp, J.

    2017-03-01

    In a recent publication [Kocić et al., Nano Lett. 15, 4406 (2015)], it was shown that gating of molecular levels in the field of an oscillating tip of an atomic force microscope can enable a periodic charging of individual molecules synchronized to the tip's oscillatory motion. Here we discuss further implications of such measurements, namely, how the force difference associated with the single-electron charging manifests itself in atomic force microscopy images and how it can be detected as a function of tip-sample distance. Moreover, we discuss how the critical voltage for the charge-state transition depends on distance and how that relates to the local contact potential difference. These measurements allow also for an estimate of the absolute tip-sample distance.

  14. Direct measurement of adsorbed gas redistribution in metal-organic frameworks.

    PubMed

    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.

  15. Spectroscopic observations of the displacement dynamics of physically adsorbed molecules-CO on C60

    NASA Astrophysics Data System (ADS)

    Yuan, Chunqing; Yates, John T.

    2016-10-01

    In this paper, we observed physically adsorbed CO molecules on C60 surface being displaced by impinging noble gas atoms (He, Ne, Ar, Kr), either through a dynamic displacement process or an exothermic replacement process, depending on their adsorption energies. This displacement mechanism could shift from one to the other depending on the surface coverage and temperature. Furthermore, rotational energy of the impinging molecules may also contribute to the dynamic displacement process by supplying additional energy.

  16. 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.

  17. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  18. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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 O2 molecules adsorbed on the surface. Using density functional theory calculations, we find that an O2 molecule adsorbed on an α-alumina surface has a magnetic moment of ˜1.8 μB . 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 X Y spins on a square lattice find 1 /f magnetization noise, consistent with flux noise in Al SQUIDs.

  20. Resonant vibrational excitation of adsorbed molecules by electron impact

    NASA Astrophysics Data System (ADS)

    Djamo, V.; Teillet-Billy, D.; Gauyacq, J. P.

    1993-11-01

    The vibrational excitation of N2 molecules adsorbed on a silver surface by low energy electron impact is studied within the newly developed coupled angular mode method. The process involves the formation of a transient negative molecular ion. The results account well for the observations of Demuth and co-workers. They also reveal that most of the vibrational excitation corresponds to electrons scattered into the metal and thus unobservable in a scattering experiment.

  1. 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.

  2. Multiple species of noninteracting molecules adsorbed on a Bethe lattice.

    PubMed

    Cohen, Michael; Harris, A B

    2008-10-01

    A simple method, previously used to calculate the equilibrium concentration of dimers adsorbed on a Bethe lattice as a function of the dimer activity, is generalized to solve the problem of a Bethe lattice in contact with a reservoir containing a mixture of molecules. The molecules may have arbitrary sizes and shapes consistent with the geometry of the lattice and the molecules do not interact with one another except for the hard-core restriction that two molecules cannot touch the same site. We obtain a set of simultaneous nonlinear equations, one equation for each species of molecule, which determines the equilibrium concentration of each type of molecule as a function of the (arbitrary) activities of the various species. Surprisingly, regardless of the number of species, the equilibrium concentrations are given explicitly in terms of the solution of a single equation in one unknown which can be solved numerically, if need be. Some numerical examples show that increasing the activity of one species need not necessarily decrease the equilibrium concentration of all other species. We also calculate the adsorption isotherm of an "annealed" Bethe lattice consisting of two types of sites which differently influence the activity of an adsorbed molecule. We prove that if the reservoir contains a finite number of molecular species, regions of two different polymer densities cannot simultaneously exist on the lattice. The widely used Guggenheim theory of mixtures, which can also be construed as a theory of adsorption, assumes for simplicity that the molecules in the mixture are composed of elementary units, which occupy sites of a lattice of coordination number q . Guggenheim's analysis relies on approximate combinatorial formulas which become exact on a Bethe lattice of the same coordination number, as we show in an appendix. Our analysis involves no combinatorics and relies only on recognizing the statistical independence of certain quantities. Despite the nominal

  3. 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

  4. 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...

  5. 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...

  6. Procedure for freeze-drying molecules adsorbed to mica flakes.

    PubMed

    Heuser, J E

    1983-09-05

    The quick-freeze, deep-etch, rotary-replication technique is useful for visualizing cells and cell fractions but does not work with suspensions of macromolecules. These inevitably clump or collapse during deep-etching, presumably due to surface tension forces that develop during their transfer from ice to vacuum. Previous protocols have attempted to overcome such forces by attaching macromolecules to freshly cleaved mica before drying and replication. I describe here an adaptation of this procedure to the deep-etch technique as otherwise practiced. My innovation is to mix the molecules with an aqueous suspension of tiny flakes of mica and then to quick-freeze and freeze-fracture the suspension exactly as if one were dealing with cells. The fracture inevitably strikes the surfaces of many mica flakes and thereby cleaves the adsorbed macromolecules cleanly enough to reveal interesting substructure within them. The subsequent step of deep-etching exposes large expanses of unfractured mica and thus reveals intact macromolecules. These macromolecules are not obscured by salt deposits, even if they were frozen in hypertonic solutions, apparently because the fracturing step removes nearly all of the overlying electrolyte. Moreover, these macromolecules are minimally freeze-dried (since exposure is sufficient after only 3 min of etching at -102 degrees C) so they retain their three-dimensional topology. I show that molluscan hemocyanin is a good internal standard for this new technique. It is available commercially in stable solutions, mixes well with all sizes of macromolecules, and consists of particles that display distinct five-start surface helices, which have been measured carefully in the past and which possess a known handedness, useful for determining the orientation of micrographs when examining the various helical patterns possessed by most types of extended macromolecules. The fractured hemocyanin particles also display characteristic internal structures, which

  7. Results of testing various natural gas desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

    Israelson, Gordon

    2004-06-01

    This article presents the results of testing many commercially available and some experimental sulfur adsorbents. The desired result of our testing was to find an effective method to reduce the quantity of sulfur in natural gas to less than 100 ppb volume (0.1 ppm volume). An amount of 100 ppb sulfur is the maximum limit permitted for Siemens Westinghouse solid oxide fuel cells (SOFCs). The tested adsorbents include some that rely only on physical adsorption such as activated carbon, some that rely on chemisorption such as heated zinc oxide, and some that may use both processes. The testing was performed on an engineering scale with beds larger than those used for typical laboratory tests. All tests were done at about 3.45 barg (50 psig). The natural gas used for testing was from the local pipeline in Pittsburgh and averaged 6 ppm volume total sulfur. The primary sulfur species were dimethyl sulfide (DMS), isopropyl mercaptan, tertiary butyl mercaptan, and tetrahydrothiophene. Some tests required several months to achieve a sulfur breakthrough of the bed. It was found that DMS always came through a desulfurizer bed first, independent of adsorption process. Since the breakthrough of DMS always exceeds the 100 ppb SOFC sulfur limit before other sulfurs were detected, an index was created to rate the adsorbents in units of ppm DMS × absorbent bed volume. This index is useful for calculating the expected adsorbent bed lifetime before sulfur breakthrough when the inlet natural gas DMS content is known. The adsorbents that are included in these reports were obtained from suppliers in the United States, the Netherlands, Japan, and England. Three activated carbons from different suppliers were found to have identical performance in removing DMS. One of these activated carbons was operated at four different space velocities and again showed the same performance. When using activated carbon as the basis of comparison for other adsorbents, three high-performance adsorbents

  8. Molecule-specific interactions of diatomic adsorbates at metal-liquid interfaces

    PubMed Central

    Kraack, Jan Philip; Kaech, Andres; Hamm, Peter

    2017-01-01

    Ultrafast vibrational dynamics of small molecules on platinum (Pt) layers in water are investigated using 2D attenuated total reflectance IR spectroscopy. Isotope combinations of carbon monoxide and cyanide are used to elucidate inter-adsorbate and substrate-adsorbate interactions. Despite observed cross-peaks in the CO spectra, we conclude that the molecules are not vibrationally coupled. Rather, strong substrate-adsorbate interactions evoke rapid (∼2 ps) vibrational relaxation from the adsorbate into the Pt layer, leading to thermal cross-peaks. In the case of CN, vibrational relaxation is significantly slower (∼10 ps) and dominated by adsorbate-solvent interactions, while the coupling to the substrate is negligible.

  9. Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces.

    PubMed

    Sykes, E Charles H; Han, Patrick; Kandel, S Alex; Kelly, Kevin F; McCarty, Gregory S; Weiss, Paul S

    2003-12-01

    Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.

  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. 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.

  12. Unconventional superconductivity induced in Nb films by adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Alpern, H.; Katzir, E.; Yochelis, S.; Katz, N.; Paltiel, Y.; Millo, O.

    2016-11-01

    Motivated by recent observations of chiral-induced magnetization and spin-selective transport we studied the effect of chiral molecules on conventional BCS superconductors. By applying scanning tunneling spectroscopy, we demonstrate that the singlet-pairing s-wave order parameter of Nb is significantly altered upon adsorption of chiral polyalanine alpha-helix molecules on its surface. The tunneling spectra exhibit zero-bias conductance peaks embedded inside gaps or gap-like features, suggesting the emergence of unconventional triplet-pairing components with either d-wave or p-wave symmetry at the Nb organic-molecules interface, as corroborated by simulations. These results may open a way for realizing simple superconducting spintronics devices.

  13. 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.

  14. 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

  15. 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].

  16. Resonant electron scattering by molecules adsorbed on a surface: N2-Ag system

    NASA Astrophysics Data System (ADS)

    Teillet-Billy, D.; Djamo, V.; Gauyacq, J. P.

    1992-05-01

    A model study of resonant electron scattering by static molecules adsorbed on a metal surface is presented, using the recently developed coupled angular mode (CAM) method. It is applied to the case of N2 molecules adsorbed on an Ag surface. The N2-2πg resonance characteristics (energy position and width) are determined and shown to be modified by the presence of the surface in qualitative agreement with the experimental results of Demuth et al. [Phys. Rev. Lett. 47 (1981) 1166].

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

    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.

  19. Study for Reduction of Outgassing Property of Adsorbed Water Gas for Improved Surface Finished Titanium Material

    NASA Astrophysics Data System (ADS)

    Takeda, Masatoshi; Kurisu, Hiroki; Uchida, Takashi; Yamamoto, Setsuo; Ishizawa, Katsunobu; Nomura, Takeru; Eda, Takahiro; Murashige, Nobuyuki

    This paper addresses the development of the surface finishing for a titanium material and the study for the reduction of outgassing property of adsorbed water (H2O) molecules. Developed surface finishing is composed of the buffing for the reduction of the surface roughness and improved chemical polishing for the thick surface oxide layer compared with the chemical polishing so far. The surface roughness of the surface finished titanium material is reduced 35% and the thickness of the surface oxide layer increases by 30%. The total amount of thermal desorbed H2O gas for the new surface finished titanium is reduced 30%. It is considered that the origin for the decrease of the amount of desorption H2O gas is the reduction of the adsorption sites due to the decrease of the surface roughness and the reduction of adsorption energy of H2O gas due to the strong surface oxidation for a titanium material.

  20. Vibrational excitation of adsorbed molecules by low-energy photon-emitted electrons: A dynamical model

    NASA Astrophysics Data System (ADS)

    González Ureña, A.; Telle, H. H.; Tornero, J.

    2013-01-01

    A simple, inelastic electron-scattering dynamical model is presented to account for vibrational excitation in molecular adsorbates. The basic two ingredients of the theoretical model are: (i) the conservation of the total angular momentum, and (ii) the requirement of a critical time to allow for the intra-molecular energy re-arrangement of the transient negative-ion complex. The model is applied to the vibrational excitation dynamics of molecules chemisorbed at sub-monolayer conditions on ordered metal surfaces. This was exemplified for Acrylonitrile adsorbed on Cu(1 0 0), whose vibrational excitation was studied via energy loss spectra of low-energy two-photon photoemission (2PPE) electrons, and for ammonia (NH3 and ND3) adsorbed on Cu(1 0 0), being probed in a STM experiment. Fits of the model to the data allowed for deducing the energy threshold of the vibrational excitation of the Cdbnd C and Ctbnd N bonds of the ACN adsorbate molecules, and the threshold for the symmetric ν1-stretch mode excitation of adsorbed NH3/ND3. Also, information about the temporal dynamics underlying the inelastic electron scattering was gained.

  1. Structure, Dynamics, and Thermodynamics of Small Molecules Adsorbed in Zeolite Micropores: Simulation and Statistical Mechanics.

    NASA Astrophysics Data System (ADS)

    van Tassel, Paul Robert

    1993-01-01

    This thesis describes a fully detailed molecular simulation and modeling effort aimed at understanding the fundamentals of adsorption and diffusion of small molecules in zeolite micropores. The primary emphasis is on determining the relationship between the structure and chemistry of the zeolite adsorbent and the structure, dynamics, and thermodynamics of the adsorbed phase. Further emphasis is on developing simple, predictive models of zeolite adsorption and diffusion. We begin by presenting a Monte Carlo simulation of single component adsorption of xenon, methane, and argon in zeolite NaA. The form of the adsorbate density distribution indicates the presence of discrete adsorption sites which arrange in polyhedra whose geometry depends on the number and position of zeolite framework ions. Isotherm plateaus are attributed to either (i) a low energy adsorbate configuration or (ii) the saturation of polyhedral sites. Viewing the adsorbed phase as an ordered arrangement differs from the conventional delocalized model, yet it helps explain certain experimental observations. Next, a study of binary mixtures of small molecules in zeolite NaA using the Monte Carlo method is presented. The mixing in the pore is determined to be highly nonideal by comparison to a simple pore volume filling model. Strong selectivity for a more polarizable molecule (xenon) is observed only at low pore loading. At higher pore loading, a smaller, less polarizable molecule (argon) adsorbs selectively at a significantly lower pressure than predicted by the model. This enhanced selectivity is due to the ability of the smaller molecule to pack more efficiently inside of the pore. Finally, we present two simple lattice models whose forms are arrived at following careful consideration of simulation results. The first describes the adsorption of small molecules in a zeolite. A polyhedral lattice is postulated whose neighboring sites interact energetically and entropically. The second model describes

  2. A quantum gas of polar molecules

    NASA Astrophysics Data System (ADS)

    Ni, Kang-Kuen

    Ultracold polar molecular gases promise new directions and exciting applications in precision measurements, ultracold chemistry, electric-field controlled collisions, dipolar quantum gases, and quantum information sciences. This thesis presents experimental realization of a near quantum degenerate gas of polar molecules, where the phase-space density of the gas achieved is more than 10 orders of magnitude higher than previous results. The near quantum degenerate gas of polar molecules is created using two coherent steps. First, atoms in an ultracold gas mixture are converted into extremely weakly bound molecules near a Fano-Feshbach resonance. Second, the weakly bound molecules are transferred to the ro-vibronic ground state using a coherent two-photon Raman technique. The fact that these ground-state molecules are polar is confirmed with a spectroscopic measurement of the permanent electric dipole moment. Finally, manipulation of the molecular hyperfine state is demonstrated; this allows molecules to be populated in a single quantum state, in particular, the lowest energy state. With an ultracold gas of molecules, full control of molecular internal state, and electric field as a new handle, ultracold molecular collisions, including ultracold chemical reactions and dipolar collisions, are studied.

  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. 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.

  5. Sorption of organic molecules on surfaces of a microporous polymer adsorbent modified with different quantities of uracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ganieva, A. G.; Kudasheva, F. Kh.

    2016-11-01

    The sorption of organic molecules on the surfaces of a number of adsorbents based on a microporous copolymer of styrene and divinylbenzene modified with different quantities of uracil is studied by means of inverse gas chromatography at infinite dilution. Samples containing 10-6, 10-5, 10-4, 10-3, 10-2, and 0.5 × 10‒1 weight parts of uracil (the pC of uracil ranges from 1.3 to 6) are studied. The contributions from different intermolecular interactions to the Helmholtz energy of sorption are calculated via the linear free energy relationship. It is found that as the concentration of uracil on the surface of the polymer adsorbent grows, the contributions from different intermolecular interactions and the conventional polarity of the surface have a bend at pC = 3, due probably to the formation of a supramolecular structure of uracil. Based on the obtained results, it is concluded that the formation of the supramolecular structure of uracil on the surface of the polymer adsorbent starts when pC < 3.

  6. 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.

  7. Chemical effects on vibrational properties of adsorbed molecules on metal surfaces: Coverage dependence

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1987-10-01

    Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage dependent chemical shift of the frequencies. Available experimental data of a CO adsorption on transition metal and noble metal surfaces are analyzed in the light of the coverage dependent back-donation into the 2 π* orbitals of chemisorbed CO molecules. The vibrational frequency ωCO of the intramolecular stretching mode exhibits a downward shift of varying magnitude, depending on the amount of back-donation into the 2 π* orbitals of the chemisorbed CO. On increasing the coverage θ, ωCO usually increases due to the dipole-dipole interaction. On Cu surfaces, however, the shifts are relatively small, or in some cases, negative. So far, this anomalous frequency shift with θ is understood as a result of competitive effect between the upward dipole Ωdip and the downward chemical shift Ωchem associated with back-donation. The purpose of this paper is to establish the possible origin of the downward frequency shift through the electronic properties of an incomplete monolayer of adsorbates. The adsorbate density of states ρa is calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account. The change of the occupied portion of ρa and ρa ( ɛF) at the Fermi level ɛF with increasing θ then manifests itself in the coverage dependent Ωchem not only due to the static back-donation, but also due to the dynamical charge fluctuation during vibrational excitation. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative Ωchem amounts to Ωdip at low θ. Consequently the apparent total frequency shift remains almost constant. As the coverage increases, Ωchem becomes larger than Ωdip due to the band effect. It is also shown that the variation of the back

  8. 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.

  9. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  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. Effects of polymer coating on the adsorption of gas molecules on carbon nanotube networks

    SciTech Connect

    Kim, Sanghun; Lee, Hyeong Rag; Yun, Yong Ju; Ji, Seungmuk; Yoo, Kwonjae; Yun, Wan Soo; Koo, Ja-Yong; Ha, Dong Han

    2007-08-27

    Functionalization of carbon nanotubes (CNTs) with polymers such as polyethyleneimine or nafion was found to not change the adsorption properties of gas molecules on CNTs, although functionalization can remarkably enhance the sensitivity of gas sensors. Charge transfer between adsorbed molecules and single-walled carbon nanotubes (SWCNTs) at defect sites causes a steep and nonlinear conductance change at low gas concentrations, while molecules physically adsorbed on the pristine surfaces result in the linear electrical responses at higher concentrations. In addition, the molecular binding energies at defect sites of SWCNTs were measured to be 0.61 eV for NO{sub 2} and 0.53 eV for NH{sub 3}.

  12. 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.

  13. 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.

  14. 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

  15. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field

    PubMed Central

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-01-01

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 106 A·cm−2, or about 1 × 1025 electrons s−1 cm−2. This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 1013 electrons per cm2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions. PMID:28230054

  16. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field.

    PubMed

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-02-23

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 10(6) A·cm(-2), or about 1 × 10(25) electrons s(-1) cm(-2). This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 10(13) electrons per cm(2) are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions.

  17. Induced IR overtone and fundamental bands of isotopic H 2 molecules adsorbed in NaCaA zeolites

    NASA Astrophysics Data System (ADS)

    Förster, H.; Frede, W.

    1984-05-01

    NIR spectroscopy has been successfully applied to surface chemical problems, using the FT transmission technique. Vibrational spectra of H 2 and D 2, adsorbed in NaA and NaCaA zeolites, have been recorded in the fundamental regions of both adsorbates and, for the first time, in the overtone region of D 2. Useful information on the properties of the adsorbed molecules can be derived from the overtone spectra of D 2 and the fine structure of the H 2 fundamental. It turns out that the properties of the D 2 molecules, e.g. dissociation energy and anharmonicity, are hardly affected by adsorption. The fine structure of the H 2 fundamental, however, indicates the rotation to be strongly hindered. The ortho-para splitting is decreased with respect to the free molecule value and approaches that for planarly rotating molecules. Due to this hindrance, the corresponding D 2 splitting is not resolved.

  18. Spins of adsorbed molecules investigated by the detection of Kondo resonance

    NASA Astrophysics Data System (ADS)

    Komeda, Tadahiro

    2014-12-01

    Surface magnetism has been one of the platforms to explore the magnetism in low dimensions. It is also a key component for the development of quantum information processes, which utilizes the spin degree of freedom. The Kondo resonance is a phenomenon that is caused by an interaction between an isolated spin and conduction electrons. First observed in the 1930s as an anomalous increase in the low-temperature resistance of metals embedded with magnetic atoms, the Kondo physics mainly studied the effects of bulk magnetic impurities in the resistivity. In the last 15 years it has undergone a revival by a scanning tunneling microscope (STM) which enables the measurement of the Kondo resonance at surfaces using an atomic scale point contact. The detection of the Kondo resonance can be a powerful tool to explore surface magnetism. In this article, I review recent studies of the surface spin of adsorbed molecules by the detection of the Kondo resonance. Researches on metal phthalocyanine (MPc) and porphyrin molecules will be examined. In addition, the Kondo resonance for double-decker lanthanoide Pc molecules will be discussed. Some of the double-decker Pc molecules show single-molecule magnet (SMM) behavior, which attracts attention as a material for electronic devices. For both classes, the ligand plays a crucial role in determining the parameters of the Kondo resonance, such as the Kondo temperature and the change of the shape from peak to Fano-dip. In addition, the spin in delocalized molecular orbital forms the Kondo resonance, which shows significant differences from the Kondo resonance formed by the metal spins. Since molecular orbital can be tuned in a flexible manner by the design of the molecule, the Kondo resonance formed by delocalized molecular orbital might expand the knowledge of this field.

  19. 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

    2014-02-07

    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.

  20. Density functional analysis of gaseous molecules adsorbed on metal ion/defective nano-sheet graphene

    NASA Astrophysics Data System (ADS)

    Deng, Jin-Pei; Chuang, Wen-Hua; Tai, Chin-Kuen; Kao, Hsien-Chang; Pan, Jiunn-Hung; Wang, Bo-Cheng

    2016-11-01

    Density functional theory was applied to calculate the adsorption property of metal/hexa-vacancy defective graphene (denoted as HDG-M, M: Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) with O- and N-dopants. We investigate the adsorption properties of these complexes between gaseous molecules and HDG-M. Our results show that HDG-Cu has a high selectivity for O2, but HDG-Fe has a good ability to capture many gases such as CO, NO and O2. Our calculations could provide useful information for designing new graphene-based adsorbents to remove undesired gases, which may poison the metal catalysts in reaction processes.

  1. 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

  2. Influence of the Adsorbent Material in the Performances of a Micro Gas Preconcentrator

    NASA Astrophysics Data System (ADS)

    Camara, E. H. M.; Breuil, P.; Briand, D.; Guillot, L.; Pijolat, C.; Viricelle, J. P.; de Rooij, N. F.

    2009-05-01

    This paper presents the evaluation of different adsorbents for the improvement of the performances of a gas preconcentrator by targeting the adsorption of a large range of volatiles organics compounds (VOCs) The objectives of this work are to find the adequate adsorbent for a given gas target in specific experimental conditions and to select an efficient deposition process. Results related to the characterization of carbon nanopowders, carbon nanotubes (single walled (SWCNTs) and multi walled (MWCNTs)) and polymer (Tenax TA) for the development of a device for benzene preconcentration are reported. These results provide guidelines to define the right adsorbent for the preconcentration of benzene according to some specific criterions such as a large specific surface, a high adsorption capacity and low desorption temperature.

  3. Ro-vibrational Stark effect on H2 and D2 molecules adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.

    1999-03-01

    In order to explain the induced infrared bands of H2 and D2 adsorbed in NaA zeolites the Stark effect on the ro-vibrational levels of these molecules is considered for electric fields created by various charge distributions. The shift and intensity of the induced ro-vibration transitions are calculated.

  4. 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).

  5. Micro-differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges.

    PubMed

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan H; Davis, Zachary J; Nicholson, Don M; Boisen, Anja; Thundat, Thomas

    2009-03-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600x10(-12) g.

  6. Micro differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges

    SciTech Connect

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan; Davis, Zachary; Nicholson, Don M; Boisen, Anja; Thundat, Thomas George

    2009-01-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600 x 10{sup -12} g.

  7. 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.

  8. Classical and quantum studies of the photodissociation of a HX (X=Cl,F) molecule adsorbed on ice.

    PubMed

    Woittequand, S; Duflot, D; Monnerville, M; Pouilly, B; Toubin, C; Briquez, S; Meyer, H-D

    2007-10-28

    The photodissociation dynamics of a HX (X = Cl,F) molecule adsorbed on a hexagonal ice surface at T = 0 K is studied using time-dependent quantum wave packets and quasiclassical trajectories. The relevant potential energy surfaces are calculated using high-level ab initio methods. We present here two dimensional calculations for the dynamics of the hydrogen photofragment for both HCl and HF molecules. The purpose of this paper is to compare the photodissociation dynamics of the two molecules which are adsorbed on the ice surface with different equilibrium geometries. The total photodissociation cross section and the angular distribution are calculated. The comparison with classical trajectory calculations provides evidence for typical quantum effects and reveals rainbow structures.

  9. Preferable binding site of gas molecules on graphene nanoribbon with Stone–Wales defect

    NASA Astrophysics Data System (ADS)

    Auzar, Zuriana; Johari, Zaharah; Sakina, S. H.; Alias, N. E.; Abidin, M. S. Z.

    2017-02-01

    The issue of sensitivity of sensing device has focused on the development of sensing devices by using new materials, such as graphene. The gas molecules in different positions such as on, near and far from the defect are placed in the same binding site in two graphene configurations for fair comparison. The interaction between two different graphene configurations such as (pristine armchair graphene nanoribbon (P-AGNR) and Stone–Wales defect on graphene surface (SW-AGNR)) with gas molecules (e.g. O2, N2 and NH3) have been investigated to observe the preferential position site of adsorbate gas molecules. The preferable position sites are investigated by using Extended-Huckel Theory. It is found that, the electronic properties of each configuration are strongly depends on the position of gas molecules and graphene system. Meanwhile, the binding site of the gas molecules on the defective site of graphene surface is a significant factor in determining the sensing behavior of graphene based gas defection device.

  10. Electric field effect observed on the infrared spectra of the N2O molecule adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.; Cohen de Lara, E.

    1995-05-01

    The spectrum of the N2O molecule adsorbed in the cavity of NaA zeolite presents two main components for each of the stretching vibrational modes. It is assumed that they correspond to molecules parallel and antiparallel to the electric field of the inner surface of the zeolite cavity. In order to verify this assumption, the frequency shifts and the intensities of these components have been calculated for the two orientations of the molecule with respect to the field, by applying the model of Bishop for the vibrational Stark effect. These calculations require the knowledge of molecular quantities such as derivatives of permanent electric moments and polarizability.

  11. 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.

  12. 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.

  13. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Reuter, Karsten

    2013-07-01

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)], 10.1103/PhysRevB.78.075441 presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  14. 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

  15. 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.

  16. Selective binding of single-stranded DNA-binding proteins onto DNA molecules adsorbed on single-walled carbon nanotubes.

    PubMed

    Nii, Daisuke; Hayashida, Takuya; Yamaguchi, Yuuki; Ikawa, Shukuko; Shibata, Takehiko; Umemura, Kazuo

    2014-09-01

    Single-stranded DNA-binding (SSB) proteins were treated with hybrids of DNA and single-walled carbon nanotubes (SWNTs) to examine the biological function of the DNA molecules adsorbed on the SWNT surface. When single-stranded DNA (ssDNA) was used for the hybridization, significant binding of the SSB molecules to the ssDNA-SWNT hybrids was observed by using atomic force microscopy (AFM) and agarose gel electrophoresis. When double-stranded DNA (dsDNA) was used, the SSB molecules did not bind to the dsDNA-SWNT hybrids in most of the conditions that we evaluated. A specifically modified electrophoresis procedure was used to monitor the locations of the DNA, SSB, and SWNT molecules. Our results clearly showed that ssDNA/dsDNA molecules on the SWNT surfaces retained their single-stranded/double-stranded structures.

  17. Infrared-Laser Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface.

    DTIC Science & Technology

    1986-11-01

    Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface m by ’ Andre Peremans, Jacques Darville , Jean-Marie...Andre Peremans, Jacques Darville , Jean-Marie Gilles and Thomas F. George 13. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr. Mo.. Dayl As...ON A METAL SURFACE h Andr& Peremans , Jacques Darville and Jean-Marie Gilles _ _ _ _ Laboratoire de Spectroscopie Mol6culaire de Surface Accesnion

  18. Preparation of activated carbon from waste plastics polyethylene terephthalate as adsorbent in natural gas storage

    NASA Astrophysics Data System (ADS)

    Yuliusman; Nasruddin; Sanal, A.; Bernama, A.; Haris, F.; Ramadhan, I. T.

    2017-02-01

    The main problem is the process of natural gas storage and distribution, because in normal conditions of natural gas in the gas phase causes the storage capacity be small and efficient to use. The technology is commonly used Compressed Natural Gas (CNG) and Liquefied Natural Gas (LNG). The weakness of this technology safety level is low because the requirement for high-pressure CNG (250 bar) and LNG requires a low temperature (-161°C). It takes innovation in the storage of natural gas using the technology ANG (Adsorbed Natural Gas) with activated carbon as an adsorbent, causing natural gas can be stored in a low pressure of about 34.5. In this research, preparation of activated carbon using waste plastic polyethylene terephthalate (PET). PET plastic waste is a good raw material for making activated carbon because of its availability and the price is a lot cheaper. Besides plastic PET has the appropriate characteristics as activated carbon raw material required for the storage of natural gas because the material is hard and has a high carbon content of about 62.5% wt. The process of making activated carbon done is carbonized at a temperature of 400 ° C and physical activation using CO2 gas at a temperature of 975 ° C. The parameters varied in the activation process is the flow rate of carbon dioxide and activation time. The results obtained in the carbonization process yield of 21.47%, while the yield on the activation process by 62%. At the optimum process conditions, the CO2 flow rate of 200 ml/min and the activation time of 240 minutes, the value % burn off amounted to 86.69% and a surface area of 1591.72 m2/g.

  19. 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.

  20. Gas molecule-molecule interaction and the gas-surface scattering effect on the rarefied gas flow through a slit into a vacuum

    SciTech Connect

    Sazhin, O.

    2009-05-15

    The effect of the gas molecule-molecule interaction and the gas-surface scattering on the gas flow through a slit into a vacuum are investigated in a wide range of the gas rarefaction using the direct simulation Monte Carlo method. To study the gas molecule-molecule interaction influence, we used the variable hard sphere and variable soft sphere models defined for an inverse-power-law potential and the generalized hard sphere model defined for the 12-6 Lennard-Jones potential. The Maxwell, Cercignani-Lampis, and Epstein models were used to simulate the gas-surface scattering. This study demonstrates that the gas molecule-molecule interaction can have a significant influence on the rarefied gas flow through a slit, while the influence of the gas-surface scattering is negligibly small. The presented numerical results are in agreement with the corresponding experimental ones.

  1. Gas molecule-molecule interaction and the gas-surface scattering effect on the rarefied gas flow through a slit into a vacuum

    NASA Astrophysics Data System (ADS)

    Sazhin, O.

    2009-05-01

    The effect of the gas molecule-molecule interaction and the gas-surface scattering on the gas flow through a slit into a vacuum are investigated in a wide range of the gas rarefaction using the direct simulation Monte Carlo method. To study the gas molecule-molecule interaction influence, we used the variable hard sphere and variable soft sphere models defined for an inverse-power-law potential and the generalized hard sphere model defined for the 12-6 Lennard-Jones potential. The Maxwell, Cercignani-Lampis, and Epstein models were used to simulate the gas-surface scattering. This study demonstrates that the gas molecule-molecule interaction can have a significant influence on the rarefied gas flow through a slit, while the influence of the gas-surface scattering is negligibly small. The presented numerical results are in agreement with the corresponding experimental ones.

  2. A discrete interaction model/quantum mechanical method for describing response properties of molecules adsorbed on metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Morton, Seth Michael; Jensen, Lasse

    2010-08-01

    A new polarizable quantum mechanics/molecular mechanics method for the calculation of response properties of molecules adsorbed on metal nanoparticles is presented. This method, which we denote the discrete interaction model/quantum mechanics (DIM/QM) method, represents the nanoparticle atomistically which enables the modeling of the influence of the local environment of a nanoparticle surface on the optical properties of a molecule. Using DIM/QM, we investigate the excitation energies of rhodamine-6G (R6G) and crystal violet (CV) adsorbed on silver and gold nanoparticles of different quasispherical shapes and sizes. The metal nanoparticle is characterized by its static total polarizability, a reasonable approximation for frequencies far from the plasmon resonance. We observe that for both R6G and CV, the presence of the nanoparticle shifts the strongest excitation to the red ˜40 nm and also increases the oscillator strength of that excitation. The shifts in excitation energies due to the nanoparticle surface are found to be comparable to those due to solvation. We find that these shifts decay quickly as the molecule is moved away from the surface. We also find that the wavelength shift is largest when the transition dipole moment is aligned with the edges of the nanoparticle surface where the electric field is expected to be the largest. These results show that the molecular excitations are sensitive to the local environment on the nanoparticle as well as the specific orientation of the molecule relative to the surface.

  3. 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.

  4. 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.

  5. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111)

    PubMed Central

    Schuler, A.; Greif, M.; Seitsonen, A. P.; Mette, G.; Castiglioni, L.; Osterwalder, J.; Hengsberger, M.

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization. PMID:28217715

  6. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111).

    PubMed

    Schuler, A; Greif, M; Seitsonen, A P; Mette, G; Castiglioni, L; Osterwalder, J; Hengsberger, M

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3',5,5'-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  7. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  8. 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.

  9. Ultraviolet absorption spectra of metalorganic molecules diluted in hydrogen gas

    NASA Astrophysics Data System (ADS)

    Itoh, Hideo; Watanabe, Masanobu; Mukai, Seiji; Yajima, Hiroyoshi

    1988-12-01

    Ultraviolet absorption spectra of trimethyl gallium, triethyl gallium, and trimethyl aluminum diluted in hydrogen gas were measured as a function of the wavelength (185-350 nm) and the concentration of the molecules (4.8×10 -6 -1.6×10 -4 mol/liter). Their absorbances changed linearly with the concentration of the molecules, which allowed us to calculate the molar absorption coefficients of the molecules on the basis of the Beer-Lambert law.

  10. 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

  11. Microscopic resolution of the interplay of Kondo screening and superconducting pairing: Mn-phthalocyanine molecules adsorbed on superconducting Pb(111)

    NASA Astrophysics Data System (ADS)

    Bauer, Johannes; Pascual, Jose I.; Franke, Katharina J.

    2013-02-01

    Magnetic molecules adsorbed on a superconductor give rise to a local competition of Cooper pair and Kondo singlet formation inducing subgap bound states. For manganese-phthalocyanine molecules on a Pb(111) substrate, scanning tunneling spectroscopy resolves pairs of subgap bound states and two Kondo screening channels. We show in a combined approach of scaling and numerical renormalization group calculations that the intriguing relation between Kondo screening and superconducting pairing is solely determined by the hybridization strength with the substrate. We demonstrate that an effective one-channel Anderson impurity model with a sizable particle-hole asymmetry captures universal and nonuniversal observations in the system quantitatively. The model parameters and disentanglement of the two screening channels are elucidated by scaling arguments.

  12. Food wastes derived adsorbents for carbon dioxide and benzene gas sorption.

    PubMed

    Opatokun, Suraj Adebayo; Prabhu, Azhagapillai; Al Shoaibi, Ahmed; Srinivasakannan, C; Strezov, Vladimir

    2017-02-01

    Food wastes are produced worldwide in large quantities that could have potential to produce higher value products, including industrial adsorbents. The present work attempts valorization of food waste by CO2 activation and functionalization through nitric acid and melamine treatment. The prepared porous materials were subjected to gas phase adsorption of CO2 and benzene gases. The resultant highly porous carbon materials with surface area range from 797 to 1025 m(2)/g were synthesized showing uptake capacities of 4.41, 4.07, 4.18 and 4.36 mmol/g of CO2 and 345, 305, 242.5 and 380.7 mg/g of C6H6 respectively for PyF515, PyF520, PyF715 and PyF720 in the absence of doped carbon matrix. Differential thermogravimetric (DTG) analysis showed the thermostability of the precursors to validate selected initial pyrolysis temperatures (500 and 700 °C). C6H6 sorption lies mainly in the physisorption region for all adsorbents ensuring re-generation potential. PyF720 and PyF520 recorded the highest isosteric enthalpy of 64.4 kJ/mol and 48.7 kJ/mol respectively, despite the low degree of coverage of the latter. Thus, PyF515 and PyF720 demonstrated the potential for use as sustainable and cost effective adsorbents for benzene gas containment suitable for swing adsorption system.

  13. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  14. 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.

  15. Amine-tethered adsorbents based on three-dimensional macroporous silica for CO(2) capture from simulated flue gas and air.

    PubMed

    Liu, Fa-Qian; Wang, Lei; Huang, Zhao-Ge; Li, Chao-Qin; Li, Wei; Li, Rong-Xun; Li, Wei-Hua

    2014-03-26

    New covalently tethered CO2 adsorbents are synthesized through the in situ polymerization of N-carboxyanhydride (NCA) of l-alanine from amine-functionalized three-dimensional (3D) interconnected macroporous silica (MPS). The interconnected macropores provide low-resistant pathways for the diffusion of CO2 molecules, while the abundant mesopores ensure the high pore volume. The adsorbents exhibit high molecular weight (of up to 13058 Da), high amine loading (more than 10.98 mmol N g(-1)), fast CO2 capture kinetics (t1/2 < 1 min), high adsorption capacity (of up to 3.86 mmol CO2 g(-1) in simulated flue gas and 2.65 mmol CO2 g(-1) in simulated ambient air under 1 atm of dry CO2), as well as good stability over 120 adsorption-desorption cycles, which allows the overall CO2 capture process to be promising and sustainable.

  16. 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.

  17. Small Molecule Catalysts for Harvesting Methane Gas

    SciTech Connect

    Baker, S. E.; Ceron-Hernandez, M.; Oakdale, J.; Lau, E. Y.

    2016-12-06

    As the average temperature of the earth increases the impact of these changes are becoming apparent. One of the most dramatic changes to the environment is the melting of arctic permafrost. The disappearance of the permafrost has resulted in release of streams of methane that was trapped in remote areas as gas hydrates in ice. Additionally, the use of fracking has also increased emission of methane. Currently, the methane is either lost to the atmosphere or flared. If these streams of methane could be brought to market, this would be an abundant source of revenue. A cheap conversion of gaseous methane to a more convenient form for transport would be necessary to economical. Conversion of methane is a difficult reaction since the C-H bond is very stable (104 kcal/mole). At the industrial scale, the Fischer-Tropsch reaction can be used to convert gaseous methane to liquid methanol but is this method is impractical for these streams that have low pressures and are located in remote areas. Additionally, the Fischer-Tropsch reaction results in over oxidation of the methane leading to many products that would need to be separated.

  18. Glass transition of adsorbed stereoregular PPMA by inverse gas chromatography at infinite dilution

    NASA Astrophysics Data System (ADS)

    Hamieh, T.; Rezzaki, M.; Grohens, Y.; Schultz, J.

    1998-10-01

    In this paper, we used inverse gas chromatography (IGC) at infinite dilution that proved to be a powerful technique to determine glass transition and other transitions of PMMA adsorbed on α-alumina. We highlighted the glass transition temperature of the system PMMA/α-Al2O3 with defined polymer tacticity at various covered surface fractions. Thus, the Tg of the adsorbed isotactic PMMA increases strongly as compared to the bulk value. The study of the physical chemical properties of PMMA/α-alumina revealed an important difference in the acidic and basic behaviour, in Lewis terms, of aluminium oxide covered by various concentrations of PMMA. It appears that there is a stabilisation of the physical chemical properties of PMMA/α-Al2O3 for a surface coverage above 50%. This study also highlighted an important effect of the tacticity of the polymer on the acid-base character of the system PMMA/Al2O3. Dans cet article, nous montrons que la chromatographie gazeuse inverse (CGI) à dilution infinie se révèle être une technique très intéressante pour la détermination de la transition vitreuse de polymères stéréoréguliers adsorbés sur des substrats solides tels que l'alumine. Nous avons mis en évidence des transitions attribuées aux phénomènes de relaxation béta, transition vitreuse et autres transitions des systèmes PMMA/Al2O3 de tacticité définie à différents taux de recouvrement. Ainsi, la Tg du PMMA isotactique adsorbé augmente de façon significative par rapport a celle du polymère massique. L'étude des propriétés physico-chimiques du système PMMA/Al2O3, révèle une différence importante dans le comportement acido-basique, au sens de Lewis, de l'alumine pour de taux de recouvrement en PMMA variables. Il apparaît qu'il y a stabilisation des propriétés physico-chimiques de PMMA/Al2O3 pour un taux de recouvrement en PMMA supérieur à 50 %. Cette étude a montré également une influence importante de la tacticité du polymère sur le

  19. 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.

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

    DOE PAGES

    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

  1. Some features of raman scattering by molecules adsorbed on metal crystal faces and a fine light structure

    NASA Astrophysics Data System (ADS)

    Polubotko, A. M.

    2013-07-01

    The paper analyzes some experiments on Raman scattering by molecules adsorbed on the face (111) of silver monocrystals performed by A. Campion et al. From the existence of the forbidden line A 2 u of benzene, the conclusion about existence of the surface field, caused by atomic structure of the surface is made. The relatively large intensity of this line allows to make a conclusion about large influence of the electromagnetic field spatial inhomogeneity in crystals on their optical properties. The difference between this field and a regular plane wave, which usually describes propagation of electromagnetic field in solids is named as a fine light structure. The influence of this structure on optical properties of solids is pointed out.

  2. Enhanced Raman scattering by molecules adsorbed at the surface of colloidal spheroids

    NASA Astrophysics Data System (ADS)

    Wang, D.-S.; Kerker, M.

    1981-08-01

    Equations are derived and calculations are presented for the electrodynamic mechanism of enhanced Raman scattering by molecules at the surface of prolate and oblate spheroids in the small-particle limit. The molecules may be arbitrarily distributed; the particles may be arbitrarily oriented. Calculations are presented for a monolayer distributed over randomly oriented spheroids. The effects of particle shape are considered for Ag, Au, and Cu hydrosols. The peak enhancement moves to longer wavelengths, and in the case of Au and Cu the magnitude of the enhancement increases strikingly as the eccentricity increases. The relation between the dependence of the Raman enhancement upon excitation wavelength and the extinction spectra is discussed, including the precariousness of extrapolating such relations beyond the small-particle limit.

  3. 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.}

  4. Aminosilane-grafted polymer/silica hollow fiber adsorbents for CO₂ capture from flue gas.

    PubMed

    Rezaei, Fateme; Lively, Ryan P; Labreche, Ying; Chen, Grace; Fan, Yanfang; Koros, William J; Jones, Christopher W

    2013-05-01

    Amine/silica/polymer composite hollow fiber adsorbents are produced using a novel reactive post-spinning infusion technique, and the obtained fibers are shown to capture CO2 from simulated flue gas. The post-spinning infusion technique allows for functionalization of polymer/silica hollow fibers with different types of amines during the solvent exchange step after fiber spinning. The post-spinning infusion of 3-aminopropyltrimethoxysilane (APS) into mesoporous silica/cellulose acetate hollow fibers is demonstrated here, and the materials are compared with hollow fibers infused with poly(ethyleneimine) (PEI). This approach results in silica/polymer composite fibers with good amine distribution and accessibility, as well as adequate porosity retained within the fibers to facilitate rapid mass transfer and adsorption kinetics. The CO2 adsorption capacities for the APS-infused hollow fibers are shown to be comparable to those of amine powders with similar amine loadings. In contrast, fibers that are spun with presynthesized, amine-loaded mesoporous silica powders show negligible CO2 uptake and low amine loadings because of loss of amines from the silica materials during the fiber spinning process. Aminosilica powders are shown to be more hydrophilic than the corresponding amine containing composite hollow fibers, the bare polymer as well as silica support. Both the PEI-infused and APS-infused fibers demonstrate reduced CO2 adsorption upon elevating the temperature from 35 to 80 °C, in accordance with thermodynamics, whereas PEI-infused powders show increased CO2 uptake over that temperature range because of competing diffusional and thermodynamic effects. The CO2 adsorption kinetics as probed via TGA show that the APS-infused hollow fiber adsorbents have more rapid uptake kinetics than their aminosilica powder analogues. The adsorption performance of the functionalized hollow fibers is also assessed in CO2 breakthrough experiments. The breakthrough results show a

  5. 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)

  6. Dissociation Chemistry of Gas Molecules on Carbon Nanotubes - Applications to Chemical Sensing.

    SciTech Connect

    Govind, Niri; Andzelm, Jan; Maiti, Amitesh

    2008-06-01

    It is well known in the literature that carbon nanotubes (CNTs) interact weakly with many gas molecules like H2O, CO, NH3, H2, NO2 and so on. Exposure to NO2, O2, and NH3 significantly affects the electrical conductance of a single wall nanotube (SWNT). These can be explained using a simple charge transfer picture, which results in the observed changes in the hole conduction of the tubes. It is also known that pure SWNTs only weakly interact with these molecules. We have recently investigated [AGM2006] how common defects in CNTs (Stone-Wales (SW), monovacancy, and interstitial) influence the chemisorption of NH3. This paper is a continuation of our previous work. Here we further investigate, via Density Functional Theory (DFT) calculations, the effects of Stone-Wales (SW) defects on the adsorption/dissociation of O2 and H2O. We also study the diffusion of adsorbed oxygen atoms on the nanotube surface in the vicinity of the SW defect as well as the dissociation of NH3 in the presence of adsorbed oxygen atoms.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. Photodissociation and caging of HBr and HI molecules on the surface of large rare gas clusters.

    PubMed

    Baumfalk, R; Nahler, N H; Buck, U

    2001-01-01

    Photodissociation experiments were carried out at a wavelength of 243 nm for single HBr and HI molecules adsorbed on the surface of large Nen, Arn, Krn and Xen clusters. The average size is about = 130; the size ranges = 62-139 for the system HBr-Arn and = 110-830 for HI-Xen were covered. In this way the dependence of the photodissociation dynamics on both the size and the rare gas host cluster was investigated. The main observable is the kinetic energy distribution of the outgoing H atoms. The key results are that we do not find any size dependence for either system but that we observe a strong dependence on the rare gas clusters. All systems exhibit H atoms with no energy loss that indicate direct cage exit and those with nearly zero energy that are an indication of complete caging. The intensity ratio of caged to uncaged H atoms is largest for Nen, decreases with increasing mass of the cage atoms, and is weakest for Xen. On the basis of accompanying calculations this behaviour is attributed to the large amplitude motion of the light H atom. This leads to direct cage exit and penetration of the atom through the cluster with different energy transfer per collision depending on the rare gas atoms. The differences between HBr and HI molecules are attributed to different surface states, a flat and an encapsulated site.

  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. Study of IR laser photoacoustic spectra of organic molecules adsorbed on metal surface

    NASA Astrophysics Data System (ADS)

    Lu, Huizong; Chen, Kaitai; Wang, Zhaoyong

    1987-06-01

    Using a branch-tuning CW CO2 laser in the range of 0.2 to 10.8 microns, the IR photoacoustic spectra of organic molecules absorbed on a silver surface were studied. The absorbed molecular spectra of four layers of arachidic acid and cellulose diacetate with different surface densities was studied. No peak shift was found in a comparison between IR photoacoustic spectra of solid arachidic acid near 944/cm and the corresponding IR Fourier spectra of solid archidic acid. The IR photoacoustic spectra of cellulose diacetate with sigma sub 1 = 14,000/sq cm and sigma sub 1 = 5.5 x 10 to the 15th/sq cm respectively was compared with the corresponding transmission spectra of solid cellulose diacetate. It was found that the peak of the former near 1054/cm had a red shift of about 5/cm while the peak of the latter had no obvious shift within the range of accuracy of the experiment.

  15. Effect of substrate thickness on ejection of phenylalanine molecules adsorbed on free-standing graphene bombarded by 10 keV C60

    NASA Astrophysics Data System (ADS)

    Golunski, M.; Verkhoturov, S. V.; Verkhoturov, D. S.; Schweikert, E. A.; Postawa, Z.

    2017-02-01

    Molecular dynamics computer simulations have been employed to investigate the effect of substrate thickness on the ejection mechanism of phenylalanine molecules deposited on free-standing graphene. The system is bombarded from the graphene side by 10 keV C60 projectiles at normal incidence and the ejected particles are collected both in transmission and reflection directions. It has been found that the ejection mechanism depends on the substrate thickness. At thin substrates mostly organic fragments are ejected by direct collisions between projectile atoms and adsorbed molecules. At thicker substrates interaction between deforming topmost graphene sheet and adsorbed molecules becomes more important. As this process is gentle and directionally correlated, it leads predominantly to ejection of intact molecules. The implications of the results to a novel analytical approach in Secondary Ion Mass Spectrometry based on ultrathin free-standing graphene substrates and a transmission geometry are discussed.

  16. Gas separation device based on electrical swing adsorption

    DOEpatents

    Judkins, Roddie R.; Burchell, Timothy D.

    1999-10-26

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

  17. 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

    2016-09-01

    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.

  18. 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

    2008-12-07

    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(+) 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.

  19. Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

    NASA Astrophysics Data System (ADS)

    Shamkhali, Amir N.; Parsafar, Gholamabbas

    2010-05-01

    The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster-Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.

  20. 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.

  1. Method for the calculation of the vibrational frequency shift of physisorbed molecules. Application to H2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Larin, A. V.; Cohen De Lara, E.

    1994-11-01

    The vibrational frequency shift of physisorbed diatomic molecules is related to the interaction with the adsorbent expressed in terms of the internuclear distance ρ. It is calculated by the Schrödinger equation, the perturbation theory, and a simplified method. We show that it is sufficient to calculate the interaction potential for the values of ρ in the ground and first vibrational states in order to get a precision of 10% on the frequency shift. The comparison between the theoretical and experimental frequency shift of H2 adsorbed in NaA zeolite is used to adjust the interaction potential, especially in terms of the ionicity of the crystal.

  2. Energy loss in gas-surface dynamics: Electron-hole pair and phonon excitation upon adsorbate relaxation

    NASA Astrophysics Data System (ADS)

    Novko, D.; Blanco-Rey, M.; Juaristi, J. I.; Alducin, M.

    2016-09-01

    We study the effect of electron and phonon degrees of freedom on the relaxation dynamics of adsorption processes in gas-surface systems by using ab initio molecular dynamics that incorporates an electronic friction force (AIMDEF). As representative cases we have chosen three systems with different adsorption energies and adsorbate-to-surface atom mass ratios: H on Pd(1 0 0), N on Ag(1 1 1), and N2 on Fe(1 1 0). We show, through inspection of the total energies and trajectories of the hot adsorbates on the surface, that electron-hole (e-h) pair excitations dominate relaxation of the light gas species, while the phonon channel is dominant for the heavy species. In the latter case e-h pairs become more important at the final thermalization stages.

  3. In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode.

    PubMed

    Tu, HsinLing; Yen, PoYu; Chen, Sihzih; Yau, ShuehLin; Dow, Wei-Ping; Lee, Yuh-Lang

    2011-06-07

    The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO(4) + 1 mM Cu(ClO(4))(2) + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS(-)-Pt(+) + RS(-) (MPS) + Cu(2+) + Cl(-), where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.

  4. Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca- and Fe-doped MgO(001) surface basic sites.

    PubMed

    Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

    2012-08-02

    The electronic properties of undoped and Ca- or Fe-doped MgO(001) surfaces, as well as their propensity toward atmospheric acidic gas (CO2, SO2, and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, O(surf), using periodic density functional theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the O(surf) sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe-doped MgO(001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca-doped MgO(001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces.

  5. 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.

  6. Silanization of polyelectrolyte-coated particles: an effective route to stabilize Raman tagging molecules adsorbed on micrometer-sized silver particles.

    PubMed

    Kim, Kwan; Lee, Hyang Bong; Shin, Kuan Soo

    2008-06-03

    Micrometer-sized Ag (microAg) powders are very efficient surface-enhanced Raman scattering (SERS) substrates. To use microAg powders as a core material for molecular sensors operating via SERS, it is necessary to stabilize the tagging (i.e., SERS-marker) molecules adsorbed onto them. We demonstrate in this work that once the tagging molecules are coated with aliphatic polyelectrolytes such as poly(allylamine hydrochloride), the base-catalyzed silanization can be readily carried out to form stable silica shells around the polyelectrolyte layers by a biomimetic process; any particle can therefore be coated with silica since polyelectrolytes can be deposited beforehand via a layer-by-layer deposition method. Even after silanization, the SERS peaks of marker molecules on microAg particles are the only observable peaks since aliphatic polyelectrolytes, as well as silica shells, are intrinsically weak Raman scatterers, and more importantly, the SERS signals must be derived mostly from the first layer of the adsorbates (i.e., the marker molecules) in direct contact with the microAg particles. Silica shells, once fabricated, can further be derivatized to possess biofunctional groups; therefore, the modified microAg particles can be used as platforms of highly stable SERS-based biological sensors, as well as barcoding materials.

  7. Ratio of the surface-enhanced anti-Stokes scattering to the surface-enhanced Stokes-Raman scattering for molecules adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Brolo, A. G.; Sanderson, A. C.; Smith, A. P.

    2004-01-01

    Surface-enhanced Raman scattering (SERS) from oxazine 720 (oxa), rhodamine 6G (R6G), and pyridine (py) adsorbed on a rough silver surface was observed. The silver electrode was immersed in aqueous solutions permitting control of the potential bias applied to the surface. SERS spectra in the Stokes and anti-Stokes regions were obtained for several applied potentials and two laser excitation energies. Normalized ratios between the anti-Stokes and the Stokes intensities K were calculated from the SERS spectra. The K ratios differed from unity for all the systems investigated. A preferential enhancement of the (surface-enhanced) Stokes scattering was observed for oxa and py. In contrast, the K ratios were higher than unity for R6G, indicating an increase in the anti-Stokes signal. The K ratios measured in this work decreased with the excitation energy and showed a dependence on the energy of the vibrational modes. These results were satisfactorily explained using resonance models, based on the charge-transfer and electromagnetic theories for SERS. No evidence for a SERS-induced nonthermal population distribution among the vibrational states of the adsorbed molecules (vibrational optical pumping) was found. Therefore, we conclude that the main features of the preferential enhancement of the anti-Stokes scattering for an adsorbed molecule on rough silver can be fully understood in the context of current SERS theories.

  8. Buffer Gas Cooled Molecule Source for Cpmmw Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Grimes, David; Barnum, Timothy J.; Klein, Ethan; Field, Robert W.

    2014-06-01

    We have built a new molecular beam source that implements 20 K Neon buffer gas cooling for the study of the spectra of small molecules. In particular, laser ablation of BaF2 pellets has been optimized to produce a molecular beam of BaF with a number density more than 100 times greater than what we have previously obtained from a typical Smalley-type photoablation supersonic beam source. Moreover, the forward beam velocity of 150 m/s in our apparatus represents an approximate 10-fold reduction, improving spectroscopic resolution from 500 kHz to better than 50 kHz at 100 GHz in a chirped-pulse millimeter-wave experiment in which resolution is limited by Doppler broadening. Novel improvements in our buffer gas source and advantages for CPmmW spectroscopy studies will be discussed. We thank David Patterson, John Barry, John Doyle, and David DeMille for help in the design of our source.

  9. 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.

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

    DOEpatents

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

    2015-06-23

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

  12. 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.

  13. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-12-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

  14. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    PubMed Central

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-01-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. PMID:27991538

  15. 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)

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    PubMed

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  2. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

    PubMed Central

    Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

  3. Bromocresol green/mesoporous silica adsorbent for ammonia gas sensing via an optical sensing instrument.

    PubMed

    Chang, Yu-Chang; Bai, Hsunling; Li, Shou-Nan; Kuo, Chun-Nan

    2011-01-01

    A meso-structured Al-MCM-41 material was impregnated with bromocresol green (BG) dye and then incorporated into a UV-Vis DRA spectroscopic instrument for the online detection of ammonia gas. The absorption response of the Al-MCM-41/BG ammonia sensing material was very sensitive at the optical absorption wavelength of 630 nm. A high linear correlation was achieved for ppmv and sub-ppmv levels of ammonia gas. The response time for the quantitative detection of ammonia gas concentrations ranging from 0.25 to 2.0 ppmv was only a few minutes. The lower detection limit achieved was 0.185 ppmv. The color change process was fully reversible during tens of cycling tests. These features together make this mesoporous Al-MCM-41 material very promising for optical sensing applications.

  4. Bromocresol Green/Mesoporous Silica Adsorbent for Ammonia Gas Sensing via an Optical Sensing Instrument

    PubMed Central

    Chang, Yu-Chang; Bai, Hsunling; Li, Shou-Nan; Kuo, Chun-Nan

    2011-01-01

    A meso-structured Al-MCM-41 material was impregnated with bromocresol green (BG) dye and then incorporated into a UV-Vis DRA spectroscopic instrument for the online detection of ammonia gas. The absorption response of the Al-MCM-41/BG ammonia sensing material was very sensitive at the optical absorption wavelength of 630 nm. A high linear correlation was achieved for ppmv and sub-ppmv levels of ammonia gas. The response time for the quantitative detection of ammonia gas concentrations ranging from 0.25 to 2.0 ppmv was only a few minutes. The lower detection limit achieved was 0.185 ppmv. The color change process was fully reversible during tens of cycling tests. These features together make this mesoporous Al-MCM-41 material very promising for optical sensing applications. PMID:22163836

  5. 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.

    2016-11-21

    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.

  6. 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...

  7. Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

    PubMed

    Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

    2012-11-01

    Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

  8. Carbon dioxide removal from natural gas using amine surface bonded adsorbents

    SciTech Connect

    Leal, O.; Bolivar, C.; Ovalles, C.; Urbina, A.

    1996-12-31

    The results of research on the greenhouse effect have shown, among other things, that the concentration of trace gases occurring in the atmosphere such as carbon dioxide, methane, nitrous oxide, ozone and halocarbons have grown significantly since the ore-industrial times. During this period, the CO{sub 2} level has risen 30% to nearly 360 ppm from a pre-industrial era level of 280 ppm. On the basis of a variety of evidence a consensus is emerging among researchers that humans beings, primarily through their burning of fossil fuels, are already perturbing Earth`s climate. All specialists agree that without drastic steps to curb greenhouse gas emissions, the average global temperature will increase 1 to 3.5{degrees}C during the next century because effective level of carbon dioxide are expected to double sometime between the years 2050 to 2100. It may be that human-generated emissions of carbon dioxide will have to be reduced by as much as 50-80% to avoid major climate changes. Such a reduction in the CO{sub 2} emissions rate probably cannot be accomplished without a massive switch to non-fossil energy sources. However, it has been proposed that emissions from fossil fuels can be moderated by three strategies: exploiting the fuels more efficiently, replacing coal by natural gas and by recovering and sequestering CO{sub 2} emissions. A rough analysis, based on the use of currently accepted values, shows that natural gas is preferable to other fossil fuels in consideration of the greenhouse effect and improvements can be obtained if natural gas is upgrading by scrubbing the carbon dioxide out of it.

  9. Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

    PubMed Central

    Komeda, Tadahiro; Isshiki, Hironari; Liu, Jie

    2010-01-01

    Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction. PMID:27877365

  10. 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.

  11. 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.

  12. 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.

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

    PubMed

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

    2015-10-01

    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.

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

    PubMed

    Mychaskiw, George

    2011-09-06

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

  15. 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.

  16. 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.

  17. Cooling, Collisions and non-Sticking of Polyatomic Molecules in a Cryogenic Buffer Gas Cell

    NASA Astrophysics Data System (ADS)

    Piskorski, Julia Hege

    We cool and study trans-Stilbene, Nile Red and Benzonitrile in a cryogenic (7K) cell filled with low density helium buffer gas. No molecule-helium cluster formation is observed, indicating limited atom-molecule sticking in this system. We place an upper limit of 5% on the population of clustered He-trans-Stilbene, consistent with a measured He-molecule collisional residence time of less than 1 mus. With several low energy torsional modes, trans-Stilbene is less rigid than any molecule previously buffer gas cooled into the Kelvin regime. We report cooling and gas phase visible spectroscopy of Nile Red, a much larger molecule. Our data suggest that buffer gas cooling will be feasible for a variety of small biological molecules. The same cell is also ideal for studying collisional relaxation cross sections. Measurements of Benzonitrile vibrational state decay results in determination of the vibrational relaxation cross sections of sigma22 = 8x10-15 cm2 and sigma 21 = 6x10-15 cm2 for the 22 (v=1) and 21 (v=1) states. For the first time, we directly observe formation of cold molecular dimers in a cryogenic buffer gas cell and determine the dimer formation cross section to be ˜10-13 cm2.

  18. Effects of gas molecules on an ultraviolet photodetector with a single-layer titania nanosheet

    NASA Astrophysics Data System (ADS)

    Matsuzaki, Koji; Taniguchi, Takaaki; Matsumoto, Yasumichi; Hara, Masahiro

    2015-01-01

    We have demonstrated an ultraviolet photodetector fabricated from a chemically exfoliated single-layer titania nanosheet. The photocurrent showed a clear on/off switching with a short time response under periodic pulsed illuminations. Suppressions of the photocurrent due to environmental gas molecules were observed under medium vacuum region (1.0-300 Pa). The observation even in inert nitrogen gas implies an enhancement of annihilations of photo-excited carriers due to collisions of inert gas molecules on the surface-sensitive titania nanosheet.

  19. Research on Sources of Gas Phase Metastable Atoms and Molecules

    DTIC Science & Technology

    1982-05-01

    PAGI(Whi DeE# WA..teod) -systems of interest to such diverse areas as gas discharge physics, chemical physics, flame chemistry and plasma physics. "A...second task involved a literature review of prior basic research meta- stable sources followed by the development and experimental testing of appro...appropriate for this phase of the program. The operation of this type of metastable source wab investigated and tested for the production of metastable argon

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

    PubMed

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

    2016-05-19

    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.

  1. 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.

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

    PubMed Central

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

    2017-01-01

    TAM receptors (Tyro-3, Axl, and Mertk) are a family of three homologous type I receptor tyrosine kinases that are implicated in several human malignancies. Overexpression of TAMs and their major ligand Growth arrest-specific factor 6 (Gas6) is associated with more aggressive staging of cancers, poorer predicted patient survival, acquired drug resistance and metastasis. Here we describe small molecule inhibitors (RU-301 and RU-302) that target the extracellular domain of Axl at the interface of the Ig-1 ectodomain of Axl and the Lg-1 of Gas6. These inhibitors effectively block Gas6-inducible Axl receptor activation with low micromolar IC50s in cell-based reporter assays, inhibit Gas6-inducible motility in Axl-expressing cell lines, and suppress H1299 lung cancer tumor growth in a mouse xenograft NOD-SCIDγ model. Furthermore, using homology models and biochemical verifications, we show that RU301 and 302 also inhibit Gas6 inducible activation of Mertk and Tyro3 suggesting they can act as pan-TAM inhibitors that block the interface between the TAM Ig1 ectodomain and the Gas6 Lg domain. Together, these observations establish that small molecules that bind to the interface between TAM Ig1 domain and Gas6 Lg1 domain can inhibit TAM activation, and support the further development of small molecule Gas6-TAM interaction inhibitors as a novel class of cancer therapeutics. PMID:28272423

  3. 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

  4. 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.

  5. 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.

  6. Positron Impact Ionization in Noble Gas Atoms and Diatomic Molecules

    NASA Astrophysics Data System (ADS)

    Marler, J. P.

    2005-05-01

    Results are presented for absolute positronium formation and direct ionization by positron impact on Ne, Ar, Kr, Xe, N2, CO and O2 at energies from threshold up to 90 eV. The experiments use a high-resolution, trap-based positron beam and exploit the properties of positron orbits in a magnetic field [1]. Results for the noble gases are compared with theoretical predictions and with measurements obtained using a significantly different method [2]. Results for diatomic molecules are compared to other available measurements and theoretical calculations where available. There is generally good agreement between the experimental measurements, providing an important benchmark for theoretical calculations. Intriguing features in Ar and O2 will be discussed. [1] J.P. Sullivan, S.J. Gilbert, J.P. Marler, R.G. Greaves, S.J. Buckman and C.M. Surko., Phys. Rev. A. 66, 042708 (2002) [2] J.P. Marler, J.P. Sullivan and C.M. Surko, Phys. Rev. A (2005), in press.

  7. Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

    PubMed

    Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

    2012-06-04

    Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry.

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

    PubMed

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

    2013-12-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  10. Generation and orientation of organoxenon molecule H-Xe-CCH in the gas phase

    SciTech Connect

    Poterya, Viktoriya; Votava, Ondrej; Farnik, Michal; Oncak, Milan; Slavicek, Petr; Buck, Udo; Friedrich, Bretislav

    2008-03-14

    We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193 nm photolysis of an acetylene molecule on Xe{sub n} clusters (n{approx_equal}390). Subsequently the molecule has been oriented via the pseudo-first-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C{sub 2}H{sub 2} on Ar{sub n} clusters (n{approx_equal}280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193 nm radiation excites the molecule predominantly into the 2 {sup 1}{sigma}{sup +} state, which cannot dissociate the Xe-H bond directly, but the system evolves along the Xe-C coordinate to a conical intersection of a slightly nonlinear configuration with the dissociative 1 {sup 1}{pi} state, which then dissociates the Xe-H bond.

  11. Generation and orientation of organoxenon molecule H-Xe-CCH in the gas phase

    NASA Astrophysics Data System (ADS)

    Poterya, Viktoriya; Votava, Ondřej; Fárník, Michal; Ončák, Milan; Slavíček, Petr; Buck, Udo; Friedrich, Břetislav

    2008-03-01

    We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193nm photolysis of an acetylene molecule on Xen clusters (n¯≈390). Subsequently the molecule has been oriented via the pseudo-first-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C2H2 on Arn clusters (n¯≈280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193nm radiation excites the molecule predominantly into the 2Σ+1 state, which cannot dissociate the Xe-H bond directly, but the system evolves along the Xe-C coordinate to a conical intersection of a slightly nonlinear configuration with the dissociative 1Π1 state, which then dissociates the Xe-H bond.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  14. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules.

    PubMed

    Boll, Rebecca; Rouzée, Arnaud; Adolph, Marcus; Anielski, Denis; Aquila, Andrew; Bari, Sadia; Bomme, Cédric; Bostedt, Christoph; Bozek, John D; Chapman, Henry N; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; De, Sankar; Decleva, Piero; Epp, Sascha W; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Gumprecht, Lars; Hömke, André; Holmegaard, Lotte; Johnsson, Per; Kienitz, Jens S; Kierspel, Thomas; Krasniqi, Faton; Kühnel, Kai-Uwe; Maurer, Jochen; Messerschmidt, Marc; Moshammer, Robert; Müller, Nele L M; Rudek, Benedikt; Savelyev, Evgeny; Schlichting, Ilme; Schmidt, Carlo; Scholz, Frank; Schorb, Sebastian; Schulz, Joachim; Seltmann, Jörn; Stener, Mauro; Stern, Stephan; Techert, Simone; Thøgersen, Jan; Trippel, Sebastian; Viefhaus, Jens; Vrakking, Marc; Stapelfeldt, Henrik; Küpper, Jochen; Ullrich, Joachim; Rudenko, Artem; Rolles, Daniel

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C(8)H(5)F) and dissociating, laser-aligned 1,4-dibromobenzene (C(6)H(4)Br(2)) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Bross, David H.; Peterson, Kirk A.

    2014-12-01

    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.

  18. 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.

  19. An adsorbent performance indicator as a first step evaluation of novel sorbents for gas separations: application to metal-organic frameworks.

    PubMed

    Wiersum, Andrew D; Chang, Jong-San; Serre, Christian; Llewellyn, Philip L

    2013-03-12

    An adsorbent performance indicator (API) is proposed in an effort to initially highlight porous materials of potential interest for PSA separation processes. This expression takes into account working capacities, selectivities, and adsorption energies and additionally uses weighting factors to reflect the specific requirements of a given process. To demonstrate the applicability of the API, we have performed the adsorption of carbon dioxide and methane at room temperature on a number of metal-organic frameworks, a zeolite and a molecular sieve carbon. The API is calculated for two different CO2/CH4 separation case scenarios: "bulk separation" and "natural gas purification". This comparison highlights how the API can be more versatile than previously proposed comparison factors for an initial indication of potential adsorbent performance.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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…

  5. 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

  6. 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.

  7. Effect of an electric field on a methane molecule. I. Infrared analysis of methane (CH4-CD4) adsorbed in NaA zeolite in the temperature range 150-20 K

    NASA Astrophysics Data System (ADS)

    De Lara, E. Cohen; Kahn, R.; Seloudoux, R.

    1985-09-01

    The spectra of methane adsorbed at low temperature in NaA zeolite show two strong effects of the field existing in the cavities: (i) the appearance of the ν1 forbidden band which increases when decreasing the temperature and (ii) the splitting of the ν3 degenerate band. The variation with T of its components lead to the conclusion that the molecule progressively is oriented in a C3V configuration with respect to the field.

  8. 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.

  9. Vibrational frequency shifts of diatomic molecules in interaction with a Na + cation by ab initio calculations. Comparison with experiment on H 2 and N 2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Koubi, Laure; Blain, Monique; de Lara, Evelyne Cohen; Leclerq, Jean-Marie

    1994-01-01

    Ab initio calculations on H 2 and N 2 and on the same molecules in the presence of a Na + cation are presented. The equilibrium configuration and the vibrational frequency shift due to the interaction are calculated. The potential energy surfaces are obtained by local osculatory interpolations and extrapolations. The vibrational frequencies are calculated by the Numerov—Cooley method. The direction of the frequency shift is found to be related to the orientation of the diatomic molecule with respect to the cation. The results are compared with experimental data on induced infrared bands of H 2 and N 2 adsorbed in NaA zeolite.

  10. 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).

  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. High Resolution Rovibrational Spectroscopy of Large Molecules Using Infrared Frequency Combs and Buffer Gas Cooling

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    We have recently demonstrated the integration of cavity-enhanced direct frequency comb spectroscopy with buffer gas cooling to acquire high resolution infrared spectra of translationally and rotationally cold (˜10 K) gas-phase molecules. Here, we extend this method to significantly larger systems, including naphthalene (C10H_8), a prototypical polyaromatic hydrocarbon, and adamantane (C10H_{16}), the fundamental building block of diamonoids. To the authors' knowledge, the latter molecule represents the largest system for which rotationally resolved spectra in the CH stretch region (3 μm) have been obtained. In addition to the measured spectra, we present several details of our experimental methods. These include introducing non-volatile species into the cold buffer gas cell and obtaining broadband spectra with single comb mode resolution. We also discuss recent modifications to the apparatus to improve its absorption sensitivity and time resolution, which facilitate the study of both larger molecular systems and cold chemical dynamics. B. Spaun, et al. Probing buffer-gas cooled molecules with direct frequency comb spectroscopy in the mid-infrared, WF02, 70th International Symposium on Molecular Spectroscopy, Champaign-Urbana, IL, 2015.

  13. Prospect for the formation of a gas of ultracold polar NaRb molecules

    NASA Astrophysics Data System (ADS)

    Quéméner, Goulven; Vexiau, Romain; Wang, Gaoren; Lepers, Maxence; Luc, Eliane; Bouloufa-Maafa, Nadia; Dulieu, Olivier; Wang, Dajun

    2015-05-01

    We present a complete theoretical model for the formation of an ultracold gas of polar NaRb molecules, based on high-precision spectroscopic data completed with accurate quantum chemistry calculations. Weakly-bound molecules are first created via a Feshbach resonance with main triplet character. The population is transfered down to the lowest rovibrational level of the ground state by a coherent STIRAP process. The efficiency of various paths via different electronically-excited molecular states is discussed in relation of the ongoing experimental implementation. Supported by Agence Nationale de la Recherche (ANR), project COPOMOL (# ANR-13-IS04-0004-01).

  14. 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.

  15. Infrared Action Spectroscopy of Low-Temperature Neutral Gas-Phase Molecules of Arbitrary Structure

    NASA Astrophysics Data System (ADS)

    Yatsyna, Vasyl; Bakker, Daniël J.; Salén, Peter; Feifel, Raimund; Rijs, Anouk M.; Zhaunerchyk, Vitali

    2016-09-01

    We demonstrate a technique for IR action spectroscopy that enables measuring IR spectra in a background-free fashion for low-temperature neutral gas-phase molecules of arbitrary structure. The method is exemplified experimentally for N -methylacetamide molecules in the mid-IR spectral range of 1000 - 1800 cm-1 , utilizing the free electron laser FELIX. The technique involves the resonant absorption of multiple mid-IR photons, which induces molecular dissociation. The dissociation products are probed with 10.49 eV vacuum ultraviolet photons and analyzed with a mass spectrometer. We also demonstrate the capability of this method to record, with unprecedented ease, mid-IR spectra for the molecular associates, such as clusters and oligomers, present in a molecular beam. In this way the mass-selected spectra of low-temperature gas-phase dimers and trimers of N -methylacetamide are measured in the full amide I-III range.

  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. 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.

  18. Rotary adsorbers for continuous bulk separations

    DOEpatents

    Baker, Frederick S [Oak Ridge, TN

    2011-11-08

    A rotary adsorber for continuous bulk separations is disclosed. The rotary adsorber includes an adsorption zone in fluid communication with an influent adsorption fluid stream, and a desorption zone in fluid communication with a desorption fluid stream. The fluid streams may be gas streams or liquid streams. The rotary adsorber includes one or more adsorption blocks including adsorbent structure(s). The adsorbent structure adsorbs the target species that is to be separated from the influent fluid stream. The apparatus includes a rotary wheel for moving each adsorption block through the adsorption zone and the desorption zone. A desorption circuit passes an electrical current through the adsorbent structure in the desorption zone to desorb the species from the adsorbent structure. The adsorbent structure may include porous activated carbon fibers aligned with their longitudinal axis essentially parallel to the flow direction of the desorption fluid stream. The adsorbent structure may be an inherently electrically-conductive honeycomb structure.

  19. High-order-harmonic generation using gas-phase H{sub 2}O molecules

    SciTech Connect

    Zhao Songfeng; Jin, Cheng; Le, Anh-Thu; Lin, C. D.; Lucchese, R. R.

    2011-03-15

    We investigate high-order-harmonic generation of isotropically distributed gas-phase H{sub 2}O molecules exposed to an intense laser field. The induced dipole of each individual molecule by the laser field is first calculated using the recently developed quantitative rescattering theory. In a thin medium, harmonic spectra generated coherently from all the molecules are then calculated by solving Maxwell's equation of propagation. By using accurate transition dipoles of H{sub 2}O, we show that the harmonics in the lower plateau region are quite different from models that employ the simpler strong-field approximation. We also examine the magnitude and phase of the harmonics and their dependence on laser focusing conditions.

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

    PubMed Central

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

    2013-01-01

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

  1. Comment on “Equilibrium constants and rate constants for adsorbates: Two-dimensional (2D) ideal gas, 2D ideal lattice gas, and ideal hindered translator models”

    SciTech Connect

    Savara, Aditya

    2016-08-15

    The paper by Campbell et al. was recently brought to my attention. This comment is written to provide greater clarity to the community to prevent misconceptions regarding the entropies being discussed in that work and to clarify the differences between the adsorbate standard states suggested by Campbell and by Savara.

  2. Numerical analysis on gas-surface interaction by molecular dynamics method. I - Simulation with Lennard-Jones molecules

    NASA Astrophysics Data System (ADS)

    Matsumoto, Yoichiro; Matsui, Jun; Ohashi, Hideo

    1992-07-01

    Rarefied gas flows in various situations are calculated successfully by the direct simulation Monte Carlo method. In the simulation, the Maxwell model, where a gas molecule reflects diffusely with the probability alpha and reflects specularly with the probability 1 - alpha, is widely used for boundary conditions on solid surfaces. However, the value of alpha is determined empirically and varies greatly with conditions such as degree of contamination and temperature of the surface. Rational prediction of the value and analysis of the interaction between gas and solid surface are required. In this paper, the behavior of a gas molecule with collides onto the solid surface is simulated by the molecular dynamics method. The numerical results reveal that the scattering behavior of the gas molecule is neither specular, diffuse, nor Maxwell-type reflection, and that the sticking probability is affected by the initial gas velocity and the potential well depth.

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

    DOE PAGES

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

    2015-04-13

    A flexible metal–organic framework (MOF) of [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

  5. The double dark resonance in a cold gas of Cs atoms and molecules.

    PubMed

    Feng, ZhiFang; Li, WeiDong; Xiao, LianTuan; Jia, SuoTang

    2008-09-29

    We theoretically investigated the properties of the effective four-level stimulated Raman adiabatic passage scheme in a cold gas of Cs atoms and molecules, where exists the tunnelling coupling between two excited molecular states due to the 0(g)- (6S,6P(3/2)) double well structure. The double dark resonance is predicted in the absorption spectrum when the tunnelling coupling strength is large enough. The double dark resonance not only reveals the formation of the ultra-cold molecules, but also provides further evidence for the tunnelling as one effective coupling mechanism between the two excited molecular states. The effect of the various experimental conditions on this phenomena has been discussed.

  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. 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

  8. Methods for Using Ab Initio Potential Energy Surfaces in Studies of Gas-Phase Reactions of Energetic Molecules

    DTIC Science & Technology

    2014-08-20

    Ab Initio Potential Energy Surfaces in Studies of Gas-Phase Reactions of Energetic Molecules The focus of this research was to apply efficient...methods for using ab initio potential energy surfaces (PESs) computed with high levels of quantum chemistry theory to predict chemical reaction properties...in non peer-reviewed journals: Methods for Using Ab Initio Potential Energy Surfaces in Studies of Gas-Phase Reactions of Energetic Molecules Report

  9. 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

    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.

  10. 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

  11. The effect of cold trap adsorbents on the gas chromatographic analysis of ambient VOCs under Peltier cooling conditions.

    PubMed

    Pal, Raktim; Kim, Ki-Hyun

    2008-04-01

    In this work, the relative analytical performance of the GC-based detection method was investigated with a major focus on cold trap (CT) adsorbent materials against four aromatic volatile organic compounds (VOCs) (e. g., benzene, toluene, xylene, and styrene). A series of calibration experiments were hence conducted under cryofocusing conditions formed by the Peltier cooling system in a thermal desorber (TD) unit. During the course of this study, comparative calibration datasets were acquired for each of the three CT types: (i) CT (I) = Carbopack B + Carbopack C, (ii) CT (II) = Carbopack B + Carboxen 1000, and (iii) CT (III) = Tenax TA. All calibration datasets were obtained under subambient temperature (-10 degrees C) conditions controlled by the Peltier cooling system. The reliability of the calibration data was also assessed in an ancillary experiment with the aid of the modified injection through a thermal desorber (MITD) method. The results demonstrated that the GC detection properties of different VOCs were not altered significantly between different CT applications under Peltier conditions, although relative sensitivity could be distinguished moderately depending on the CT type.

  12. Relativistic ultrafast electron diffraction from molecules in the gas phase (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Yang, Jie; Guehr, Markus; Vecchione, Theodore; Robinson, Matthew S.; Li, Renkai; Hartmann, Nick; Shen, Xiaozhe; Centurion, Martin; Wang, Xijie

    2016-10-01

    Ultrafast electron diffraction (UED) is a powerful technique that can be used to resolve structural changes of gas molecules during a photochemical reaction. However, the temporal resolution in pump-probe experiments has been limited to the few-ps level by the space-charge effect that broadens the electron pulse duration and by velocity mismatch between the pump laser pulses and the probe electron pulses, making only long-lived intermediate states accessible. Taking advantage of relativistic effects, Mega-electron-volt (MeV) electrons can be used to suppress both the space-charge effect and the velocity mismatch, and hence to achieve a temporal resolution that is fast enough to follow coherent nuclear motion in the target molecules. In this presentation, we show the first MeV UED experiments on gas phase targets. These experiments not only demonstrate that femtosecond temporal resolution is achieved, but also show that the spatial resolution is not compromised. This unprecedented combination of spatiotemporal resolution is sufficient to image coherent nuclear motions, and opens the door to a new class of experiments where the structural changes can be followed simultaneously in both space and time.

  13. 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.

  14. Computational study of peptide bond formation in the gas phase through ion-molecule reactions.

    PubMed

    Redondo, Pilar; Martínez, Henar; Cimas, Alvaro; Barrientos, Carmen; Largo, Antonio

    2013-08-21

    A computational study of peptide bond formation from gas-phase ion-molecule reactions has been carried out. We have considered the reaction between protonated glycine and neutral glycine, as well as the reaction between two neutral glycine molecules for comparison purposes. Two different mechanisms, concerted and stepwise, were studied. Both mechanisms show significant energy barriers for the neutral reaction. The energy requirements for peptide bond formation are considerably reduced upon protonation of one of the glycine molecules. For the reaction between neutral glycine and N-protonated glycine the lowest energy barrier is observed for the concerted mechanism. For the reaction between neutral glycine and protonated glycine at carbonyl oxygen, the preferred mechanism is the stepwise one, with a relatively small energy barrier (23 kJ mol(-1) at 0 K) and leading to the lowest-lying protonated glycylglycine isomer. In the case that the reaction could be initiated by protonated glycine at hydroxyl oxygen the process would be barrier-free and clearly exothermic. In that case peptide bond formation could take place even under interstellar conditions if glycine is present in space.

  15. 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.

  16. 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

  17. 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.

  18. Ab initio calculations of the intermolecular chemical shift in nuclear magnetic resonance in the gas phase and for adsorbed species

    NASA Astrophysics Data System (ADS)

    Jameson, Cynthia J.; de Dios, Angel C.

    1992-07-01

    The chemical shifts observed in nuclear magnetic resonance experiments are the differences in shielding of the nuclear spin in different electronic environments. These are known to depend on intermolecular interactions as evidenced by density-dependent chemical shifts in the gas phase, gas-to-liquid shifts, and adsorption shifts on surfaces. We present the results of the first ab initio intermolecular chemical shielding function calculated for a pair of interacting atoms for a wide range of internuclear separations. We used the localized orbital local origin (LORG) approach of Hansen and Bouman and also investigated the second-order electron correlation contributions using second-order LORG (SOLO). The 39Ar shielding in Ar2 passes through zero at some very short distance, going through a minimum, and asymptotically approaches zero at larger separations. The 21Ne shielding function in Ne2 has a similar shape. The Drude model suggests a method of scaling that portion of the shielding function that is weighted most heavily by exp[-V(R)/kT]. The scaling factors, which have been verified in the comparison of 21Ne in Ne2 against 39Ar in Ar2 ab initio results, allows us to project out from the same 39Ar in Ar2 ab initio values the appropriate 129Xe shielding functions in the Xe-Ar, Xe-Kr, and Xe-Xe interacting pairs. These functions lead to temperature-dependent second virial coefficients of chemical shielding which agree with experiments in the gas phase. Ab initio calculations of 39Ar shielding in clusters of argon are used to model the observed 129Xe chemical shifts of Xe, Xe2,...,Xe8 trapped in the cages of zeolite NaA.

  19. 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.

  20. 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.

  1. Accurate Structure Parameters for Tunneling Ionization Rates of Gas-Phase Linear Molecules

    NASA Astrophysics Data System (ADS)

    Zhao, Song-Feng; Li, Jian-Ke; Wang, Guo-Li; Li, Peng-Cheng; Zhou, Xiao-Xin

    2017-03-01

    In the molecular Ammosov–Delone–Krainov (MO-ADK) model of Tong et al. [Phys. Rev. A 66 (2002) 033402], the ionization rate depends on the structure parameters of the molecular orbital from which the electron is removed. We determine systematically and tabulate accurate structure parameters of the highest occupied molecular orbital (HOMO) for 123 gas-phase linear molecules by solving time-independent Schrödinger equation with B-spline functions and molecular potentials which are constructed numerically using the modified Leeuwen–Baerends (LBα) model. Supported by National Natural Science Foundation of China under Grant Nos. 11664035, 11674268, 11465016, 11364038, 11364039, the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No. 20116203120001 and the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province

  2. 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

  3. 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.

  4. Detection of water molecules in inert gas based plasma by the ratios of atomic spectral lines

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Ochkin, V. N.

    2017-01-01

    A new approach is considered to detect the water leaks in inert plasma-forming gas present in the reactor chamber. It is made up of the intensity ratio of D α and H α spectral lines in combination with O, Ar and Xe lines intensity. The concentrations of H2O, O, H and D particles have been measured with high sensitivity. At the D2 admixture pressure {{p}{{\\text{D}\\text{2}}}}   =  0.025 mbar, we used the acquisition time of 10 s to measure the rate of water molecules injected from the outside, Γ0  =  1.4 · 10-9 mbar · m3 · s-1, and the incoming water molecules to plasma, Γ  =  5 ·10-11 mbar · m3 · s-1. The scaling proves that at small D2 admixtures (10-4 mbar), the leaks with the rates Γ0  ≈  6 · 10-12 mbar · m3 · s-1 and Γ  ≈  2 · 10-13 mbar · m3 · s-1 can be detected and measured. The difference between Γ0 and Γ values is due to the high degree of H2O dissociation, which can be up to 97-98%.

  5. Gas phase ion - molecule reactions studied by Fourier transform ion cyclotron resonance mass spectrometry

    SciTech Connect

    Ross, C.W. III.

    1993-01-01

    Intrinsic thermodynamic information of molecules can easily be determined in the low pressure FT/ICR mass spectrometer. The gas phase basicity of two carbenes were measured by isolating the protonated carbene ion and reacting it with neutral reference compounds by the bracketing method. A fundamentally new-dimensional FT/ICR/MS experiment, SWIM (stored waveform ion modulation) 2D-FT/ICR MS/MS, is described. Prior encodement of the second dimension by use of two identical excitation waveforms separated by a variable delay period is replaced by a new encodement in which each row of the two-dimensional data array is obtained by use of a single stored excitation waveform whose frequency-domain magnitude spectrum is a sinusoid whose frequency increases from one row to the next. In the two-dimensional mass spectrum, the conventional one-dimensional FT/ICR mass spectrum appears along the diagonal, and each off-diagonal peak corresponds to an ion-neutral reaction whose ionic components may be identified by horizontal and vertical projections to the diagonal spectrum. All ion-molecule reactions in a gaseous mixture may be identified from a single 2D-FT/ICR MS/MS experiment, without any prior knowledge of the system. In some endoergic reactions there is a minimum energy threshold that must overcome for a reaction to occur. Hence, a simple sinusoidal modulation of parent ion cyclotron radius leads to a clipped sinusoidal signal of the product ion abundance in the second dimension, which upon Fourier transformation produces signals with harmonic and combination ion cyclotron resonance frequencies. Moreover, ion-molecule reaction rates may vary directly within kinetic energy rather than cyclotron radius. With SWIM, it is possible to tailor the excitation profile so as to produce a sinusoidal modulation of ion kinetic energy as a function of cyclotron frequency.

  6. Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

    NASA Astrophysics Data System (ADS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2017-02-01

    Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

  7. Formation of novel rare-gas-containing molecules by molecular photodissociation in clusters.

    PubMed

    Cohen, A; Niv, M Y; Gerber, R B

    2001-01-01

    Recent work by Räsänen and coworkers showed that photolysis of hydrides in rare-gas matrices results in part in formation of novel, rare-gas-containing molecules. Thus, photolysis of HCl in Xe and of H2O in Xe result respectively in formation of HXeCl and HXeOH in the Xe matrices. Ab initio calculations show that the compounds HRgY so formed are stable in isolation, and that by the strength and nature of the bonding these are molecules, very different from the corresponding weakly bound clusters Rg...HY. This paper presents a study of the formation mechanism of HRgY following the photolysis of HY in clusters Rgn(HY). Calculations are described for HXeCl, as a representative example. Potential energy surfaces that govern the formation of HXeCl in the photolysis of HCl in xenon clusters are obtained, and the dynamics on these surfaces is analyzed, partly with insight from trajectories of molecular dynamics simulations. The potential surfaces are obtained by a new variant of the DIM (diatomics in molecules) and DIIS (diatomics in ionic systems) models. Non-adiabatic couplings are also obtained. The main results are: (1) Properties of HXeCl predicted by the DIM-DIIS model are in reasonable accord with results of ab initio calculations. (2) The potential along the isomerization path HXeCl-->Xe...HCl predicted by DIM is in semiquantitative accord with the ab initio results. (3) Surface-hopping molecular dynamics simulations of the process in clusters, with "on the fly" calculations of the DIM-DIIS potentials and non-adiabatic couplings are computationally feasible. (4) Formation of HXeCl, following photolysis of HCl in Xe54(HCl), requires cage-exit of the H atom as a precondition. The H atom and the Cl can then attack the same Xe atom on opposite sides, leading to charge transfer and production of the ionic HXeCl. (5) Non-adiabatic processes play an important role, both in the reagent configurations, and at the charge-transfer stage. The results open the way to

  8. 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.

  9. Incorporation and thermal evolution of rhodamine 6G dye molecules adsorbed in porous columnar optical SiO2 thin films.

    PubMed

    Sánchez-Valencia, Juan R; Blaszczyk-Lezak, Iwona; Espinós, Juan P; Hamad, Said; González-Elipe, Agustín R; Barranco, Angel

    2009-08-18

    Rhodamine 6G (Rh6G) dye molecules have been incorporated into transparent and porous SiO2 thin films prepared by evaporation at glancing angles. The porosity of these films has been assessed by analyzing their water adsorption isotherms measured for the films deposited on a quartz crystal monitor. Composite Rh6G/SiO2 thin films were prepared by immersion of a SiO2 thin film into a solution of the dye at a given pH. It is found that the amount of Rh6G molecules incorporated into the film is directly dependent on the pH of the solution and can be accounted for by a model based on the point of zero charge (PZC) concepts originally developed for colloidal oxides. At low pHs, the dye molecules incorporate in the form of monomers, while dimers or higher aggregates are formed if the pH increases. Depending on the actual preparation and treatment conditions, they also exhibit high relative fluorescence efficiency. The thermal stability of the composite films has been also investigated by characterizing their optical behavior after heating in an Ar atmosphere at increasing temperatures up to 275 degrees C. Heating induces a progressive loss of active dye molecules, a change in their agglomeration state, and an increment in their relative fluorescence efficiency. The obtained Rh6G/SiO2 composite thin films did not disperse the light and therefore can be used for integration into optical and photonic devices.

  10. Adsorbate Diffusion on Transition Metal Nanoparticles

    DTIC Science & Technology

    2015-01-01

    systematically studied adsorption and diffusion of atomic and diatomic species (H, C, N, O, CO, and NO) on nanometer-sized Pt and Cu nanoparticles with...species and two diatomic molecules (H, C, N, O, CO, and NO) as adsorbates and study the adsorption and diffusion of these adsorbates across the edges

  11. Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule

    NASA Astrophysics Data System (ADS)

    Furtenbacher, Tibor; Szidarovszky, Tamás; Hrubý, Jan; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Császár, Attila G.

    2016-12-01

    A much improved temperature-dependent ideal-gas internal partition function, Qint(T), of the H216O molecule is reported for temperatures between 0 and 6000 K. Determination of Qint(T) is principally based on the direct summation technique involving all accurate experimental energy levels known for H216O (almost 20 000 rovibrational energies including an almost complete list up to a relative energy of 7500 cm-1), augmented with a less accurate but complete list of first-principles computed rovibrational energy levels up to the first dissociation limit, about 41 000 cm-1 (the latter list includes close to one million bound rovibrational energy levels up to J = 69, where J is the rotational quantum number). Partition functions are developed for ortho- and para-H216O as well as for their equilibrium mixture. Unbound rovibrational states of H216O above the first dissociation limit are considered using an approximate model treatment. The effect of the excited electronic states on the thermochemical functions is neglected, as their contribution to the thermochemical functions is negligible even at the highest temperatures considered. Based on the high-accuracy Qint(T) and its first two moments, definitive results, in 1 K increments, are obtained for the following thermochemical functions: Gibbs energy, enthalpy, entropy, and isobaric heat capacity. Reliable uncertainties (approximately two standard deviations) are estimated as a function of temperature for each quantity determined. These uncertainties emphasize that the present results are the most accurate ideal-gas thermochemical functions ever produced for H216O. It is recommended that the new value determined for the standard molar enthalpy increment at 298.15 K, 9.904 04 ± 0.000 01 kJ mol-1, should replace the old CODATA datum, 9.905 ± 0.005 kJ mol-1.

  12. 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.

  13. Desorption of Hot Molecules from Photon Irradiated Interstellar Ices

    NASA Astrophysics Data System (ADS)

    Thrower, J. D.; Burke, D. J.; Collings, M. P.; Dawes, A.; Holtom, P. D.; Jamme, F.; Kendall, P.; Brown, W. A.; Clark, I. P.; Fraser, H. J.; McCoustra, M. R. S.; Mason, N. J.; Parker, A. W.

    2008-02-01

    We present experimental measurements of photodesorption from ices of astrophysical relevance. Layers of benzene and water ice were irradiated with a laser tuned to an electronic transition in the benzene molecule. The translational energy of desorbed molecules was measured by time-of-flight (ToF) mass spectrometry. Three distinct photodesorption processes were identified: a direct adsorbate-mediated desorption producing benzene molecules with a translational temperature of around 1200 K, an indirect adsorbate-mediated desorption resulting in water molecules with a translational temperature of around 450 K, and a substrate-mediated desorption of both benzene and water producing molecules with translational temperatures of around 530 and 450 K, respectively. The translational temperature of each population of desorbed molecules is well above the temperature of the ice matrix. The implications for gas-phase chemistry in the interstellar medium are discussed.

  14. 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.

  15. 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)

  16. Comparative investigation of pure and mixed rare gas atoms on coronene molecules.

    PubMed

    Rodríguez-Cantano, Rocío; Bartolomei, Massimiliano; Hernández, Marta I; Campos-Martínez, José; González-Lezana, Tomás; Villarreal, Pablo; Pérez de Tudela, Ricardo; Pirani, Fernando; Hernández-Rojas, Javier; Bretón, José

    2017-01-21

    Clusters formed by the combination of rare gas (RG) atoms of He, Ne, Ar, and Kr on coronene have been investigated by means of a basin-hopping algorithm and path integral Monte Carlo calculations at T = 2 K. Energies and geometries have been obtained and the role played by the specific RG-RG and RG-coronene interactions on the final results is analysed in detail. Signatures of diffuse behavior of the He atoms on the surface of the coronene are in contrast with the localization of the heavier species, Ar and Kr. The observed coexistence of various geometries for Ne suggests the motion of the RG atoms on the multi-well potential energy surface landscape offered by the coronene. Therefore, the investigation of different clusters enables a comparative analysis of localized versus non-localized features. Mixed Ar-He-coronene clusters have also been considered and the competition of the RG atoms to occupy the docking sites on the molecule is discussed. All the obtained information is crucial to assess the behavior of coronene, a prototypical polycyclic aromatic hydrocarbon clustering with RG atoms at a temperature close to that of interstellar medium, which arises from the critical balance of the interactions involved.

  17. Comparative investigation of pure and mixed rare gas atoms on coronene molecules

    NASA Astrophysics Data System (ADS)

    Rodríguez-Cantano, Rocío; Bartolomei, Massimiliano; Hernández, Marta I.; Campos-Martínez, José; González-Lezana, Tomás; Villarreal, Pablo; Pérez de Tudela, Ricardo; Pirani, Fernando; Hernández-Rojas, Javier; Bretón, José

    2017-01-01

    Clusters formed by the combination of rare gas (RG) atoms of He, Ne, Ar, and Kr on coronene have been investigated by means of a basin-hopping algorithm and path integral Monte Carlo calculations at T = 2 K. Energies and geometries have been obtained and the role played by the specific RG-RG and RG-coronene interactions on the final results is analysed in detail. Signatures of diffuse behavior of the He atoms on the surface of the coronene are in contrast with the localization of the heavier species, Ar and Kr. The observed coexistence of various geometries for Ne suggests the motion of the RG atoms on the multi-well potential energy surface landscape offered by the coronene. Therefore, the investigation of different clusters enables a comparative analysis of localized versus non-localized features. Mixed Ar-He-coronene clusters have also been considered and the competition of the RG atoms to occupy the docking sites on the molecule is discussed. All the obtained information is crucial to assess the behavior of coronene, a prototypical polycyclic aromatic hydrocarbon clustering with RG atoms at a temperature close to that of interstellar medium, which arises from the critical balance of the interactions involved.

  18. C-C stretching Raman spectra and stabilities of hydrocarbon molecules in natural gas hydrates: a quantum chemical study.

    PubMed

    Liu, Yuan; Ojamäe, Lars

    2014-12-11

    The presence of specific hydrocarbon gas molecules in various types of water cavities in natural gas hydrates (NGHs) are governed by the relative stabilities of these encapsulated guest molecule-water cavity combinations. Using molecular quantum chemical dispersion-corrected hybrid density functional computations, the interaction (ΔE(host--guest)) and cohesive energies (ΔE(coh)), enthalpies, and Gibbs free energies for the complexes of host water cages and hydrocarbon guest molecules are calculated at the ωB97X-D/6-311++G(2d,2p) level of theory. The zero-point energy effect of ΔE(host-guest) and ΔE(coh) is found to be quite substantial. The energetically optimal host-guest combinations for seven hydrocarbon gas molecules (CH4, C2H6, C3H6, C3H8, C4H8, i-C4H10, and n-C4H10) and various water cavities (D, ID, T, P, H, and I) in NGHs are found to be CH4@D, C2H6@T, C3H6@T, C3H8@T, C4H8@T/P/H, i-C4H10@H, and n-C4H10@H, as the largest cohesive energy magnitudes will be obtained with these host-guest combinations. The stabilities of various water cavities enclosing hydrocarbon molecules are evaluated from the computed cohesive Gibbs free energies: CH4 prefers to be trapped in a ID cage; C2H6 prefer T cages; C3H6 and C3H8 prefer T and H cages; C4H8 and i-C4H10 prefer H cages; and n-C4H10 prefer I cages. The vibrational frequencies and Raman intensities of the C-C stretching vibrational modes for these seven hydrocarbon molecules enclosed in each water cavity are computed. A blue shift results after the guest molecule is trapped from gas phase into various water cages due to the host-guest interactions between the water cage and hydrocarbon molecule. The frequency shifts to the red as the radius of water cages increases. The model calculations support the view that C-C stretching vibrations of hydrocarbon molecules in the water cavities can be used as a tool to identify the types of crystal phases and guest molecules in NGHs.

  19. Molecularly Imprinted Filtering Adsorbents for Odor Sensing

    PubMed Central

    Shinohara, Sho; Chiyomaru, You; Sassa, Fumihiro; Liu, Chuanjun; Hayashi, Kenshi

    2016-01-01

    Versatile odor sensors that can discriminate among huge numbers of environmental odorants are desired in many fields, including robotics, environmental monitoring, and food production. However, odor sensors comparable to an animal’s nose have not yet been developed. An animal’s olfactory system recognizes odor clusters with specific molecular properties and uses this combinatorial information in odor discrimination. This suggests that measurement and clustering of odor molecular properties (e.g., polarity, size) using an artificial sensor is a promising approach to odor sensing. Here, adsorbents composed of composite materials with molecular recognition properties were developed for odor sensing. The selectivity of the sensor depends on the adsorbent materials, so specific polymeric materials with particular solubility parameters were chosen to adsorb odorants with various properties. The adsorption properties of the adsorbents could be modified by mixing adsorbent materials. Moreover, a novel molecularly imprinted filtering adsorbent (MIFA), composed of an adsorbent substrate covered with a molecularly imprinted polymer (MIP) layer, was developed to improve the odor molecular recognition ability. The combination of the adsorbent and MIP layer provided a higher specificity toward target molecules. The MIFA thus provides a useful technique for the design and control of adsorbents with adsorption properties specific to particular odor molecules. PMID:27886070

  20. 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.

  1. Application of microwave-assisted desorption/headspace solid-phase microextraction as pretreatment step in the gas chromatographic determination of 1-naphthylamine in silica gel adsorbent.

    PubMed

    Yan, Cheing-Tong; Jen, Jen-Fon; Shih, Tung-Sheng

    2007-03-30

    Pretreatment of silica gel sample containing 1-naphthylamine by microwave-assisted desorption (MAD) coupled to in situ headspace solid phase microextraction (HS-SPME) has been investigated as a possible alternative to conventional methods prior to gas chromatographic (GC) analysis. The 1-naphthylamine desorbs from silica gel to headspace under microwave irradiation, and directly absorbs onto a SPME fiber located in a controlled-temperature headspace area. After being collected on the SPME fiber, and desorbed in the GC injection port, 1-naphthylamine is analyzed by GC-FID. Parameters that influence the extraction efficiency of the MAD/HS-SPME, such as the extraction media and its pH, the microwave irradiation power and irradiation time as well as desorption conditions of the GC injector, have been investigated. Experimental results indicate that the extraction of a 150mg silica gel sample by using 0.8ml of 1.0M NaOH solution and a PDMS/DVB fiber under high-powered irradiation (477W) for 5min maximizes the extraction efficiency. Desorption of 1-naphthylamine from the SPME fiber in GC injector is optimal at 250 degrees C held for 3min. The detection limit of method is 8.30ng. The detected quantity of 1-naphthylamine obtained by the proposed method is 33.3 times of that obtained by the conventional solvent extraction method for the silica gel sample containing 100ng of 1-naphthylamine. It provides a simple, fast, sensitive and organic-solvent-free pretreatment procedure prior to the analysis of 1-naphthylamine collected on a silica gel adsorbent.

  2. 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.

  3. [Extraction of triazine herbicides from environmental water samples with magnetic graphene nanoparticles as the adsorbent followed by determination using gas chromatography-mass spectrometry].

    PubMed

    Zhang, Guijiang; Zang, Xiaohuan; Zhou, Xin; Wang, Lu; Wang, Chun; Wang, Zhi

    2013-11-01

    A novel method was developed for the determination of seven triazine herbicides in environmental water samples by magnetic solid-phase extraction with graphene-based magnetic nanoparticles (G-Fe3O4 MNPs) as the adsorbent coupled with gas chromatography-mass spectrometry detection. The main factors influencing the extraction efficiency including the amount of G-Fe3O4, the extraction time, the pH and the ionic strength of sample solution and the desorption conditions were optimized. Under the optimized experimental conditions, the enrichment factors of the method for the analytes were in the range from 574 to 968; the linearities of the method ranged from 0.01 to 10.0 microg/L for simazine, propazine, metribuzin, simetryn and cyanazine, from 0.05 to 10.0 microg/L for atrazine and from 0.01 to 8.0 microg/L for prometryn, with the correlation coefficients (r) ranging from 0.996 8 to 0.999 8. The limits of detection were in the range between 1.0 and 5.0 ng/L. Good reproducibilities were obtained with the relative standard deviations below 10.5%. The developed method was applied to the analysis of the triazine herbicides in different water samples (lake, well and tap). The recoveries of the method were in the range from 79.8% to 118.3% at the spiked levels of 0.5 microg/L and 2.0 microg/L. The results indicated that the developed method can be used as a simple and efficient technique for the determination of the triazine herbicides in environmental water samples.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

    PubMed

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

    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.

  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. Laser Adaptive System for Measurement of Molecule Mass and Concentration

    NASA Astrophysics Data System (ADS)

    Romashko, R. V.; Kulchin, Y. N.; Efimov, T. A.; Sergeev, A. A.; Nepomnyashiy, A. V.

    A Laser adaptive microweighting system for measurement of molecules mass based on the principles of adaptive holog aphic interferometry is proposed and experimentally tested in task of gas concentration measurement. A sensitive element of the system is a microcantilever coated by a layer of chitosan, which can adsorb different molecules. Changes in gas concentration re ult in change in mass of molecules adsorbed in chitosan, and, as sequence, result in change in natural frequency of cantilever oscillations, which are measured by an adaptive holographic interferometer. The operation of the system has been experimentally demonstrated in measurement of water vapor concentration. The detected change in concentration of H2O molecules amounted to 125 ppm.

  9. 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.

  10. Photodissociation of HBr molecules in clusters: from rare gas clusters to water nanoparticles

    NASA Astrophysics Data System (ADS)

    Fárník, M.; Buck, Udo

    2007-09-01

    Experiments on the photodissociation of molecules in different cluster environments are described and illustrated based on the example of HBr molecules photolysed at 193 nm in various clusters. The photolysis of HBr molecules incorporated in the hydrogen bonded network of (HBr)n clusters exhibits pronounced direct exits of the H-fragments. On the other hand, the H-fragments from HBr molecules bound by much weaker van der Waals forces at the surface of large Arn clusters are trapped efficiently by the cluster cage. These observations are mainly explained by the geometry of the molecule bound to the cluster. The HBr molecules deposited on the large (H2O)n clusters behave quite differently. They undergo acid dissociation and the resulting zwitterionic form is excited by the radiation giving rise to the generation of the hydronium H3O molecule and its subsequent dissociation.

  11. Molecular orbital studies of gas-phase interactions between complex molecules.

    PubMed

    Gaudreault, Roger; Whitehead, M A; van de Ven, Theo G M

    2006-03-16

    Describing interactions among large molecules theoretically is a challenging task. As an example, we investigated gas-phase interactions between a linear nonionic oligomer and various model compounds (cofactors), which have been reported to associate experimentally, using PM3 semiempirical molecular orbital theory. As oligomer, we studied the hexamer of poly(ethylene oxide) (PEO), and as cofactors, we studied corilagin and related compounds containing phenolic groups (R-OH). These systems are of interest because they are models for PEO/cofactor flocculation systems, used in industrial applications. The PM3 delocalized molecular orbitals (DLMO) describe the bonding between (PEO)6 and cofactors, and some of them cover the complete complex. The DLMOs which cover the traditionally considered hydrogen bonds R-OH...O or R-CH...O show a distinct "pinch", a decrease of the electron density, between the H...O atoms. Calculations of Gibbs free energy, entropy, and enthalpy show that the PEO/cofactor complexes do not form at room temperature, because the loss of entropy exceeds the increase in enthalpy. The change in enthalpy is linearly related to the change in entropy for the different complexes. Even though bond lengths, bond angles, DLMOs, and electron densities for the PEO/cofactor complexes are consistent with the definition of hydrogen bonds, the number of intermolecular R-OH...O and R-CH...O bonds does not correlate with the enthalpy of association, indicating that the bonding mechanism for these systems is the sum of many small contributions of many delocalized orbitals.

  12. 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.

  13. Regenerable activated bauxite adsorbent alkali monitor probe

    SciTech Connect

    Lee, S.H.D.

    1991-01-22

    This invention relates to a regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor 5 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 10 exhaust gases.

  14. 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.

  15. Ab initio potential energy surface for the carbon dioxide molecule pair and thermophysical properties of dilute carbon dioxide gas

    NASA Astrophysics Data System (ADS)

    Hellmann, Robert

    2014-10-01

    A four-dimensional intermolecular potential energy surface (PES) for two rigid carbon dioxide molecules was determined from quantum-chemical ab initio calculations. Interaction energies for 1229 CO2-CO2 configurations were computed at the CCSD(T) level of theory using basis sets up to aug-cc-pVQZ supplemented with bond functions. An analytical site-site potential function with seven sites per CO2 molecule was fitted to the interaction energies. The PES was validated by calculating the second virial coefficient as well as viscosity and thermal conductivity in the dilute-gas limit.

  16. Thermodynamic properties of water in the lattice gas model with consideration of the vibrational motions of molecules

    NASA Astrophysics Data System (ADS)

    Titov, S. V.; Tovbin, Yu. K.

    2016-11-01

    A molecular model developed earlier for a polar fluid within the lattice gas model is supplemented by considering the vibrational motions of molecules using water as an example. A combination of point dipole and Lennard-Jones potentials from SPC parametrization is chosen as the force field model for the molecule. The main thermodynamic properties of liquid water (density, internal energy, and entropy) are studied as functions of temperature. There is qualitative agreement between the calculation results and the experimental data. Ways of refining the molecular theory are discussed.

  17. 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.

  18. 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.

  19. 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.

  20. Anomalous Enhancement of Mechanical Properties in the Ammonia Adsorbed Defective Graphene

    PubMed Central

    Ma, Fengxian; Jiao, Yalong; Gu, Yuantong; Bilic, Ante; Chen, Ying; Chen, Zhongfang; Du, Aijun

    2016-01-01

    Pure graphene is known as the strongest material ever discovered. However, the unavoidable defect formation in the fabrication process renders the strength of defective graphene much lower (~14%) than that of its perfect counterpart. By means of density functional theory computations, we systematically explored the effect of gas molecules (H2, N2, NH3, CO, CO2 and O2) adsorption on the mechanical strength of perfect/defective graphene. The NH3 molecule is found to play a dominant role in enhancing the strength of defective graphene by up to ~15.6%, while other gas molecules decrease the strength of graphene with varying degrees. The remarkable strength enhancement can be interpreted by the decomposition of NH3, which saturates the dangling bond and leads to charge redistribution at the defect site. The present work provides basic information for the mechanical failure of gas-adsorbed graphene and guidance for manufacturing graphene-based electromechanical devices. PMID:27667709

  1. Picosecond adsorbate dynamics at condensed phase interfaces

    SciTech Connect

    Scott, T.W.; Chang, Y.J.; Martorell, J.

    1993-12-31

    Picosecond surface second harmonic generation has been used to probe a variety of elementary adsorbate reactions at liquid-solid interfaces. Electron transfer reactions at semiconductor-liquid junctions, geminate recombination of photogenerated free radical pairs and the orientational dynamics of dipolar adsorbates have all been explored in varying degrees of detail. These kinetic studies have led to a detailed analysis of adsorbate detection on the surface of non-centrosymmetric substrates as well as the use of total internal reflection geometries for signal enhancement from optically absorbing liquids. Particular emphasis has been placed on the static and dynamic characterization of adsorbate orientational distribution functions and how these are determined from the torque exerted on adsorbates by the angular part of the molecule-surface interaction potential.

  2. 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.

  3. 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.

  4. 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.

  5. Database of Novel and Emerging Adsorbent Materials

    National Institute of Standards and Technology Data Gateway

    SRD 205 NIST/ARPA-E Database of Novel and Emerging Adsorbent Materials (Web, free access)   The NIST/ARPA-E Database of Novel and Emerging Adsorbent Materials is a free, web-based catalog of adsorbent materials and measured adsorption properties of numerous materials obtained from article entries from the scientific literature. Search fields for the database include adsorbent material, adsorbate gas, experimental conditions (pressure, temperature), and bibliographic information (author, title, journal), and results from queries are provided as a list of articles matching the search parameters. The database also contains adsorption isotherms digitized from the cataloged articles, which can be compared visually online in the web application or exported for offline analysis.

  6. Investigating the nature of noble gas-copper bonds by the quantum theory of atoms in molecules.

    PubMed

    Rodrigues, Eduardo F F; de Sá, Eduardo L; Haiduke, Roberto L A

    2010-04-22

    We investigated noble gas-copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy of noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

  7. Characterization of a DAPI-RIT-DAPI system for gas-phase ion/molecule and ion/ion reactions.

    PubMed

    Lin, Ziqing; Tan, Lei; Garimella, Sandilya; Li, Linfan; Chen, Tsung-Chi; Xu, Wei; Xia, Yu; Ouyang, Zheng

    2014-01-01

    The discontinuous atmospheric pressure interface (DAPI) has been developed as a facile means for efficiently introducing ions generated at atmospheric pressure to an ion trap in vacuum [e.g., a rectilinear ion trap (RIT)] for mass analysis. Introduction of multiple beams of ions or neutral species through two DAPIs into a single RIT has been previously demonstrated. In this study, a home-built instrument with a DAPI-RIT-DAPI configuration has been characterized for the study of gas-phase ion/molecule and ion/ion reactions. The reaction species, including ions or neutrals, can be introduced from both ends of the RIT through the two DAPIs without complicated ion optics or differential pumping stages. The primary reactant ions were isolated prior to reaction and the product ions were mass analyzed after controlled reaction time period. Ion/molecule reactions involving peptide radical ions and proton-transfer ion/ion reactions have been carried out using this instrument. The gas dynamic effect due to the DAPI operation on internal energy deposition and the reactivity of peptide radical ions has been characterized. The DAPI-RIT-DAPI system also has a unique feature for allowing the ion reactions to be carried out at significantly elevated pressures (in 10(-1) Torr range), which has been found to be helpful to speed up the reactions. The viability and flexibility of the DAPI-RIT-DAPI system for the study of gas-phase ion reactions have been demonstrated.

  8. Characterization of a DAPI-RIT-DAPI System for Gas-Phase Ion/Molecule and Ion/Ion Reactions

    NASA Astrophysics Data System (ADS)

    Lin, Ziqing; Tan, Lei; Garimella, Sandilya; Li, Linfan; Chen, Tsung-Chi; Xu, Wei; Xia, Yu; Ouyang, Zheng

    2014-01-01

    The discontinuous atmospheric pressure interface (DAPI) has been developed as a facile means for efficiently introducing ions generated at atmospheric pressure to an ion trap in vacuum [e.g., a rectilinear ion trap (RIT)] for mass analysis. Introduction of multiple beams of ions or neutral species through two DAPIs into a single RIT has been previously demonstrated. In this study, a home-built instrument with a DAPI-RIT-DAPI configuration has been characterized for the study of gas-phase ion/molecule and ion/ion reactions. The reaction species, including ions or neutrals, can be introduced from both ends of the RIT through the two DAPIs without complicated ion optics or differential pumping stages. The primary reactant ions were isolated prior to reaction and the product ions were mass analyzed after controlled reaction time period. Ion/molecule reactions involving peptide radical ions and proton-transfer ion/ion reactions have been carried out using this instrument. The gas dynamic effect due to the DAPI operation on internal energy deposition and the reactivity of peptide radical ions has been characterized. The DAPI-RIT-DAPI system also has a unique feature for allowing the ion reactions to be carried out at significantly elevated pressures (in 10-1 Torr range), which has been found to be helpful to speed up the reactions. The viability and flexibility of the DAPI-RIT-DAPI system for the study of gas-phase ion reactions have been demonstrated.

  9. An investigation of the interaction of intense laser radiation with molecules of sulfur hexafluoride through the buffer gas technique

    NASA Astrophysics Data System (ADS)

    Eletskii, A. V.; Klimov, V. D.; Udalova, T. A.

    1981-02-01

    Measurements of the coefficient of the absorption of intense (approximately 10 to the 7th W/sq cm) radiation from a CO2 laser by SF6 molecules in the presence of noble gases and at pressures up to 40 bars are presented. The dependence of the coefficient of absorption on the pressure and type of buffer gas, as well as on the wavelength and intensity of the incident radiation, makes it possible to follow the formation of the vibrational state distribution function of the molecules. The character of the distribution function depends on the competition between vibrational relaxation processes and laser radiation absorption. At high pressures, that is, at helium pressures greater than approximately 20-40 bars, a two-level scheme for the interaction of intense laser radiation with SF6 is implemented experimentally for the first time. Here, molecules excited by light to the v = 1 state relax instantaneously upon collision. The dependence of the rate constant for the destruction of SF6 molecular states on the number of the vibrational level v upon collision with helium atoms can be evaluated from the experimental data. Taken as a whole, the data confirm the assumption of the linear, single-photon nature of the interaction of laser radiation with SF6 molecules.

  10. 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.

  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. 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.

  13. 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.

  14. Multispectral actinometry of water and water-derivative molecules in moist, inert gas discharge plasmas

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Ochkin, V. N.; Kochetov, I. V.

    2016-10-01

    A new version of optical actinometry (OA) is used to determine the concentrations of water molecules and their fragments in hollow cathode discharge plasma in moist inert gases. Use is made of two actinometer particles, namely, the atoms Xe and Ar, for concurrent measurements of the concentrations of the H2O molecule and its fragments O, H, and OH. A self-consistent method is suggested for the determination of particle concentrations with due regard for the quenching of the emitting states. The temporal behavior of particles during discharge glow is studied. Noted are fast variations (lasting from a few to a few tens of s) in the concentrations of all the particles, followed by their stabilization (within a few to a few tens of mins). The scheme of the processes responsible for the observed dynamics of the plasma composition is discussed.

  15. Radiation and Laser Potential of Homo and Heteronuclear Rare-Gas Diatomic Molecules.

    DTIC Science & Technology

    1982-12-01

    SUPPLEMENTARY NOTES " .. . . , 19 KEy WOODS (Continue on reverse side if necessary and identify by block number) Ll Vacuum Ultraviolet Spectroscopy Rare-Gas...absorption we used the same "C. H. Chen, P. E. Siska, and Y. T. Lee, J. Chem. Phys. terminology. See G. Herzberg, Spectrs of Diatomi Mole- 5, 601

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

    DOE PAGES

    Kierspel, Thomas; Wiese, Joss; Mullins, Terry; ...

    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

  17. 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.

  18. Beams of fast neutral atoms and molecules in low-pressure gas-discharge plasma

    SciTech Connect

    Metel, A. S.

    2012-03-15

    Fast neutral atom and molecule beams have been studied, the beams being produced in a vacuum chamber at nitrogen, argon, or helium pressure of 0.1-10 Pa due to charge-exchange collisions of ions accelerated in the sheath between the glow discharge plasma and a negative grid immersed therein. From a flat grid, two broad beams of molecules with continuous distribution of their energy from zero up to e(U + U{sub c}) (where U is voltage between the grid and the vacuum chamber and U{sub c} is cathode fall of the discharge) are propagating in opposite directions. The beam propagating from the concave surface of a 0.2-m-diameter grid is focused within a 10-mm-diameter spot on the target surface. When a 0.2-m-diameter 0.2-m-high cylindrical grid covered by end disks and composed of parallel 1.5-mm-diameter knitting needles spaced by 4.5 mm is immersed in the plasma, the accelerated ions pass through the gaps between the needles, turn inside the grid into fast atoms or molecules, and escape from the grid through the gaps on its opposite side. The Doppler shift of spectral lines allows for measuring the fast atom energy, which corresponds to the potential difference between the plasma inside the chamber and the plasma produced as a result of charge-exchange collisions inside the cylindrical grid.

  19. 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.

  20. Quantum Engineering of a Low-Entropy Gas of Heteronuclear Bosonic Molecules in an Optical Lattice

    NASA Astrophysics Data System (ADS)

    Reichsöllner, Lukas; Schindewolf, Andreas; Takekoshi, Tetsu; Grimm, Rudolf; Nägerl, Hanns-Christoph

    2017-02-01

    We demonstrate a generally applicable technique for mixing two-species quantum degenerate bosonic samples in the presence of an optical lattice, and we employ it to produce low-entropy samples of ultracold Rb 87 Cs 133 Feshbach molecules with a lattice filling fraction exceeding 30%. Starting from two spatially separated Bose-Einstein condensates of Rb and Cs atoms, Rb-Cs atom pairs are efficiently produced by using the superfluid-to-Mott insulator quantum phase transition twice, first for the Cs sample, then for the Rb sample, after nulling the Rb-Cs interaction at a Feshbach resonance's zero crossing. We form molecules out of atom pairs and characterize the mixing process in terms of sample overlap and mixing speed. The dense and ultracold sample of more than 5000 RbCs molecules is an ideal starting point for experiments in the context of quantum many-body physics with long-range dipolar interactions.

  1. Photophysics of sunscreen molecules in the gas phase: a stepwise approach towards understanding and developing next-generation sunscreens

    PubMed Central

    Rodrigues, Natércia D. N.; Staniforth, Michael

    2016-01-01

    The relationship between exposure to ultraviolet (UV) radiation and skin cancer urges the need for extra photoprotection, which is presently provided by widespread commercially available sunscreen lotions. Apart from having a large absorption cross section in the UVA and UVB regions of the electromagnetic spectrum, the chemical absorbers in these photoprotective products should also be able to dissipate the excess energy in a safe way, i.e. without releasing photoproducts or inducing any further, harmful, photochemistry. While sunscreens are tested for both their photoprotective capability and dermatological compatibility, phenomena occurring at the molecular level upon absorption of UV radiation are largely overlooked. To date, there is only a limited amount of information regarding the photochemistry and photophysics of these sunscreen molecules. However, a thorough understanding of the intrinsic mechanisms by which popular sunscreen molecular constituents dissipate excess energy has the potential to aid in the design of more efficient, safer sunscreens. In this review, we explore the potential of using gas-phase frequency- and time-resolved spectroscopies in an effort to better understand the photoinduced excited-state dynamics, or photodynamics, of sunscreen molecules. Complementary computational studies are also briefly discussed. Finally, the future outlook of expanding these gas-phase studies into the solution phase is considered. PMID:27956888

  2. Photophysics of sunscreen molecules in the gas phase: a stepwise approach towards understanding and developing next-generation sunscreens

    NASA Astrophysics Data System (ADS)

    Rodrigues, Natércia D. N.; Staniforth, Michael; Stavros, Vasilios G.

    2016-11-01

    The relationship between exposure to ultraviolet (UV) radiation and skin cancer urges the need for extra photoprotection, which is presently provided by widespread commercially available sunscreen lotions. Apart from having a large absorption cross section in the UVA and UVB regions of the electromagnetic spectrum, the chemical absorbers in these photoprotective products should also be able to dissipate the excess energy in a safe way, i.e. without releasing photoproducts or inducing any further, harmful, photochemistry. While sunscreens are tested for both their photoprotective capability and dermatological compatibility, phenomena occurring at the molecular level upon absorption of UV radiation are largely overlooked. To date, there is only a limited amount of information regarding the photochemistry and photophysics of these sunscreen molecules. However, a thorough understanding of the intrinsic mechanisms by which popular sunscreen molecular constituents dissipate excess energy has the potential to aid in the design of more efficient, safer sunscreens. In this review, we explore the potential of using gas-phase frequency- and time-resolved spectroscopies in an effort to better understand the photoinduced excited-state dynamics, or photodynamics, of sunscreen molecules. Complementary computational studies are also briefly discussed. Finally, the future outlook of expanding these gas-phase studies into the solution phase is considered.

  3. Is there a difference in van der Waals interactions between rare gas atoms adsorbed on metallic and semiconducting single-walled carbon nanotubes?

    PubMed

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

    2013-03-29

    The differences in the 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 that the binding energies of Xe adsorbed on M- and S-SWNTs are nearly identical. Temperature programed desorption experiments 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 density functional theory are in good agreement with experiments.

  4. 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.

  5. 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

    2015-09-04

    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

  6. Neutralization of solvated protons and formation of noble-gas hydride molecules: Matrix-isolation indications of tunneling mechanisms?

    SciTech Connect

    Khriachtchev, Leonid; Lignell, Antti; Raesaenen, Markku

    2005-08-08

    The (NgHNg){sup +} cations (Ng=Ar and Kr) produced via the photolysis of HF/Ar, HF/Kr, and HBr/Kr solid mixtures are studied, with emphasis on their decay mechanisms. The present experiments provide a large variety of parameters connected to this decay phenomenon, which allows us to reconsider various models for the decay of the (NgHNg){sup +} cations in noble-gas matrices. As a result, we propose that this phenomenon could be explained by the neutralization of the solvated protons by electrons. The mechanism of this neutralization reaction probably involves tunneling of an electron from an electronegative fragment or another trap to the (NgHNg){sup +} cation. The proposed electron-tunneling mechanism should be considered as a possible alternative to the literature models based on tunneling-assisted or radiation-induced diffusion of protons in noble-gas solids. As a novel experimental observation of this work, the efficient formation of HArF molecules occurs at 8 K in a photolyzed HF/Ar matrix. It is probable that the low-temperature formation of HArF involves local tunneling of the H atom to the Ar-F center, which in turn supports the locality of HF photolysis in solid Ar. In this model, the decay of (ArHAr){sup +} ions and the formation of HArF molecules observed at low temperatures are generally unconnected processes; however, the decaying (ArHAr){sup +} ions may contribute to some extent to the formation of HArF molecules.

  7. Gas phase chemical kinetics at high temperature of carbonaceous molecules: application to circumstellar envelopes

    NASA Astrophysics Data System (ADS)

    Biennier, L.; Gardez, A.; Saidani, G.; Georges, R.; Rowe, B.; Reddy, K. P. J.

    2011-05-01

    Circumstellar shells of evolved stars are a theater of extremely rich physical and chemical processes. More than seventy molecules of varied nature have been identified in the envelopes through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals and a significant number are unique to the circumstellar medium. However, observational data remain scarce and more than half of the detected species have been observed in only one object, the nearby carbon star IRC + 10216. Chemical kinetic models are needed to describe the formation of molecules in evolved circumstellar outflows. Upcoming terrestrial telescopes such as ALMA will increase the spatial resolution by several orders of magnitude and provide a wealth of data. The determination of relevant laboratory kinetics data is critical to keep up with the development of the observations and of the refinement of chemical models. Today, the majority of reactions studied in the laboratory are the ones involved in combustion and concerning light hydrocarbons. Our objective is to provide the scientific community with rate coefficients of reactions between abundant species in these warm environments. Cyanopolyynes from HC_2N to HC_9N have all been detected in carbon rich circumstellar envelopes in up to 10 sources for HC_3N. Neutral-neutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures. Our approach aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high enthalpy source (Moudens et al. 2011) with a flow tube and a pulsed laser photolysis and laser induced fluorescence system to probe the undergoing chemical reactions. The high enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane, propene

  8. 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.

  9. Gas Separation Membranes Derived from High-Performance Immiscible Polymer Blends Compatibilized with Small Molecules.

    PubMed

    Panapitiya, Nimanka P; Wijenayake, Sumudu N; Nguyen, Do D; Huang, Yu; Musselman, Inga H; Balkus, Kenneth J; Ferraris, John P

    2015-08-26

    An immiscible polymer blend comprised of high-performance copolyimide 6FDA-DAM:DABA(3:2) (6FDD) and polybenzimidazole (PBI) was compatibilized using 2-methylimidazole (2-MI), a commercially available small molecule. Membranes were fabricated from blends of 6FDD:PBI (50:50) with and without 2-MI for H2/CO2 separations. The membranes demonstrated a matrix-droplet type microstructure as evident with scanning electron microscopy (SEM) imaging where 6FDD is the dispersed phase and PBI is the continuous phase. In addition, membranes with 2-MI demonstrated a uniform microstructure as observed by smaller and more uniformly dispersed 6FDD domains in contrast to 6FDD:PBI (50:50) blend membranes without 2-MI. This compatibilization effect of 2-MI was attributed to interfacial localization of 2-MI that lowers the interfacial energy similar to a surfactant. Upon the incorporation of 2-MI, the H2/CO2 selectivity improved remarkably, compared to the pure blend, and surpassed the Robeson's upper bound. To our knowledge, this is the first report of the use of a small molecule to compatibilize a high-performance immiscible polymer blend. This approach could afford a novel class of membranes in which immiscible polymer blends can be compatibilized in an economical and convenient fashion.

  10. 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.

  11. 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.

  12. Interactions of molecules with HCl in the gas and matrix phases

    NASA Astrophysics Data System (ADS)

    George, W. O.; Lewis, Rh.; Hussain, G.; Rees, G. J.

    1988-10-01

    The FT-IR spectra of mixtures of HCl and the following compounds have been recorded in the gaseous and matrix isolated phases: argon, ethene, ethyne, d 6-benzene, fluorobenzene, CO, CO 2, SO 2, CCl 4, CHCl 3, d 6-acetone, ethanal, HCN, acrylonitrile. The features which are measured are: firstly the changes in the integrated intensity of lines in the rotation—vibration spectrum of the fundamental HCl band as a function of non-specific interactions with other components of the mixture and secondly bands associated with specific interactions forming hydrogen bonded complexes in the gas and matrix isolated phases. The relationship between the two kinds of interactions is discussed.

  13. Gas-phase Reactions of Polycyclic Aromatic Hydrocarbon Anions with Molecules of Interstellar Relevance

    NASA Astrophysics Data System (ADS)

    Demarais, Nicholas J.; Yang, Zhibo; Martinez, Oscar; Wehres, Nadine; Snow, Theodore P.; Bierbaum, Veronica M.

    2012-02-01

    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 (C6H- 5), naphthalenide (C10H- 7), and anthracenide (C14H- 9) with atomic H, H2, and D2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O2, CO2, N2O, C2H2, CH3OH, CH3CN, (CH3)2CO, CH3CHO, CH3Cl, and (CH3CH2)2O) 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.

  14. Molecular structure and the EPR calculation of the gas phase succinonitrile molecule

    NASA Astrophysics Data System (ADS)

    Kepceoǧlu, A.; Kılıç, H. Ş.; Dereli, Ö.

    2017-02-01

    Succinonitrile (i.e. butanedinitrile) is a colorless nitrile compound that can be used in the gel polymer batteries as a solid-state solvent electrolytes and has a plastic crystal structure. Prior to the molecular structure calculation of the succinonitrile molecule, the conformer analysis were calculated by using semi empirical method PM3 core type Hamiltonian and eight different conformer structures were determined. Molecular structure with energy related properties of these conformers having the lowest energy was calculated by using DFT (B3LYP) methods with 6-311++G(d,p) basis set. Possible radicals, can be formed experimentally, were modeled in this study. EPR parameters of these model radicals were calculated and then compared with that obtained experimentally.

  15. Far-infrared permanent and induced dipole absorption of diatomic molecules in rare-gas fluids. I. Spectral theory

    NASA Astrophysics Data System (ADS)

    Roco, J. M. M.; Hernández, A. Calvo; Velasco, S.

    1995-12-01

    We present a spectral theory for the far-infrared absorption spectrum of a very diluted solution of diatomic molecules in a rare-gas fluid, that includes permanent and induced contributions. The absorption coefficient is given as the convolution of a translational spectrum and a rotational spectrum. The former is described in terms of time correlation functions associated to the induced dipole moment. The latter is discussed on the basis of a model consisting of a quantum rigid rotor interacting with a thermal bath, making use of time correlation functions associated to the different anisotropic orders of the solute-solvent intermolecular potential. Non-Markovian and line mixing effects are taken into account. Explicit expressions for the five leading contributions of the induced dipole moment are given.

  16. 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.

  17. 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.

  18. Use of inverse gas chromatography to characterize cotton fabrics and their interactions with fragrance molecules at controlled relative humidity.

    PubMed

    Cantergiani, Ennio; Benczédi, Daniel

    2002-09-06

    The present work focused on the surface characterization and fragrance interactions of a common cotton towel at different relative humidities (RHs) using inverse gas chromatography (IGC) and dynamic vapour sorption. The sigmoidal water sorption isotherms showed a maximum of 16% (w/w) water uptake with limited swelling at 100% RH. This means that water interacts strongly with cotton and might change its initial physico-chemical properties. The same cotton towel was then packed in a glass column and characterized by IGC at different relative humidities, calculating the dispersive and specific surface energy components. The dispersive component of the surface energy decreases slightly as a function of relative humidity (42 mJ/m2 at 0% RH to 36 mJ/m2 at 80% RH) which would be expected from swelling of the humidified cotton. The Gutmann's donor constant Kd increased from 0.28 kJ/mol at 0% RH to 0.42 kJ/mol at 80% RH, indicating that a greater hydrophilic surface exists at 80% RH, which is also as expected. Water, undecane and four fragrance molecules (dimetol, benzyl acetate, decanal and phenylethanol) were used to investigate cotton-fragrance interactions between 0 and 80% RH. The adsorption enthalpies and the Henry's constants were calculated and are discussed. The higher values for the adsorption enthalpies of polar molecules such as dimetol and phenylethanol suggest the presence of hydrogen bonds as the main adsorption mechanism. The Henry's constant of dimetol was also determined by headspace gas chromatography measurements at 20% RH, giving a similar value (230 nmol/Pa g by IGC and 130 nmol/Pa g by headspace GC), supporting the usefulness of IGC for such determinations. This work confirms the usefulness of chromatographic methods to investigate biopolymers such as textiles, starches and hairs.

  19. 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

    2015-08-07

    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.

  20. 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.

  1. Absorption into fluorescence. A method to sense biologically relevant gas molecules

    NASA Astrophysics Data System (ADS)

    Strianese, Maria; Varriale, Antonio; Staiano, Maria; Pellecchia, Claudio; D'Auria, Sabato

    2011-01-01

    In this work we present an innovative optical sensing methodology based on the use of biomolecules as molecular gating nano-systems. Here, as an example, we report on the detection ofanalytes related to climate change. In particular, we focused our attention on the detection ofnitric oxide (NO) and oxygen (O2). Our methodology builds on the possibility of modulating the excitation intensity of a fluorescent probe used as a transducer and a sensor molecule whose absorption is strongly affected by the binding of an analyte of interest used as a filter. The two simple conditions that have to be fulfilled for the method to work are: (a) the absorption spectrum of the sensor placed inside the cuvette, and acting as the recognition element for the analyte of interest, should strongly change upon the binding of the analyte and (b) the fluorescence dye transducer should exhibit an excitation band which overlaps with one or more absorption bands of the sensor. The absorption band of the sensor affected by the binding of the specific analyte should overlap with the excitation band of the transducer. The high sensitivity of fluorescence detection combined with the use of proteins as highly selective sensors makes this method a powerful basis for the development of a new generation of analytical assays. Proof-of-principle results showing that cytochrome c peroxidase (CcP) for NO detection and myoglobin (Mb) for O2 detection can be successfully used by exploiting our new methodology are reported. The proposed technology can be easily expanded to the determination of different target analytes.

  2. Absorption into fluorescence. A method to sense biologically relevant gas molecules.

    PubMed

    Strianese, Maria; Varriale, Antonio; Staiano, Maria; Pellecchia, Claudio; D'Auria, Sabato

    2011-01-01

    In this work we present an innovative optical sensing methodology based on the use of biomolecules as molecular gating nano-systems. Here, as an example, we report on the detection of analytes related to climate change. In particular, we focused our attention on the detection of nitric oxide (NO) and oxygen (O2). Our methodology builds on the possibility of modulating the excitation intensity of a fluorescent probe used as a transducer and a sensor molecule whose absorption is strongly affected by the binding of an analyte of interest used as a filter. The two simple conditions that have to be fulfilled for the method to work are: (a) the absorption spectrum of the sensor placed inside the cuvette, and acting as the recognition element for the analyte of interest, should strongly change upon the binding of the analyte and (b) the fluorescence dye transducer should exhibit an excitation band which overlaps with one or more absorption bands of the sensor. The absorption band of the sensor affected by the binding of the specific analyte should overlap with the excitation band of the transducer. The high sensitivity of fluorescence detection combined with the use of proteins as highly selective sensors makes this method a powerful basis for the development of a new generation of analytical assays. Proof-of-principle results showing that cytochrome c peroxidase (CcP) for NO detection and myoglobin (Mb) for O2 detection can be successfully used by exploiting our new methodology are reported. The proposed technology can be easily expanded to the determination of different target analytes.

  3. 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

  4. Evaluation of Chemical Interactions between Small Molecules in the Gas Phase Using Chemical Force Microscopy.

    PubMed

    Lee, Jieun; Ju, Soomi; Kim, In Tae; Jung, Sun-Hwa; Min, Sun-Joon; Kim, Chulki; Sim, Sang Jun; Kim, Sang Kyung

    2015-12-04

    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.

  5. 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.

  6. Interaction energy and itinerant ferromagnetism in a strongly interacting Fermi gas in the absence of molecule formation

    DOE PAGES

    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

  7. Energy gap modulation in V2O5 nanowires by gas adsorption

    NASA Astrophysics Data System (ADS)

    Kim, Byung Hoon; Kim, Ansoon; Oh, Soon-Young; Bae, Sung-Soo; Yun, Yong Ju; Yu, Han Young

    2008-12-01

    The current-voltage characteristics at various pressures (2-10 atm) and the scanning tunneling microscopy of vanadium pentoxide nanowires (VONs) with the inert gases (He, Ne, and Ar) and diatomic molecules (H2,N2, O2) have been investigated. The gas dependent conductance (G) is consistent with the inverse energy gap obtained from the scanning tunneling spectroscopy study for the gas-adsorbed single VON. The three possible interactions for gas adsorption of the VON have been discussed. Among them, we have found that the induced dipole-dipole interaction between adsorbed gases plays an important role in conductance variation in the gas adsorbed VON using the conductance per molecule (G /N).

  8. 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.

  9. 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.

  10. Effects of London dispersion correction in density functional theory on the structures of organic molecules in the gas phase.

    PubMed

    Grimme, Stefan; Steinmetz, Marc

    2013-10-14

    A benchmark set of 25 rotational constants measured in the gas phase for nine molecules (termed ROT25) was compiled from available experimental data. The medium-sized molecules with 18-35 atoms cover common (bio)organic structure motifs including hydrogen bonding and flexible side chains. They were each considered in a single conformation. The experimental B0 values were back-corrected to reference equilibrium rotational constants (Be) by computation of the vibrational corrections ΔBvib. Various density functional theory (DFT) methods and Hartree-Fock with and without dispersion corrections as well as MP2 type methods and semi-empirical quantum chemical approaches are investigated. The ROT25 benchmark tests their ability to describe covalent bond lengths, longer inter-atomic distances, and the relative orientation of functional groups (intramolecular non-covalent interactions). In general, dispersion corrections to DFT and HF increase Be values (shrink molecular size) significantly by about 0.5-1.5% thereby in general improving agreement with the reference data. Regarding DFT methods, the overall accuracy of the optimized structures roughly follows the 'Jacobs ladder' classification scheme, i.e., it decreases in the series double-hybrid > (meta)hybrid > (meta)GGA > LDA. With B2PLYP-D3, SCS-MP2, B3LYP-D3/NL, or PW6B95-D3 methods and extended QZVP (def2-TZVP) AO basis sets, Be values, accurate to about 0.3-0.6 (0.5-1)% on average, can be computed routinely. The accuracy of B2PLYP-D3/QZVP with a mean deviation of only 3 MHz and a standard deviation of 0.24% is exceptional and we recommend this method when highly accurate structures are required or for problematic conformer assignments. The correlation effects for three inter-atomic distance regimes (covalent, medium-range, long) and the performance of minimal basis set (semi-empirical) methods are discussed.

  11. Effect of Solvent Molecule in Pore for Flexible Porous Coordination Polymer upon Gas Adsorption and Iodine Encapsulation.

    PubMed

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat; Demiral, Hakan

    2015-12-07

    Four new Zn(II)-coordination polymers, namely, [Zn2(μ6-ao2btc)(μ-obix)2]n (1), [Zn2(μ4-ao2btc)(μ-obix)2]n (2), [Zn2(μ4-ao2btc)(μ-mbix)2]n (3), and {[Zn2(μ4-ao2btc)(μ-pbix)2] · 2DMF · 8H2O}n (4), where ao2btc = dioxygenated form of 3,3',5,5'-azobenzenetetracarboxylate and obix, mbix, and pbix = 1,2-, 1,3-, and 1,4-bis(imidazol-1-ylmethyl)benzene, have been synthesized with azobenzenetetracarboxylic acid and isomeric bis(imidazole) ligands and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analyses. X-ray results showed that 1, 2, and 4 had two-dimensional structures with 3,4L13 topology, while 3 was a three-dimensional coordination polymer with bbf topology. For 4, two types of activation strategies, solvent exchange + heating (which produced 4a) and direct heating (which produced 4b), were used to investigate the effect of a guest molecule in a flexible framework. Gas adsorption and iodine encapsulation properties of activated complexes were studied. The CO2 uptake capacities for 4a and 4b were 3.62% and 9.50%, respectively, and Langmuir surface areas calculated from CO2 isotherms were 167.4 and 350.7 m(2)/g, respectively. Moreover, 4b exhibited 19.65% and 15.27% iodine uptake in vapor phase and cyclohexane solution, respectively, which corresponded to 1.47 and 0.97 molecules of iodine/formula unit, respectively. Moreover, photoluminescence properties of the complexes were studied.

  12. Hemoglobin: a gas transport molecule that is hormonally regulated in the ovarian follicle in mice and humans.

    PubMed

    Brown, Hannah M; Anastasi, Marie R; Frank, Laura A; Kind, Karen L; Richani, Dulama; Robker, Rebecca L; Russell, Darryl L; Gilchrist, Robert B; Thompson, Jeremy G

    2015-01-01

    An increasing number of nonerythroid tissues are found to express hemoglobin mRNA and protein. Hemoglobin is a well-described gas transport molecule, especially for O2, but also for NO, CO2, and CO, and also acts as a reactive oxygen species scavenger. We previously found Hba-a1 and Hbb mRNA and protein at high levels within mouse periovulatory cumulus cells, but not in cumulus following in vitro maturation. This led us to investigate the temporal and spatial regulation in follicular cells during the periovulatory period. Cumulus-oocyte complexes were collected from equine chorionic gonadotropin/human chorionic gonadotropin-treated peripubertal SV129 female mice and collected and analyzed for gene expression and protein localization at a variety of time points over the periovulatory period. A further cohort matured in vitro with different forms of hemoglobin (ferro- and ferrihemoglobin) under different O2 atmospheric conditions (2%, 5%, and 20% O2) were subsequently fertilized in vitro and cultured to the blastocyst stage. Murine mRNA transcripts for hemoglobin were regulated by stimulation of the ovulatory cascade, in both granulosa and cumulus cells, and expression of HBA1 and HBB was highly significant in human granulosa and cumulus, but erythrocyte cell marker genes were not. Several other genes involved in hemoglobin function were similarly luteinizing hormone-regulated, including genes for heme biosynthesis. Immunohistochemistry revealed a changing localization pattern of HBA-A1 protein in murine cumulus cells and oocytes following the ovulatory signal. Significantly, no positive staining for HBA-A1 protein was observed within in vitro-matured oocytes, but, if coincubated with ferro- or ferrihemoglobin, cytoplasmic HBA-A1 was observed, similar to in vivo-derived oocytes. Addition of ferro-, but not ferrihemoglobin, had a small, positive effect on blastocyst yield, but only under either 2% or 20% O2 gas atmosphere. The identification of hemoglobin within

  13. [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.

  14. Time Resolved Studies Of Adsorbed Species

    NASA Astrophysics Data System (ADS)

    Howard, J.; Nicol, J. M.

    1985-12-01

    A time-resolved Fourier transform IR study of ethyne adsorbed on ZnNaA zeolite yields results very different from those reported for related systems. Initially two species (A and B) are formed by the interaction of C2H2 with the cations. Whereas species A (π-bonded C2H2) was found to be removed immediately on evacuation, species B (probably Zn-acetylide) was not fully removed after 60 mins evacuation. In the presence of the gas phase, bands due to Species A decreased slowly in intensity as new bands due to adsorbed ethanal were observed.

  15. The reactivity of CO2 with K atoms adsorbed on MgO powders.

    PubMed

    Preda, Gloria; Pacchioni, Gianfranco; Chiesa, Mario; Giamello, Elio

    2009-10-01

    In this combined quantum chemical and EPR study we have investigated the formation of CO(2)(-) radicals by contact of CO(2) molecules with a K precovered MgO surface. K atoms have been deposited on polycrystalline MgO samples, and then exposed to CO(2). The typical EPR signal of the isolated K atoms disappears when the reaction with CO(2) takes place and a new paramagnetic species attributed to CO(2)(-) is observed. DFT cluster model calculations show that there is a spontaneous electron transfer from the adsorbed K atom to the CO(2) molecule, with formation of K(+)CO(2)(-) surface complexes. These species have the same electronic characteristics and spin distribution of gas-phase M(+)CO(2)(-) (M = Li, Na, K) molecules, but are stabilized by the presence of the ionic surface. The most stable MgO sites where the adsorption of CO(2) occurs and the computed EPR properties are discussed.

  16. Infrared Spectroscopy of Gas-Phase M(+)(CO2)n (M = Co, Rh, Ir) Ion-Molecule Complexes.

    PubMed

    Iskra, Andreas; Gentleman, Alexander S; Kartouzian, Aras; Kent, Michael J; Sharp, Alastair P; Mackenzie, Stuart R

    2017-01-12

    The structures of gas-phase M(+)(CO2)n (M = Co, Rh, Ir; n = 2-15) ion-molecule complexes have been investigated using a combination of infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy and density functional theory. The results provide insight into fundamental metal ion-CO2 interactions, highlighting the trends with increasing ligand number and with different group 9 ions. Spectra have been recorded in the region of the CO2 asymmetric stretch around 2350 cm(-1) using the inert messenger technique and their interpretation has been aided by comparison with simulated infrared spectra of calculated low-energy isomeric structures. All vibrational bands in the smaller complexes are blue-shifted relative to the asymmetric stretch in free CO2, consistent with direct binding to the metal center dominated by charge-quadrupole interactions. For all three metal ions, a core [M(+)(CO2)2] structure is identified to which subsequent ligands are less strongly bound. No evidence is observed in this size regime for complete activation or insertion reactions.

  17. 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.

  18. 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.

  19. Collision-induced migration of adsorbates on solid surfaces: an experimental approach.

    PubMed

    Danziger, I M; Asscher, M

    2006-07-13

    Collision-induced migration (CIM) is a process in which energetic gas-phase atoms or molecules at the tail of the Boltzmann distribution enhance surface migration of adsorbates upon collision. It is believed to exist and play an important role in any realistic high pressure-high-temperature heterogeneous catalytic system. Combining supersonic beam-surface collision setup with in-situ optical second harmonic generation diffraction technique from a coverage grating, we have shown, for the first time, that indeed energetic collisions (Kr seeded in He) promote surface mobility of CO-K surface complex on Ru(001) with a threshold total kinetic energy of 3 eV. An average migration distance/collision of more than 30 adsorption sites was estimated from the experimental data at Kr total energy of 3.8 eV. This long-range migration distance per collision is understood in terms of a cascade migration mechanism, where adsorbed CO molecules collide and push their neighbors from high to low coverage areas, in a direction dictated by the collision momentum vector. A similar mechanism has recently been suggested to explain adsorbate mobility at high coverage induced by an STM tip.

  20. 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.

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

    PubMed

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

    2016-06-15

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

  2. 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

  3. 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.

  4. 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.

  5. Solid phase extraction with silicon dioxide microsphere adsorbents in combination with gas chromatography-electron capture detection for the determination of DDT and its metabolites in water samples.

    PubMed

    Zhou, Qingxiang; Wu, Wei; Xie, Guohong

    2013-01-01

    The goal of the present study was to investigate the feasibility of silicon dioxide (SiO(2)) microspheres without special modification to enrich dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p'-dichlorodiphenyl-2,2-dichloroethylene (p,p'-DDD) and p,p'-dichlorodiphenyldichloroethylene (DDE) in combination with gas chromatography-electron-capture detection. The experimental results indicated that an excellent linear relationship between the recoveries and the concentrations of DDT and its main metabolites was obtained in the range of 0.2-30 ng mL(-1) and the correlation coefficients were in the range of 99.96-99.99%. The detection limits based on the ratio of signal to the baseline noise (S/N = 3) were 2.2, 2.9, 3.8 and 4.1 ng L(-1) for p,p'-DDD, p,p'-DDT, o,p'-DDT, and p,p'-DDE, respectively. The precisions of the proposed method were all below 10% (n = 6). Four real water samples were utilized for validation of the proposed method, and satisfactory spiked recoveries in the range of 72.4-112.9% were achieved. These results demonstrated that the developed method was a simple, sensitive, and robust analytical method for the monitoring of pollutants in the environment.

  6. Luminescence characteristics of Xe{sub 2}Cl excimer molecules under pumping the dense Xe-CCl{sub 4} gas mixtures with a pulsed electron beam

    SciTech Connect

    Mis'kevich, A I; Jinbo, Guo

    2013-05-31

    Temporal and spectral characteristics of the luminescence of dense Xe-CCl{sub 4} gas mixtures of different composition, excited by a 5-ns pulsed electron beam, were measured. The energy of the electrons amounted to 150 keV and the electron beam current pulse amplitude was 5 A. The gas mixtures were used containing Xe (38-700 Torr) and CCl{sub 4} (0.03-0.3 Torr). The studies were performed within the wavelength range 200-1200 nm using a MAYA-2000Pro diffraction grating spectrometer and a RIGOL DS 5022 ME fast digital oscilloscope. The luminescence lifetimes of the excimer molecules XeCl* (band with {lambda}{sub max} = 308 nm) and Xe{sub 2}Cl* (band with {lambda}{sub max} = 486 nm) were measured, as well as the constants of quenching by the components of the gas mixture for Xe{sub 2}Cl* molecules. A model of plasma-chemical processes for dense Xe-CCl{sub 4} gas mixtures with a very low content of the CCl{sub 4} donor is proposed. It is shown that in such 'poor' mixtures Xe{sub 2}Cl* molecules are mainly produced as a result of recombination of the Xe{sub 2}{sup +} and Cl{sup -} ions. (active media)

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

    DOEpatents

    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.

  8. 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 ...

  9. 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.

  10. Gas-phase infrared and ab initio study of the unstable CF3CNO molecule and its stable furoxan ring dimer.

    PubMed

    Havasi, Balázs; Pasinszki, Tibor; Westwood, Nicholas P C

    2005-05-05

    The unstable trifluoroacetonitrile N-oxide molecule, CF3CNO, has been generated in high yield in the gas phase from CF3BrC=NOH and studied for the first time by gas-phase mid-infrared spectroscopy. Cold trapping of this molecule followed by slow warming forms the stable ring dimer, bis(trifluoromethyl)furoxan, also investigated by gas-phase infrared spectroscopy. The spectroscopy provides an investigation into the vibrational character of the two molecules, the assignments supported by calculations of the harmonic vibrational frequencies using in the case of CF3CNO both ab initio (CCSD(T)) and density functional theory (B3LYP) and B3LYP for the ring dimer. The ground-state structures of both molecules were investigated at the B3LYP level of theory, with CF3CNO further investigated using coupled-cluster. The CCSD(T) method suggests a slightly bent (C(s)) structure for CF3CNO, while the B3LYP method (with basis sets ranging from 6-311G(d) to cc-pVTZ) suggests a close-to-linear or linear CCNO chain. The CCN bending potential in CF3CNO was explored at the CCSD(T)(fc)/cc-pVTZ level, with the results suggesting that CF3CNO exhibits strong quasi-symmetric top behavior with a barrier to linearity of 174 cm(-1). Since both isomerization and dimerization are feasible loss processes for this unstable molecule, the relative stability of CF3CNO with respect to the known cyanate (CF3OCN), isocyanate (CF3NCO), and fulminate (CF3ONC) isomers and the mechanism of the dimerization process to the ring furoxan and other isomers were studied with density functional theory.

  11. 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…

  12. Determination of local concentration of H2O molecules and gas temperature in the process of hydrogen - oxygen gas mixture heating by means of linear and nonlinear laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Kozlov, D. N.; Kobtsev, V. D.; Stel'makh, O. M.; Smirnov, Valery V.; Stepanov, E. V.

    2013-01-01

    Employing the methods of linear absorption spectroscopy and nonlinear four-wave mixing spectroscopy using laserinduced gratings we have simultaneously measured the local concentrations of H2O molecules and the gas temperature in the process of the H2 - O2 mixture heating. During the measurements of the deactivation rates of pulsed-laser excited singlet oxygen O2 (b 1Σ+g) in collisions with H2 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, H2O molecules are formed by 'dark' reactions of H2 with O2 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 H2O concentration in the O2 laser excitation volume, if the gas temperature in this volume is known. When studying the collisional deactivation of O2 (b 1Σ+g) molecules, the necessary measurements of the local temperature can be implemented using laser-induced gratings, arising due to spatially periodic excitation of O2 (X3Σ-g) molecules to the b 1Σ+g state by radiation of the pump laser of the four-wave mixing spectrometer.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Kronecker-product periodic systems of small gas-phase molecules and the search for order in atomic ensembles of any phase.

    PubMed

    Hefferlin, Ray

    2008-11-01

    The periodic law, manifested in the chart of the elements, is so fundamental in chemistry and related areas of physics that the question arises "Might periodicity among molecules also be embodied in a periodic system?" This review paper details how a particular periodic system of gas-phase diatomic molecules, allowing for the forecasting of thousands of new data, was developed. It can include ionized and even quarked-nuclei molecules and it coincides with locality (averaging) and the additivity found in some data; it has interesting vector properties, and it may be related in challenging ways to partial order. The review then explains how periodic systems for triatomic and four-atomic species are evolving along a similar path. The systems rest largely upon exhaustive comparisons of tabulated data, relate to some extent to the octet rule, and include reducible representations of the dynamic group SO(4) in higher spaces. Finally, the paper shows how periodicity can be quantified in data for larger molecules. Data for properties of homologous or substituted molecules, in any phase, are quantified with a vector index, and the index for one set can be transformed into that for another set.

  18. Ab-initio investigation of adsorption of CO and CO2 molecules on graphene: Role of intrinsic defects on gas sensing

    NASA Astrophysics Data System (ADS)

    Tit, Nacir; Said, Khadija; Mahmoud, Nadin M.; Kouser, Summayya; Yamani, Zain H.

    2017-02-01

    We determine the chemical activity of (a) carbon site of pristine graphene (pG), (b) Stone-Wales (SW) defect site, and (c) Single-vacancy of graphene (vG) site towards the adsorption of CO and CO2 molecules, through comparative analysis based on first-principles density-functional calculations incorporating van der Waals (vdW) interactions, but excluding the heat effects (i.e., at T = 0 °K). The results show that the chemisorption of both latter molecules to possibly occur only on vG. The response (sensitivity) of vG towards detecting CO molecule was confirmed by the rise of conductance with the increasing CO gas dose. The selectivity was investigated by testing the response of vG towards detecting eight different gases (i.e., CO, CO2, N2, O2, H2O, H2S, H2, and NH3). Three gases are found to exhibit physisorption (namely: N2, H2O, and H2S) and the other five gases alter chemisorption (namely: CO, CO2, O2, H2, and NH3). The chemisorption of CO molecule is distinct by being direct and not involving dissociation. This fact made defected graphene have the highest sensitivity and selectivity towards the detection of CO molecules.

  19. Recent advances in experimental techniques to probe fast excited-state dynamics in biological molecules in the gas phase: dynamics in nucleotides, amino acids and beyond

    PubMed Central

    Staniforth, Michael; Stavros, Vasilios G.

    2013-01-01

    In many chemical reactions, an activation barrier must be overcome before a chemical transformation can occur. As such, understanding the behaviour of molecules in energetically excited states is critical to understanding the chemical changes that these molecules undergo. Among the most prominent reactions for mankind to understand are chemical changes that occur in our own biological molecules. A notable example is the focus towards understanding the interaction of DNA with ultraviolet radiation and the subsequent chemical changes. However, the interaction of radiation with large biological structures is highly complex, and thus the photochemistry of these systems as a whole is poorly understood. Studying the gas-phase spectroscopy and ultrafast dynamics of the building blocks of these more complex biomolecules offers the tantalizing prospect of providing a scientifically intuitive bottom-up approach, beginning with the study of the subunits of large polymeric biomolecules and monitoring the evolution in photochemistry as the complexity of the molecules is increased. While highly attractive, one of the main challenges of this approach is in transferring large, and in many cases, thermally labile molecules into vacuum. This review discusses the recent advances in cutting-edge experimental methodologies, emerging as excellent candidates for progressing this bottom-up approach. PMID:24204191

  20. Multi-walled carbon nanotubes as solid-phase extraction adsorbents for determination of atrazine and its principal metabolites in water and soil samples by gas chromatography-mass spectrometry.

    PubMed

    Min, Guang; Wang, Shuo; Zhu, Huaping; Fang, Guozhen; Zhang, Yan

    2008-06-15

    A novel, simple, cost-effective, and sensitive method was developed for the determination of atrazine and its principal metabolites namely deisopropyl-atrazine (DIA) and deethyl-atrazine (DEA) in water and soil samples using multi-walled carbon nanotubes as solid-phase extraction (SPE) adsorbents coupled with gas chromatography-mass spectrometry (GC-MS). Several condition parameters, such as sample loading flow-rate, eluent and elution volume, extractant and ratio of extraction solvent to sample, were optimized to achieve good sensitivity and precision for the extraction and elution of analytes. A methanol/water solution (50%, v/v) was used to extract atrazine, DIA and DEA from soil. After the extracts went through SPE cartridges (packed with multi-walled carbon nanotubes) at a flow-rate of 4 mL min(-1), the analytes were eluted by 4 mL ethyl acetate at the rate of 1 mL min(-1) under a vacuum pump. The limit of detection (S/N=3) of the proposed method was 0.02 microg kg(-1) for atrazine in water and 0.3 microg kg(-1) in soil; 0.04 microg kg(-1) for DIA in water and 1.0 microg kg(-1) in soil; 0.05 microg kg(-1) for DEA in water and 0.8 microg kg(-1) in soil. Mean recoveries were in the range of 72.27-109.68%, and the reproducibility was accepted (RSD <13%) under the optimum conditions. This developed method was applied to determine the analytes in real environmental samples, and the concentrations of atrazine were 0.77-10.83 microg kg(-1), while DEA and DIA were not detected.

  1. 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.

  2. 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

  3. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    NASA Astrophysics Data System (ADS)

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-05-01

    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.

  4. Heterogeneous reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on particles

    NASA Astrophysics Data System (ADS)

    Miet, K.; Le Menach, K.; Flaud, P. M.; Budzinski, H.; Villenave, E.

    This work deals with the kinetic study of the reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene, adsorbed on model particles. Experiments were performed at room temperature and atmospheric pressure, using a quasi-static flow reactor in the absence of light. Compounds were extracted from particles using pressurized fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different O 3 concentrations from which second order rate constants were calculated. The following rate constant values were obtained at 293 K: k(O 3 + Pyrene) = (3.2 ± 0.7) × 10 -16 cm 3 molecule -1 s -1; k(O 3 + 1OHP) = (7.7 ± 1.4) ×10 -16 cm 3 molecule -1 s -1; and k(O 3 + 1NP) = (2.2 ± 0.5) × 10 -17 cm 3 molecule -1 s -1, for pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on silica particles. The variation in the rate constants demonstrates the strong influence of the substituent (OH or NO 2) on the heterogeneous reactivity of pyrene. The pyrene particulate concentration was also varied in order to check how this parameter may influence the experiments. Finally, oxidation products were investigated for all reactions and some were detected and identified for the first time for ozone heterogeneous reaction with pyrene adsorbed on particles.

  5. Driving force behind adsorption-induced protein unfolding: a time-resolved X-ray reflectivity study on lysozyme adsorbed at an air/water interface.

    PubMed

    Yano, Yohko F; Uruga, Tomoya; Tanida, Hajime; Toyokawa, Hidenori; Terada, Yasuko; Takagaki, Masafumi; Yamada, Hironari

    2009-01-06

    Time-resolved X-ray reflectivity measurements for lysozyme (LSZ) adsorbed at an air/water interface were performed to study the mechanism of adsorption-induced protein unfolding. The time dependence of the density profile at the air/water interface revealed that the molecular conformation changed significantly during adsorption. Taking into account previous work using Fourier transform infrared (FTIR) spectroscopy, we propose that the LSZ molecules initially adsorbed on the air/water interface have a flat unfolded structure, forming antiparallel beta-sheets as a result of hydrophobic interactions with the gas phase. In contrast, as adsorption continues, a second layer forms in which the molecules have a very loose structure having random coils as a result of hydrophilic interactions with the hydrophilic groups that protrude from the first layer.

  6. 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.

  7. Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules

    PubMed Central

    Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

    2017-01-01

    Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE). PMID:28134754

  8. 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.

  9. Gas adsorption, energetics and electronic properties of boron- and nitrogen-doped bilayer graphenes

    NASA Astrophysics Data System (ADS)

    Fujimoto, Yoshitaka; Saito, Susumu

    2016-10-01

    We study stabilities and electronic properties of several environmental polluting or toxic gas molecules (CO, CO2, NO, and NO2) adsorbed on B and N atoms in bilayer graphene using first-principles electronic-structure calculations. We find that NO and NO2 molecules can be bound chemically on B-doped bilayer graphene with large adsorption energies, while CO and CO2 molecules are not adsorbed chemically on B-doped one. In the case of the N-doped graphene, all four gases do not bind with chemical bonds but adsorb rather physically with small adsorption energies at long distances between gases and graphene. The adsorptions of NO and NO2 molecules on B-doped bilayer graphene induce the acceptor states above the Fermi energy, and we also find that the charge transfer takes place when the NO and the NO2 molecules are adsorbed. Thereby, the B-doped bilayer graphene is expected to be useful for NO and NO2 gas sensor materials.

  10. Effective method to compute vibrationally resolved optical spectra of large molecules at finite temperature in the gas phase and in solution.

    PubMed

    Santoro, Fabrizio; Lami, Alessandro; Improta, Roberto; Barone, Vincenzo

    2007-05-14

    The authors present a new method for the computation of vibrationally resolved optical spectra of large molecules, including the Duschinsky rotation of the normal modes and the effect of thermal excitation. The method automatically selects the relevant vibronic contributions to the spectrum, independently of their frequency, and it is able to provide fully converged spectra with moderate computational times, both in vacuo and in solution. By describing the electronic states in the frame of the density functional theory and its time-dependent extension, they computed the room temperature absorption spectra of coumarin C153 and trans-stilbene in cyclohexane and the phosphorescence spectrum of porphyrazine in gas phase, showing that the method is fast and efficient. The comparison with experiment for trans-stilbene and coumarin C153 is very satisfactory, confirming the progress made toward a reliable method for the computation and interpretation for the optical spectra of large molecules.

  11. Formation and Fragmentation of Protonated Molecules after Ionization of Amino Acid and Lactic Acid Clusters by Collision with Ions in the Gas Phase.

    PubMed

    Poully, Jean-Christophe; Vizcaino, Violaine; Schwob, Lucas; Delaunay, Rudy; Kocisek, Jaroslav; Eden, Samuel; Chesnel, Jean-Yves; Méry, Alain; Rangama, Jimmy; Adoui, Lamri; Huber, Bernd

    2015-08-03

    Collisions between O(3+) ions and neutral clusters of amino acids (alanine, valine and glycine) as well as lactic acid are performed in the gas phase, in order to investigate the effect of ionizing radiation on these biologically relevant molecular systems. All monomers and dimers are found to be predominantly protonated, and ab initio quantum-chemical calculations on model systems indicate that for amino acids, this is due to proton transfer within the clusters after ionization. For lactic acid, which has a lower proton affinity than amino acids, a significant non-negligible amount of the radical cation monomer is observed. New fragment-ion channels observed from clusters, as opposed to isolated molecules, are assigned to the statistical dissociation of protonated molecules formed upon ionization of the clusters. These new dissociation channels exhibit strong delayed fragmentation on the microsecond time scale, especially after multiple ionization.

  12. 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

  13. Towards reliable modelling of large clusters: on the overall accuracy of the diatomics-in-molecule method for rare gas cluster ions

    NASA Astrophysics Data System (ADS)

    Naumkin, Fedor Yu.; Knowles, Peter J.; Murrell, John N.

    1995-04-01

    The accuracy of the diatomics-in-molecules (DIM) method is examined for the case of rare gas ionic clusters through a series of careful calibration calculations. Ab initio potential energy functions for Rg 3+ and Rg 4+ (RgHe, Ne, Ar) are compared with the DIM model, taking diatomic potentials computed at exactly the same level of ab initio theory as input. For Ne n+, agreement is satisfactory (in most important regions within 0.05 eV), whereas for He n+, large deviations occur.

  14. Towards reliable modelling of large clusters: On the overall accuracy of the diatomics-in-molecule method for rare gas cluster ions

    NASA Astrophysics Data System (ADS)

    Naumkin, Fedor Yu.; Knowles, Peter J.; Murrell, John N.

    1995-04-01

    The accuracy of the diatomics-in-molecules (DIM) method is examined for the case of rare gas ionic clusters through a series of careful calibration calculations. Ab initio potential energy functions for Rg3(+) and Rg4(+) (Rg=He, Ne, Ar) are compared with the DIM model, taking diatomic potentials computed at exactly the same level of ab initio theory as input. For Ne(n)(+) and Ar(n)(+), agreement is satisfactory (in most important regions within 0.05 eV), whereas for He(n)(+), large deviations occur.

  15. Determination of the adsorption model of alkenes and alcohols on sulfonic copolymer by inverse gas chromatography.

    PubMed

    Słomkiewicz, P M

    2004-04-23

    The determination of a number of adsorption sites on sulfonated styrene-divinylbenzene copolymer for alkenes (propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1-pentene, 2-methyl-2-pentene and 2-methyl-2-hexene) and alcohols (methanol, ethanol and n-propanol, n-butanol, 2-butanol and tert-butanol) was performed by the saturation copolymer with vapors of adsorbate, by removing the excess of adsorbate from copolymer by blowing the inert gas through copolymer bed and by the desorption of adsorbed alcohol in the programmed increase of temperature. The adsorption measurements were performed on sulfonated ion-exchange resin (Amberlyst 15) with different concentrations of the acid group, which means with a varying number of adsorption sites. The following adsorption models for alkenes were suggested: the first in which one molecule of alkene is adsorbed by two sulfonic groups, for linear alcohols, the second in which one sulfonic group can adsorb one molecule of alcohol and for non-linear alcohols the third where one molecule of alcohol is adsorbed by two or more sulfonic groups.

  16. Spectroscopic STM studies of single gold(III) porphyrin molecules.

    PubMed

    Müllegger, Stefan; Schöfberger, Wolfgang; Rashidi, Mohammad; Reith, Lorenz M; Koch, Reinhold

    2009-12-16

    Low-temperature scanning tunneling microscopy, a well-established technique for single-molecule investigations in an ultrahigh vacuum environment, has been used to study the electronic properties of Au(III) 5,10,15,20-tetraphenylporphyrin (AuTPP) molecules on Au(111) at the submolecular scale. AuTPP serves as a model system for chemotherapeutically relevant Au(III) porphyrins. For the first time, real-space images and local scanning tunneling spectroscopy data of the frontier molecular orbitals of AuTPP are presented. A comparison with results from density functional theory reveals significant deviations from gas-phase behavior due to a non-negligible molecule/substrate interaction. We identify the oxidation state of the central metal ion in the adsorbed AuTPP as Au(3+).

  17. 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

  18. Tuning the composition of guest molecules in clathrate hydrates: NMR identification and its significance to gas storage.

    PubMed

    Seo, Yutaek; Lee, Jong-Won; Kumar, Rajnish; Moudrakovski, Igor L; Lee, Huen; Ripmeester, John A

    2009-08-03

    Gas hydrates represent an attractive way of storing large quantities of gas such as methane and carbon dioxide, although to date there has been little effort to optimize the storage capacity and to understand the trade-offs between storage conditions and storage capacity. In this work, we present estimates for gas storage based on the ideal structures, and show how these must be modified given the little data available on hydrate composition. We then examine the hypothesis based on solid-solution theory for clathrate hydrates as to how storage capacity may be improved for structure II hydrates, and test the hypothesis for a structure II hydrate of THF and methane, paying special attention to the synthetic approach used. Phase equilibrium data are used to map the region of stability of the double hydrate in P-T space as a function of the concentration of THF. In situ high-pressure NMR experiments were used to measure the kinetics of reaction between frozen THF solutions and methane gas, and (13)C MAS NMR experiments were used to measure the distribution of the guests over the cage sites. As known from previous work, at high concentrations of THF, methane only occupies the small cages in structure II hydrate, and in accordance with the hypothesis posed, we confirm that methane can be introduced into the large cage of structure II hydrate by lowering the concentration of THF to below 1.0 mol %. We note that in some preparations the cage occupancies appear to fluctuate with time and are not necessarily homogeneous over the sample. Although the tuning mechanism is generally valid, the composition and homogeneity of the product vary with the details of the synthetic procedure. The best results, those obtained from the gas-liquid reaction, are in good agreement with thermodynamic predictions; those obtained for the gas-solid reaction do not agree nearly as well.

  19. Testing of chemically treated adsorbent air purifiers

    SciTech Connect

    Kelly, T.J. . Dept. of Atmospheric Science and Applied Technology); Kinkead, D.A. )

    1993-07-01

    New highly sensitive continuous monitors permit testing of air filters at parts-per-billion contaminant concentrations. This article describes testing of air purification filters intended for use in the National Archives 2 building in College Park, Maryland, using a test procedure that simulates the actual conditions of use. This test demonstrates both the effectiveness of the adsorbers at low contaminant levels, and the capability of existing instruments for conducting such tests. ASHRAE TC 2.3 (Gaseous Air Contaminants and Gas Contaminant Removal Equipment) is currently sponsoring research projects (follow-on studies to ASHRAE Project RP-674) aimed at developing a standard that will test and rate the performance of different types of gas phase air purification equipment at low concentrations. The work detailed in this article represents a first of this type of testing and a technical benchmark that may aid in the further development of ASHRAE gas phase performance standards.

  20. 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.

  1. Production of hyperpolarized H_{2} molecules from H[over →] atoms in gas-storage cells.

    PubMed

    Engels, R; Gaißer, M; Gorski, R; Grigoryev, K; Mikirtychyants, M; Nass, A; Rathmann, F; Seyfarth, H; Ströher, H; Weiss, P; Kochenda, L; Kravtsov, P; Trofimov, V; Tschernov, N; Vasilyev, A; Vznuzdaev, M; Schieck, H Paetz Gen

    2015-09-11

    The preservation of the nuclear polarization of hydrogen atoms during the recombination to molecules was observed on different surface materials in the temperature range from 45 to 100 K and for magnetic fields up to 1 T. On a gold and a fused quartz surface, the expected molecular polarization of about 50% or lower of the atomic polarization was measured, while a surface layer of perfluoropolyether (Fomblin) shows a nearly complete preservation (at least 97%) of the atomic polarization during the recombination process. Further experiments have the possibility of storing polarized deuterium molecules and to use them in nuclear-fusion installations. Another application might be the production of polarized substances for enhanced NMR techniques.

  2. Theoretical analysis of coverage-dependent rotational hindrance of PF 3 adsorbed on Ru(001)

    NASA Astrophysics Data System (ADS)

    Kaji, H.; Kakitani, K.; Yagi, Y.; Yoshimori, A.

    1996-08-01

    Distribution of the azimuthal orientation of PF 3 molecules adsorbed on Ru(001) measured by ESDIAD shows interesting temperature and coverage dependences. It is interpreted in this analysis as due to the short range order in the locative distribution of the PF 3 molecules. Monte Carlo simulations are performed to obtain the temperature and coverage-dependent distribution of the adsorbed molecules. The distribution of the azimuthal orientation of the molecule is discussed on the basis of the obtained locative distribution of the molecules by using simple models for rotational hindrance to be compared with the experimental results.

  3. Adsorption of oxygen molecule in NaA zeolite: Isotherms and infrared measurements

    NASA Astrophysics Data System (ADS)

    Soussen-Jacob, Janine; Tsakiris, Jean; Cohen De Lara, Evelyne

    1989-08-01

    Isotherm and infrared induced band of O2 have been studied in the temperature range 93-193 K. At low temperature and low coverage, two components of the fundamental vibrational band appear on both sides of the gas frequency. Their intensities with respect to T and to the number of adsorbed molecules have been measured in order to understand the interaction of O2 with NaA zeolite. The frequency shift of each component has been related to the orientation of the molecule, from considerations about the interaction potential.

  4. Trapping of xenon gas in closed inner spaces of carbon nanomaterials for stable gas storage under high-vacuum condition

    NASA Astrophysics Data System (ADS)

    Kobayashi, Keita; Yasuda, Hidehiro

    2017-01-01

    Xe gas can be trapped in the closed inner spaces of glassy carbon derived from C60 fullerene by thermal coalescence of C60 in Xe atmosphere and in cap-opened carbon nanotubes (CNTs) covered with an ionic liquid by soaking Xe-adsorbing CNTs in an ionic liquid. The trapped Xe gas is detected by energy dispersive X-ray spectrometry using a spectrometer mounted on an analytical transmission electron microscope. The closed inner spaces store gas molecules even under high-vacuum condition (˜10-5 Pa).

  5. 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}.

  6. Tuning the electronic and magnetic properties of germanene by surface adsorption of small nitrogen-based molecules

    NASA Astrophysics Data System (ADS)

    Pang, Qing; Li, Long; Gao, Dang-li; Chai, Rui-peng; Zhang, Chun-ling; Song, Yu-ling

    2017-04-01

    The structural, energetic and electronic properties of germanene adsorbed with small nitrogen-based molecules, including N2, NH3, NO2 and NO, have been investigated by using first-principles calculations. The results show that all nitrogen-based molecules considered bind much stronger to germanene than to graphene due to the hybridized sp2-sp3 bonding of Ge atoms. The N2, NO and NO2 molecules all act as an acceptor, while the NH3 molecule donates electrons to germanene. We also found sizable band gaps (2-158 meV) are opened at the Dirac point of germanene through N2, NH3, and NO2 adsorptions, but with only slightly destroying its Dirac cone shape. The NO2 molecule also shows a heavy p-type doping character and makes germanene to be metallic. Moreover, when adsorbed by NO molecule, the germanene can change to be a ferromagnetic half-metal with 100% spin-polarization at the Fermi level. Overall, the different adsorption behaviors of small nitrogen-based gas molecules on germanene provide a feasible way to exploit chemically modified germanene for a wide range of practical applications, such as field-effect transistors, gas sensors and spintronic devices.

  7. 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.

  8. Leonardite char adsorbents

    DOEpatents

    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.

  9. Concentrating materials covered by molecular imprinted nanofiltration layer with reconfigurability prepared by a surface sol-gel process for gas-selective detection.

    PubMed

    Imahashi, Masahiro; Hayashi, Kenshi

    2013-09-15

    Sensors that recognize molecules are acquired for the comprehensive detection of great many kinds of gases. Adsorbents with high molecular recognition and condensation ability were developed for selective gas sensing with a molecular imprinting technique. Developed adsorbents have multilayer structures consisted of a chemically modified polymer layer on the surface of a substrate covered by a TiO2 gel monolayer by the surface sol-gel process. Ellipsometry measurements showed that the 6-nm-thick layers deposited on the substrate. Cavities of molecular templates were imprinted on these layers, and thus, the film acts as a molecular gas filter without concentrating ability, which could form specific binding sites for various molecules that confirmed using solid-phase microextraction and gas chromatography-mass spectrometry. Gases were selectively absorbed into an accumulating adsorption layer and other gas molecules were blocked by the nanofiltration. These developed adsorbents enabled effective concentration ability and the filtration of gases or odors. In addition, these filters possess the flexibility to be easily configured with specific surface properties to interact with volatile molecules under appropriate conditions. A successful multiplex filter, imprinted simultaneously on an adsorbent with different sites, was demonstrated.

  10. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    NASA Astrophysics Data System (ADS)

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-09-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

  11. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry.

    PubMed

    Silber, David; Kowalski, Piotr M; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-09-30

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

  12. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    PubMed Central

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-01-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface. PMID:27686286

  13. MTBE adsorption on alternative adsorbents and packed bed adsorber performance.

    PubMed

    Rossner, Alfred; Knappe, Detlef R U

    2008-04-01

    Widespread use of the fuel additive methyl tertiary-butyl ether (MTBE) has led to frequent MTBE detections in North American and European drinking water sources. The overall objective of this research was to evaluate the effectiveness of a silicalite zeolite, a carbonaceous resin, and a coconut-shell-based granular activated carbon (GAC) for the removal of MTBE from water. Isotherm and short bed adsorber tests were conducted in ultrapure water and river water to obtain parameters describing MTBE adsorption equilibria and kinetics and to quantify the effect of natural organic matter (NOM) on MTBE adsorption. Both the silicalite zeolite and the carbonaceous resin exhibited larger MTBE adsorption uptakes than the tested GAC. Surface diffusion coefficients describing intraparticle MTBE mass transfer rates were largest for the GAC and smallest for the carbonaceous resin. Pilot tests were conducted to verify MTBE breakthrough curve predictions obtained with the homogeneous surface diffusion model and to evaluate the effect of NOM preloading on packed bed adsorber performance. Results showed that GAC was the most cost-competitive adsorbent when considering adsorbent usage rate only; however, the useful life of an adsorber containing silicalite zeolite was predicted to be approximately 5-6 times longer than that of an equally sized adsorber containing GAC. Pilot column results also showed that NOM preloading did not impair the MTBE removal efficiency of the silicalite zeolite. Thus, it may be possible to regenerate spent silicalite with less energy-intensive methods than those required to regenerate GAC.

  14. 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.

  15. Controlled growth of conical nickel oxide nanocrystals and their high performance gas sensing devices for ammonia molecule detection.

    PubMed

    Wang, Jian; Yang, Fan; Wei, Xiaowei; Zhang, Yafei; Wei, Liangming; Zhang, Jianjun; Tang, Qifeng; Guo, Biao; Xu, Lei

    2014-08-21

    NiO nanocones with good symmetry and highly ordered structure on NiO foil substrate have been successfully fabricated via a facile wet chemical approach combined with subsequent high temperature oxidation. These organized conical superstructures grow only along a certain direction and be controlled via the self-assembly and oriented attachment of a nucleus, which mainly rely on the similar surface energies and the extent of lattice matching of the oriented attached surfaces. During high temperature oxidation, the electric field created via the Ni(2+) and O(2-) facilitates Ni(2+) diffusion outward along the grain boundaries and O(2-) diffusion inward toward to meet the Ni(2+) ions, forming NiO. The as-grown NiO nanocones are 50-350 nm in diameter and 50-400 nm in height. The tip diameter of the nanocone is about 30 nm and the apex angle of the nanocone is about 40°. Meanwhile, we systematically investigated the gas sensing properties of the sensors based on the as-fabricated NiO foil covered with nanocone arrays for ammonia detection at room temperature. The results show that the gas sensing devices have outstanding sensitivity, reproducibility and selectivity, which are mainly because of the excellent connection between the NiO sensing materials and the Au electrodes, the strong electron donating ability of ammonia and the large active surface of selective physisorption for ammonia.

  16. Coherent Rayleigh-Brillouin scattering for in situ detection of nanoparticles and large molecules in gas and plasma

    NASA Astrophysics Data System (ADS)

    Gerakis, A.; Shneider, M. N.; Stratton, B. C.; Santra, B.; Car, R.; Raitses, Y.

    2016-09-01

    Laser-based diagnostics methods, such as Spontaneous and Coherent Rayleigh and Rayleigh-Brillouin scattering (SRBS and CRBS), can be used for in-situ detection and characterization of nanoparticle shape and size as well as their concentration in an inert gas atmosphere. We recently developed and tested this advanced diagnostic at PPPL. It was shown that the signal intensity of the CRBS signal depends on the gas-nanoparticle mixture composition, density and the polarizabilities of the mixture components. The measured results agree well with theoretical predictions of Refs. In this work, we report the application of this diagnostic to monitor nucleation and growth of nanoparticles in a carbon arc discharge. In support of these measurements, A time-dependent density functional theory was used to compute the frequency-dependent polarizabilities of various nanostructures in order to predict the corresponding Rayleigh scattering intensities as well as light depolarization. Preliminary results of measurements demonstrate that CRBS is capable to detect nanoparticles in volume. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  17. Structure of adsorbed organometallic rhodium: model single atom catalysts.

    PubMed

    Bennett, R A; McCavish, N D; Basham, M; Dhanak, V R; Newton, M A

    2007-02-02

    We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

  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. Second virial coefficient of helium adsorbed on liquid hydrogen

    SciTech Connect

    Paine, C.G.; Seidel, G.M. )

    1994-08-01

    The nonlinear dependence of the surface energy of liquid hydrogen as a function of the density of helium gas in equilibrium with the liquid surface has been used to determine the second virial coefficient of the two-dimensional gas of helium atoms adsorbed on the surface. The surface energy of both liquid hydrogen and liquid deuterium has been measured in the presence of [sup 4]He and [sup 3]He. The experimental results are in rough agreement with theoretical prediction.

  20. Evidence for Adsorbate-Enhanced Field Emission from Carbon Nanotube Fibers (Postprint)

    DTIC Science & Technology

    2013-07-31

    microscopy from single wall nanotube ( SWNT ) caps,9 and by current satura- tion measurements10 from adsorbate-covered SWNTs , were consistent with this...assertion. Comparison of the FE electron energy distributions acquired from clean and adsorbate- covered SWNTs led11 to the conclusion that enhancement...Residual Gas Analysis FE Field Emission CNT Carbon Nanotube SWNT Single Wall Nanotube CSA Chlorosulfonic Acid

  1. Molecular-scale interface engineering of nanocrystalline titania by co-adsorbents for solar energy conversion.

    PubMed

    Wang, Mingkui; Plogmaker, Stefan; Humphry-Baker, Robin; Pechy, Peter; Rensmo, Håkan; Zakeeruddin, Shaik M; Grätzel, Michael

    2012-01-09

    The use of mixed self-assembled monolayers, combining hydrophobic co-adsorbents with the sensitizer, has been demonstrated to enhance the efficiency of dye-sensitized solar cells (DSCs). Herein, the influence of the anchoring groups of the co-adsorbents on the performance of the DSCs is carefully examined by selecting two model molecules: neohexyl phosphonic acid (NHOOP) and bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP). The effect of these co-adsorbents on the photovoltaic performance (J-V curves, incident photon-to-electron conversion efficiency) is investigated. Photoelectron spectroscopy and electrochemical impedance spectroscopy are performed to assess the spatial configuration of adsorbed dye and co-adsorbent molecules. The photoelectron spectroscopy studies indicate that the ligands of the ruthenium complex, containing thiophene groups, point out away from the surface of TiO(2) in comparison with the NCS group.

  2. Interactions of neutral and singly charged keV atomic particles with gas-phase adenine molecules

    SciTech Connect

    Alvarado, Fresia; Bari, Sadia; Hoekstra, Ronnie; Schlathoelter, Thomas

    2007-07-21

    KeV atomic particles traversing biological matter are subject to charge exchange and screening effects which dynamically change this particle's effective charge. The understanding of the collision cascade along the track thus requires a detailed knowledge of the interaction dynamics of radiobiologically relevant molecules, such as DNA building blocks or water, not only with ionic but also with neutral species. We have studied collisions of keV H{sup +}, He{sup +}, and C{sup +} ions and H{sup 0}, He{sup 0}, and C{sup 0} atoms with the DNA base adenine by means of high resolution time-of-flight spectrometry. For H{sup 0} and H{sup +} we find qualitatively very similar fragmentation patterns, while for carbon, strong differences are observed when comparing C{sup 0} and C{sup +} impact. For collisions with He{sup 0} and He{sup +} projectiles, a pronounced delayed fragmentation channel is observed, which has not been reported before.

  3. Hydrogen gas acts as a novel bioactive molecule in enhancing plant tolerance to paraquat-induced oxidative stress via the modulation of heme oxygenase-1 signalling system.

    PubMed

    Jin, Qijiang; Zhu, Kaikai; Cui, Weiti; Xie, Yanjie; Han, Bin; Shen, Wenbiao

    2013-05-01

    Hydrogen gas (H2) was recently proposed as a novel antioxidant and signalling molecule in animals. However, the physiological roles of H2 in plants are less clear. Here, we showed that exposure of alfalfa seedlings to paraquat stress increased endogenous H2 production. When supplied with exogenous H2 or the heme oxygenase-1 (HO-1)-inducer hemin, alfalfa plants displayed enhanced tolerance to oxidative stress induced by paraquat. This was evidenced by alleviation of the inhibition of root growth, reduced lipid peroxidation and the decreased hydrogen peroxide and superoxide anion radical levels. The activities and transcripts of representative antioxidant enzymes were induced after exposure to either H2 or hemin. Further results showed that H2 pretreatment could dramatically increase levels of the MsHO-1 transcript, levels of the protein it encodes and HO-1 activity. The previously mentioned H2-mediated responses were specific for HO-1, given that the potent HO-1-inhibitor counteracted the effects of H2. The effects of H2 were reversed after the addition of an aqueous solution of 50% carbon monoxide (CO). We also discovered enhanced tolerance of multiple environmental stresses after plants were pretreated with H2 . Together, these results suggested that H2 might function as an important gaseous molecule that alleviates oxidative stress via HO-1 signalling.

  4. Mechanism for the atomic layer deposition of copper using diethylzinc as the reducing agent: a density functional theory study using gas-phase molecules as a model.

    PubMed

    Dey, Gangotri; Elliott, Simon D

    2012-09-06

    We present theoretical studies based on first-principles density functional theory calculations for the possible gas-phase mechanism of the atomic layer deposition (ALD) of copper by transmetalation from common precursors such as Cu(acac)(2), Cu(hfac)(2), Cu(PyrIm(R))(2) with R = (i)Pr and Et, Cu(dmap)(2), and CuCl(2) where diethylzinc acts as the reducing agent. An effect on the geometry and reactivity of the precursors due to differences in electronegativity, steric hindrance, and conjugation present in the ligands was observed. Three reaction types, namely, disproportionation, ligand exchange, and reductive elimination, were considered that together comprise the mechanism for the formation of copper in its metallic state starting from the precursors. A parallel pathway for the formation of zinc in its metallic form was also considered. The model Cu(I) molecule Cu(2)L(2) was studied, as Cu(I) intermediates at the surface play an important role in copper deposition. Through our study, we found that accumulation of an LZnEt intermediate results in zinc contamination by the formation of either Zn(2)L(2) or metallic zinc. Ligand exchange between Cu(II) and Zn(II) should proceed through a Cu(I) intermediate, as otherwise, it would lead to a stable copper molecule rather than copper metal. Volatile ZnL(2) favors the ALD reaction, as it carries the reaction forward.

  5. A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

    2016-11-01

    Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

  6. 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.

  7. Structure and Redox Properties of 5-Amino-3-nitro-1H-1,2,4-triazole (ANTA) Adsorbed on a Silica Surface: A DFT M05 Computational Study.

    PubMed

    Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Leszczynski, Jerzy

    2015-07-23

    A cluster approximation was applied at the M05/tzvp level to model an adsorption of 5-amino-3-nitro-1H-1,2,4-triazole (ANTA) on the (001) surface of α-quartz. Structures of the obtained ANTA-silica complexes confirm a nearly parallel orientation of the nitro compound toward the surface. The atoms in molecules (AIM) method was applied to analyze binding between ANTA and the silica surface. Attachment or loss of an electron was found to lead to a significant deviation from coplanarity in the complexes and to a strengthening of a hydrogen bonding. Redox properties of the adsorbed ANTA were compared with those of gas-phase and hydrated species by calculation of the ionization potential, electron affinity, oxidation and reduction Gibbs free energies, and oxidation and reduction potentials. It was shown that the adsorbed ANTA has a lower ability to undergo redox transformations as compared to that of the hydrated one.

  8. 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)

  9. 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...

  10. Feasibility of fullerene waste as carbonaceous adsorbent

    SciTech Connect

    Cleveland, T.G.; Garg, S.; Rixey, W.G.

    1996-03-01

    This note investigates using the waste soot generated in fullerene manufacture as an adsorbent. Both oven-dried and air-activated samples of waste soot are compared with three commercially available powdered activated carbons (PACs): Nuchar-SA, HDH, and Calgon-RC. Three model compounds were chosen for adsorption tests--TCE, Benzene, and Phenol--representing a small branched molecule, a small nonpolar ring molecule, and relatively polar ring molecule. Additionally, the effectiveness of total organic carbon (TOC) removal from wastewater was evaluated. Oven-dried soot performed poorly as compared to the commercial carbons, but activation of the waste soot for 60 min at 450 C in air resulted in an activated carbon (aFWS) with properties similar to those of commercially available PACs. The aFWS performed better than one would predict from the typical characterization measures of iodine number, molasses number, and methylene blue number. The data for phenol suggest some functional groups are created during the activation of the waste soot. These results show that large-scale fullerene manufacturing can be a zero-waste industry, because its primary waste product can be converted into a useful material.

  11. Uremic toxins and oral adsorbents.

    PubMed

    Goto, Shunsuke; Yoshiya, Kunihiko; Kita, Tomoyuki; Fujii, Hideki; Fukagawa, Masafumi

    2011-04-01

    Uremic toxins are associated with various disorders in patients with end-stage renal disease and it is difficult to remove some of these toxins by dialysis. Since some uremic toxins are generated by bacterial metabolites in the colon, oral adsorbents that interfere with the absorption of uremic toxins or their precursors are believed to prevent their accumulation in the body. AST-120 adsorbs various uremic retention solutes in the gastrointestinal system and has potential for providing clinical benefit. Sevelamer hydrochloride binds some harmful compounds in addition to phosphate and seems to have pleiotropic effects that include lowering serum LDL cholesterol levels and reduction of inflammation. The effect of sevelamer hydrochloride on indoxyl sulfate and p-cresol has been shown in an in vitro study; however, in vivo studies in mice or humans did not demonstrate this effect on protein-binding uremic toxins. Oral adsorbents are thus one of the important modalities in the treatment of uremic syndrome.

  12. The condensation of water on adsorbed viruses.

    PubMed

    Alonso, José María; Tatti, Francesco; Chuvilin, Andrey; Mam, Keriya; Ondarçuhu, Thierry; Bittner, Alexander M

    2013-11-26

    The wetting and dewetting behavior of biological nanostructures and to a greater degree single molecules is not well-known even though their contact with water is the basis for all biology. Here, we show that environmental electron microscopy (EM) can be applied as a means of imaging the condensation of water onto viruses. We captured the formation of submicrometer water droplets and filaments on single viral particles by environmental EM and by environmental transmission EM. The condensate structures are compatible with capillary condensation between adsorbed virus particles and with known droplet shapes on patterned surfaces. Our results confirm that such droplets exist down to <50 nm. The viruses preserved their shape after a condensation/evaporation cycle as expected from their stability in air and water. Moreover we developed procedures that overcome problems of beam damage and of resolving structures with a low atomic number.

  13. 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.

  14. Accuracy of density functional theory in the prediction of carbon dioxide adsorbent materials.

    PubMed

    Cazorla, Claudio; Shevlin, Stephen A

    2013-04-07

    Density functional theory (DFT) has become the computational method of choice for modeling and characterization of carbon dioxide adsorbents, a broad family of materials which at present are urgently sought after for environmental applications. The description of polar carbon dioxide (CO(2)) molecules in low-coordinated environments like surfaces and porous materials, however, may be challenging for local and semi-local DFT approximations. Here, we present a thorough computational study in which the accuracy of DFT methods in describing the interactions of CO(2) with model alkali-earth-metal (AEM, Ca and Li) decorated carbon structures, namely anthracene (C(14)H(10)) molecules, is assessed. We find that gas-adsorption energies and equilibrium structures obtained with standard (i.e. LDA and GGA), hybrid (i.e. PBE0 and B3LYP) and van der Waals exchange-correlation functionals of DFT dramatically differ from the results obtained with second-order Møller-Plesset perturbation theory (MP2), an accurate computational quantum chemistry method. The major disagreements found can be mostly rationalized in terms of electron correlation errors that lead to wrong charge-transfer and electrostatic Coulomb interactions between CO(2) and AEM-decorated anthracene molecules. Nevertheless, we show that when the concentration of AEM atoms in anthracene is tuned to resemble as closely as possible the electronic structure of AEM-decorated graphene (i.e. an extended two-dimensional material), hybrid exchange-correlation DFT and MP2 methods quantitatively provide similar results.

  15. Chemical speciation of adsorbed glycine on metal surfaces

    NASA Astrophysics Data System (ADS)

    Han, Jeong Woo; James, Joanna N.; Sholl, David S.

    2011-07-01

    Experimental studies have reported that glycine is adsorbed on the Cu(110) and Cu(100) surfaces in its deprotonated form at room temperature, but in its zwitterionic form on Pd(111) and Pt(111). In contrast, recent density functional theory (DFT) calculations indicated that the deprotonated molecules are thermodynamically favored on Cu(110), Cu(100), and Pd(111). To explore the source of this disagreement, we have tested three possible hypotheses. Using DFT calculations, we first show that the kinetic barrier for the deprotonation reaction of glycine on Pd(111) is larger than on Cu(110) or Cu(100). We then report that the presence of excess hydrogen would have little influence on the experimentally observed results, especially for Pd(111). Lastly, we perform Monte Carlo simulations to demonstrate that the aggregates of zwitterionic species on Pt(111) are energetically preferred to those of neutral species. Our results strongly suggest that the formation of aggregates with relatively large numbers of adsorbed molecules is favored under experimentally relevant conditions and that the adsorbate-adsorbate interactions in these aggregates stabilize the zwitterionic species.

  16. High-capacity hydrogen storage in Al-adsorbed graphene

    NASA Astrophysics Data System (ADS)

    Ao, Z. M.; Peeters, F. M.

    2010-05-01

    A high-capacity hydrogen storage medium—Al-adsorbed graphene—is proposed based on density-functional theory calculations. We find that a graphene layer with Al adsorbed on both sides can store hydrogen up to 13.79wt% with average adsorption energy -0.193eV/H2 . Its hydrogen storage capacity is in excess of 6wt% , surpassing U. S. Department of Energy (DOE’s) target. Based on the binding-energy criterion and molecular-dynamics calculations, we find that hydrogen storage can be recycled at near ambient conditions. This high-capacity hydrogen storage is due to the adsorbed Al atoms that act as bridges to link the electron clouds of the H2 molecules and the graphene layer. As a consequence, a two-layer arrangement of H2 molecules is formed on each side of the Al-adsorbed graphene layer. The H2 concentration in the hydrogen storage medium can be measured by the change in the conductivity of the graphene layer.

  17. Experimental and theoretical comparison of gas desorption energies on metallic and semiconducting single-walled carbon nanotubes.

    PubMed

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

    2013-05-22

    Single-walled carbon nanotubes (SWNTs) exhibit high surface areas and precisely defined pores, making them potentially useful materials for gas adsorption and purification. A thorough understanding of the interactions between adsorbates and SWNTs is therefore critical to predicting adsorption isotherms and selectivities. Metallic (M-) and semiconducting (S-) SWNTs have extremely different polarizabilities that might be expected to significantly affect the adsorption energies of molecules. We experimentally and theoretically show that this expectation is contradicted, for both a long chain molecule (n-heptane) and atoms (Ar, Kr, and Xe). Temperature-programmed desorption experiments are combined with van der Waals corrected density functional theory, examining adsorption on interior and exterior sites of the SWNTs. Our calculations show a clear dependence of the adsorption energy on nanotube diameter but not on whether the tubes are conducting or insulating. We find no significant experimental or theoretical difference in adsorption energies for molecules adsorbed on M- and S-SWNTs having the same diameter. Hence, we conclude that the differences in polarizabilities between M- and S-SWNTs have a negligible influence on gas adsorption for spherical molecules as well as for highly anisotropic molecules such as n-heptane. We expect this conclusion to apply to all types of adsorbed molecules where van der Waals interactions govern the molecular interaction with the SWNT.

  18. 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.

  19. 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.

  20. 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.

  1. Determination of delta9-tetrahydrocannabinol in indoor air as an indicator of marijuana cigarette smoking using adsorbent sampling and in-injector thermal desorption gas chromatography-mass spectrometry.

    PubMed

    Chou, Su-Lien; Ling, Yong-Chien; Yang, Mo-Hsiung; Pai, Chung-Yen

    2007-08-13

    The marijuana leaves are usually mixed with tobaccos and smoked at amusement places in Taiwan. Recently, for investigation-legal purposes, the police asked if we can identify the marijuana smoke in a KTV stateroom (a private room at the entertainment spot for singing, smoking, alcohol drinking, etc.) without marijuana residues. A personal air-sampler pump fitted with the GC liner-tube packed with Tenax-TA adsorbent was used for air sampling. The GC-adsorbent tube was placed in the GC injector port and desorbed directly, followed by GC-MS analysis for the determination of delta9-tetrahydrocannabinol (delta9-THC) in indoor air. The average desorption efficiency and limit of detection for delta9-THC were 89% and 0.1 microg m(-3), respectively, approximately needing 1.09 mg of marijuana leaves smoked in an unventilated closed room (3.0 m x 2.4 m x 2.7 m) to reach this level. The mean delta9-THC contained in the 15 marijuana plants seized from diverse locations was measured to be 0.32%. The delta9-THC in room air can be successfully identified from mock marijuana cigarettes, mixtures of marijuana and tobacco, and an actual case. The characteristic delta9-THC peak in chromatogram can serve as the indicator of marijuana. Positive result suggests marijuana smoking at the specific scene in the recent past, facilitating the formulation of further investigation.

  2. Thermodynamics of the adsorption of organic molecules on graphitized carbon black modified with a monolayer of 5-hydroxy-6-methyluracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ivanov, S. P.; Shaikhitdinova, Yu. F.; Kudasheva, F. Kh.

    2016-10-01

    Thermodynamic characteristics of the adsorption of alkanes, alcohols, arenes, and esters on graphitized carbon black with a deposited monolayer (0.17%) of 5-hydroxy-6-methyluracil are studied by means of inverse gas chromatography at infinite dilution. It is established that size effects (violation of the additivity of molar changes in internal energy and the entropy of adsorption for pairs of molecules of one homologous series that differ by one methyl group) are observed when organic molecules are adsorbed on the surface of the resulting adsorbent. The size effects are similar to those observed when 1% 5-hydroxy-6-methyluracil is deposited on graphitized carbon black. It is concluded that the observed violation of additivity is associated with cavities in the supramolecular structure.

  3. 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.

  4. Nanoscience: Single-molecule instant replay

    NASA Astrophysics Data System (ADS)

    Camillone, Nicholas

    2016-11-01

    A nanoscale imaging method that uses ultrashort light pulses to initiate and follow the motion of a single molecule adsorbed on a solid surface opens a window onto the physical and chemical dynamics of molecules on surfaces. See Letter p.263

  5. A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

    NASA Astrophysics Data System (ADS)

    Mkhonto, Donald; Ngoepe, Phuti E.; Cooper, Timothy G.; de Leeuw, Nora H.

    2006-08-01

    Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol-1, but methylamine containing only the NH2 functional group adsorbs to the surfaces to a much lesser extent (25 95 kJ mol-1). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.

  6. Hydration level dependence of the microscopic dynamics of water adsorbed in ultramicroporous carbon

    SciTech Connect

    Mamontov, Eugene; Yue, Yanfeng; Bahadur, Jitendra; Guo, Junjie; Contescu, Cristian I.; Gallego, Nidia C.; Melnichenko, Yuri B.

    2016-10-20

    Even when not functionalized intentionally, most carbon materials are not hydrophobic and readily adsorb water molecules from atmospheric water vapor. We have equilibrated an ultramicroporous carbon at several levels of relative humidity, thereby attaining various hydration levels. The water molecules were adsorbed on the pore walls (but did not fill completely the pore volume) and thus could be better described as hydration, or surface, rather than confined, water. We used quasielastic neutron scattering to perform a detailed investigation of the dependence of microscopic dynamics of these adsorbed water species on the hydration level and temperature. The behavior of hydration water in ultramicroporous carbon clearly demonstrates the same universal traits that characterize surface (hydration) water in other materials that are surface-hydrated. In addition, unless special treatment is intentionally applied to ultramicroporous carbon, the species filling its pores in various applications, ranging from hydrogen molecules to electrolytes, likely find themselves in contact with non-freezing water molecules characterized by rich microscopic dynamics.

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

    PubMed

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

    2016-08-08

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

  8. 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

  9. 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.

  10. Do methanethiol adsorbates on the Au(111) surface dissociate?

    PubMed

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-28

    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.

  11. 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.

  12. Application of 1H NMR spectroscopy method for determination of characteristics of thin layers of water adsorbed on the surface of dispersed and porous adsorbents.

    PubMed

    Turov, V V; Leboda, R

    1999-02-01

    The paper presents 1H NMR spectroscopy as a perspective method of the studies of the characteristics of water boundary layers in the hydrated powders and aqueous dispergated suspensions of the adsorbents. The method involves measurements of temperature dependence proton signals intensity in the adsorbed water at temperatures lower than 273 K. Free energy of water molecules at the adsorbent/water interface is diminished due to the adsorption interactions causing the water dosed to the adsorbent surface freezes at T < 273 K. Thickness of a non-freezing layer of water can be determined from the intensity of the water signal of 1H NMR during the freezing-thawing process. Due to a disturbing action of the adsorbent surface, water occurs in the quasi-liquid state. As a result, it is observed in the 1H NMR spectra as a relatively narrow signal. The signal of ice is not registered due to great differences in the transverse relaxation times of the adsorbed water and ice. The method of measuring the free surface energy of the adsorbents from the temperature dependence of the signal intensity of non-freezing water is based on the fact that the temperature of water freezing decreases by the quantity which depends on the surface energy and the distance of the adsorbed molecules from the solid surface. The water at the interface freezes when the free energies of the adsorbed water and ice are equal. To illustrate the applicability of the method under consideration the series of adsorption systems in which the absorbents used differed in the surface chemistry and porous structure. In particular, the behaviour of water on the surface of the following adsorbents is discussed: non-porous and porous silica (aerosils, silica gels); chemically and physically modified non-porous and porous silica (silanization, carbonization, biopolymer deposition); and pyrogeneous Al2O3 and aluminasilicas. The effect of preliminary treatment of the adsorbent (thermal, high pressure, wetting with polar

  13. 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.

  14. Gas sensing with surface acoustic wave devices

    NASA Astrophysics Data System (ADS)

    Martin, S. J.; Schweizer, K. S.; Ricco, A. J.; Zipperian, T. E.

    1985-03-01

    The use of a ZnO-on-Si surface acoustic wave (SAW) resonator as a gas sensor is discussed. In particular, the sensitivity of the device to organic vapors is examined. The planar nature of the SAW device, in which the acoustic energy is confined to within roughly one acoustic wavelength of the surface, makes the device extremely sensitive to surface perturbations. This characteristic has been exploited in the construction of SAW gas sensors in which the surface wave propagation characteristics are altered by species adsorbed from the ambient gas. The porous nature of the sputtered ZnO film, in conjunction with the microbalance capability of the SAW device, gives the sensor the ability to distinguish molecules on the basis of both size and mass.

  15. Thermodynamic formalism of water uptakes on solid porous adsorbents for adsorption cooling applications

    NASA Astrophysics Data System (ADS)

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-01

    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.

  16. 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.

  17. A theoretical study of the interaction of hydrogen and oxygen with palladium or gold adsorbed on pyridine-like nitrogen-doped graphene.

    PubMed

    Rangel, Eduardo; Magana, Luis Fernando; Sansores, Luis Enrique

    2014-12-15

    The interaction of H2 and O2 molecules in the presence of nitrogen-doped graphene decorated with either a palladium or gold atom was investigated by using density functional theory. It was found that two hydrogen molecules were adsorbed on the palladium atom. The interaction of these adsorbed hydrogen molecules with two oxygen molecules generates two hydrogen peroxide molecules first through a Eley-Rideal mechanism and then through a Langmuir-Hinshelwood mechanism. The barrier energies for this reaction were small; therefore, we expect that this process may occur spontaneously at room temperature. In the case of gold, a single hydrogen molecule is adsorbed and dissociated on the metal atom. The interaction of the dissociated hydrogen molecule on the surface with one oxygen molecule generates a water molecule. The competitive adsorption between oxygen and hydrogen molecules slightly favors oxygen adsorption.

  18. 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.

  19. Contacting organic molecules by soft methods: towards molecule-based electronic devices.

    PubMed

    Haick, Hossam; Cahen, David

    2008-03-01

    Can we put organic molecules to use as electronic components? The answer to this question is to no small degree limited by the ability to contact them electrically without damaging the molecules. In this Account, we present some of the methods for contacting molecules that do not or minimally damage them and that allow formation of electronic junctions that can become compatible with electronics from the submicrometer to the macroscale. In "Linnaean" fashion, we have grouped contacting methods according to the following main criteria: (a) is a chemical bond is required between contact and molecule, and (b) is the contact "ready-made", that is, preformed, or prepared in situ? Contacting methods that, so far, seem to require a chemical bond include spin-coating a conductive polymer and transfer printing. In the latter, a metallic pattern on an elastomeric polymer is mechanically transferred to molecules with an exposed terminal group that can react chemically with the metal. These methods allow one to define structures from several tens of nanometers size upwards and to fabricate devices on flexible substrates, which is very difficult by conventional techniques. However, the requirement for bifunctionality severely restricts the type of molecules that can be used and can complicate their self-assembly into monolayers. Methods that rely on prior formation of the contact pad are represented by two approaches: (a) use of a liquid metal as electrode (e.g., Hg, Ga, various alloys), where molecules can be adsorbed on the liquid metal and the molecularly modified drop is brought into contact with the second electrode, the molecules can be adsorbed on the second electrode and then the liquid metal brought into contact with them, or bilayers are used, with a layer on both the metal and the second electrode and (b) use of preformed metal pads from a solid substrate and subsequent pad deposition on the molecules with the help of a liquid. These methods allow formation of

  20. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks.

    PubMed

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V; Ku Kang, Jeung; Yaghi, Omar M; Terasaki, Osamu

    2015-11-26

    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.

  1. 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.

  2. Activity of alkaline phosphatase adsorbed and grafted on "polydopamine" films.

    PubMed

    Ball, Vincent

    2014-09-01

    The oxidation of dopamine in slightly basic solutions and in the presence of oxygen as an oxidant allows for the deposition of dopamine-eumelanin ("polydopamine") films on almost all kinds of materials allowing for an easy secondary functionalization. Molecules carrying nucleophilic groups like thiols and amines can be easily grafted on those films. Herein we show that alkaline phosphatase (ALP), as a model enzyme, adsorbs to "polydopamine" films and part of the adsorbed enzyme is rapidly desorbed in contact with Tris buffer. However a significant part of the enzyme remains irreversibly adsorbed and keeps some enzymatic activity for at least 2 weeks whereas ALP adsorbed on quartz slides is rapidly and quantitatively deactivated. In addition we estimated the Michaelis constant Km of the enzyme irreversibly bound to the "polydopamine" film. The Michaelis constant, and hence the affinity constant between paranitrophenol phosphate and ALP are almost identical between the enzyme bound on the film and the free enzyme in solution. Complementarily, it was found that "polydopamine" films display some phosphatase like catalytic activity.

  3. 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.

  4. 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 Astrophysics Data System (ADS)

    Chiou, E. W.; McCormick, M. P.; McMaster, L. R.; Chu, W. P.; Larsen, J. C.; Rind, D.; Oltmans, S.

    1993-03-01

    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°N and 50°S; and, SAGE II continues to make measurements since its launch in October 1984. For both 30°N and 50°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.

  5. 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.

  6. 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.

  7. Perfluorobutane sulfonic acid hydration and interactions with O2 adsorbed on Pt3.

    PubMed

    Yan, Liuming; Balbuena, Perla B; Seminario, Jorge M

    2006-04-06

    The side chain of NAFION, a proton conductive membrane used as electrolyte in low-temperature fuel cells, is modeled with perfluorobutane sulfonic acid. Density functional theory is used to characterize structures and energetics of hydration of the model system interacting with a proton solvated with up to 24 water molecules and analyze interactions of some of these hydrated complexes with O(2) adsorbed on Pt(3). It is found that at least three water molecules are needed to ionize the sulfonic acid, and higher degrees of hydration induce the formation of cages where the water molecules are held together via complex hydrogen-bond networks. The interaction between the complex formed by the ionized acid and the hydrated proton, in contact with a bridge-adsorbed O(2)-Pt(3), promotes the protonation of the adsorbed O(2). Upon protonation, the O(2)-Pt(3) system evolves from hydrophobic to hydrophilic behavior, which may facilitate further interfacial contact.

  8. 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.

  9. Mechanism of dialkyl phthalates removal from aqueous solution using γ-cyclodextrin and starch based polyurethane polymer adsorbents.

    PubMed

    Okoli, Chukwunonso Peter; Adewuyi, Gregory Olufemi; Zhang, Qian; Diagboya, Paul N; Guo, Qingjun

    2014-12-19

    Phthalate esters have been known as potent endocrine disruptors and carcinogens; and their removal from water have been of considerable concern recently. In the present study, γ-cyclodextrin polyurethane polymer (GPP), γ-cyclodextrin/starch polyurethane copolymer (GSP), and starch polyurethane polymer (SPP) have been synthesized and characterized. Their adsorption efficiencies for the removal of dimethyl phthalate (DMP) and diethyl phthalate (DEP) from aqueous solutions were investigated. The characterization results showed the success of the synthesis. The isotherms were L-type, and both the Langmuir and Freundlich adsorption isotherm gave good fittings to the adsorption data. Adsorption mechanisms suggested that these adsorbents spontaneously adsorb phthalate molecules driven mainly by enthalpy change, and the adsorption process was attributed to multiple adsorbent-adsorbate interactions such as hydrogen bonding, π-π stacking, and pore filling. The results showed that starch and γ-cyclodextrin polyurethane polymer adsorbents have excellent potential as adsorbent materials for the removal of phthalates from the contaminated water.

  10. On the reactive uptake of gaseous PAH molecules by micron-sized atmospheric water droplets

    NASA Astrophysics Data System (ADS)

    Raja, S.; Valsaraj, K. T.

    2006-10-01

    A falling droplet reactor was used to study the heterogeneous oxidation of gaseous PAH molecules adsorbed on a 92 μm diameter water droplet by ozone. The dynamic partition constant for the PAH between the droplet and air and the first-order surface rate constant was measured. The increase in uptake with ozone concentration was due to increased mass transfer via surface reaction of co-adsorbed ozone and PAH. The surface rate constant was rationalized through the Langmuir-Hinshelwood mechanism. The rate constant was smaller for phenanthrene than naphthalene. The main reaction products identified in the aqueous phase indicated the peroxidic route for surface reaction of ozone with PAH. The heterogeneous reaction rate of ozone with adsorbed phenanthrene at the air-water interface of a 92-μm droplet was estimated to be 9300 times larger than the homogeneous reaction of ozone with phenanthrene in the gas phase and it was 76 times larger than the homogeneous oxidation by hydroxyl radical in the gas phase. For naphthalene that is more volatile, however, the homogeneous reaction with hydroxyl was more important. Increased organic carbon added to the droplet increased both the partition constant for phenanthrene and surface reaction with ozone. The partition constant for a droplet formed from actual fog water was much larger than for pure distilled water.

  11. 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.

  12. Allantoin as a solid phase adsorbent for removing endotoxins.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

    2013-10-04

    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.

  13. 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.

  14. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    PubMed

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  15. Gas storage potential of ExBox⁴⁺ and its Li-decorated derivative.

    PubMed

    Das, Ranjita; Chattaraj, Pratim Kumar

    2014-10-28

    The newly synthesized compound ExBox(4+) is investigated for possible gas storage ability. The presence of high charge as well as aromatic rings which are some of the anticipated criteria for favorable gas storage makes ExBox(4+) a promising compound for gas adsorption. Considering the two important problems being faced by humankind, viz., energy and environment, possible adsorption of H2 and CO respectively on recently synthesized compound ExBox(4+) is studied with the help of density functional theory (DFT). Endohedral hydrogen molecules interact more strongly than exohedral molecules. The hydrogen storage capacity appears to be ∼4.3 wt% which is close to that of some recently studied materials like ZIF and PAF. The endohedral CO sorption is also analyzed with the help of DFT. The dynamics of the gas bound compound are studied with the help of ADMP simulation. The effects of counter ions on the adsorption energy and bonding interaction are also investigated. The first principle DFT calculation and MD simulation are performed to investigate the effect of lithium doping on the gas adsorbing capacity and adsorption enthalpy as well as adsorption energy of ExBox(4+). The Li decorated ExBox(4+) is capable of adsorbing 6.23 wt% of hydrogen which almost satisfies the goal of DOE. Adsorption of CO on the metal decorated ExBox(4+) is also studied. The nature of the bonding interaction between the gas molecule and the adsorbent is studied with the help of AIM and EDA as well as charge decomposition analysis is performed.

  16. Photocontrolled adsorption of polyelectrolyte molecules on a silicon substrate.

    PubMed

    Malyar, Ivan V; Gorin, Dmitry A; Santer, Svetlana; Stetsyura, Svetlana V

    2013-12-31

    We report on a change in the properties of monomolecular films of polyelectrolyte molecules, induced by illuminating the silicon substrate on which they adsorb. It was found that under illumination the thickness of the adsorbed layer decreases by at least 27% and at the same time the roughness is significantly reduced in comparison to a layer adsorbed without irradiation. Furthermore, the homogeneity of the film topography and the surface potential is shown to be improved by illumination. The effect is explained by a change in surface charge density under irradiation of n- and p-type silicon wafers. The altered charge density in turn induces conformational changes of the adsorbing polyelectrolyte molecules. Their photocontrolled adsorption opens new possibilities for selective manipulation of adsorbed films. This possibility is of potential importance for many applications such as the production of well-defined coatings in biosensors or microelectronics.

  17. 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.

  18. 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.

  19. 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.

  20. On the orientational effects in monolayers of diatomic molecules

    NASA Astrophysics Data System (ADS)

    Patrykiejew, A.; Sałamacha, A.; Sokołowski, S.; Zientarski, T.; Binder, K.

    2001-09-01

    The Monte Carlo simulation method is used to study orientational ordering in monolayer films of diatomic molecules on the (100) plane of face centered cubic crystal. Systems of admolecules with different elongation are studied and their orientational and positional ordering discussed. It is shown that in the case of small elongations the adsorbed monolayer orders into a simple (1×1) structure. When the elongation of adsorbed molecules increases, the film orders into more complex structures. In such cases, the adsorbate lattice decomposes into four interpenetrating sublattices.

  1. 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.

  2. 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.

  3. 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

  4. Gas adsorption properties of graphene-based materials.

    PubMed

    Szczęśniak, Barbara; Choma, Jerzy; Jaroniec, Mietek

    2017-03-20

    Clean energy sources and global warming are among the major challenges of the 21st century. One of the possible actions toward finding alternative energy sources and reducing global warming are storage of H2 and CH4, and capture of CO2 by using highly efficient and low-cost adsorbents. Graphene and graphene-based materials attracted a great attention around the world because of their potential for a variety applications ranging from electronics, gas sensing, energy storage and CO2 capture. Large specific surface area of these materials up to ~3000m(2)/g and versatile modification make them excellent adsorbents for diverse applications. Here, graphene-based adsorbents are reviewed with special emphasis on their adsorption affinity toward CO2, H2 and CH4. This review shows that graphene derivatives obtained mainly via "chemical exfoliation" of graphite and further modification with polymers and/or metal species can be very effective sorbents for CO2 and other gases and can compete with the currently used carbonaceous or non-carbonaceous adsorbents. The high adsorption capacities of graphene-based materials are mainly determined by their unique nanostructures, high specific surface areas and tailorable surface properties, which make them suitable for storage or capture of various molecules relevant for environmental and energy-related applications.

  5. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    DOE PAGES

    Gill, Gary A.; Kuo, Li -Jung; Janke, Christopher James; ...

    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

  6. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    SciTech Connect

    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; Wood, Jordana R.; Warner, Marvin G.; Peterson, Sonja; Abrecht, David G.; Mayes, Richard T.; Tsouris, Costas; Oyola, Yatsandra; Strivens, Jonathan E.; Schlafer, Nicholas J.; Addleman, Shane R.; Chouyyok, Wilaiwan; Das, Sadananda; Kim, Jungseung; Buesseler, Ken; Breier, Crystal; D'Alessandro, Evan

    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 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

  7. Modeling Adsorption and Reactions of Organic Molecules at Metal Surfaces

    PubMed Central

    2014-01-01

    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+vdWsurf method that accurately accounts for the collective electronic

  8. 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

  9. 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.

  10. 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.

  11. Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Brucato, John Robert; Pace, Emanuele; Pucci, Amaranta; Branciamore, Sergio; Cestelli Guidi, Mariangela; Fornaro, Teresa

    The interaction between electromagnetic radiation and bio-molecules in heterogeneous environments is a prebiotically relevant process. Minerals may have a pivotal role in the prebiotic evolution of complex chemical systems, mediating the effects of electromagnetic radiation, influencing the photostability of bio-molecules, catalyzing important chemical reactions and/or protecting molecules against degradation. In particular, nucleobases are relevant bio-molecules to investigate both in the prebiotic context, because they are coding components of nucleic acids, and from the standpoint of the survival of biological systems in space conditions. In this talk, laboratory results on photostability of nucleobases adsorbed on minerals will be presented.

  12. 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

  13. SDS-assisted hydrothermal synthesis of NiO flake-flower architectures with enhanced gas-sensing properties

    NASA Astrophysics Data System (ADS)

    Miao, Ruiyang; Zeng, Wen; Gao, Qi

    2016-10-01

    A facile hydrothermal route was developed for the preparation of well-aligned hierarchical flower-like NiO nanostructure with the assistance of SDS that served as a structure-directing agent as well as a capping agent in the process of aggregation and assembly. Notably, the NiO sensors exhibit enhanced gas-sensing performance towards ethanol, which could be explained in association with the ultrathin nanosheets that are close to Debye length (LD) scale and thus get the majority carriers fully depleted due to the ionization of adsorbed oxygen, abundant effective gas diffusion paths as well as high surface-to-volume ratio to promote sufficient contact and reaction between the NiO sample and ethanol molecules, and numerous miniature reaction rooms assembled with nanosheets to make the test gas molecules stay long enough for completed gas-sensing reactions. Besides, a novel growth mechanism with the passage of reaction time was also proposed in detail.

  14. Dynamics of Activated Molecules

    SciTech Connect

    Mullin, Amy S.

    2016-11-16

    Experimental studies have been performed to investigate the collisional energy transfer processes of gas-phase molecules that contain large amounts of internal energy. Such molecules are prototypes for molecules under high temperature conditions relevant in combustion and information about their energy transfer mechanisms is needed for a detailed understanding and modeling of the chemistry. We use high resolution transient IR absorption spectroscopy to measure the full, nascent product distributions for collisions of small bath molecules that relax highly vibrationally excited pyrazine molecules with E=38000 cm-1 of vibrational energy. To perform these studies, we developed new instrumentation based on modern IR light sources to expand our experimental capabilities to investigate new molecules as collision partners. This final report describes our research in four areas: the characterization of a new transient absorption spectrometer and the results of state-resolved collision studies of pyrazine(E) with HCl, methane and ammonia. Through this research we have gained fundamental new insights into the microscopic details of relatively large complex molecules at high energy as they undergo quenching collisions and redistribute their energy.

  15. Miscibility and interaction between 1-alkanol and short-chain phosphocholine in the adsorbed film and micelles.

    PubMed

    Takajo, Yuichi; Matsuki, Hitoshi; Kaneshina, Shoji; Aratono, Makoto; Yamanaka, Michio

    2007-09-01

    The miscibility and interaction of 1-hexanol (C6OH) and 1-heptanol (C7OH) with 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the adsorbed films and micelles were investigated by measuring the surface tension of aqueous C6OH-DHPC and aqueous C7OH-DHPC solutions. The surface density, the mean molecular area, the composition of the adsorbed film, and the excess Gibbs energy of adsorption g(H,E), were estimated. Further, the critical micelle concentration of the mixtures was determined from the surface tension versus molality curves; the micellar composition was calculated. The miscibility of the 1-alkanols and DHPC molecules in the adsorbed film and micelles was examined using the phase diagram of adsorption (PDA) and that of micellization (PDM). The PDA and the composition dependence of g(H,E) indicated the non-ideal mixing of the 1-alkanols and DHPC molecules due to the attractive interaction between the molecules in the adsorbed film, while the PDM indicated that the 1-alkanol molecules were not incorporated in the micelles within DHPC rich region. The dependence of the mean molecular area of the mixtures on the surface composition suggested that the packing property of the adsorbed film depends on the chain length of 1-alkanol: C6OH expands the DHPC adsorbed film more than C7OH.

  16. 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)

  17. Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of three barbiturates in pork by ion trap gas chromatography-tandem mass spectrometry (GC/MS/MS) following microwave assisted derivatization.

    PubMed

    Zhao, Haixiang; Wang, Liping; Qiu, Yueming; Zhou, Zhiqiang; Zhong, Weike; Li, Xiang

    2007-03-14

    A new method was developed for the rapid screening and confirmation analysis of barbital, amobarbital and phenobarbital residues in pork by gas chromatography-tandem mass spectrometry (GC/MS/MS) with ion trap MSD. The residual barbiturates in pork were extracted by ultrasonic extraction, cleaned up on a multiwalled carbon nanotubes (MWCNTs) packed solid phase extraction (SPE) cartridge and applied acetone-ethyl acetate (3:7, v/v) mixture as eluting solvent and derivatized with CH3I under microwave irradiation. The methylated barbiturates were separated on a TR-5MS capillary column and detected with an ion trap mass detector. Electron impact ion source (EI) operating MS/MS mode was adopted for identification and external standard method was employed for quantification. One precursor ion m/z 169 was selected for analysis of barbital and amobarbital and m/z 232 was selected for phenobarbital. The product ions were obtained under 1.0 V excitation voltage. Good linearities (linear coefficient R > 0.99) were obtained at the range of 0.5-50 microg kg(-1). Limit of detection (LOD) of barbital was 0.2 microg kg(-1) and that of amobarbital and phenobarbital were both 0.1 microg kg(-1) (S/N > or = 3). Limit of quantification (LOQ) was 0.5 microg kg(-1) for three barbiturates (S/N > or = 10). Satisfying recoveries ranging from 75% to 96% of the three barbiturates spiked in pork were obtained, with relative standard deviations (R.S.D.) in the range of 2.1-7.8%.

  18. NOx adsorber and method of regenerating same

    DOEpatents

    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.

  19. 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

    SciTech Connect

    Makarov, G N; Petin, A N

    2016-03-31

    We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with 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. (laser separation of isotopes)

  20. 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.

  1. 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.

  2. Scanning tunneling microscopy and spectroscopy of individual C 60 molecules on Si(100)-(2 × 1) surfaces

    NASA Astrophysics Data System (ADS)

    Yao, Xiaowei; Ruskell, Todd G.; Workman, Richard K.; Sarid, Dror; Chen, Dong

    1996-11-01

    Individual C 60 molecules chemisorbed on Si(100)-(2 × 1) surfaces have been studied by scanning tunneling microscopy and spectroscopy. Chemisorption was realized by annealing the samples with room-temperature deposited adsorbates to 600°C. Spectroscopic results on individual adsorbates reveal a transition of their electronic structure from that of a near-free adsorbate to that of SiC, as the adsorbate-substrate interaction increases.

  3. Comparison of adsorbents for H2S and D4 removal for biogas conversion in a solid oxide fuel cell.

    PubMed

    Sigot, Léa; Ducom, Gaëlle; Benadda, Belkacem; Labouré, Claire

    2016-01-01

    Biogas contains trace compounds detrimental for solid oxide fuel cell (SOFC) application, especially sulphur-containing compounds and volatile organic silicon compounds (VOSiCs). It is therefore necessary to remove these impurities from the biogas for fuelling an SOFC. In this paper, dynamic lab-scale adsorption tests were performed on synthetic polluted gas to evaluate the performance of a polishing treatment to remove hydrogen sulphide (H2S - sulphur compound) and octamethylcyclotetrasiloxane (D4 - VOSiC). Three kinds of adsorbents were tested: an activated carbon, a silica gel (SG) and a zeolite (Z). Z proved to be the best adsorbent for H2S removal, with an adsorbed quantity higher than [Formula: see text] at the SOFC tolerance limit. However, as concerns D4 removal, SG was the most efficient adsorbent, with an adsorbed quantity of about 184 mgD4/gSG at the SOFC tolerance limit. These results could not be explained by structural characteristics of the adsorbents, but they were partly explained by chemical interactions between the adsorbate and the adsorbent. In these experiments, internal diffusion was the controlling step, Knudsen diffusion being predominant to molecular diffusion. As Z was also a good adsorbent for D4 removal, competition phenomena were investigated with Z for the simultaneous removal of H2S and D4. It was shown that H2S retention was dramatically decreased in the presence of D4, probably due to D4 polymerization resulting in pore blocking.

  4. Structure of CO2 adsorbed on the KCl(100) surface.

    PubMed

    Traeger, Franziska; Hadnadjev, Milica; Vogt, Jochen; Weiss, Helmut

    2011-06-30

    The structure and dynamics of the adsorbate CO(2)/KCl(100) from a diluted phase to a saturated monolayer have been investigated with He atom scattering (HAS), low-energy electron diffraction (LEED), and polarization dependent infrared spectroscopy (PIRS). Two adsorbate phases with different CO(2) coverage have been found. The low-coverage phase is disordered at temperatures near 80 K and becomes at least partially ordered at lower temperatures, characterized by a (2√2×√2)R45° diffraction pattern. The saturated 2D phase has a high long-range order and exhibits (6√2×√2)R45° symmetry. Its isosteric heat of adsorption is 26 ± 4 kJ mol(-1). According to PIRS, the molecules are oriented nearly parallel to the surface, the average tilt angle in the saturated monolayer phase is 10° with respect to the surface plane. For both phases, structure models are proposed by means of potential calculations. For the saturated monolayer phase, a striped herringbone structure with 12 inequivalent molecules is deduced. The simulation of infrared spectra based on the proposed structures and the vibrational exciton approach gives reasonable agreement between experimental and simulated infrared spectra.

  5. Thin Film Transistor Gas Sensors Incorporating High-Mobility Diketopyrrolopyrole-Based Polymeric Semiconductor Doped with Graphene Oxide.

    PubMed

    Cheon, Kwang Hee; Cho, Jangwhan; Kim, Yun-Hi; Chung, Dae Sung

    2015-07-01

    In this work, we fabricated a diketopyrrolopyrole-based donor-acceptor copolymer composite film. This is a high-mobility semiconductor component with a functionalized-graphene-oxide (GO) gas-adsorbing dopant, used as an active layer in gas-sensing organic-field-effect transistor (OFET) devices. The GO content of the composite film was carefully controlled so that the crystalline orientation of the semiconducting polymer could be conserved, without compromising its gas-adsorbing ability. The resulting optimized device exhibited high mobility (>1 cm(2) V(-1) s(-1)) and revealed sensitive response during programmed exposure to various polar organic molecules (i.e., ethanol, acetone, and acetonitrile). This can be attributed to the high mobility of polymeric semiconductors, and also to their high surface-to-volume ratio of GO. The operating mechanism of the gas sensing GO-OFET is fully discussed in conjunction with charge-carrier trap theory. It was found that each transistor parameter (e.g., mobility, threshold voltage), responds independently to each gas molecule, which enables high selectivity of GO-OFETs for various gases. Furthermore, we also demonstrated practical GO-OFET devices that operated at low voltage (<1.5 V), and which successfully responded to gas exposure.

  6. Interstellar Molecules

    ERIC Educational Resources Information Center

    Solomon, Philip M.

    1973-01-01

    Radioastronomy reveals that clouds between the stars, once believed to consist of simple atoms, contain molecules as complex as seven atoms and may be the most massive objects in our Galaxy. (Author/DF)

  7. Modeling Molecules

    NASA Technical Reports Server (NTRS)

    2000-01-01

    The molecule modeling method known as Multibody Order (N) Dynamics, or MBO(N)D, was developed by Moldyn, Inc. at Goddard Space Flight Center through funding provided by the SBIR program. The software can model the dynamics of molecules through technology which stimulates low-frequency molecular motions and properties, such as movements among a molecule's constituent parts. With MBO(N)D, a molecule is substructured into a set of interconnected rigid and flexible bodies. These bodies replace the computation burden of mapping individual atoms. Moldyn's technology cuts computation time while increasing accuracy. The MBO(N)D technology is available as Insight II 97.0 from Molecular Simulations, Inc. Currently the technology is used to account for forces on spacecraft parts and to perform molecular analyses for pharmaceutical purposes. It permits the solution of molecular dynamics problems on a moderate workstation, as opposed to on a supercomputer.

  8. Mobius Molecules

    ERIC Educational Resources Information Center

    Eckert, J. M.

    1973-01-01

    Discusses formation of chemical molecules via Mobius strip intermediates, and concludes that many special physics-chemical properties of the fully closed circular form (1) of polyoma DNA are explainable by this topological feature. (CC)

  9. 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.

  10. Enumerating molecules.

    SciTech Connect

    Visco, Donald Patrick, Jr.; Faulon, Jean-Loup Michel; Roe, Diana C.

    2004-04-01

    This report is a comprehensive review of the field of molecular enumeration from early isomer counting theories to evolutionary algorithms that design molecules in silico. The core of the review is a detail account on how molecules are counted, enumerated, and sampled. The practical applications of molecular enumeration are also reviewed for chemical information, structure elucidation, molecular design, and combinatorial library design purposes. This review is to appear as a chapter in Reviews in Computational Chemistry volume 21 edited by Kenny B. Lipkowitz.

  11. Infrared Analysis Of Enzymes Adsorbed Onto Model Surfaces

    NASA Astrophysics Data System (ADS)

    Story, Gloria M.; Rauch, Deborah S.; Brode, Philip F.; Marcott, Curtis A.

    1989-12-01

    The adsorption of the enzymes, subtilisin BPN' and lysozyme, onto model surfaces was examined using attenuated total reflectance (ATR) infrared (IR) spectroscopy. Using a cylindrical internal reflection (CIRcle) cell with a Germanium (Ge) internal reflection element (IRE), model hydrophilic surfaces were made by plasma cleaning the IRE and model hydrophobic surfaces were made by precoating the IRE with a thin film of polystyrene. Gas chromatography (GC)-IR data collection software was used to monitor adsorption kinetics during the first five minutes after injection of the enzyme into the CIRcle cell. It was found that for both lysozyme and BPN', most of the enzyme that was going to adsorb onto the model surface did so within ten seconds after injection. Nearly an order-of-magnitude more BPN' adsorbed on the hydrophobic Ge surface than the hydrophilic one, while lysozyme adsorbed somewhat more strongly to the hydrophilic Ge surface. Overnight, the lysozyme layer continued to increase in thickness, while BPN' maintained its initial coverage. The appearance of carboxylate bands in some of the adsorbed BPN' spectra suggests the occurrence of peptide bond hydrolysis. A Au/Pd coating on the CIRcle cell o-rings had a significant effect on the adsorption of BPN'. (This coating was applied in an attempt to eliminate interfering Teflon absorption bands.) An apparent electrochemical reaction occurred, involving BPN', Ge, Au/Pd, and the salt solution used to stabilize BPN'. The result of this reaction was enhanced adsorption of the enzyme around the coated o-rings, etching of the Ge IRE at the o-ring site, and some autolysis of the enzyme. No such reaction was observed with lysozyme.

  12. Heat transfer to the adsorbent in solar adsorption cooling device

    NASA Astrophysics Data System (ADS)

    Pilat, Peter; Patsch, Marek; Papucik, Stefan; Vantuch, Martin

    2014-08-01

    The article deals with design and construction of solar adsorption cooling device and with heat transfer problem in adsorber. The most important part of adsorption cooling system is adsorber/desorber containing adsorbent. Zeolith (adsorbent) type was chosen for its high adsorption capacity, like a coolant was used water. In adsorber/desorber occur, at heating of adsorbent, to heat transfer from heat change medium to the adsorbent. The time required for heating of adsorber filling is very important, because on it depend flexibility of cooling system. Zeolith has a large thermal resistance, therefore it had to be adapted the design and construction of adsorber. As the best shows the tube type of adsorber with double coat construction. By this construction is ensured thin layer of adsorbent and heating is quick in all volume of adsorbent. The process of heat transfer was experimentally measured, but for comparison simulated in ANSYS, too.

  13. New BET-like models for heterogeneous adsorption in microporous adsorbents

    NASA Astrophysics Data System (ADS)

    Milewska-Duda, Janina; Duda, Jan T.

    2002-08-01

    The paper presents a package of isotherm equations for heterogeneous adsorption aimed at the analysis of pore structure of sub- and microporous materials. One considers adsorption of small nearly spherical molecules in irregular pores of molecular size. The generalized BET theory is exploited respecting restrictions for multilayer adsorption (LBET approach). The model is based on thermodynamic relationships expressing changes of internal energy and configurational entropy due to the process. The adsorption energy is evaluated by using the Berthelot rule, and corrected with a factor Z a representing a fraction of effective contacts enabling full adsorbent-adsorbate interaction. Side adsorbate-adsorbate interactions are neglected and constrained multilayer adsorption is considered. One assumes the values for Z a to be uniformly distributed over the first layer adsorption sites within a range depending on the pore size. New models make it possible to obtain information on structure of pores and adsorption mechanisms on the basis of adsorption isotherms of small molecule adsorbates. Exemplary results of new models application for adsorption of CO 2 and CH 4 in an activated carbon are discussed.

  14. Adsorption mechanism of water molecule on goethite (010) surface

    NASA Astrophysics Data System (ADS)

    Xiu, Fangyuan; Zhou, Long; Xia, Shuwei; Yu, Liangmin

    2016-12-01

    Goethite widely exists among ocean sediments; it plays an important role in fixing heavy metals and adsorbing organic contaminants. So the understanding of the adsorbing process of water molecule on its surface will be very helpful to further reveal such environmental friendly processes. The configuration, electronic properties and interaction energy of water molecules adsorbed on pnma goethite (010) surface were investigated in detail by using density functional theory on 6-31G (d,p) basis set and projector- augment wave (PAW) method. The mechanism of the interaction between goethite surface and H2O was proposed. Despite the differences in total energy, there are four possible types of water molecule adsorption configurations on goethite (010) surface (Aa, Ab, Ba, Bb), forming coordination bond with surface Fe atom. Results of theoretical modeling indicate that the dissociation process of adsorbed water is an endothermic reaction with high activation energy. The dissociation of adsorbed water molecule is a proton transportation process between water's O atoms and surface. PDOS results indicate that the bonding between H2O and (010) surface is due to the overlapping of water's 2p orbitals and Fe's 3d orbitals. These results clarify the mechanism on how adsorbed water is dissociated on the surface of goethite and potentially provide useful information of the surface chemistry of goethite.

  15. Universal singularities of multilayer adsorption isotherms and determination of surface area of adsorbents

    SciTech Connect

    Aranovich, G.L.; Donohue, M.D.

    1996-07-15

    The singularity in the adsorption isotherm for macroporous and nonporous adsorbents is considered as a universal function that can be characterized with two parameters: a coefficient of proportionality, K, and an exponent, d. It is shown that the value of K is proportional to the adsorbent surface area but does not depend on the nature of the adsorbent. This leads to a new method to determine the surface area of an adsorbent, S, that is independent of the form of the adsorption isotherm at low and moderate reduced pressures. Comparison with the BET areas for nitrogen shows that the new method gives the values of S which are very close to the BET results if K = 1.47 {times} 10{sup {minus}5} mol/m{sup 2} (for nitrogen). Analysis of adsorption data for macroporous adsorbents shows that the BET isotherm gives systematic deviations and that the experimental amount adsorbed is smaller than the value predicted by the BET equation (even in the range of the best agreement with experiment). These deviations lead to systematic error in the values of S of about 43%. Using K equal to K{sub f} = 1/{sigma}N{sub A} (=1.025 {times} 10{sup {minus}5} mol/m{sup 2} for nitrogen), the authors are able to eliminate systematic error in the surface area determination. Here {sigma} is the area occupied by one molecule and N{sub A} is the Avogadro number.

  16. Activity of catalase adsorbed to carbon nanotubes: effects of carbon nanotube surface properties.

    PubMed

    Zhang, Chengdong; Luo, Shuiming; Chen, Wei

    2013-09-15

    Nanomaterials have been studied widely as the supporting materials for enzyme immobilization. However, the interactions between enzymes and carbon nanotubes (CNT) with different morphologies and surface functionalities may vary, hence influencing activities of the immobilized enzyme. To date how the adsorption mechanisms affect the activities of immobilized enzyme is not well understood. In this study the adsorption of catalase (CAT) on pristine single-walled carbon nanotubes (SWNT), oxidized single-walled carbon nanotubes (O-SWNT), and multi-walled carbon nanotubes (MWNT) was investigated. The adsorbed enzyme activities decreased in the order of O-SWNT>SWNT>MWNT. Fourier transforms infrared spectroscopy (FTIR) and circular dichrois (CD) analyses reveal more significant loss of α-helix and β-sheet of MWNT-adsorbed than SWNT-adsorbed CAT. The difference in enzyme activities between MWNT-adsorbed and SWNT-adsorbed CAT indicates that the curvature of surface plays an important role in the activity of immobilized enzyme. Interestingly, an increase of β-sheet content was observed for CAT adsorbed to O-SWNT. This is likely because as opposed to SWNT and MWNT, O-SWNT binds CAT largely via hydrogen bonding and such interaction allows the CAT molecule to maintain the rigidity of enzyme structure and thus the biological function.

  17. High resolution UV resonance enhanced two-photon ionization spectroscopy with mass selection of biologically relevant molecules in the gas phase

    NASA Astrophysics Data System (ADS)

    Chervenkov, S.; Wang, P. Q.; Karaminkov, R.; Chakraborty, T.; Braun, Juergen E.; Neusser, Hans J.

    2005-04-01

    The high resolution Doppler-free resonance-enhanced two-photon ionization (R2PI) spectroscopy with mass selection of jet-cooled (2-12 K) molecular species is a powerful experimental method providing comprehensive information on both isolated molecules and molecular clusters. We have demonstrated for the first time that this technique can be applied to large molecules and provides detailed information on their conformational structure. It allows rotationally resolved (FWHM = 70 MHz) spectra of the vibronic bands of the S1<--S0 electronic transition of the studied molecular systems to be measured. A specially designed computer-assisted fitting routine based on genetic algorithms is used to determine their rotational constants in the ground and excited electronic states, respectively, and the transition moment ratio. To interpret the experimental information and to discriminate and unambiguously assign the observed approach to the study of the neurotransmitter molecule, ephedrine. The results elucidate the role of the intramolecular hydrogen bonds stabilizing the respective conformations and affecting their intrinsic properties.

  18. PERVAPORATION USING ADSORBENT-FILLED MEMBRANES

    EPA Science Inventory

    Membranes containing selective fillers, such as zeolites and activated carbon, can improve the separation by pervaporation. Applications of adsorbent-filled membranes in pervaporation have been demonstrated by a number of studies. These applications include removal of organic co...

  19. Chitin Adsorbents for Toxic Metals: A Review

    PubMed Central

    Anastopoulos, Ioannis; Bhatnagar, Amit; Bikiaris, Dimitrios N.; Kyzas, George Z.

    2017-01-01

    Wastewater treatment is still a critical issue all over the world. Among examined methods for the decontamination of wastewaters, adsorption is a promising, cheap, environmentally friendly and efficient procedure. There are various types of adsorbents that have been used to remove different pollutants such as agricultural waste, compost, nanomaterials, algae, etc., Chitin (poly-β-(1,4)-N-acetyl-d-glucosamine) is the second most abundant natural biopolymer and it has attracted scientific attention as an inexpensive adsorbent for toxic metals. This review article provides information about the use of chitin as an adsorbent. A list of chitin adsorbents with maximum adsorption capacity and the best isotherm and kinetic fitting models are provided. Moreover, thermodynamic studies, regeneration studies, the mechanism of adsorption and the experimental conditions are also discussed in depth. PMID:28067848

  20. Monitoring by Control Technique - Activated Carbon Adsorber

    EPA Pesticide Factsheets

    Stationary source emissions monitoring is required to demonstrate that a source is meeting the requirements in Federal or state rules. This page is about Activated Carbon Adsorber control techniques used to reduce pollutant emissions.

  1. IR investigations of surfaces and adsorbates

    SciTech Connect

    Gwyn Williams

    2001-12-10

    Synchrotron infrared reflection-absorption measurements on single crystal metal surfaces with adsorbates have led to the determination of many key parameters related to the bonding vibrational modes and the dynamics of adsorbates. In particular, energy couplings between electrons and adsorbate motion have been shown to be a dominant mechanism on metal surfaces. Excellent agreement has been obtained with calculations for many of the observations, and the synergy between theory and experiment has led to a deeper understanding of the roles of electrons and phonons in determining the properties of interfaces and their roles in phenomena as diverse as friction, lubrication, catalysis and adhesion. Nonetheless, as the experiments are pushed harder, to describe such effects as co-adsorbed systems, disagreements continue to challenge the theory and our comprehension also is still evolving.

  2. Growth and Dissolution of Calcite in the Presence of Adsorbed Stearic Acid.

    PubMed

    Ricci, Maria; Segura, Juan José; Erickson, Blake W; Fantner, Georg; Stellacci, Francesco; Voïtchovsky, Kislon

    2015-07-14

    The interaction of organic molecules with the surface of calcite plays a central role in many geochemical, petrochemical, and industrial processes and in biomineralization. Adsorbed organics, typically fatty acids, can interfere with the evolution of calcite when immersed in aqueous solutions. Here we use atomic force microscopy in liquid to explore in real-time the evolution of the (1014) surface of calcite covered with various densities of stearic acid and exposed to different saline solutions. Our results show that the stearic acid molecules tend to act as "pinning points" on the calcite's surface and slow down the crystal's restructuring kinetics. Depending on the amount of material adsorbed, the organic molecules can form monolayers or bilayer islands that become embedded into the growing crystal. The growth process can also displaces the organic molecules and actively concentrate them into stacked multilayers. Our results provide molecular-level insights into the interplay between the adsorbed fatty acid molecules and the evolving calcite crystal, highlighting mechanisms that could have important implications for several biochemical and geochemical processes and for the oil industry.

  3. [Effects of adsorbents on partitioning and fixation of heavy metals in the incineration process of sewage sludge].

    PubMed

    Liu, Jing-Yong; Sun, Shui-Yu; Chen, Tao

    2013-03-01

    Experiments were carried out on laboratory-scale electrically heated tube furnace sewage sludge combustion with different adsorbents. Four solid adsorbents (calcium oxide, Alumina, fly ash and kaolin) were used to control the emission of heavy metals (Pb, Cd, Cu, Cr, Ni, Zn) during the sewage sludge incineration. The results showed that the heavy metals tended to be fixed and left over in the incineration bottom ash with the addition of calcium oxide, Alumina, fly ash and kaolin. With the increase of the solid adsorbent ratio, the residual rate of heavy metals in the bottom ash also increased. Incineration temperature had a great influence on the heavy metal adsorption effect of the solid adsorbent. The forms, melting point and boiling point of the heavy metals were found to be important factors that determined its volatility. There was huge difference in the inhibitory effect of different adsorbents on heavy metals migration. From the view of controlling heavy metal evaporation, the adsorbents kaolin and CaO were superior to the other adsorbents. The interaction between the active center of the solid adsorbent and the molecules of the heavy metal compounds depended on the distribution of these active sites and the chemical properties of the heavy metals.

  4. Modulation of the molecular spintronic properties of adsorbed copper corroles

    PubMed Central

    Wu, Fan; Liu, Jie; Mishra, Puneet; Komeda, Tadahiro; Mack, John; Chang, Yi; Kobayashi, Nagao; Shen, Zhen

    2015-01-01

    The ability to modulate the spin states of adsorbed molecules is in high demand for molecular spintronics applications. Here, we demonstrate that the spin state of a corrole complex can be tuned by expanding its fused ring as a result of the modification to the d–π interaction between the metal and ligand. A bicyclo[2.2.2]octadiene-fused copper corrole can readily be converted into a tetrabenzocorrole radical on an Au(111) substrate during the sublimation process. In the scanning tunnelling spectroscopy spectrum, a sharp Kondo resonance appears near the Fermi level on the corrole ligand of the tetrabenzocorrole molecule. In contrast, a non-fused-ring-expanded copper corrole molecule, copper 5,10,15-triphenylcorrole, shows no such Kondo feature. Mapping of the Kondo resonance demonstrates that the spin distribution of the tetrabenzocorrole molecule can be further modified by the rotation of the meso-aryl groups, in a manner that could lead to applications in molecular spintronics. PMID:26112968

  5. Quartz crystal studies of {sup 4}He adsorbed to C{sub 60}

    SciTech Connect

    Ketola, K.S.; Wang, S.; Hallock, B.

    1993-04-01

    The authors report measurements of the frequency of oscillation of quartz crystals as a function of {sup 4}He adsorption for the case of bare quartz crystals and quartz crystals coated with 400 {angstrom} and 800 {angstrom} of C{sub 60}. The superfluid transition is seen in the {sup 4}He adsorbed to the C{sub 60}. A preliminary analysis of the data at T = 1.51 K indicates that no more than 0.24 helium atoms per C{sub 60} molecules are adsorbed into the C{sub 60} matrix at 1.51 K.

  6. Carbon 1s photoemission line analysis of C-based adsorbate on (111)In2O3 surface: The influence of reducing and oxidizing conditions

    NASA Astrophysics Data System (ADS)

    Brinzari, V.; Cho, B. K.; Korotcenkov, G.

    2016-12-01

    Synchrotron radiation photoemission study of C 1s line of (111) In2O3 surface was carried out under HV (high vacuum) doses of oxygen, carbon monoxide and water. Gas interaction with the surface was activated by heating of In2O3 monocrystalline film at temperatures of 160 or 250 °C. The study of complex structure of C 1 s line and evolution of its fine components allowed to establish their nature and to propose possible surface adsorbed species and reactions, including a direct chemisorption and dissociation of CO molecules. Reduction or oxidation of the surface determines whether the first (chemisorption) or the second (dissociation) process takes place. The latter is responsible for additional formation of ionosorbed oxygen. Both processes have not been previously reported for In2O3 and for conductive metal oxides.

  7. Critical lines for an unequal size of molecules in a binary gas-liquid mixture around the van Laar point using the combination of the Tompa model and the van der Waals equation.

    PubMed

    Gençaslan, Mustafa; Keskin, Mustafa

    2012-02-14

    We combine the modified Tompa model with the van der Waals equation to study critical lines for an unequal size of molecules in a binary gas-liquid mixture around the van Laar point. The van Laar point is coined by Meijer and it is the only point at which the mathematical double point curve is stable. It is the intersection of the tricritical point and the double critical end point. We calculate the critical lines as a function of χ(1) and χ(2), the density of type I molecules and the density of type II molecules for various values of the system parameters; hence the global phase diagrams are presented and discussed in the density-density plane. We also investigate the connectivity of critical lines at the van Laar point and its vicinity and discuss these connections according to the Scott and van Konynenburg classifications. It is also found that the critical lines and phase behavior are extremely sensitive to small modifications in the system parameters.

  8. Processing of giant graphene molecules by soft-landing mass spectrometry.

    PubMed

    Räder, Hans Joachim; Rouhanipour, Ali; Talarico, Anna Maria; Palermo, Vincenzo; Samorì, Paolo; Müllen, Klaus

    2006-04-01

    The processability of giant (macro)molecules into ultrapure and highly ordered structures at surfaces is of fundamental importance for studying chemical, physical and biological phenomena, as well as their exploitation as active units in the fabrication of hybrid devices. The possibility of handling larger and larger molecules provides access to increasingly complex functions. Unfortunately, larger molecules commonly imply lower processability due to either their low solubility in liquid media or the occurrence of thermal cracking during vacuum sublimation. The search for novel strategies to process and characterize giant building blocks is therefore a crucial goal in materials science. Here we describe a new general route to process, at surfaces, extraordinarily large molecules, that is, synthetic nanographenes, into ultrapure crystalline architectures. Our method relies on the soft-landing of ions generated by solvent-free matrix-assisted laser desorption/ionization (MALDI). The nanographenes are transferred to the gas phase, purified and adsorbed at surfaces. Scanning tunnelling microscopy reveals the formation of ordered nanoscale semiconducting supramolecular architectures. The unique flexibility of this approach allows the growth of ultrapure crystalline films of various systems, including organic, inorganic and biological molecules, and therefore it can be of interest for technological applications in the fields of electronics, (bio)catalysis and nanomedicine.

  9. Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

    NASA Astrophysics Data System (ADS)

    Rigoni, F.; Drera, G.; Pagliara, S.; Perghem, E.; Pintossi, C.; Goldoni, A.; Sangaletti, L.

    2017-01-01

    The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.

  10. Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules.

    PubMed

    Rigoni, F; Drera, G; Pagliara, S; Perghem, E; Pintossi, C; Goldoni, A; Sangaletti, L

    2017-01-20

    The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.

  11. First-principles study of the dielectric functions of carbon nanotubes with adsorbed water

    NASA Astrophysics Data System (ADS)

    Iwasaki, Daisuke; Suzuki, Yasumitsu; Watanabe, Kazuyuki

    2017-04-01

    A recent study demonstrated adsorption of water molecules on the surfaces of carbon nanotubes (CNTs). Importantly, it was reported that the peak positions in the absorption and photoluminescence spectra of the CNTs were shifted to lower energy as the number of adsorbed water molecules increased. Here, we investigated the mechanism by which this redshift occurs by calculating the dielectric functions of CNTs following water adsorption using density functional theory. Our calculations reproduced the redshifts and demonstrated that they can be attributed to decreases in the band gaps, which result from electronic coupling between the CNTs and the water molecules.

  12. Search for evidence of life in space: analysis of enantiomeric organic molecules by N,N-dimethylformamide dimethylacetal derivative dependant Gas Chromatography-Mass Spectrometry.

    PubMed

    Freissinet, C; Buch, A; Sternberg, R; Szopa, C; Geffroy-Rodier, C; Jelinek, C; Stambouli, M

    2010-01-29

    Within the context of the future space missions to Mars (MSL 2011 and Exomars 2016), which aim at searching for traces of life at the surface, the detection and quantitation of enantiomeric organic molecules is of major importance. In this work, we have developed and optimized a method to derivatize and analyze chiral organic molecules suitable for space experiments, using N,N-dimethylformamide dimethylacetal (DMF-DMA) as the derivatization agent. The temperature, duration of the derivatization reaction, and chromatographic separation parameters have been optimized to meet instrument design constraints imposed upon space experiment devices. This work demonstrates that, in addition to its intrinsic qualities, such as production of light-weight derivatives and a great resistance to drastic operating conditions, DMF-DMA facilitates simple and fast derivatization of organic compounds (three minutes at 140 degrees C in a single-step) that is suitable for an in situ analysis in space. By using DMF-DMA as the derivatization agent, we have successfully identified 19 of the 20 proteinic amino acids and been able to enantiomerically separate ten of the potential 19 (glycine being non-chiral). Additionally, we have minimized the percentage of racemized amino acid compounds produced by optimizing the conditions of the derivatization reaction itself. Quantitative linearity studies and the determination of the limit of detection show that the proposed method is also suitable for the quantitative determination of both enantiomeric forms of most of the tested amino acids, as limits of detection obtained are lower than the ppb level of organic molecules already detected in Martian meteorites.

  13. Desorption of isopropyl alcohol from adsorbent with non-thermal plasma.

    PubMed

    Shiau, Chen Han; Pan, Kuan Lun; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

    2016-11-24

    Effective desorption of isopropyl alcohol (IPA) from adsorbents with non-thermal plasma is developed. In this system, IPA is effectively adsorbed with activated carbon while dielectric barrier discharge is applied to replace the conventional thermal desorption process to achieve good desorption efficiency, making the treatment equipment smaller in size. Various adsorbents including molecular sieves and activated carbon are evaluated for IPA adsorption capacity. The results indicate that BAC has the highest IPA adsorption capacity (280.31 mg IPA/g) under the operating conditions of room temperature, IPA of 400 ppm, and residence time of 0.283 s among 5 adsorbents tested. For the plasma desorption process, the IPA selectivity of 89% is achieved with BAC as N2 is used as desorbing gas. In addition, as air or O2 is used as desorbing gas, the IPA desorption concentration is reduced, because air and O2 plasmas generate active species to oxidize IPA to form acetone, CO2, and even CO. Furthermore, the results of the durability test indicate that the amount of IPA desorbed increases with increasing desorption times and plasma desorption process has a higher energy efficiency if compared with thermal desorption. Overall, this study indicates that non-thermal plasma is a viable process for removing VOCs to regenerate adsorbent.

  14. Density functional study of adsorptions of CO2, NO2 and SO2 molecules on Zn(0002) surfaces

    NASA Astrophysics Data System (ADS)

    Nugraha; Saputro, A. G.; Agusta, M. K.; Yuliarto, B.; Dipojono, H. K.; Maezono, R.

    2016-08-01

    We report on a theoretical study of adsorptions of CO2, NO2 and SO2 molecules on ZnO(0002) surfaces using density functional theory-based (DFT-based) calculations. These adsorptions are done on perfect and defective ZnO(0002) surfaces. We find that all of these molecules are chemically adsorbed on the perfect ZnO(0002) surface. In the presence of Zn vacancy, we find that the surface is only active toward SO2 molecule. On the hydroxylated ZnO(0002) surfaces, CO2 and SO2 molecules can react with the preadsorbed OH molecule to form various adsorbates such as: carboxyl (COOH), bicarbonate (CO3H), sulfonyl hydroxide (SO3H), SO3 and water. However, NO2 molecule cannot react with the pre-adsorbed OH molecule and only physically adsorbed on the surface.

  15. Gas-Solid Dynamics at Disordered and Adsorbate Covered Surfaces.

    DTIC Science & Technology

    1987-05-15

    Schrodinger equation . Specific numerical results are presented for pulses of area equal to v, 21r, 31r, 4r and 51r for both symmetric and asymmetric... Semiclassical Perturbation Theory for Atom Scattering from Surfaces with Defects 1 Presented here is an extension of semiclassical perturbation theory (SCP...Involved in solving the AWM equations in equivalent to that Involved for elastic scattering in the same formulation. As an initial Illustration, expUclt

  16. Morphology-Driven High-Performance Polymer Transistor-based Ammonia Gas Sensor.

    PubMed

    Yu, Seong Hoon; Cho, Jangwhan; Sim, Kyu Min; Ha, Jae Un; Chung, Dae Sung

    2016-03-01

    Developing high-performance gas sensors based on polymer field-effect transistors (PFETs) requires enhancing gas-capture abilities of polymer semiconductors without compromising their high charge carrier mobility. In this work, cohesive energies of polymer semiconductors were tuned by strategically inserting buffer layers, which resulted in dramatically different semiconductor surface morphologies. Elucidating morphological and structural properties of polymer semiconductor films in conjunction with FET studies revealed that surface morphologies containing large two-dimensional crystalline domains were optimal for achieving high surface areas and creating percolation pathways for charge carriers. Ammonia molecules with electron lone pairs adsorbed on the surface of conjugated semiconductors can serve as efficient trapping centers, which negatively shift transfer curves for p-type PFETs. Therefore, morphology optimization of polymer semiconductors enhances their gas sensing abilities toward ammonia, leading to a facile method of manufacturing high-performance gas sensors.

  17. The Effect of Gas Absorption on Multilayer Black Phosphorus Field Effect Transistor

    NASA Astrophysics Data System (ADS)

    Liu, Xue; Hu, Jin; Yue, Chunlei; Della Fera, Nicholas; Mao, Zhiqiang; Wei, Jiang

    2015-03-01

    Multilayer black phosphorus (BP) is drawing much attention recently due to its reported high mobility (up to 1000 cm2V-1s-1) and on/off ratio (up to 105) as the channel material for field effect transistor (FET). We investigated the interplay between the electrical response of high performing BPFET and gas adsorbate introduced to its surrounding environment. Different type of gas including CO2, H2O, Ethanol, CO, NO, NH3, etc. has been tested. We observed that the absorption of gas molecules generally reduces the overall on-state conductance of the device with an order of 10 ~ 100. And such reduction can be fully recovered by purging with inert gas or baking at mild temperature (about 100°C). The absorption dynamics and detailed mechanism are also been investigated. We conclude that multilayer black phosphorus is an excellent material for chemical sensing.

  18. Insight into the adsorption of PPCPs by porous adsorbents: Effect of the properties of adsorbents and adsorbates.

    PubMed

    Zhu, Zengyin; Xie, Jiawen; Zhang, Mancheng; Zhou, Qing; Liu, Fuqiang

    2016-07-01

    Adsorption is an efficient method for removal of pharmaceuticals and personal care products (PPCPs). Magnetic resins are efficient adsorbents for water treatment and exhibit potential for PPCP removal. In this study, the magnetic hypercrosslinked resin Q100 was used for adsorption of PPCPs. The adsorption behavior of this resin was compared with those of two activated carbons, namely, Norit and F400D. Norit exhibited the fastest adsorption kinetics, followed by Q100. Norit featured a honeycomb shape and long-range ordered pore channels, which facilitated the diffusion of PPCPs. Moreover, the large average pore size of Q100 reduced diffusion resistance. The adsorbed amounts of 11 PPCPs on the three adsorbents increased with increasing adsorbate hydrophobicity. For Q100, a significant linear correlation was observed between the adsorption performance for PPCPs and hydrophobicity (logD value) of adsorbates (R(2) = 0.8951); as such, PPCPs with high logD values (>1.69) could be efficiently removed. Compared with those of Norit and F400D, the adsorption performance of Q100 was less affected by humic acid because of the dominant hydrophobic interaction. Furthermore, Q100 showed improved regeneration performance, which renders it promising for PPCP removal in practical applications.

  19. Crystallographic studies of gas sorption in metal–organic frameworks

    PubMed Central

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

    2014-01-01

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

  20. Infrared spectroscopic and thermodynamic assessment of extraframework cationic adsorption sites in the zeolite K-L by using CO as probe molecule

    NASA Astrophysics Data System (ADS)

    Delgado, Montserrat R.; de Yuso, Alicia Martínez; Bulánek, Roman; Arean, Carlos O.

    2015-10-01

    Zeolites are often used as the host material for holding and organizing adsorbed molecules and supramolecular species inside their void channels and cages, in order to exploit space confinement and host-guest interaction for engineering composite materials having novel electronic and optical properties. That endeavour would benefit from improved knowledge about the type and strength of the zeolite adsorption sites. To this end, variable temperature infrared spectroscopy (a technique capable of giving simultaneous information on the type and strength of gas-adsorption complexes) was used herein to characterize the zeolite K-L by means of adsorbed CO. Two types of cationic adsorption sites (termed D‧ and D″) were found on the wall of the zeolite main channel; formation of the corresponding CO adsorption complexes was found to involve a standard enthalpy change of -23.4 and -26.7 kJ mol-1, respectively.