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Sample records for adsorption barrier energy

  1. Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

    PubMed

    Luo, Jing; Farrell, James

    2013-01-01

    Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE. PMID:23626602

  2. Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation

    PubMed Central

    Luo, Jing; Farrell, James

    2013-01-01

    Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE. PMID:23626602

  3. Permeable Adsorptive Barrier (PAB) for the remediation of groundwater simultaneously contaminated by some chlorinated organic compounds.

    PubMed

    Erto, A; Bortone, I; Di Nardo, A; Di Natale, M; Musmarra, D

    2014-07-01

    In this paper, a Permeable Reactive Barrier (PRB) made with activated carbon, namely a Permeable Adsorptive Barrier (PAB), is put forward as an effective technique for the remediation of aquifers simultaneously contaminated by some chlorinated organic compounds. A design procedure, based on a computer code and including different routines, is presented as a tool to accurately describe mass transport within the aquifer and adsorption/desorption phenomena occurring inside the barrier. The remediation of a contaminated aquifer near a solid waste landfill in the district of Napoli (Italy), where Tetrachloroethylene (PCE) and Trichloroethylene (TCE) are simultaneously present, is considered as a case study. A complete hydrological and geotechnical site characterization, as well as a number of dedicated adsorption laboratory tests for the determination of activated carbon PCE/TCE adsorption capacity in binary systems, are carried out to support the barrier design. By means of a series of numerical simulations it is possible to determine the optimal barrier location, orientation and dimensions. PABs appear to be an effective remediation tool for the in-situ treatment of an aquifer contaminated by PCE and TCE simultaneously, as the concentration of both compounds flowing out of the barrier is everywhere lower than the regulatory limits on groundwater quality. PMID:24747934

  4. Market barriers to energy efficiency

    SciTech Connect

    Howarth, R.B.; Andersson, B.

    1992-06-01

    Discussions of energy policy in an environmentally constrained world often focus on the use of tax instruments to internalize the external effects of energy utilization or achieve specified reductions in energy use in the most cost-effective manner. A substantial literature suggests, however, that significant opportunities exist to reduce energy utilization by implementing technologies that are cost-effective under prevailing economic conditions but that are not fully implemented by existing market institutions. This paper examines the theory of the market for energy-using equipment, showing that problems of imperfect information and transaction costs may bias rational consumers to purchase devices that use more energy than those that would be selected by a well-informed social planner guided by the criterion of economic efficiency. Consumers must base their purchase decisions on observed prices and expectations of postpurchase equipment performance. If it is difficult or costly for individuals to form accurate and precise expectations, the level of energy efficiency achieved by competitive markets will vary from the socially efficient outcome. Such ``market barriers`` suggest a role for regulatory intervention to improve market performance at prevailing energy prices.

  5. Market barriers to energy efficiency

    SciTech Connect

    Howarth, R.B. ); Andersson, B. )

    1992-06-01

    Discussions of energy policy in an environmentally constrained world often focus on the use of tax instruments to internalize the external effects of energy utilization or achieve specified reductions in energy use in the most cost-effective manner. A substantial literature suggests, however, that significant opportunities exist to reduce energy utilization by implementing technologies that are cost-effective under prevailing economic conditions but that are not fully implemented by existing market institutions. This paper examines the theory of the market for energy-using equipment, showing that problems of imperfect information and transaction costs may bias rational consumers to purchase devices that use more energy than those that would be selected by a well-informed social planner guided by the criterion of economic efficiency. Consumers must base their purchase decisions on observed prices and expectations of postpurchase equipment performance. If it is difficult or costly for individuals to form accurate and precise expectations, the level of energy efficiency achieved by competitive markets will vary from the socially efficient outcome. Such market barriers'' suggest a role for regulatory intervention to improve market performance at prevailing energy prices.

  6. Barriers to improvements in energy efficiency

    SciTech Connect

    Reddy, A.K.N.

    1991-10-01

    To promote energy-efficiency improvements, actions may be required at one or more levels -- from the lowest level of the consumer (residential, commercial, industrial, etc.) through the highest level of the global agencies. But barriers to the implementation of energy-efficiency improvements exist or can arise at all these levels. Taking up each one of these barriers in turn, the paper discusses specific measures that can contribute to overcoming the barriers. However, a one-barrier-one-measure approach must be avoided. Single barriers may in fact involve several sub-barriers. Also, combinations of measures are much more effective in overcoming barriers. In particular, combinations of measures that simultaneously overcome several barriers are most successful. The paper discusses the typology of barriers, explores their origin and suggests measures that by themselves or in combination with other measures, will overcome these barriers. Since most of the barriers dealt with can be found in the ``barriers`` literature, any originality in the paper lies in its systematic organization, synoptic view and holistic treatment of this issue. This paper is intended to initiate a comprehensive treatment of barriers, their origins and the measures that contribute to overcoming them. Hopefully, such a treatment will facilitate the implementation of energy-efficiency improvements involving a wide diversity of ever-changing energy end uses and consumer preferences.

  7. Barriers to improvements in energy efficiency

    SciTech Connect

    Reddy, A.K.N.

    1991-10-01

    To promote energy-efficiency improvements, actions may be required at one or more levels -- from the lowest level of the consumer (residential, commercial, industrial, etc.) through the highest level of the global agencies. But barriers to the implementation of energy-efficiency improvements exist or can arise at all these levels. Taking up each one of these barriers in turn, the paper discusses specific measures that can contribute to overcoming the barriers. However, a one-barrier-one-measure approach must be avoided. Single barriers may in fact involve several sub-barriers. Also, combinations of measures are much more effective in overcoming barriers. In particular, combinations of measures that simultaneously overcome several barriers are most successful. The paper discusses the typology of barriers, explores their origin and suggests measures that by themselves or in combination with other measures, will overcome these barriers. Since most of the barriers dealt with can be found in the barriers'' literature, any originality in the paper lies in its systematic organization, synoptic view and holistic treatment of this issue. This paper is intended to initiate a comprehensive treatment of barriers, their origins and the measures that contribute to overcoming them. Hopefully, such a treatment will facilitate the implementation of energy-efficiency improvements involving a wide diversity of ever-changing energy end uses and consumer preferences.

  8. Methane Adsorption on Aggregates of Fullerenes: Site-Selective Storage Capacities and Adsorption Energies

    PubMed Central

    Kaiser, Alexander; Zöttl, Samuel; Bartl, Peter; Leidlmair, Christian; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Echt, Olof; Scheier, Paul

    2013-01-01

    Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118–281 meV are in the optimal range for high-density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane–methane and fullerene–methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes. PMID:23744834

  9. A procedure to design a Permeable Adsorptive Barrier (PAB) for contaminated groundwater remediation.

    PubMed

    Erto, A; Lancia, A; Bortone, I; Di Nardo, A; Di Natale, M; Musmarra, D

    2011-01-01

    A procedure to optimize the design of a Permeable Adsorptive Barrier (PAB) for the remediation of a contaminated aquifer is presented in this paper. A computer code, including different routines that describe the groundwater contaminant transport and the pollutant capture by adsorption in unsteady conditions over the barrier solid surface, has been developed. The complete characterization of the chemical-physical interactions between adsorbing solids and the contaminated water, required by the computer code, has been obtained by experimental measurements. A case study in which the procedure developed has been applied to a tetrachloroethylene (PCE)-contaminated aquifer near a solid waste landfill, in the district of Napoli (Italy), is also presented and the main dimensions of the barrier (length and width) have been evaluated. Model results show that PAB is effective for the remediation of a PCE-contaminated aquifer, since the concentration of PCE flowing out of the barrier is everywhere always lower than the concentration limit provided for in the Italian regulations on groundwater quality. PMID:20846781

  10. Study of polystyrene-poly(ethylene oxide) diblock copolymer monolayers as barriers to protein adsorption

    NASA Astrophysics Data System (ADS)

    Jogikalmath, Gangadhar

    Protein adsorption resistant surfaces find use in many biomedical applications, such as catheters, dialysis devices and biosensors that involve blood contacting surfaces. To ensure long-term functioning of a device in an environment containing protein, there is a need to produce homogeneous surfaces that are resistant to protein adsorption. A polymer brush covered surface, produced by either physical adsorption or chemical grafting of hydrophilic polymers to surfaces, is one of the approaches used in creating such surfaces. High grafting densities needed to make an effective barrier are usually not realized in chemical grafting/adsorption from solution, due to self-exclusion of surface grafted molecules. In this dissertation polymer brush surfaces formed by chemically grafted PEO molecules and transferred monolayers of PS-b-PEO diblock copolymers are investigated using atomic force microscopy (AFM), surface plasmon resonance (SPR) and surface pressure measurement techniques. An AFM adhesion mapping technique was used to evaluate the surface heterogeneity of chemically modified PEO and transferred diblock copolymer monolayer surfaces. The behavior of PS-b-PEO molecules at the air-water interface was studied using Langmuir trough. The stability of transferred diblock copolymer monolayers was investigated using AFM. Using SPR, protein adsorption to the diblock copolymer layers was investigated as a function of protein size (using HSA and ferritin) as a function of grafting density of PEO in the monolayer. It was seen that a lower density of the PS-b-PEO monolayer was sufficient to prevent ferritin adsorption (larger protein) while a higher density brush layer was required to achieve complete prevention of HSA adsorption to the surface. The effect of mobility of the polymer brush layer on protein adsorption prevention was analyzed using SPR and surface pressure measurements. It was seen that the copolymer monolayer (at the air-buffer interface) rearranged itself to

  11. Diffusion barriers in the kinetics of water vapor adsorption/desorption on activated carbons

    SciTech Connect

    Harding, A.W.; Foley, N.J.; Thomas, K.M.; Norman, P.R.; Francis, D.C.

    1998-07-07

    The adsorption of water vapor on a highly microporous coconut-shell-derived carbon and a mesoporous wood-derived carbon was studied. These carbons were chosen as they had markedly different porous structures. The adsorption and desorption characteristics of water vapor on the activated carbons were investigated over the relative pressure range p/p{degree} = 0--0.9 for temperatures in the range 285--313 K in a static water vapor system. The adsorption isotherms were analyzed using the Dubinin-Serpinski equation, and this provided an assessment of the polarity of the carbons. The kinetics of water vapor adsorption and desorption were studied with different amounts of preadsorbed water for set changes in pressure relative to the saturated vapor pressure (p/p{degree}). The adsorption kinetics for each relative pressure step were compared and used to calculate the activation energies for the vapor pressure increments. The kinetic results are discussed in relation to their relative position on the equilibrium isotherm and the adsorption mechanism of water vapor on activated carbons.

  12. Quasifission at extreme sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Scheid, W.; Zhang, H. Q.

    2012-12-01

    With the quantum diffusion approach the behavior of the capture cross-section is investigated in the reactions 92, 94Mo + 92, 94Mo , 100Ru + 100Ru , 104Pd + 104Pd , and 78Kr + 112Sn at deep sub-barrier energies which are lower than the ground-state energies of the compound nuclei. Because the capture cross-section is the sum of the complete fusion and quasifission cross-sections, and the complete fusion cross-section is zero at these sub-barrier energies, one can study experimentally the unique quasifission process in these reactions after the capture.

  13. Energy Barriers for Defects in Disordered Solids

    NASA Astrophysics Data System (ADS)

    Wijtmans, Sven; Manning, Lisa

    2015-03-01

    In solids, defects govern flow and failure. In crystals, defects are easily-identified dislocations, while in disordered solids, defects can be found by analyzing the vibrational modes of the system, which are eigenvectors of the matrix describing the linear response. The low frequency modes are typically quasi-localized hybrids of excitations localized at the defects and plane-wave like modes. Additional analysis can separate these components, giving the location of a defect and displacement of particles along that defect. To define an energy barrier for each defect, we displace particles along an isolated defect mode and calculate the energy at which the system transitions to a new energy basin. Different definitions of a new basin, such as a change in the particle contact network or particle displacements above a specific threshold, give different results. We identify several criteria that are consistent and provide a reasonable, robust definition of an energy barrier. Somewhat surprisingly, we find that energy barriers for isolated defects are generally higher than energy barriers for typical quasi-localized modes in the system.

  14. Computation of Adsorption Energies of Some Interstellar Species

    NASA Astrophysics Data System (ADS)

    Sil, Milan; Chakrabarti, Sandip Kumar; Das, Ankan; Majumdar, Liton; Gorai, Prasanta; Etim, Emmanuel; Arunan, Elangannan

    2016-07-01

    Adsorption energies of surface species are most crucial for chemical complexity of interstellar grain mantle. Aim of this work is to study the variation of the adsorption energies depending upon the nature of adsorbent. We use silicate and carbonaceous grains for the absorbents. For silicate grains, we use very simple crystalline ones, namely, Enstatite (MgSiO_3)_n, Ferrosilite (FeSiO_3)_n, Forsterite (Mg_2SiO_4)_n and Fayalite (Fe_2SiO_4)_n. We use n=1, 2, 4, 8 to study the variation of adsorption energies with the increase in cluster size. For carbonaceous grain, we use Coronene (polyaromatic hydrocarbon surface). Adsorption energy of all these species are calculated by means of quantum chemical calculation using self consistent density functional theory (DFT). MPWB1K hybrid meta-functional is employed since it has been proven useful to study the systems with weak interactions such as van der Waals interactions. Optimization are also carried out with MPWB1K/6-311g(d) and MPWB1K/6311g(d,p) and a comparison of adsorption energies are discussed for these two different basis sets. We use crystalline structure of the adsorbent. The adsorbate is placed in the different site of the grain with a suitable distance. The energy of adsorption for a species on the grain surface is defined as follows: E_a_d_s = E_s_s - (E_s_u_r_f_a_c_e + E_s_p_e_c_i_e_s), where E_a_d_s is the adsorption energy, E_s_s is the optimized energy for species placed in a suitable distance from the grain surface, E_s_u_r_f_a_c_e and E_s_p_e_c_i_e_s respectively are the optimized energies of the surface and species separately.

  15. Only Above Barrier Energy Components Contribute to Barrier Traversal Time

    NASA Astrophysics Data System (ADS)

    Galapon, Eric A.

    2012-04-01

    A time of arrival operator across a square potential barrier is constructed. The expectation value of the barrier time of arrival operator for a sufficiently localized incident wave packet is compared with the expectation value of the free particle time of arrival operator for the same wave packet. The comparison yields an expression for the expected traversal time across the barrier. It is shown that only the above barrier components of the momentum distribution of the incident wave packet contribute to the barrier traversal time, implying that below the barrier components are transmitted without delay. This is consistent with the recent experiment in attosecond ionization in helium indicating that there is no real tunneling delay time [P. Eckle , Science 322, 1525 (2008)SCIEAS0036-807510.1126/science.1163439].

  16. A mechanistic study of H2S adsorption and dissociation on Cu2O(1 1 1) surfaces: Thermochemistry, reaction barrier

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Liu, Hongyan; Li, Jingrui; Ling, Lixia; Wang, Baojun

    2012-10-01

    The interaction mechanism of H2S with different Cu2O(1 1 1) surfaces, including perfect, oxygen-vacancy and sulfur-containing surfaces, have been systematically studied using periodic density functional calculations. Different kinds of possible modes of H2S, as well as the resultant SH and S species adsorbed on these surfaces are identified. Two types of pathways via molecular and dissociative adsorption processes are mapped out. Our results show that sulfur species (H2S, SH and S) interact with surface Cu centers; H2S exists in the form of molecular adsorption on perfect and sulfur-containing surfaces; the dissociative adsorption of H2S occurs predominantly on oxygen-vacancy surface, suggesting that oxygen-vacancy exhibits a strong catalytic activity toward the dissociation of H2S. On the other hand, the dissociation processes of the molecular and dissociative adsorption H2S, leading to final product S species on these Cu2O(1 1 1) surfaces, show that the overall dissociation process is exothermic. Meanwhile, with respect to molecular adsorption H2S, the activation barrier and reaction energy of the overall dissociation process on perfect and oxygen-vacancy surfaces indicate that H2S can easily dissociate into S species. Importantly, in the case of dissociative adsorption of H2S, the dissociation of H2S into S species is a spontaneous process with respect to molecular adsorption H2S. However, on sulfur-containing surface, the presence of surface S atom goes against the Hsbnd S bond-breaking process both thermodynamically and kinetically. Finally, the vibrational frequencies for the adsorbed H2S, SH and S species on these surfaces have been obtained, which can be applied to guide surface vibrational spectroscopy in experiment.

  17. Peptide adsorption on the hydrophobic surface: A free energy perspective

    NASA Astrophysics Data System (ADS)

    Sheng, Yuebiao; Wang, Wei; Chen, P.

    2011-05-01

    Protein adsorption is a very attractive topic which relates to many novel applications in biomaterials, biotechnology and nanotechnology. Ionic complementary peptides are a group of novel nano-biomaterials with many biomedical applications. In this work, molecular dynamics simulations of the ionic-complementary peptide EAK16-II on a hydrophobic graphite surface were performed under neutral, acidic and basic solution conditions. Adsorption free energy contour maps were obtained by analyzing the dynamical trajectories. Hydrophobic interactions were found to govern the adsorption of the first peptide molecule, and both hydrophobic and electrostatic interactions contributed to the adsorption of the second peptide molecule. Especially under acidic and basic solution conditions, interplay existed among chain-chain hydrophobic, chain-surface hydrophobic and chain-chain electrostatic interactions during the adsorption of the second peptide molecule. Non-charged residues were found to lie on the graphite surface, while charged residue side-chains oriented towards the solution after the peptide deposited on the surface. These results provide a basis for understanding peptide adsorption on the hydrophobic surface under different solution conditions, which is useful for novel applications such as bioactive implant devices and drug delivery material design.

  18. Threshold energy for sub-barrier fusion hindrance phenomenon

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Scheid, W.; Zhang, H. Q.

    2013-02-01

    The relationship between the threshold energy for a deep sub-barrier fusion hindrance phenomenon and the energy at which the regime of interaction changes (the turning-off of the nuclear forces and friction) in the sub-barrier capture process is studied within the quantum diffusion approach. The quasielastic barrier distribution is shown to be a useful tool to clarify whether the slope of capture cross section changes at sub-barrier energies.

  19. Energy barriers, entropy barriers, and non-Arrhenius behavior in a minimal glassy model

    NASA Astrophysics Data System (ADS)

    Du, Xin; Weeks, Eric R.

    2016-06-01

    We study glassy dynamics using a simulation of three soft Brownian particles confined to a two-dimensional circular region. If the circular region is large, the disks freely rearrange, but rearrangements are rarer for smaller system sizes. We directly measure a one-dimensional free-energy landscape characterizing the dynamics. This landscape has two local minima corresponding to the two distinct disk configurations, separated by a free-energy barrier that governs the rearrangement rate. We study several different interaction potentials and demonstrate that the free-energy barrier is composed of a potential-energy barrier and an entropic barrier. The heights of both of these barriers depend on temperature and system size, demonstrating how non-Arrhenius behavior can arise close to the glass transition.

  20. Surface free energy analysis of adsorbents used for radioiodine adsorption

    NASA Astrophysics Data System (ADS)

    González-García, C. M.; Román, S.; González, J. F.; Sabio, E.; Ledesma, B.

    2013-10-01

    In this work, the surface free energy of biomass-based activated carbons, both fresh and impregnated with triethylenediamine, has been evaluated. The contribution of Lifshitz van der Waals components was determined by the model proposed by van Oss et al. The results obtained allowed predicting the most probable configurations of the impregnant onto the carbon surface and its influence on the subsequent adsorption of radioactive methyl iodide.

  1. Barriers to electric energy efficiency in Ghana

    NASA Astrophysics Data System (ADS)

    Berko, Joseph Kofi, Jr.

    Development advocates argue that sustainable development strategies are the best means to permanently improve living standards in developing countries. Advocates' arguments are based on the technical, financial, and environmental advantages of sustainable development. However, they have not addressed the organizational and administrative decision-making issues which are key to successful implementation of sustainable development in developing countries. Using the Ghanaian electricity industry as a case study, this dissertation identifies and analyzes organizational structures, administrative mechanisms, and decision-maker viewpoints that critically affect the success of adoption and implementation of energy efficiency within a sustainable development framework. Utilizing semi-structured interviews in field research, decision-makers' perceptions of the pattern of the industry's development, causes of the electricity supply shortfall, and barriers to electricity-use efficiency were identified. Based on the initial findings, the study formulated a set of policy initiatives to establish support for energy use efficiency. In a second set of interviews, these policy suggestions were presented to some of the top decision-makers to elicit their reactions. According to the decision-makers, the electricity supply shortfall is due to rapid urbanization and increased industrial consumption as a result of the structural adjustment program, rural electrification, and the sudden release of suppressed loads. The study found a lack of initiative and collaboration among industry decision-makers, and a related divergence in decision-makers' concerns and viewpoints. Also, lacking are institutional support systems and knowledge of proven energy efficiency strategies and technologies. As a result, planning, and even the range of perceived solutions to choose from are supply-side oriented. The final chapter of the study presents implications of its findings and proposes that any

  2. Adsorption of Water Monomer and Clusters on Platinum(111) Terrace and Related Steps and Kinks I. Configurations, Energies, and Hydrogen Bonding

    SciTech Connect

    Arnadottir, Liney; Stuve, Eric M.; Jonsson, Hannes

    2010-10-01

    Adsorption and rotation of water monomer, dimer, and trimer on the (111) terrace, (221) and (322) stepped, and (763) and (854) kinked surfaces of platinum were studied by density functional theory calculations using the PW91 approximation to the energy functional. On the (111) terrace, water monomer and the donor molecule of the dimer and trimer adsorb at atop sites. The permolecule adsorption energies of the monomer, dimer, and trimer are 0.30, 0.45, and 0.48 eV, respectively. Rotation of monomers, dimers, and trimers on the terrace is facile with energy barriers of 0.02 eV or less. Adsorption on steps and kinks is stronger than on the terrace, as evidenced by monomer adsorption energies of 0.46 to 0.55 eV. On the (221) stepped surface the zigzag extended configuration is most stable with a per-molecule adsorption energy of 0.57 eV. On the (322) stepped surface the dimer, two configurations of the trimer, and the zigzag configuration have similar adsorption energies of 0.55 ± 0.02 eV. Hydrogen bonding is strongest in the dimer and trimer adsorbed on the terrace, with respective energies of 0.30 and 0.27 eV, and accounts for their increased adsorption energies relative to the monomer. Hydrogen bonding is weak to moderate for adsorption at steps, with energies of 0.04 to 0.15 eV, as the much stronger water-metal interactions inhibit adsorption geometries favorable to hydrogen bonding. Correlations of hydrogen bond angles and energies with hydrogen bond lengths are presented. On the basis of these DFT/PW91 results, a model for water cluster formation on the Pt(111) surface can be formulated where kink sites nucleate chains along the top of step edges, consistent with the experimental findings of Morgenstern et al., Phys. Rev. Lett., 77 (1996) 703.

  3. Barriers to Industrial Energy Efficiency - Study (Appendix A), June 2015

    SciTech Connect

    2015-06-01

    This study examines barriers that impede the adoption of energy efficient technologies and practices in the industrial sector, and identifies successful examples and opportunities to overcome these barriers. Three groups of energy efficiency technologies and measures were examined: industrial end-use energy efficiency, industrial demand response, and industrial combined heat and power. This study also includes the estimated economic benefits from hypothetical Federal energy efficiency matching grants, as directed by the Act.

  4. Barriers to Industrial Energy Efficiency - Report to Congress, June 2015

    SciTech Connect

    2015-06-01

    This report examines barriers that impede the adoption of energy efficient technologies and practices in the industrial sector, and identifies successful examples and opportunities to overcome these barriers. Three groups of energy efficiency technologies and measures were examined: industrial end-use energy efficiency, industrial demand response, and industrial combined heat and power. This report also includes the estimated economic benefits from hypothetical Federal energy efficiency matching grants, as directed by the Act.

  5. Atomistic Simulations of Ion Diffusion in Clay Barriers: Diffusive Path Energy Barriers

    NASA Astrophysics Data System (ADS)

    Newton, A. G.; Kozaki, T.

    2010-12-01

    Ion diffusion in clay-rich media is an important transport process relevant to models of contaminant fate and transport in groundwater and risk assessments for the geologic disposal of high-level radioactive waste (HLW). Smectite clay minerals are used as a buffer material in the geologic disposal of HLW due to their low permeability. Ion diffusion experiments with water-saturated, compacted clays have revealed a non-linear trend in which the diffusive energy barrier in clay media at dry densities near 1.0 Mg m-3 exhibited a smaller energy barrier to diffusion than in liquid water (Kozaki, et al. 2005). Although it is likely that the decreased energy barrier is related to preferential diffusion along smectite basal surfaces, experimental methods cannot unambiguously isolate this diffusion pathway. Atomistic simulations were designed to isolate this diffusive pathway and to test if the decreased energy barrier is related to preferential diffusion along the smectite basal surface. In addition, the simulations provide an atomic-scale perspective of this diffusion pathway as a function of temperature. In the present study, we report the energy barrier to diffusion for sodium ions (Na+) at the smectite basal surface. The energy barrier to diffusion at the Na-montmorillonite basal surface was determined by investigating the temperature dependence of ion diffusion through a series of long (9.0 ns) molecular dynamics (MD) simulations in the canonical ensemble (NVT). We show that the energy barrier to diffusion at the clay basal surface is less than the energy barrier to diffusion in free water and demonstrate that this methodology can provide results that are consistent with laboratory diffusion experiments and nanoscale insights into the interpretation of macroscale experimental investigations of ion diffusion in smectite-rich media. Kozaki, T., A. Fujishima, et al. (2005). Engineering Geology, 81(3): 246-254.

  6. Nontechnical Barriers to Solar Energy Use: Review of Recent Literature

    SciTech Connect

    Margolis, R.; Zuboy, J.

    2006-09-01

    This paper reviews the nontechnical barriers to solar energy use, drawing on recent literature to help identify key barriers that must be addressed as part of the Technology Acceptance efforts under the U.S. Department of Energy (DOE) Solar America Initiative. A broad literature search yielded more than 400 references, which were narrowed to 19 recent documents on nontechnical barriers to the use of solar energy and other energy efficiency and renewable energy (EE/RE) technologies. Some of the most frequently identified barriers included lack of government policy supporting EE/RE, lack of information dissemination and consumer awareness about energy and EE/RE, high cost of solar and other EE/RE technologies compared with conventional energy, and inadequate financing options for EE/RE projects.

  7. Synthesis of Ordered Mesoporous Silica for Energy-efficient Adsorption Systems

    NASA Astrophysics Data System (ADS)

    Endo, Akira; Komori, Kou; Inagi, Yuki; Fujisaki, Satoko; Yamamoto, Takuji

    Energy-efficient adsorption systems, such as adsorption heat pump, desiccant cooling, humidity control system, and so on, are expected as a energy exchange process because they are able to utilize low temperature exhaust heat. As an adsorbent for such systems, materials with large adsorption capacity in the pressure range of practical operation are preferable. To enable the design and synthesis of materials with large heat storage capacity, the pore structure of adsorbents should be optimized for each systems. In this paper, we synthesized ordered mesoporous silica (MPS) with an arrow pore size distribution of around 2nm by a solvent evaporation method and evaluated their water adsorption properties. The adsorption isotherms for MPSs showed steep increase at a relative humidity corresponding to their pore size. Since MPSs have a large adsorption capacity than conventional materials in the relative humidity region of practical operation, they are expected for new adsorbents for energy-efficient adsorption systems.

  8. Equation of Energy Injection to a Dielectric Barrier Discharge Reactor

    NASA Astrophysics Data System (ADS)

    Yao, Shuiliang; Weng, Shan; Jin, Qi; Han, Jingyi; Jiang, Boqiong; Wu, Zuliang

    2016-08-01

    The electric energy injection from a pulsed power supply to a planar type of dielectric barrier discharge (DBD) reactor at atmospheric pressure was studied. Relations of the energy injection with barrier materials, barrier thickness, peak voltage, gap distance, electrode area, and operation temperature were experimentally investigated. The energy injection is a function of relative permittivity, barrier thickness, peak voltage, gap distance, and electrode area. The influence of operation temperature on energy injection is slight in the range of 27–300 °C but becomes obvious in the range of 300–500 °C. A model was established using which the energy injection can be easily predicted. supported by National Natural Science Foundation of China (No. 11575159), Zhejiang Provincial Natural Science Foundation of China (No. LY13B070004), Program for Zhejiang Leading Team of S&T Innovation (No. 2013TD07), and National Natural Science Foundation of China (No. 51206146)

  9. Densely-packed ZnTPPs Monolayer on the Rutile TiO2(110)-(1×1) Surface: Adsorption Behavior and Energy Level Alignment

    PubMed Central

    Rangan, Sylvie; Ruggieri, Charles; Bartynski, Robert; Martínez, José Ignacio; Flores, Fernando; Ortega, José

    2016-01-01

    The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights. PMID:26998188

  10. Adsorption and simultaneous dechlorination of PCBs on GAC/Fe/Pd: mechanistic aspects and reactive capping barrier concept.

    PubMed

    Choi, Hyeok; Agarwal, Shirish; Al-Abed, Souhail R

    2009-01-15

    There are many concerns and challenges in current remediation strategies for sediments contaminated with polychlorinated biphenyls (PCBs). Our efforts have been geared toward the development of granular activated carbon (GAC) impregnated with reactive iron/palladium (Fe/Pd) bimetallic nanoparticles (reactive activated carbon (RAC)). In this study, we elucidate the mechanistic aspects of the hybrid RAC system dechlorinating 2-chlorobiphenyl (2-CIBP) in the aqueous phase. The following reactions occurred in parallel or consecutively: (i) 2-CIBP is promptly and completely sequestrated to RAC phase, (ii) the adsorbed 2-CIBP is almost simultaneously dechlorinated by Fe/Pd particles to form a reaction product biphenyl (BP), and (iii) the BP formed is instantly and strongly adsorbed to RAC. The 2-CIBP adsorption and dechlorination rate constants were estimated through simple first-order reaction kinetic models with an assumption for unextractable portion of carbon in RAC. The extent of 2-CIBP accumulation and BP formation in RAC phase could be well explained by the kinetic model and adsorption was found to be the rate limiting step for overall reaction. On the basis of our observations, a new strategy and concept of "reactive" cap/barrier composed of RAC was proposed as a new environmental risk management option for PCBs-contaminated sites. PMID:19238984

  11. Radiant Barriers Save Energy in Buildings

    NASA Technical Reports Server (NTRS)

    2014-01-01

    Langley Research Center needed to coat the Echo 1 satellite with a fine mist of vaporized metal, and collaborated with industry to create "radiant barrier technology." In 2010, Ryan Garrett learned about a new version of the technology resistant to oxidation and founded RadiaSource in Ogden, Utah, to provide the NASA-derived technology for applications in homes, warehouses, gymnasiums, and agricultural settings.

  12. An improved single crystal adsorption calorimeter for determining gas adsorption and reaction energies on complex model catalysts

    NASA Astrophysics Data System (ADS)

    Fischer-Wolfarth, Jan-Henrik; Hartmann, Jens; Farmer, Jason A.; Flores-Camacho, J. Manuel; Campbell, Charles T.; Schauermann, Swetlana; Freund, Hans-Joachim

    2011-02-01

    A new ultrahigh vacuum microcalorimeter for measuring heats of adsorption and adsorption-induced surface reactions on complex single crystal-based model surfaces is described. It has been specifically designed to study the interaction of gaseous molecules with well-defined model catalysts consisting of metal nanoparticles supported on single crystal surfaces or epitaxial thin oxide films grown on single crystals. The detection principle is based on the previously described measurement of the temperature rise upon adsorption of gaseous molecules by use of a pyroelectric polymer ribbon, which is brought into mechanical/thermal contact with the back side of the thin single crystal. The instrument includes (i) a preparation chamber providing the required equipment to prepare supported model catalysts involving well-defined nanoparticles on clean single crystal surfaces and to characterize them using surface analysis techniques and in situ reflectivity measurements and (ii) the adsorption/reaction chamber containing a molecular beam, a pyroelectric heat detector, and calibration tools for determining the absolute reactant fluxes and adsorption heats. The molecular beam is produced by a differentially pumped source based on a multichannel array capable of providing variable fluxes of both high and low vapor pressure gaseous molecules in the range of 0.005-1.5 × 1015 molecules cm-2 s-1 and is modulated by means of the computer-controlled chopper with the shortest pulse length of 150 ms. The calorimetric measurements of adsorption and reaction heats can be performed in a broad temperature range from 100 to 300 K. A novel vibrational isolation method for the pyroelectric detector is introduced for the reduction of acoustic noise. The detector shows a pulse-to-pulse standard deviation ≤15 nJ when heat pulses in the range of 190-3600 nJ are applied to the sample surface with a chopped laser. Particularly for CO adsorption on Pt(111), the energy input of 15 nJ (or 120 nJ cm

  13. Optimal smoothing of site-energy distributions from adsorption isotherms

    SciTech Connect

    Brown, L.F.; Travis, B.J.

    1983-01-01

    The equation for the adsorption isotherm on a heterogeneous surface is a Fredholm integral equation. In solving it for the site-energy distribution (SED), some sort of smoothing must be carried out. The optimal amount of smoothing will give the most information that is possible without introducing nonexistent structure into the SED. Recently, Butler, Reeds, and Dawson proposed a criterion (the BRD criterion) for choosing the optimal smoothing parameter when using regularization to solve Fredholm equations. The BRD criterion is tested for its suitability in obtaining optimal SED's. This criterion is found to be too conservative. While using it never introduces nonexistent structure into the SED, significant information is often lost. At present, no simple criterion for choosing the optimal smoothing parameter exists, and a modeling approach is recommended.

  14. Critical energy barrier for capillary condensation in mesopores: Hysteresis and reversibility

    NASA Astrophysics Data System (ADS)

    Hiratsuka, Tatsumasa; Tanaka, Hideki; Miyahara, Minoru T.

    2016-04-01

    Capillary condensation in the regime of developing hysteresis occurs at a vapor pressure, Pcond, that is less than that of the vapor-like spinodal. This is because the energy barrier for the vapor-liquid transition from a metastable state at Pcond becomes equal to the energy fluctuation of the system; however, a detailed mechanism of the spontaneous transition has not been acquired even through extensive experimental and simulation studies. We therefore construct accurate atomistic silica mesopore models for MCM-41 and perform molecular simulations (gauge cell Monte Carlo and grand canonical Monte Carlo) for argon adsorption on the models at subcritical temperatures. A careful comparison between the simulation and experiment reveals that the energy barrier for the capillary condensation has a critical dimensionless value, Wc* = 0.175, which corresponds to the thermal fluctuation of the system and depends neither on the mesopore size nor on the temperature. We show that the critical energy barrier Wc* controls the capillary condensation pressure Pcond and also determines a boundary between the reversible condensation/evaporation regime and the developing hysteresis regime.

  15. Critical energy barrier for capillary condensation in mesopores: Hysteresis and reversibility.

    PubMed

    Hiratsuka, Tatsumasa; Tanaka, Hideki; Miyahara, Minoru T

    2016-04-28

    Capillary condensation in the regime of developing hysteresis occurs at a vapor pressure, Pcond, that is less than that of the vapor-like spinodal. This is because the energy barrier for the vapor-liquid transition from a metastable state at Pcond becomes equal to the energy fluctuation of the system; however, a detailed mechanism of the spontaneous transition has not been acquired even through extensive experimental and simulation studies. We therefore construct accurate atomistic silica mesopore models for MCM-41 and perform molecular simulations (gauge cell Monte Carlo and grand canonical Monte Carlo) for argon adsorption on the models at subcritical temperatures. A careful comparison between the simulation and experiment reveals that the energy barrier for the capillary condensation has a critical dimensionless value, Wc (*) = 0.175, which corresponds to the thermal fluctuation of the system and depends neither on the mesopore size nor on the temperature. We show that the critical energy barrier Wc (*) controls the capillary condensation pressure Pcond and also determines a boundary between the reversible condensation/evaporation regime and the developing hysteresis regime. PMID:27131561

  16. Deep inelastic scattering at energies near the Coulomb barrier

    SciTech Connect

    Gehring, J.; Rehm, K.E.; Schiffer, J.P.

    1993-10-01

    A large yield for a process that appears to have many of the features of deep inelastic scattering has been observed at energies, near the Coulomb barrier in the systems {sup 112,124}Sn + {sup 58}Ni by Wolfs et al. In order to better understand the mechanisms by which energy dissipation takes place close to the barrier, we have extended the measurements of Wolfs to the system {sup 136}Xe + {sup 64}Ni. The use of inverse kinematics in the present measurements resulted in better mass and energy resolution due to reduced target effects and in more complete angular coverage. We have obtained angular distributions, mass distributions, and total cross sections for deep inelastic scattering at two energies near the barrier. The results on the closed neutron shell nucleus {sup 136}Xe complement those from the closed proton shell Sn nuclei.

  17. An improved single crystal adsorption calorimeter for determining gas adsorption and reaction energies on complex model catalysts.

    PubMed

    Fischer-Wolfarth, Jan-Henrik; Hartmann, Jens; Farmer, Jason A; Flores-Camacho, J Manuel; Campbell, Charles T; Schauermann, Swetlana; Freund, Hans-Joachim

    2011-02-01

    A new ultrahigh vacuum microcalorimeter for measuring heats of adsorption and adsorption-induced surface reactions on complex single crystal-based model surfaces is described. It has been specifically designed to study the interaction of gaseous molecules with well-defined model catalysts consisting of metal nanoparticles supported on single crystal surfaces or epitaxial thin oxide films grown on single crystals. The detection principle is based on the previously described measurement of the temperature rise upon adsorption of gaseous molecules by use of a pyroelectric polymer ribbon, which is brought into mechanical∕thermal contact with the back side of the thin single crystal. The instrument includes (i) a preparation chamber providing the required equipment to prepare supported model catalysts involving well-defined nanoparticles on clean single crystal surfaces and to characterize them using surface analysis techniques and in situ reflectivity measurements and (ii) the adsorption∕reaction chamber containing a molecular beam, a pyroelectric heat detector, and calibration tools for determining the absolute reactant fluxes and adsorption heats. The molecular beam is produced by a differentially pumped source based on a multichannel array capable of providing variable fluxes of both high and low vapor pressure gaseous molecules in the range of 0.005-1.5 × 10(15) molecules cm(-2) s(-1) and is modulated by means of the computer-controlled chopper with the shortest pulse length of 150 ms. The calorimetric measurements of adsorption and reaction heats can be performed in a broad temperature range from 100 to 300 K. A novel vibrational isolation method for the pyroelectric detector is introduced for the reduction of acoustic noise. The detector shows a pulse-to-pulse standard deviation ≤15 nJ when heat pulses in the range of 190-3600 nJ are applied to the sample surface with a chopped laser. Particularly for CO adsorption on Pt(111), the energy input of 15 n

  18. Renewable Energy Permitting Barriers in Hawaii: Experience from the Field

    SciTech Connect

    Busche, S.; Donnelly, C.; Atkins, D.; Fields, R.; Black, C.

    2013-03-01

    This white paper presents a summary of the solicited input from permitting agencies and renewable energy developers on the permitting process in Hawaii to provide stakeholders in Hawaii, particularly those involved in permitting, with information on current permitting barriers that renewable energy developers are experiencing.

  19. Renewable energy technologies adoption in Kazakhstan: potentials, barriers and solutions

    NASA Astrophysics Data System (ADS)

    Karatayev, Marat; Marazza, Diego; Contin, Andrea

    2015-04-01

    The growth in environmental pollution alongside an increasing demand for electricity in Kazakhstan calls for a higher level of renewable energy penetration into national power systems. Kazakhstan has great potential for renewable energies from wind, solar, hydro and biomass resources that can be exploited for electricity production. In 2013, the Kazakhstani Ministry of Energy initiated a new power development plan, which aims to bring the share of renewable energy to 3% by 2020 rising to 30% by 2030 and 50% by 2050. The current contribution of renewable energy resources in the national electricity mix, however, is less than 1%. As a developing country, Kazakhstan has faced a number of barriers to increase renewable energy use, which have to be analysed and translated into a comprehensive renewable energy policy framework. This study presents an overview of the current conditions of renewable energy development in Kazakhstan. Secondly, it identifies and describes the main barriers that prevent diffusion of renewable energy technologies in Kazakhstan. Finally, the paper provides solutions to overcome specific barriers in order to successfully develop a renewable energy technology sector in Kazakhstan.

  20. Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Abild-Pedersen, F.; Greeley, J.; Studt, F.; Rossmeisl, J.; Munter, T. R.; Moses, P. G.; Skúlason, E.; Bligaard, T.; Nørskov, J. K.

    2007-07-01

    Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorption energy of the central, C, N, O, or S atom, the scaling constant depending only on x. A model is proposed to understand this behavior. The scaling model is developed into a general framework for estimating the reaction energies for hydrogenation and dehydrogenation reactions.

  1. Directed transport of active particles over asymmetric energy barriers.

    PubMed

    Koumakis, N; Maggi, C; Di Leonardo, R

    2014-08-21

    We theoretically and numerically investigate the transport of active colloids to target regions, delimited by asymmetric energy barriers. We show that it is possible to introduce a generalized effective temperature that is related to the local variance of particle velocities. The stationary probability distributions can be derived from a simple diffusion equation in the presence of an inhomogeneous effective temperature resulting from the action of external force fields. In particular, transition rates over asymmetric energy barriers can be unbalanced by having different effective temperatures over the two slopes of the barrier. By varying the type of active noise, we find that equal values of diffusivity and persistence time may produce strongly varied effective temperatures and thus stationary distributions. PMID:24978345

  2. Implementing District Energy Systems: Municipal Approaches To Overcoming Barriers

    NASA Astrophysics Data System (ADS)

    Simpson, Kevin George

    Climate change and energy security are issues facing municipalities throughout the world. Efficient, resilient, sustainable, community-based energy systems, such as district energy systems (DES), fuelled mostly by renewables, are an important tool for addressing both climate change and energy security at the municipal level. In spite of their benefits, DES are not widely adopted in Canada (CDEA, 2011). This is due to the complex nature of the barriers which project proponents face. This thesis examines the experience of the City of Prince George in adopting and implementing the Downtown DES. Using a case study methodology, data was collected through a review of relevant municipal documents and a series of semi-structured, open-ended interviews. A thematic analysis revealed unexpected barriers related to lack of adequate public consultation and negative perceptions regarding biomass as a fuel for the DES. These `lessons learned' were then developed into recommendations for other municipalities considering DES.

  3. Optimization of adsorption processes for climate control and thermal energy storage

    SciTech Connect

    Narayanan, S; Yang, S; Kim, H; Wang, EN

    2014-10-01

    Adsorption based heat-pumps have received significant interest owing to their promise of higher efficiencies and energy savings when coupled with waste heat and solar energy compared to conventional heating and cooling systems. While adsorption systems have been widely studied through computational analysis and experiments, general design guidelines to enhance their overall performance have not been proposed. In this work, we identified conditions suitable for the maximum utilization of the adsorbent to enhance the performance of both intermittent as well as continuously operating adsorption systems. A detailed computational model was developed based on a general framework governing adsorption dynamics in a single adsorption layer and pellet. We then validated the computational analysis using experiments with a model system of zeolite 13X-water for different operating conditions. A dimensional analysis was subsequently carried out to optimize adsorption performance for any desired operating condition, which is determined by the choice of adsorbent-vapor pair, adsorption duration, operational pressure, intercrystalline porosity, adsorbent crystal size, and intracrystalline vapor diffusivity. The scaling analysis identifies the critical dimensionless parameters and provides a simple guideline to determine the most suitable geometry for the adsorbent particles. Based on this selection criterion, the computational model was used to demonstrate maximum utilization of the adsorbent for any given operational condition. By considering a wide range of parametric variations for performance optimization, these results offer important insights for designing adsorption beds for heating and cooling systems. (C) 2014 Elsevier Ltd. All rights reserved.

  4. Quantum Mechanical Free Energy Barrier for an Enzymatic Reaction

    NASA Astrophysics Data System (ADS)

    Rod, Thomas H.; Ryde, Ulf

    2005-04-01

    We discuss problems related to in silico studies of enzymes and show that accurate and converged free energy changes for complex chemical reactions can be computed if a method based on a thermodynamic cycle is employed. The method combines the sampling speed of molecular mechanics with the accuracy of a high-level quantum mechanics method. We use the method to compute the free energy barrier for a methyl transfer reaction catalyzed by the enzyme catechol O-methyltransferase at the level of density functional theory. The surrounding protein and solvent are found to have a profound effect on the reaction, and we show that energies can be extrapolated easily from one basis set and exchange-correlation functional to another. Using this procedure we calculate a barrier of 69 kJ/mol, in excellent agreement with the experimental value of 75 kJ/mol.

  5. Developing effective rockfall protection barriers for low energy impacts

    NASA Astrophysics Data System (ADS)

    Mentani, Alessio; Giacomini, Anna; Buzzi, Olivier; Govoni, Laura; Gottardi, Guido; Fityus, Stephen

    2016-04-01

    Recently, important progresses have been made towards the development of high capacity rockfall barriers (100 kJ - 8000 kJ). The interest of researchers and practitioners is now turning to the development of fences of minor capacity, whose use becomes essential in areas where rockfall events generally have low intensity and the use of high capacity barriers would be accompanied by excessive costs and high environmental impact. Low energy barriers can also provide a cost-effective solution even in areas where high energies events are expected. Results of full-scale tests are vital to any investigation on the behaviour of these structures. An experimental set-up has been developed at The University of Newcastle (AUS), to investigate the response of low energy rockfall barrier prototypes to low energy impacts. The Australian territory, and in particular New South Wales, is in fact characterised by rockfall events of low-to-medium intensity (50 kJ - 500 kJ) and the need of protection structures working within such energy range, is particularly felt [1]. The experiments involved the impact of a test block onto three spans, low energy barrier prototypes, made of steel structural posts, fully fixed at the base, side cables and a steel meshwork constituted by a double twist hexagonal wire net [2]. Test data enabled the development, calibration and assessment of FE models [3], on which non-linear and dynamic analyses have been performed addressing the effect of the block size. Results have shown that the response of the structure is strongly governed by the net. Data from tests conducted on the sole net and on the entire barrier showed in fact a similar trend, different to what typically observed for high capacity barriers, whose behaviour is also led by the presence of uphill cables and brakes. In particular, the numerical analyses have demonstrated a dependence of the net performance on the block size. In particular, a loss of capacity in the order of 50% occurred as the

  6. Energy management action plan: Developing a strategy for overcoming institutional barriers to municipal energy conservation

    SciTech Connect

    Not Available

    1992-12-31

    Energy offices working to improve efficiency of local government facilities face not only technical tasks, but institutional barriers, such as budget structures that do not reward efficiency, a low awareness of energy issues, and purchasing procedures based only on minimizing initial cost. The bureau, in working to remove such barriers in San Francisco, has identified 37 institutional barriers in areas such as operations & maintenance, purchasing, and facility design; these barriers were then reorganized into three groupings-- policy & attitudes, budget & incentives, and awareness & information-- and mapped. This map shows that the barriers mutually reinforce each other, and that a holistic approach is required for permanent change. The city`s recreation & parks department was used as a model department, and information about facility energy use was compiled into a departmental energy review. Staff interviews showed how barriers affect conservation. The bureau then generated ideas for projects to remove specific barriers and rated them according to potential impact and the resources required to implement them. Four of the six projects selected focused on maintenance staff: a cost- sharing lighting retrofit program, a boiler efficiency program, a departmental energy tracking system, and a budgetary incentive program for conservation. The other two projects are city-wide: promotion of a new term contract supplying energy-efficient light materials, and publication/distribution of ENERGY NEWS newsletter. A general methodology, the EMAP Strategy Guide, has been created to assist other energy offices in developing EMAPs.

  7. Barriers to household investment in residential energy conservation: preliminary assessment

    SciTech Connect

    Hoffman, W.L.

    1982-12-01

    A general assessment of the range of barriers which impede household investments in weatherization and other energy efficiency improvements for their homes is provided. The relationship of similar factors to households' interest in receiving a free energy audits examined. Rates of return that underly household investments in major conservation improvements are assessed. A special analysis of household knowledge of economically attractive investments is provided that compares high payback improvements specified by the energy audit with the list of needed or desirable conservation improvements identified by respondents. (LEW)

  8. Screened Hybrid Exact Exchange Schemes to Adsorption Energies on Perovskite Oxides

    NASA Astrophysics Data System (ADS)

    Santos, Elton; Vojvodic, Aleksandra; Norskov, Jens K.

    The bond formation between an oxide surface and oxygen, which is one of the important intermediates for oxygen evolution reaction, is investigated using hybrid functionals. We show that there exists a linear correlation between the adsorption energies of oxygen on LaMO3 (M =Sc-Cu) oxides at hybrid calculations to those computed using semilocal density functionals through the magnetic properties of the bulk phase. The energetics of the spin-polarized surfaces follow the same trend as corresponding bulk systems, which can be treated at a much lower computational cost. The difference in adsorption energy due to magnetism is linearly correlated to the magnetization energy of bulk, i.e., the energy difference between the spin-polarized and the non spin-polarized solutions. This suggests that one could estimate the correction to the semilocal density functional adsorption energies directly from the hybrid bulk magnetization energy.

  9. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

    NASA Astrophysics Data System (ADS)

    Geweke, Jan; Shirhatti, Pranav R.; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M.

    2016-08-01

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed—presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]—50 times smaller than those reported here—were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

  10. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111).

    PubMed

    Geweke, Jan; Shirhatti, Pranav R; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M

    2016-08-01

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed-presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]-50 times smaller than those reported here-were influenced by erroneous assignment of spectroscopic lines used in the data analysis. PMID:27497574

  11. Deformation energy of a toroidal nucleus and plane fragmentation barriers

    NASA Astrophysics Data System (ADS)

    Fauchard, C.; Royer, G.

    1996-02-01

    The path leading to pumpkin-like configurations and toroidal shapes is investigated using a one-parameter shape sequence. The deformation energy is determined within the analytical expressions obtained for the various shape-dependent functions and the generalized rotating liquid drop model taking into account the proximity energy and the temperature. With increasing mass and angular momentum, a potential well appears in the toroidal shape path. For the heaviest systems, the pocket is large and locally favourable with respect to the plane fragmentation barriers which might allow the formation of evanescent toroidal systems which would rapidly decay in several fragments to minimize the surface tension.

  12. Market and policy barriers to energy storage deployment : a study for the energy storage systems program.

    SciTech Connect

    Bhatnagar, Dhruv; Currier, Aileen B.; Hernandez, Jacquelynne; Ma, Ookie; Kirby, Brendan

    2013-09-01

    Electric energy storage technologies have recently been in the spotlight, discussed as essential grid assets that can provide services to increase the reliability and resiliency of the grid, including furthering the integration of variable renewable energy resources. Though they can provide numerous grid services, there are a number of factors that restrict their current deployment. The most significant barrier to deployment is high capital costs, though several recent deployments indicate that capital costs are decreasing and energy storage may be the preferred economic alternative in certain situations. However, a number of other market and regulatory barriers persist, limiting further deployment. These barriers can be categorized into regulatory barriers, market (economic) barriers, utility and developer business model barriers, crosscutting barriers and technology barriers. This report, through interviews with stakeholders and review of regulatory filings in four regions roughly representative of the United States, identifies the key barriers restricting further energy storage development in the country. The report also includes a discussion of possible solutions to address these barriers and a review of initiatives around the country at the federal, regional and state levels that are addressing some of these issues. Energy storage could have a key role to play in the future grid, but market and regulatory issues have to be addressed to allow storage resources open market access and compensation for the services they are capable of providing. Progress has been made in this effort, but much remains to be done and will require continued engagement from regulators, policy makers, market operators, utilities, developers and manufacturers.

  13. Nucleosome positioning by genomic excluding-energy barriers.

    PubMed

    Milani, Pascale; Chevereau, Guillaume; Vaillant, Cédric; Audit, Benjamin; Haftek-Terreau, Zofia; Marilley, Monique; Bouvet, Philippe; Argoul, Françoise; Arneodo, Alain

    2009-12-29

    Recent genome-wide nucleosome mappings along with bioinformatics studies have confirmed that the DNA sequence plays a more important role in the collective organization of nucleosomes in vivo than previously thought. Yet in living cells, this organization also results from the action of various external factors like DNA-binding proteins and chromatin remodelers. To decipher the code for intrinsic chromatin organization, there is thus a need for in vitro experiments to bridge the gap between computational models of nucleosome sequence preferences and in vivo nucleosome occupancy data. Here we combine atomic force microscopy in liquid and theoretical modeling to demonstrate that a major sequence signaling in vivo are high-energy barriers that locally inhibit nucleosome formation rather than favorable positioning motifs. We show that these genomic excluding-energy barriers condition the collective assembly of neighboring nucleosomes consistently with equilibrium statistical ordering principles. The analysis of two gene promoter regions in Saccharomyces cerevisiae and the human genome indicates that these genomic barriers direct the intrinsic nucleosome occupancy of regulatory sites, thereby contributing to gene expression regulation. PMID:20018700

  14. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

    SciTech Connect

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng

    2013-11-28

    Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O{sub 2} adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N{sub 4} chelation, as well as the molecular and electronic structures for the O{sub 2} adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O{sub 2} on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d{sub z{sup 2}}, d{sub xy}, d{sub xz}, and d{sub yz}) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O{sub 2} adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  15. Summary of Workshop: Barriers to Energy Efficient Residential Ventilation

    SciTech Connect

    Sherman, Max; Sherman, Max

    2008-01-10

    The objectives for this workshop were to bring together those with different viewpoints on the implementation of energy efficient ventilation in homes to share their perspectives. The primary benefit of the workshop is to allow the participants to get a broader understanding of the issues involved and thereby make themselves more able to achieve their own goals in this area. In order to achieve this objective each participant was asked to address four objectives from their point of view: (1) Drivers for energy efficient residential ventilation: Why is this an important issue? Who cares about it? Where is the demand: occupants, utilities, regulation, programs, etc? What does sustainability mean in this context? (2) Markets & Technologies: What products, services and systems are out there? What kinds of things are in the pipeline? What is being installed now? Are there regional or other trends? What are the technology interactions with other equipment and the envelope? (3) Barriers to Implementation: What is stopping decision makers from implementing energy-efficient residential ventilation systems? What kind of barriers are there: technological, cost, informational, structural, etc. What is the critical path? (4) Solutions: What can be done to overcome the barriers and how can/should we do it? What is the role of public vs. private institutions? Where can investments be made to save energy while improving the indoor environment? Ten participants prepared presentations for the workshop. Those presentations are included in sections at the end of this workshop report. These presentations provided the principal context for the discussions that happened during the workshop. Critical path issues were raised and potential solutions discussed during the workshop. As a secondary objective they have listed key issues and some potential consensus items which resulted from the discussions.

  16. Site energy distribution analysis of Cu (Ⅱ) adsorption on sediments and residues by sequential extraction method.

    PubMed

    Jin, Qiang; Yang, Yan; Dong, Xianbin; Fang, Jimin

    2016-01-01

    Many models (e.g., Langmuir model, Freundlich model and surface complexation model) have been successfully used to explain the mechanism of metal ion adsorption on the pure mineral materials. These materials usually have a homogeneous surface where all sites have the same adsorption energies. However, it's hardly appropriate for such models to describe the adsorption on heterogeneous surfaces (e.g., sediment surface), site energy distribution analysis can be to. In the present study, the site energy distribution analysis was used to describe the surface properties and adsorption behavior of the non-residual and residual components extracted from the natural aquatic sediment samples. The residues were prepared "in-situ" by using the sequential extraction procedure. The present study is intended to investigate the roles of different components and the change of site energy distribution at different temperatures of the sediment samples in controlling Cu (Ⅱ) adsorption. The results of the site energy distribution analysis indicated firstly, that the sorption sites of iron/manganese hydrous oxides (IMHO) and organic matter (OM) have higher energy. Secondly, light fraction (LF) and carbonates have little influence on site energy distribution. Finally, there was increase in site energies with the increase of temperature. Specially, low temperature (5 °C) significantly influenced the site energies of IMHO and OM, and also had obvious effect on the energy distribution of the sediments after removing target components. The site energy distribution analysis proved to be a useful method for us to further understand the energetic characteristics of sediment in comparison with those previously obtained. PMID:26552542

  17. Anti-terrorist vehicle crash impact energy absorbing barrier

    DOEpatents

    Swahlan, David J.

    1989-01-01

    An anti-terrorist vehicle crash barrier includes side support structures, crushable energy absorbing aluminum honeycomb modules, and an elongated impact-resistant beam extending between, and at its opposite ends through vertical guideways defined by, the side support structures. An actuating mechanism supports the beam at its opposite ends for movement between a lowered barrier-withdrawn position in which a traffic-supporting side of the beam is aligned with a traffic-bearing surface permitting vehicular traffic between the side support structures and over the beam, and a raised barrier-imposed position in which the beam is aligned with horizontal guideways defined in the side support structures above the traffic-bearing surface, providing an obstruction to vehicular traffic between the side support structures. The beam is movable rearwardly in the horizontal guideways with its opposite ends disposed transversely therethrough upon being impacted at its forward side by an incoming vehicle. The crushable modules are replaceably disposed in the horizontal guideways between aft ends thereof and the beam. The beam, replaceable modules, side support structures and actuating mechanism are separate and detached from one another such that the beam and replaceable modules are capable of coacting to disable and stop an incoming vehicle without causing structural damage to the side support structures and actuating mechanism.

  18. Anti-terrorist vehicle crash impact energy absorbing barrier

    SciTech Connect

    Swahlan, D.J.

    1989-04-18

    An anti-terrorist vehicle crash barrier includes side support structures, crushable energy absorbing aluminum honeycomb modules, and an elongated impact-resistant beam extending between, and at its opposite ends through vertical guideways defined by, the side support structures. An actuating mechanism supports the beam at its opposite ends for movement between a lowered barrier-withdrawn position in which a traffic-supporting side of the beam is aligned with a traffic-bearing surface permitting vehicular traffic between the side support structures and over the beam, and a raised barrier-imposed position in which the beam is aligned with horizontal guideways defined in the side support structures above the traffic-bearing surface, providing an obstruction to vehicular traffic between the side support structures. The beam is movable rearwardly in the horizontal guideways with its opposite ends disposed transversely therethrough upon being impacted at its forward side by an incoming vehicle. The crushable modules are replaceably disposed in the horizontal guideways between aft ends thereof and the beam. The beam, replaceable modules, side support structures and actuating mechanism are separate and detached from one another such that the beam and replaceable modules are capable of coacting to disable and stop an incoming vehicle without causing structural damage to the side support structures and actuating mechanism. 6 figs.

  19. Carbon monoxide adsorption on beryllium surfaces

    NASA Astrophysics Data System (ADS)

    Allouche, A.

    2013-02-01

    Density functional calculations are here carried out to study the carbon monoxide molecule adsorption on pristine, hydrogenated and hydroxylated beryllium Be (0001) surfaces. The adsorption energies and structures, the activation barriers to molecular adsorption and dissociation are calculated. These reactions are described in terms of potential energy surfaces and electronic density of states. The quantum results are discussed along two directions: the beryllium surface reactivity in the domain of nuclear fusion devices and the possible usage of beryllium as a catalyst of Fischer-Tropsch-type synthesis.

  20. Correlation between diffusion barriers and alloying energy in binary alloys.

    PubMed

    Vej-Hansen, Ulrik Grønbjerg; Rossmeisl, Jan; Stephens, Ifan E L; Schiøtz, Jakob

    2016-01-28

    In this paper, we explore the notion that a negative alloying energy may act as a descriptor for long term stability of Pt-alloys as cathode catalysts in low temperature fuel cells. Using density functional theory calculations, we show that there is a correlation between the alloying energy of an alloy, and the diffusion barriers of the minority component. Alloys with a negative alloying energy may show improved long term stability, despite the fact that there is typically a greater thermodynamic driving force towards dissolution of the solute metal over alloying. In addition to Pt, we find that this trend also appears to hold for alloys based on Al and Pd. PMID:26750475

  1. Phenolic resin-based porous carbons for adsorption and energy storage applications

    NASA Astrophysics Data System (ADS)

    Wickramaratne, Nilantha P.

    The main objective of this dissertation research is to develop phenolic resin based carbon materials for range of applications by soft-templating and Stober-like synthesis strategies. Applications Studied in this dissertation are adsorption of CO2, bio-molecular and heavy metal ions, and energy storage devices. Based on that, our goal is to design carbon materials with desired pore structure, high surface area, graphitic domains, incorporated metal nanoparticles, and specific organic groups and heteroatoms. In this dissertation the organic-organic self-assembly of phenolic resins and triblock copolymers under acidic conditions will be used to obtain mesoporous carbons/carbon composites and Stober-like synthesis involving phenolic resins under basic condition will be used to prepare polymer/carbon particles and their composites. The structure of this dissertation consists of an introductory chapter (Chapter 1) discussing the general synthesis of carbon materials, particularly the soft-templating strategy and Stober-like carbon synthesis. Also, Chapter 1 includes a brief outline of applications namely adsorption of CO2, biomolecule and heavy metal ions, and supercapacitors. Chapter 2 discusses the techniques used for characterization of the carbon materials studied. This chapter starts with nitrogen adsorption analysis, which is used to measure the specific surface area, pore volume, distribution of pore sizes, and pore width. In addition to nitrogen adsorption, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution thermogravimetric analysis (HR-TGA), cyclic voltammetry (CV) and CHNS elemental analysis (EA) are mentioned too. Chapter 3 is focused on carbon materials for CO2 adsorption. There are different types of porous solid materials such as silicate, MOFs, carbons, and zeolites studied for CO2 adsorption. However, the carbon based materials are considered to be the best candidates for CO 2 adsorption to the industrial point of

  2. Scaling Relationships for Adsorption Energies of C2 Hydrocarbons on Transition Metal Surfaces

    SciTech Connect

    Jones, G

    2011-08-18

    Using density functional theory calculations we show that the adsorption energies for C{sub 2}H{sub x}-type adsorbates on transition metal surfaces scale with each other according to a simple bond order conservation model. This observation generalizes some recently recognized adsorption energy scaling laws for AH{sub x}-type adsorbates to unsaturated hydrocarbons and establishes a coherent simplified description of saturated as well as unsaturated hydrocarbons adsorbed on transition metal surfaces. A number of potential applications are discussed. We apply the model to the dehydrogenation of ethane over pure transition metal catalysts. Comparison with the corresponding full density functional theory calculations shows excellent agreement.

  3. Multi-neutron transfer reactions at sub-barrier energies.

    SciTech Connect

    Rehm, K. E.

    1998-01-20

    The optimum conditions for multi-neutron transfer have been studied in the system {sup 58}Ni + {sup 124}Sn at bombarding energies at and below the Coulomb barrier. The experiments were performed in inverse kinematics with a {sup 124}Sn beam bombarding a {sup 58}Ni target. The particles were identified with respect to mass and Z in the split-pole spectrograph with a hybrid focal plane detector with mass and Z-resolutions of A/{Delta}A = 150 and Z/{Delta}Z = 70. At all energies the transfer of up to 6 neutrons was observed. The yields for these transfer reactions are found to decrease by about a factor of four for each transferred neutron.

  4. Atomistic simulations of the adsorption and migration barriers of Cu adatoms on ZnO surfaces using COMB potentials

    NASA Astrophysics Data System (ADS)

    Cheng, Yu-Ting; Shan, Tzu-Ray; Devine, Bryce; Lee, Donghwa; Liang, Tao; Hinojosa, Beverly B.; Phillpot, Simon R.; Asthagiri, Aravind; Sinnott, Susan B.

    2012-08-01

    Cu/ZnO heterogeneous systems are used to catalyze the CO2 hydrogenation to methanol, but questions remain about the nature of the active site and the role of Cu-ZnO interactions in the catalyst performance. The way in which ZnO surfaces support Cu clusters and stabilize their active sites is a key factor for maintaining catalyst activity. Processes such as sintering, alloying and encapsulation may play an important role in the activity of the catalyst but are difficult to model directly with density functional theory (DFT). In this work, we report the development of charge-optimized many-body (COMB) potentials to model the Cu/ZnO system. This potential is then used in conjugation with the dimer method, which uses the first derivative of the potential energy and the initial state of the transition to find saddle points, to examine the migration barriers of Cu adatoms on Cu and ZnO surfaces. These findings are validated against the results of density functional theory (DFT) calculations and published experimental data.

  5. Microgravimetric Analysis Method for Activation-Energy Extraction from Trace-Amount Molecule Adsorption.

    PubMed

    Xu, Pengcheng; Yu, Haitao; Li, Xinxin

    2016-05-01

    Activation-energy (Ea) value for trace-amount adsorption of gas molecules on material is rapidly and inexpensively obtained, for the first time, from a microgravimetric analysis experiment. With the material loaded, a resonant microcantilever is used to record in real time the adsorption process at two temperatures. The kinetic parameter Ea is thereby extracted by solving the Arrhenius equation. As an example, two CO2 capture nanomaterials are examined by the Ea extracting method for evaluation/optimization and, thereby, demonstrating the applicability of the microgravimetric analysis method. The achievement helps to solve the absence in rapid quantitative characterization of sorption kinetics and opens a new route to investigate molecule adsorption processes and materials. PMID:27100734

  6. Benchmark Experimental Data Set and Assessment of Adsorption Free Energy for Peptide-Surface Interactions

    PubMed Central

    Wei, Yang; Latour, Robert A.

    2009-01-01

    With the increasing interest in protein adsorption in fields ranging from bionanotechnology to biomedical engineering, there is a growing need to understand protein-surface interactions at a fundamental level, such as the interaction between individual amino acid residues of a protein and functional groups presented by a surface. However, relatively little data are available that experimentally provide a quantitative, comparative measure of these types of interactions. To address this deficiency, the objective of this study was to generate a database of experimentally measured standard state adsorption free energy (ΔGoads) values for a wide variety of amino acid residue-surface interactions using a host-guest peptide and alkanethiol self-assembled monolayers (SAMs) with polymer-like functionality as the model system. The host-guest amino acid sequence was synthesized in the form of TGTG-X-GTGT where G & T are glycine and threonine amino acid residues and X represents a variable residue. In this paper, we report ΔGoads values for the adsorption of twelve different types of the host-guest peptides on a set of nine different SAM surfaces, for a total of 108 peptide-surface systems. The ΔGoads values for these 108 peptide-surface combinations show clear trends in adsorption behavior that are dependent on both peptide composition and surface chemistry. These data provide a benchmark experimental data set from which fundamental interactions that govern peptide and protein adsorption behavior can be better understood and compared. PMID:19432493

  7. Low formation energy and kinetic barrier of Stone-Wales defect in infinite and finite silicene

    NASA Astrophysics Data System (ADS)

    Manjanath, Aaditya; Singh, Abhishek K.

    2014-01-01

    Stone-Wales (SW) defects in materials having hexagonal lattice are the most common topological defects that affect the electronic and mechanical properties. Using first principles density functional theory based calculations, we study the formation energy and kinetic barrier of SW-defect in infinite and finite sheets of silicene. The formation energies as well as the barriers in both the cases are significantly lower than those of graphene. Furthermore, compared with the infinite sheets, the energy barriers and formation energies are lower for finite sheets. However, due to low barriers these defects are expected to heal out of the finite sheets.

  8. Parametric modeling of energy filtering by energy barriers in thermoelectric nanocomposites

    SciTech Connect

    Zianni, Xanthippi E-mail: xzianni@gmail.com; Narducci, Dario

    2015-01-21

    We present a parametric modeling of the thermoelectric transport coefficients based on a model previously used to interpret experimental measurements on the conductivity, σ, and Seebeck coefficient, S, in highly Boron-doped polycrystalline Si, where a very significant thermoelectric power factor (TPF) enhancement was observed. We have derived analytical formalism for the transport coefficients in the presence of an energy barrier assuming thermionic emission over the barrier for (i) non-degenerate and (ii) degenerate one-band semiconductor. Simple generic parametric equations are found that are in agreement with the exact Boltzmann transport formalism in a wide range of parameters. Moreover, we explore the effect of energy barriers in 1-d composite semiconductors in the presence of two phases: (a) the bulk-like phase and (b) the barrier phase. It is pointed out that significant TPF enhancement can be achieved in the composite structure of two phases with different thermal conductivities. The TPF enhancement is estimated as a function of temperature, the Fermi energy position, the type of scattering, and the barrier height. The derived modeling provides guidance for experiments and device design.

  9. Parametric modeling of energy filtering by energy barriers in thermoelectric nanocomposites

    NASA Astrophysics Data System (ADS)

    Zianni, Xanthippi; Narducci, Dario

    2015-01-01

    We present a parametric modeling of the thermoelectric transport coefficients based on a model previously used to interpret experimental measurements on the conductivity, σ, and Seebeck coefficient, S, in highly Boron-doped polycrystalline Si, where a very significant thermoelectric power factor (TPF) enhancement was observed. We have derived analytical formalism for the transport coefficients in the presence of an energy barrier assuming thermionic emission over the barrier for (i) non-degenerate and (ii) degenerate one-band semiconductor. Simple generic parametric equations are found that are in agreement with the exact Boltzmann transport formalism in a wide range of parameters. Moreover, we explore the effect of energy barriers in 1-d composite semiconductors in the presence of two phases: (a) the bulk-like phase and (b) the barrier phase. It is pointed out that significant TPF enhancement can be achieved in the composite structure of two phases with different thermal conductivities. The TPF enhancement is estimated as a function of temperature, the Fermi energy position, the type of scattering, and the barrier height. The derived modeling provides guidance for experiments and device design.

  10. Free Energy Wells and Barriers to Ion Transport Across Membranes

    NASA Astrophysics Data System (ADS)

    Rempe, Susan

    2014-03-01

    The flow of ions across cellular membranes is essential to many biological processes. Ion transport is also important in synthetic materials used as battery electrolytes. Transport often involves specific ions and fast conduction. To achieve those properties, ion conduction pathways must solvate specific ions by just the ``right amount.'' The right amount of solvation avoids ion traps due to deep free energy wells, and avoids ion block due to high free energy barriers. Ion channel proteins in cellular membranes demonstrate this subtle balance in solvation of specific ions. Using ab initio molecular simulations, we have interrogated the link between binding site structure and ion solvation free energies in biological ion binding sites. Our results emphasize the surprisingly important role of the environment that surrounds ion-binding sites for fast transport of specific ions. We acknowledge support from Sandia's LDRD program. Sandia National Labs is a multi-program laboratory operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the US DOE's NNSA under contract DE-AC04-94AL85000.

  11. Water films on transition metal surfaces: A physical disclosure of adsorption energy

    NASA Astrophysics Data System (ADS)

    Revilla-López, Guillem; López, Nuria; Theoretical Heterogeneous Catalysis Group Team

    2014-03-01

    Our work reports novel physical models derived from DFT calculations including van der Waals forces for the adsorption of different water motifs: ice bilayer, √37 x √37-R 25.3° and rosette on transition metal surfaces. This energy decomposition scheme is obtained by analyzing the two driving energies of adsorption: water-water and water-metal interactions. The former explained by single water adsorption and the latter by ice resonance stabilization. These two magnitudes drive, to different extent, the adsorption of ice bilayer and √37 whereas rosette motif lacks the resonance contribution. The equations successfully reproduce and predict the experimental results for the wettability and the dissociation of water films on the fcc(111) and hcp(0001) facets of Pd, Pt, Ru Ir, Rh, Au, and Ag. So happens for the temperature of the hydrophobic/hydrophilic water film transition and for the effect of the surface roughness on it. Furthermore, the metastability and the wettability of other water films like √39 x √39-R 16.1° can be anticipated by the rationalization of their geometry and their dissociation state. The authors thank the ERC-2010-StG-258406 Bio2chem-d project, MINECO (CTQ2012-33826) and BSC-RES for supporting this work.

  12. NO adsorption and dissociation on palladium clusters: The importance of charged state and metal doping

    NASA Astrophysics Data System (ADS)

    Gao, Yang; Zhang, Li Mei; Kong, Chun Cai; Yang, Zhi Mao; Chen, Yong Mei

    2016-08-01

    The NO adsorption and dissociation on neutral, charged and Ni-doped Pd13 clusters were studied by using density functional calculations. Our results revealed that NO always prefers to adsorb on the hollow site rather than the top or bridge sites. However, the charge state and Ni doping remarkably influence NO adsorption energy, dissociation barrier and reaction energy. The reaction on Pd13- has the lowest energy barrier and largest reaction energy. The Hirshfeld charge analysis discloses that the origin of the catalytic activity difference is the charge transfer from clusters to NO in the metastable NO adsorption state.

  13. Comment on "Compound nucleus aspect of sub-barrier fusion: A new energy scaling behavior"

    NASA Astrophysics Data System (ADS)

    Karpov, A. V.; Rachkov, V. A.; Zagrebaev, V. I.

    2016-01-01

    We comment on a recently published paper by R. Wolski entitled "Compound nucleus aspect of sub-barrier fusion: A new energy scaling behavior" [1], which claims that the sub-barrier fusion is determined mostly by the Q value of the compound nucleus formation. This ignores the dynamical channel-coupling effects at near-barrier energies. We demonstrate that this simplified scaling of fusion cross sections is not a common case and has no predictive power.

  14. Fusion of {sup 6}Li with {sup 159}Tb at near-barrier energies

    SciTech Connect

    Pradhan, M. K.; Mukherjee, A.; Basu, P.; Goswami, A.; Kshetri, R.; Roy, Subinit; Chowdhury, P. Roy; Sarkar, M. Saha; Palit, R.; Parkar, V. V.; Santra, S.; Ray, M.

    2011-06-15

    Complete and incomplete fusion cross sections for {sup 6}Li + {sup 159}Tb have been measured at energies around the Coulomb barrier by the {gamma}-ray method. The measurements show that the complete fusion cross sections at above-barrier energies are suppressed by {approx}34% compared to coupled-channel calculations. A comparison of the complete fusion cross sections at above-barrier energies with the existing data for {sup 11,10}B + {sup 159}Tb and {sup 7}Li + {sup 159}Tb shows that the extent of suppression is correlated with the {alpha} separation energies of the projectiles. It has been argued that the Dy isotopes produced in the reaction {sup 6}Li + {sup 159}Tb at below-barrier energies are primarily due to the d transfer to unbound states of {sup 159}Tb, while both transfer and incomplete fusion processes contribute at above-barrier energies.

  15. Identical Binding Energies and Work Functions for Distinct Adsorption Structures: Olympicenes on the Cu(111) Surface.

    PubMed

    Liu, Wei; Schuler, Bruno; Xu, Yong; Moll, Nikolaj; Meyer, Gerhard; Gross, Leo; Tkatchenko, Alexandre

    2016-03-17

    Reliability is one of the major concerns and challenges in designing organic/inorganic interfaces for (opto)electronic applications. Even small structural differences for molecules on substrates can result in a significant variation in the interface functionality, due to the strong correlation between geometry, stability, and electronic structure. Here, we employed state-of-the-art first-principles calculations with van der Waals interactions, in combination with atomic force microscopy experiments, to explore the interaction mechanism for three structurally related olympicene molecules adsorbed on the Cu(111) surface. The substitution of a single atom in the olympicene molecule switches the nature of adsorption from predominantly physisorptive character [olympicene on Cu(111)], to an intermediate state [olympicene-derived ketone on Cu(111)], then to chemisorptive character [olympicene radical on Cu(111)]. Despite the remarkable difference in adsorption structures (by up to 0.9 Å in adsorption height) and different nature of bonding, the olympicene, its ketone, and its radical derivatives have essentially identical binding energies and work functions upon interaction with the metal substrate. Our findings suggest that the stability and work functions of molecular adsorbates could be rendered insensitive to their adsorption structures, which could be a useful property for (opto)electronic applications. PMID:26928143

  16. Technical Barriers, Gaps,and Opportunities Related to Home Energy Upgrade Market Delivery

    SciTech Connect

    Bianchi, Marcus V.A.

    2011-11-01

    This report outlines the technical barriers, gaps, and opportunities that arise in executing home energy upgrade market delivery approaches, as identified through research conducted by the U.S. Department of Energy's Building America program.

  17. Linear solvation energy relationships (LSER) for adsorption of organic compounds by carbon nanotubes.

    PubMed

    Ersan, Gamze; Apul, Onur G; Karanfil, Tanju

    2016-07-01

    The objective of this paper was to create a comprehensive database for the adsorption of organic compounds by carbon nanotubes (CNTs) and to use the Linear Solvation Energy Relationship (LSER) technique for developing predictive adsorption models of organic compounds (OCs) by multi-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs). Adsorption data for 123 OCs by MWCNTs and 48 OCs by SWCNTs were compiled from the literature, including some experimental results obtained in our laboratory. The roles of selected OCs properties and CNT types were examined with LSER models. The results showed that the r(2) values of the LSER models displayed small variability for aromatic compounds smaller than 220 g/mol, after which a decreasing trend was observed. The data available for aliphatics was mainly for molecular weights smaller than 250 g/mol, which showed a similar trend to that of aromatics. The r(2) values for the LSER model on the adsorption of aromatic and aliphatic OCs by SWCNTs and MWCNTs were relatively similar indicating the linearity of LSER models did not depend on the CNT types. Among all LSER model descriptors, V term (molecular volume) for aromatic OCs and B term (basicity) for aliphatic OCs were the most predominant descriptors on both type of CNTs. The presence of R term (excess molar refractivity) in LSER model equations resulted in decreases for both V and P (polarizability) parameters without affecting the r(2) values. Overall, the results demonstrate that successful predictive models can be developed for the adsorption of OCs by MWCNTs and SWCNTs with LSER techniques. PMID:27064209

  18. Revisiting Bangham's law of adsorption-induced deformation: changes of surface energy and surface stress.

    PubMed

    Gor, Gennady Y; Bernstein, Noam

    2016-04-14

    When fluids are adsorbed on a solid surface they induce noticeable stresses, which cause the deformation of the solid. D. H. Bangham and co-authors performed a series of experimental measurements of adsorption-induced strains, and concluded that physisorption causes expansion, which is proportional to the lowering of the surface energy Δγ. This statement is referred to as the Bangham effect or Bangham's law. However, it is known that the quantity that controls the deformation is actually the change in surface stress Δf rather than surface energy Δγ, but this difference has not been considered in the context of adsorption-induced deformation of mesoporous materials. We use the Brunauer-Emmett-Teller (BET) theory to derive both values and show the difference between them. We find the condition when the difference between the two vanishes, and Bangham's law is applicable; it is likely that this condition is satisfied in most cases, and prediction of strain based on Δγ is a good approximation. We show that this is the case for adsorption of argon and water on Vycor glass. Finally, we show that the difference between Δγ and Δf can explain some of the experimental data that contradicts Bangham's law. PMID:27001041

  19. Making AlN(x) Tunnel Barriers Using a Low-Energy Nitrogen-Ion Beam

    NASA Technical Reports Server (NTRS)

    Kaul, Anupama; Kleinsasser, Alan; Bumble, Bruce; LeDuc, Henry; Lee, Karen

    2005-01-01

    A technique based on accelerating positive nitrogen ions onto an aluminum layer has been demonstrated to be effective in forming thin (<2 nm thick) layers of aluminum nitride (AlN(x)) for use as tunnel barriers in Nb/Al-AlN(x)/Nb superconductor/insulator/ superconductor (SIS) Josephson junctions. AlN(x) is the present material of choice for tunnel barriers because, to a degree greater than that of any other suitable material, it offers the required combination of low leakage current at high current density and greater thermal stability. While ultra-thin AlN films with good thickness and stoichiometry control are easily formed using techniques such as reactive molecular beam epitaxy and chemical vapor deposition, growth temperatures of 900 C are necessary for the dissociative adsorption of nitrogen from either nitrogen (N2) or ammonia (NH3). These growth temperatures are prohibitively high for the formation of tunnel barriers on Nb films because interfacial reactions at temperatures as low as 200 to 300 C degrade device properties. Heretofore, deposition by reactive sputtering and nitridation of thin Al layers with DC and RF nitrogen plasmas have been successfully used to form AlN barriers in SIS junctions. However, precise control over critical current density Jc has proven to be a challenge, as is attaining adequate process reproducibility from system to system. The present ion-beam technique is an alternative to the plasma or reactive sputtering techniques as it provides a highly controlled arrival of reactive species, independent of the electrical conditions of the substrate or vacuum chamber. Independent and accurate control of parameters such as ion energy, flux, species, and direction promises more precise control of film characteristics such as stoichiometry and thickness than is the case with typical plasma processes. In particular, the background pressure during ion-beam nitride growth is 2 or 3 orders of magnitude lower, minimizing the formation of

  20. First principles total energy studies of the adsorption of disilane on Ge(001)-c(2x4)

    NASA Astrophysics Data System (ADS)

    Cocoletzi, Gregorio H.; Sanchez-Castillo, A.; Takeuchi, N.

    2004-03-01

    We perform first principles total energy calculations to investigate the energetics and the atomic structure of the adsorption of silane (SiH_4) and disilane (Si_2H_6) on the Ge(001)-c(2× 4) surface. The adsorption of Si_2H6 is a dissociative process which first yields SiH3 and then SiH2 fragments. We first study the adsorption of SiH2 considering two different models; the intra-row and the on-dimer geometries. Our results show that the on-dimer site is more stable than the intra-row geometry. This is not a surprise since in the absence of H atoms adsorption in the on-dimer site leaves no dangling bonds. In contrast, when the SiH2 fragment is considered together with two H atoms, the intra-row geometry is favored energetically as compared with the on-dimer site. Similar results have been previously obtained for the adsorption of SiH2 on Si(001). Disilane adsorption is explored according to two different geometries. In the first one, we have considered the adsorption as two SiH3 fragments, while in the second, we have considered the adsorption as two SiH2 fragments plus 2 H fragments. It is found that the later geometry is energetically more favorable.

  1. Barriers to Energy Efficiency and the Uptake of Green Revolving Funds in Canadian Universities

    ERIC Educational Resources Information Center

    Maiorano, John; Savan, Beth

    2015-01-01

    Purpose: The purpose of this paper is to investigate the barriers to the implementation of energy efficiency projects in Canadian universities, including access to capital, bounded rationality, hidden costs, imperfect information, risk and split incentives. Methods to address these barriers are investigated, including evaluating the efficacy of…

  2. On the economic analysis of problems in energy efficiency: Market barriers, market failures, and policy implications

    SciTech Connect

    Sanstad, A.H.; Koomey, J.G.; Levine, M.D.

    1993-01-01

    In his recent paper in The Energy Journal, Ronald Sutherland argues that several so-called market barriers'' to energy efficiency frequently cited in the literature are not market failures in the conventional sense and are thus irrelevant for energy policy. We argue that Sutherland has inadequately analyzed the idea of market barrier and misrepresented the policy implications of microeconomics. We find that economic theory, correctly interpreted, does not provide for the categorical dismissal of market barriers. We explore important methodological issues underlying the debate over market barriers, and discuss the importance of reconciling the findings of non-economic social sciences with the economic analysis of energy demand and consumer decision-making. We also scrutinize Sutherland's attempt to apply finance theory to rationalize high implicit discount rates observed in energy-related choices, and find this use of finance theory to be inappropriate.

  3. On the economic analysis of problems in energy efficiency: Market barriers, market failures, and policy implications

    SciTech Connect

    Sanstad, A.H.; Koomey, J.G.; Levine, M.D.

    1993-01-01

    In his recent paper in The Energy Journal, Ronald Sutherland argues that several so-called ``market barriers`` to energy efficiency frequently cited in the literature are not market failures in the conventional sense and are thus irrelevant for energy policy. We argue that Sutherland has inadequately analyzed the idea of market barrier and misrepresented the policy implications of microeconomics. We find that economic theory, correctly interpreted, does not provide for the categorical dismissal of market barriers. We explore important methodological issues underlying the debate over market barriers, and discuss the importance of reconciling the findings of non-economic social sciences with the economic analysis of energy demand and consumer decision-making. We also scrutinize Sutherland`s attempt to apply finance theory to rationalize high implicit discount rates observed in energy-related choices, and find this use of finance theory to be inappropriate.

  4. Building America Top Innovations 2012: Thermal Bypass Air Barriers in the 2009 International Energy Conservation Code

    SciTech Connect

    none,

    2013-01-01

    This Building America Top Innovations profile describes Building America research supporting Thermal Bypass Air Barrier requirements. Since these were adopted in the 2009 IECC, close to one million homes have been mandated to include this vitally important energy efficiency measure.

  5. Barriers and opportunities: A review of selected successful energy-efficiency programs

    SciTech Connect

    Worrell, Ernst; Price, Lynn

    2001-03-20

    In industry, barriers may exist at various points in the decision making process, and in the implementation and management of measures to improve energy efficiency. Barriers may take many forms, and are determined by the business environment and include decision-making processes, energy prices, lack of information, a lack of confidence in the information, or high transaction costs for obtaining reliable information, as well as limited capital availability. Other barriers are the ''invisibility'' of energy efficiency measures and the difficulty of quantifying the impacts, and slow diffusion of innovative technology into markets while firms typically under-invest in R and D, despite the high pay-backs. Various programs try to reduce the barriers to improve the uptake of innovative technologies. A wide array of policies has been used and tested in the industrial sector in industrialized countries, with varying success rates. We review some new approaches to industrial energy efficiency improvement in industrialized countries, focusing on voluntary agreements.

  6. Role of neutron transfer in asymmetric fusion reactions at sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Ogloblin, A. A.; Zhang, H. Q.; Lin, C. J.; Jia, H. M.; Khlebnikov, S. V.; Kuzmin, E. A.; Trzaska, W. H.; Xu, X. X.; Yan, F.; Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Scheid, W.

    2014-10-01

    The measured complete fusion (capture) excitation function is presented for the 28Si + 208Pb reaction at deep sub-barrier energies. This excitation function is compared with the one predicted with the quantum diffusion approach.

  7. Energy barriers for dipole moment flipping in PVDF-related ferroelectric polymers

    NASA Astrophysics Data System (ADS)

    Yu, Ying-Ju; McGaughey, Alan J. H.

    2016-01-01

    Energy barriers for flipping the transverse dipole moments in poly(vinylidene fluoride) (PVDF) and related copolymers and terpolymers are predicted using the nudged elastic band method. The dipole moments flip individually along the chain, with an order and energy barrier magnitudes (0.1-1.2 eV) that depend on the chain composition and environment. Trifluoroethylene (TrFE) and chlorofluoroethylene (CFE) monomers have larger energy barriers than VDF monomers, while a chain in an amorphous environment has a similar transition pathway as that of an isolated molecule. In a crystalline environment, TrFE and CFE monomers expand the lattice and lower the energy barriers for flipping VDF monomers. This finding is consistent with experimental observations of a large electrocaloric effect in P(VDF-TrFE-CFE) terpolymers.

  8. Heavy ion fusion at sub-barrier energies: Progress and questions

    SciTech Connect

    Betts, R.R.

    1993-01-01

    The current status of the experimental study of heavy-ion fusion at sub-barrier energies is reviewed. Emphasis is placed on areas of disagreement between experimental data and theoretical predictions. Suggestions for future experiments are discussed.

  9. Heavy ion fusion at sub-barrier energies: Progress and questions

    SciTech Connect

    Betts, R.R.

    1993-04-01

    The current status of the experimental study of heavy-ion fusion at sub-barrier energies is reviewed. Emphasis is placed on areas of disagreement between experimental data and theoretical predictions. Suggestions for future experiments are discussed.

  10. Reaction Pathway and Free Energy Barrier for Urea Elimination in Aqueous Solution

    PubMed Central

    Yao, Min; Chen, Xi; Zhan, Chang-Guo

    2015-01-01

    To accurately predict the free energy barrier for urea elimination in aqueous solution, we examined the reaction coordinates for the direct and water-assisted elimination pathways, and evaluated the corresponding free energy barriers by using the surface and volume polarization for electrostatics (SVPE) model-based first-principles electronic-structure calculations. Based on the computational results, the water-assisted elimination pathway is dominant for urea elimination in aqueous solution, and the corresponding free energy barrier is 25.3 kcal/mol. The free energy barrier of 25.3 kcal/mol predicted for the dominant reaction pathway of urea elimination in aqueous solution is in good agreement with available experimental kinetic data. PMID:25821238

  11. Physical and chemical nature of the scaling relations between adsorption energies of atoms on metal surfaces.

    PubMed

    Calle-Vallejo, F; Martínez, J I; García-Lastra, J M; Rossmeisl, J; Koper, M T M

    2012-03-16

    Despite their importance in physics and chemistry, the origin and extent of the scaling relations between the energetics of adsorbed species on surfaces remain elusive. We demonstrate here that scalability is not exclusive to adsorbed atoms and their hydrogenated species but rather a general phenomenon between any set of adsorbates bound similarly to the surface. On the example of the near-surface alloys of Pt, we show that scalability is a result of identical variations of adsorption energies with respect to the valence configuration of both the surface components and the adsorbates. PMID:22540492

  12. Mesoscale geomorphic change on low energy barrier islands in Chesapeake Bay, U.S.A.

    NASA Astrophysics Data System (ADS)

    Cooper, J. Andrew G.

    2013-10-01

    This paper presents an analysis of decadal (mesoscale) geomorphic change on sandy barrier islands in the fetch-limited environment of Chesapeake Bay. Low energy barrier islands exist in two settings: on the fringe of marshes and in open water and this analysis shows the various types of barrier island to be genetically related. Barrier islands that face the dominant wind and wave direction (E or W) retreat via barrier translation, preserving the barrier island volume. Those that exist in re-entrants are dominated by longshore transport processes, are strongly affected by sediment supply and are subject to disintegration. Marsh fringe barrier islands are perched on or draped over the surface of the underlying marsh. They migrate landwards via barrier translation during periodic high water events accompanied by large waves (hurricanes and northeasters). The underlying marsh surface erodes under all water levels and the rate of retreat of the barrier island and underlying marsh may take place at different rates, leading to various configurations from perched barrier islands several metres landward of the marsh edge, to barrier islands that have a sandy shoreface extending into the subtidal zone. The coastal configuration during landward retreat of marsh fringe barrier islands is subject to strong local control exerted by the underyling marsh topography. As erosion of marsh promontories occurs and marsh creeks are intersected and bypassed, the configuration is subject to rapid change. Periodic sediment influxes cause spits to develop at re-entrants in the marsh. The spits are initiated as extensions of adjacent marsh fringe barrier islands, but as the sediment volume is finite, the initial drift-aligned spits become sediment-starved and begin to develop a series of swash-aligned cells as they strive for morphodynamic equilibrium. The individual cells are stretched until breaches form in the barrier islands, creating inlets with tidal deltas. At this stage the low

  13. Energy deposition characteristics of nanosecond dielectric barrier discharge plasma actuators: Influence of dielectric material

    NASA Astrophysics Data System (ADS)

    Correale, G.; Winkel, R.; Kotsonis, M.

    2015-08-01

    An experimental study aimed at the characterization of energy deposition of nanosecond Dielectric Barrier Discharge (ns-DBD) plasma actuators was carried out. Special attention was given on the effect of the thickness and material used for dielectric barrier. The selected materials for this study were polyimide film (Kapton), polyamide based nylon (PA2200), and silicone rubber. Schlieren measurements were carried out in quiescent air conditions in order to observe density gradients induced by energy deposited. Size of heated area was used to qualify the energy deposition coupled with electrical power measurements performed using the back-current shunt technique. Additionally, light intensity measurements showed a different nature of discharge based upon the material used for barrier, for a fixed thickness and frequency of discharge. Finally, a characterisation study was performed for the three tested materials. Dielectric constant, volume resistivity, and thermal conductivity were measured. Strong trends between the control parameters and the energy deposited into the fluid during the discharge were observed. Results indicate that efficiency of energy deposition mechanism relative to the thickness of the barrier strongly depends upon the material used for the dielectric barrier itself. In general, a high dielectric strength and a low volumetric resistivity are preferred for a barrier, together with a high heat capacitance and a low thermal conductivity coefficient in order to maximize the efficiency of the thermal energy deposition induced by an ns-DBD plasma actuator.

  14. Adsorption Energy Trends on UO2 and ThO2 Surfaces

    NASA Astrophysics Data System (ADS)

    Skomurski, F. N.; Shuller, L. C.; Ewing, R. C.; Becker, U.

    2006-05-01

    Uranium dioxide (UO2) comprises approximately 96 percent of spent nuclear fuel (SNF). Therefore, the interaction of UO2 surfaces with adsorbates such as water and oxygen affects the stability of SNF as a wasteform in a geologic repository. While spectroscopic studies are used to observe surface-adsorbate interactions, questions remain regarding the mechanisms driving the initial reactions between UO2 surfaces and adsorbates. Through the use of quantum mechanical techniques, adsorption and dissociation interactions between different UO2 surfaces and oxygen and water are explored as a function of surface structure. Comparisons are also made with thorium dioxide (ThO2), a nuclear material that is isostructural with UO2, in order to test surface-adsorbate interactions as a function of insulating versus semi-conducting material properties, respectively. In this study, the density functional theory-based quantum mechanical code, CASTEP (CAmbridge Serial Total Energy Package), is used to calculate adsorption energies and changes in electronic structure between clean and adsorbate-covered UO2 and ThO2 surfaces. Four different adsorption cases are tested on the UO2 (111) and (110) surfaces: (i) one-half mono-layer (ML) of molecular water, (ii) one-half ML of dissociated water, (iii) one-half ML of dissociated oxygen, and (iv) a combined molecular water and dissociated oxygen case. The same cases are also tested on the ThO2 (111) surface. Calculations involving the oxidation of bulk UO2 are also performed for comparison with surface processes.

  15. Summary of Gaps and Barriers for Implementing Residential Building Energy Efficiency Strategies

    SciTech Connect

    none,

    2010-08-01

    This report presents the key gaps and barriers to implementing residential energy efficiency strategies in the U.S. market, as identified in sessions at the U.S. Department of Energy's Building America 2010 Residential Energy Efficiency Meeting held in Denver, Colorado, on July 20-22, 2010.

  16. Energy barriers for point-defect reactions in 3C-SiC

    NASA Astrophysics Data System (ADS)

    Zheng, Ming-Jie; Swaminathan, Narasimhan; Morgan, Dane; Szlufarska, Izabela

    2013-08-01

    Energy barriers of the key annealing reactions of neutral and charged point defects in SiC are calculated with ab initio density functional theory methods. In order to effectively search for the lowest energy migration paths the preliminary path is first established based on ab initio molecular dynamics (AIMD) simulations. The energy barrier of each hop is then calculated via climbing image nudged elastic band methods for paths guided by the AIMD simulations. The final paths and barriers are determined by comparing different pathways. The annealing reactions have important implications in understanding the amorphization, recovery, and other aspects of the radiation response of SiC. The results are compared with the literature data and experimental results on SiC recovery and amorphization. We propose that the C interstitial and Si antisite annealing reaction may provide a critical barrier that governs both the recovery stage III and amorphization processes.

  17. A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress

    SciTech Connect

    Tchitchekova, Deyana S.; Morthomas, Julien; Perez, Michel; Ribeiro, Fabienne; Ducher, Roland

    2014-07-21

    A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ∼3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress.

  18. A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress.

    PubMed

    Tchitchekova, Deyana S; Morthomas, Julien; Ribeiro, Fabienne; Ducher, Roland; Perez, Michel

    2014-07-21

    A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ∼3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress. PMID:25053312

  19. A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress

    NASA Astrophysics Data System (ADS)

    Tchitchekova, Deyana S.; Morthomas, Julien; Ribeiro, Fabienne; Ducher, Roland; Perez, Michel

    2014-07-01

    A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ˜3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress.

  20. Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

    SciTech Connect

    Massimi, Lorenzo Angelucci, Marco; Gargiani, Pierluigi; Betti, Maria Grazia; Montoro, Silvia; Mariani, Carlo

    2014-06-28

    Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption, and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.

  1. Adsorption of CO Molecules on Si(001) at Room Temperature

    NASA Astrophysics Data System (ADS)

    Seo, Eonmi; Eom, Daejin; Kim, Hanchul; Koo, Ja-Yong

    2015-03-01

    Initial adsorption of CO molecules on Si(001) is investigated by using room-temperature (RT) scanning tunneling microscopy (STM) and density functional theory calculations. Theoretical calculations show that only one adsorption configuration of terminal-bond CO (T-CO) is stable and that the bridge-bond CO is unstable. All the abundantly observed STM features due to CO adsorption can be identified as differently configured T-COs. The initial sticking probability of CO molecules on Si(001) at RT is estimated to be as small as ~ 1 x 10-4 monolayer/Langmuir, which is significantly increased at high-temperature adsorption experiments implying a finite activation barrier for adsorption. Thermal annealing at 900 K for 5 min results in the dissociation of the adsorbed CO molecules with the probability of 60-70% instead of desorption, indicating both a strong chemisorption state and an activated dissociation process. The unique adsorption state with a large binding energy, a tiny sticking probability, and a finite adsorption barrier is in stark contrast with the previous low-temperature (below 100 K) observations of a weak binding, a high sticking probability, and a barrierless adsorption. We speculate that the low-temperature results might be a signature of a physisorption state in the condensed phase.

  2. Adsorption of Organic Compounds to Diesel Soot: Frontal Analysis and Polyparameter Linear Free-Energy Relationship.

    PubMed

    Lu, Zhijiang; MacFarlane, John K; Gschwend, Philip M

    2016-01-01

    Black carbons (BCs) dominate the sorption of many hydrophobic organic compounds (HOCs) in soils and sediments, thereby reducing the HOCs' mobilities and bioavailabilities. However, we do not have data for diverse HOCs' sorption to BC because it is time-consuming and labor-intensive to obtain isotherms on soot and other BCs. In this study, we developed a frontal analysis chromatographic method to investigate the adsorption of 21 organic compounds with diverse functional groups to NIST diesel soot. This method was precise and time-efficient, typically taking only a few hours to obtain an isotherm. Based on 102 soot-carbon normalized sorption coefficients (KsootC) acquired at different sorbate concentrations, a sorbate-activity-dependent polyparameter linear free-energy relationship was established: logKsootC = (3.74 ± 0.11)V + ((-0.35 ± 0.02)log ai)E + (-0.62 ± 0.10)A + (-3.35 ± 0.11)B + (-1.45 ± 0.09); (N = 102, R(2) = 0.96, SE = 0.18), where V, E, A, and B are the sorbate's McGowan's characteristic volume, excess molar refraction, and hydrogen acidity and basicity, respectively; and ai is the sorbate's aqueous activity reflecting the system's approach to saturation. The difference in dispersive interactions with the soot versus with the water was the dominant factor encouraging adsorption, and H-bonding interactions discouraged this process. Using this relationship, soot-water and sediment-water or soil-water adsorption coefficients of HOCs of interest (PAHs and PCBs) were estimated and compared with the results reported in the literature. PMID:26587648

  3. Managing Free-energy Barriers in Nuclear Pore Transport

    PubMed Central

    Nielsen, Brian; Jeppesen, Claus

    2006-01-01

    The Nuclear Pore Complexes (NPC) facilitate highly selective gateways for transport of macromolecules across the Nuclear Envelope (NE). Based on the current accumulated knowledge of the architecture of NPC we have established a minimal physical model of the pore and the transport mechanism. The barrier properties of the NPC model are analyzed by the recently established Wang–Landau Monte Carlo computer simulation technique and the transport properties are extracted by employing Kramers’ theory of reaction rates. We show that our physical model can account for a range of characteristics observed for nuclear pore transport. PMID:19669451

  4. Evaporation protons from 8B+58Ni at near barrier energies

    NASA Astrophysics Data System (ADS)

    Amador-Valenzuela, P.; Aguilera, E. F.; Martinez-Quiroz, E.; Lizcano, D.; Kolata, J. J.; Roberts, A.; Becchetti, F. D.; Ojaruega, M.; Febbraro, M.; Guimarães, V.; Rossi, E. S., Jr.; Huiza, J. F. P.; Acosta, L.; Belyaeva, T. L.

    2011-10-01

    Yields of evaporated protons from the 8B+58Ni reaction are measured at backward angles, for several near barrier energies. Statistical model calculations using the code PACE are used to extrapolate the measurements to the whole angular region in order to get angle integrated cross sections. Fusion cross sections are deduced by using the calculated proton multiplicities. The obtained fusion excitation function shows a large enhancement as compared to BPM calculations using conventional barrier parameters.

  5. Necessity of an energy barrier for self-correction of Abelian quantum doubles

    NASA Astrophysics Data System (ADS)

    Kómár, Anna; Landon-Cardinal, Olivier; Temme, Kristan

    2016-05-01

    We rigorously establish an Arrhenius law for the mixing time of quantum doubles based on any Abelian group Zd. We have made the concept of the energy barrier therein mathematically well defined; it is related to the minimum energy cost the environment has to provide to the system in order to produce a generalized Pauli error, maximized for any generalized Pauli errors, not only logical operators. We evaluate this generalized energy barrier in Abelian quantum double models and find it to be a constant independent of system size. Thus, we rule out the possibility of entropic protection for this broad group of models.

  6. Field-dependent energy barriers in Co/CoO core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Nieves, P.; Kechrakos, D.; Chubykalo-Fesenko, O.

    2016-02-01

    We perform atomistic modeling of Co/CoO nanoparticles with a diameter of a few nanometers and realistic values of the exchange and anisotropy parameters in order to study the field-dependent energy barriers under forward and backward reversal of the magnetization. The barriers are extracted from the constrained energy minimization using the integration of the Landau-Lifshitz-Gilbert equations and the Lagrange multiplier method. We show that the applied field and the interface exchange strength have opposite effects on the values of the energy barriers. In particular, while the backward (forward) energy barrier increases (decreases) linearly with the strength of the interface exchange coupling, it decreases (increases) almost quadratically with the applied magnetic field. Our results are in good agreement with the well-known Meiklejohn-Bean model of exchange bias, and allow us to analyze the limits of applicability of the macrospin approach to the study of energy barriers in core-shell Co/CoO nanoparticles.

  7. Financing Projects That Use Clean-Energy Technologies. An Overview of Barriers and Opportunities

    SciTech Connect

    Goldman, D. P.; McKenna, J. J.; Murphy, L. M.

    2005-10-01

    This technical paper describes the importance of project financing for clean-energy technology deployment. It describes the key challenges in financing clean-energy technology projects, including technical risks, credit worthiness risk, revenue security risk, market competition, scale and related cost, as well as first-steps to overcome those barriers.

  8. Factors Affecting Energy Barriers for Pyramidal Inversion in Amines and Phosphines: A Computational Chemistry Lab Exercise

    ERIC Educational Resources Information Center

    Montgomery, Craig D.

    2013-01-01

    An undergraduate exercise in computational chemistry that investigates the energy barrier for pyramidal inversion of amines and phosphines is presented. Semiempirical calculations (PM3) of the ground-state and transition-state energies for NR[superscript 1]R[superscript 2]R[superscript 3] and PR[superscript 1]R[superscript 2]R[superscript 3] allow…

  9. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study.

    PubMed

    Jia, Juanjuan; Kara, Abdelkader; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A

    2015-09-14

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S-C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments. PMID:26374051

  10. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    SciTech Connect

    Jia, Juanjuan; Kara, Abdelkader E-mail: vladimir.esaulov@u-psud.fr; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A. E-mail: vladimir.esaulov@u-psud.fr

    2015-09-14

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

  11. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Jia, Juanjuan; Kara, Abdelkader; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A.

    2015-09-01

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S-C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

  12. Dissociative versus molecular adsorption of phenol on Si(100)2×1 : A first-principles calculation

    NASA Astrophysics Data System (ADS)

    Carbone, Marilena; Meloni, Simone; Caminiti, Ruggero

    2007-08-01

    We investigated the competitive adsorption of a bifunctional molecule, phenol, on Si(100)2×1 by ab initio calculations. We performed geometry optimizations of phenol adsorbed either molecularly or dissociatively, on five possible sites (top, bridge, valley bridge, cave, and pedestal), in the low coverage regime. We found that the dissociative adsorption of phenol on top of a silicon dimer is the most favorable adsorption configuration. In the group of dissociative adsorption the phenol initially placed on the bridge or the valley-bridge sites ends up as a toplike local minima. The pedestal and cave sites remain as low-adsorption energy “open” sites. In the group of molecular adsorption, a higher adsorption energy is associated to the adsorption through an addition reaction and loss of the aromatic character (bridge, valley-bridge, and pedestal sites). Standard butterfly or diagonal butterfly are the corresponding optimized geometries. Retention of aromatic character and lower adsorption energy are associated to the adsorption on the top and cave sites. The ordering of adsorption sites according to the adsorption energy shows a mixture of the dissociative and the molecular sites. In the case of adsorption on the top site, the adsorption energies after a rotation of the phenoxy fragment along the bonding axis and hydrogen migration on the surface are very similar. The bend of the phenoxy fragment on the surface, instead, is not favored (the adsorption energy is 1.004eV lower compared to the vertical position). Different electron density maps were calculated for different adsorption sites and modes. Finally, we investigated the possibility that molecularly adsorbed phenol behaves as a precursor for the dissociative one by nudged elastic band calculations. We found a barrier of the same order of magnitude of the thermodynamic energy at room temperature for the conversion of the valley-bridge molecular into the top dissociative site.

  13. Environmental Barrier Coatings for the Energy Efficient Heat Engines Program

    SciTech Connect

    Katherine Faber

    2004-10-31

    This program aimed to develop a fundamental understanding of the microstructural, mechanical, and chemical properties of Ta{sub 2}O{sub 5}-based coatings for Si{sub 3}N{sub 4} (AS800) substrates and optimize such coatings for environmental barriers. The program consisted of three tasks: processing of Ta{sub 2}O{sub 5} coatings, phase and microstructural development, and life-limiting phenomena. Northwestern University formed a cross-functional team with Lehigh University, Honeywell Inc., and Oak Ridge National Laboratory. The major accomplishments are: (1) Conditions for the plasma spray of Ta{sub 2}O{sub 5} and its alloys were optimized to provide maximum density and thickness. (2) Adherent small particle plasma spray coatings of Ta{sub 2}O{sub 5} can be routinely prepared. (3) Ta{sub 2}O{sub 5} can be stabilized against its disruptive phase transformation to 1400 C by the addition of one or more oxides of Al, La, and/or Nb. (4) Residual stresses in the Ta{sub 2}O{sub 5} coatings were measured using X-rays and changed with thermal exposure. (5) Properly doped coatings are more resistant against thermal cycling than undoped coatings, and can be cycled many thousand times without spallation. (6) Water vapor testing in the ORNL Keiser Rig of adherent coatings showed that undoped Ta{sub 2}O{sub 5} is not an effective barrier at preventing chemical changes to the AS800. (7) Limited water vapor testing of doped and adherent coatings, which had successfully survived many thermal cycles, showed that in the water vapor environment, de-cohesion may occur.

  14. Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage

    NASA Astrophysics Data System (ADS)

    Xu, Fei; Tang, Zhiwei; Huang, Siqi; Chen, Luyi; Liang, Yeru; Mai, Weicong; Zhong, Hui; Fu, Ruowen; Wu, Dingcai

    2015-06-01

    Exceptionally large surface area and well-defined nanostructure are both critical in the field of nanoporous carbons for challenging energy and environmental issues. The pursuit of ultrahigh surface area while maintaining definite nanostructure remains a formidable challenge because extensive creation of pores will undoubtedly give rise to the damage of nanostructures, especially below 100 nm. Here we report that high surface area of up to 3,022 m2 g-1 can be achieved for hollow carbon nanospheres with an outer diameter of 69 nm by a simple carbonization procedure with carefully selected carbon precursors and carbonization conditions. The tailor-made pore structure of hollow carbon nanospheres enables target-oriented applications, as exemplified by their enhanced adsorption capability towards organic vapours, and electrochemical performances as electrodes for supercapacitors and sulphur host materials for lithium-sulphur batteries. The facile approach may open the doors for preparation of highly porous carbons with desired nanostructure for numerous applications.

  15. Volumetric Interpretation of Protein Adsorption: Capacity Scaling with Adsorbate Molecular Weight and Adsorbent Surface Energy

    PubMed Central

    Parhi, Purnendu; Golas, Avantika; Barnthip, Naris; Noh, Hyeran; Vogler, Erwin A.

    2009-01-01

    Silanized-glass-particle adsorbent capacities are extracted from adsorption isotherms of human serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa) for adsorbent surface energies sampling the observable range of water wettability. Adsorbent capacity expressed as either mass-or-moles per-unit-adsorbent-area increases with protein molecular weight (MW) in a manner that is quantitatively inconsistent with the idea that proteins adsorb as a monolayer at the solution-material interface in any physically-realizable configuration or state of denaturation. Capacity decreases monotonically with increasing adsorbent hydrophilicity to the limit-of-detection (LOD) near τo = 30 dyne/cm (θ~65o) for all protein/surface combinations studied (where τo≡γlvocosθ is the water adhesion tension, γlvo is the interfacial tension of pure-buffer solution, and θ is the buffer advancing contact angle). Experimental evidence thus shows that adsorbent capacity depends on both adsorbent surface energy and adsorbate size. Comparison of theory to experiment implies that proteins do not adsorb onto a two-dimensional (2D) interfacial plane as frequently depicted in the literature but rather partition from solution into a three-dimensional (3D) interphase region that separates the physical surface from bulk solution. This interphase has a finite volume related to the dimensions of hydrated protein in the adsorbed state (defining “layer” thickness). The interphase can be comprised of a number of adsorbed-protein layers depending on the solution concentration in which adsorbent is immersed, molecular volume of the adsorbing protein (proportional to MW), and adsorbent hydrophilicity. Multilayer adsorption accounts for adsorbent capacity over-and-above monolayer and is inconsistent with the idea that protein adsorbs to surfaces primarily through protein/surface interactions because proteins within second (or higher

  16. Analyzing Barriers to Energy Conservation in Residences and Offices: The Rewire Program at the University of Toronto

    ERIC Educational Resources Information Center

    Stokes, Leah C.; Mildenberger, Matto; Savan, Beth; Kolenda, Brian

    2012-01-01

    Conducting a barriers analysis is an important first step when designing proenvironmental behavior change interventions. Yet, detailed information on common barriers to energy conservation campaigns remains unavailable. Using a pair of original surveys, we leverage the theory of planned behavior to report on the most important barriers for…

  17. The energy barrier at noble metal/TiO{sub 2} junctions

    SciTech Connect

    Hossein-Babaei, F. E-mail: fhbabaei@yahoo.com; Lajvardi, Mehdi M. Alaei-Sheini, Navid

    2015-02-23

    Nobel metal/TiO{sub 2} structures are used as catalysts in chemical reactors, active components in TiO{sub 2}-based electronic devices, and connections between such devices and the outside circuitry. Here, we investigate the energy barrier at the junctions between vacuum-deposited Ag, Au, and Pt thin films and TiO{sub 2} layers by recording their electrical current vs. voltage diagrams and spectra of optical responses. Deposited Au/, Pt/, and Ag/TiO{sub 2} behave like contacts with zero junction energy barriers, but the thermal annealing of the reverse-biased devices for an hour at 523 K in air converts them to Schottky diodes with high junction energy barriers, decreasing their reverse electric currents up to 10{sup 6} times. Similar thermal processing in vacuum or pure argon proved ineffective. The highest energy barrier and the lowest reverse current among the devices examined belong to the annealed Ag/TiO{sub 2} contacts. The observed electronic features are described based on the physicochemical parameters of the constituting materials. The formation of higher junction barriers with rutile than with anatase is demonstrated.

  18. Direct measurement of free-energy barrier to nucleation of crystallites in amorphous silicon thin films

    NASA Technical Reports Server (NTRS)

    Shi, Frank G.

    1994-01-01

    A method is introduced to measure the free-energy barrier W(sup *), the activation energy, and activation entropy to nucleation of crystallites in amorphous solids, independent of the energy barrier to growth. The method allows one to determine the temperature dependence of W(sup *), and the effect of the preparation conditions of the initial amorphous phase, the dopants, and the crystallization methds on W(sup *). The method is applied to determine the free-energy barrier to nucleation of crystallites in amorphous silicon (a-Si) thin films. For thermally induced nucleation in a-Si thin films with annealing temperatures in the range of from 824 to 983 K, the free-energy barrier W(sup *) to nucleation of silicon crystals is about 2.0 - 2.1 eV regardless of the preparation conditions of the films. The observation supports the idea that a-Si transforms into an intermediate amorphous state through the structural relaxation prior to the onset of nucleation of crystallites in a-Si. The observation also indicates that the activation entropy may be an insignificant part of the free-energy barrier for the nucleation of crystallites in a-Si. Compared with the free-energy barrier to nucleation of crystallites in undoped a-Si films, a significant reduction is observed in the free-energy barrier to nucleation in Cu-doped a-Si films. For a-Si under irradiation of Xe(2+) at 10(exp 5) eV, the free-energy barrier to ion-induced nucleation of crystallites is shown to be about half of the value associated with thermal-induced nucleation of crystallites in a-Si under the otherwise same conditions, which is much more significant than previously expected. The present method has a general kinetic basis; it thus should be equally applicable to nucleation of crystallites in any amorphous elemental semiconductors and semiconductor alloys, metallic and polymeric glasses, and to nucleation of crystallites in melts and solutions.

  19. Calculation of adsorption free energy for solute-surface interactions using biased replica-exchange molecular dynamics

    PubMed Central

    Wang, Feng; Stuart, Steven J.; Latour, Robert A.

    2009-01-01

    The adsorption behavior of a biomolecule, such as a peptide or protein, to a functionalized surface is of fundamental importance for a broad range of applications in biotechnology. The adsorption free energy for these types of interactions can be determined from a molecular dynamics simulation using the partitioning between adsorbed and nonadsorbed states, provided that sufficient sampling of both states is obtained. However, if interactions between the solute and the surface are strong, the solute will tend to be trapped near the surface during the simulation, thus preventing the adsorption free energy from being calculated by this method. This situation occurs even when using an advanced sampling algorithm such as replica-exchange molecular dynamics (REMD). In this paper, the authors demonstrate the fundamental basis of this problem using a model system consisting of one sodium ion (Na+) as the solute positioned over a surface functionalized with one negatively charged group (COO−) in explicit water. With this simple system, the authors show that sufficient sampling in the coordinate normal to the surface cannot be obtained by conventional REMD alone. The authors then present a method to overcome this problem through the use of an adaptive windowed-umbrella sampling technique to develop a biased-energy function that is combined with REMD. This approach provides an effective method for the calculation of adsorption free energy for solute-surface interactions. PMID:19768127

  20. Finessing the fracture energy barrier in ballistic seed dispersal.

    PubMed

    Deegan, Robert D

    2012-04-01

    Fracture is a highly dissipative process in which much of the stored elastic energy is consumed in the creation of new surfaces. Surprisingly, many plants use fracture to launch their seeds despite its seemingly prohibitive energy cost. Here we use Impatiens glandulifera as model case to study the impact of fracture on a plant's throwing capacity. I. glandulifera launches its seeds with speeds up to 4 m/s using cracks to trigger an explosive release of stored elastic energy. We find that the seed pod is optimally designed to minimize the cost of fracture. These characteristics may account for its success at invading Europe and North America. PMID:22431608

  1. Finessing the fracture energy barrier in ballistic seed dispersal

    PubMed Central

    Deegan, Robert D.

    2012-01-01

    Fracture is a highly dissipative process in which much of the stored elastic energy is consumed in the creation of new surfaces. Surprisingly, many plants use fracture to launch their seeds despite its seemingly prohibitive energy cost. Here we use Impatiens glandulifera as model case to study the impact of fracture on a plant’s throwing capacity. I. glandulifera launches its seeds with speeds up to 4 m/s using cracks to trigger an explosive release of stored elastic energy. We find that the seed pod is optimally designed to minimize the cost of fracture. These characteristics may account for its success at invading Europe and North America. PMID:22431608

  2. Scattering of Halo Nuclei at Energies below and around the Coulomb Barrier

    NASA Astrophysics Data System (ADS)

    Borge, M. J. G.; Cubero, M.; Fernández-García, J. P.; Moro, A. M.; Pesudo, V.; Acosta, L.; Alcorta, M.; Alvarez, M. A. G.; Bender, P.; Buchmann, L.; Diget, C. A.; Di Pietro, A.; Escrig, D.; Falou, H. A.; Figuera, P. P.; Fulton, B. R.; Fynbo, H. O. U.; Galaviz, D.; Garnsworthy, A.; Gómez-Camacho, J.; Hackman, G.; Kanungo, R.; Lay, J. A.; Madurga, M.; Martel, I.; Mukha, I.; Nilsson, T.; Rodríguez-Gallardo, M.; Rusek, K.; Sánchez-Benítez, A. M.; Rajabali, M.; Sarazin, F.; Shotter, A.; Tengblad, O.; Unsworth, C.; Walden, P.

    The loosely bound structure of halo nuclei is predicted to affect the collisions with heavy targets at energies around the Coulomb barrier. We report here on the results on a series of experiments done at different facilities to study the behaviour of the scattering of the archetype of the halo nuclei: 6He, 11Li, and 11Be on heavy targets at energies below and around the Coulomb barrier. The results are interpreted in the framework of Continuum-Discretized Coupled-Channel calculations (CDCC). The departure from Rutherford scattering is larger than expected. In first approximation the effect certainly scales with the loosely bound character of the projectile.

  3. Elastic scattering of {sup 9}Li on {sup 208}Pb at energies around the Coulomb barrier

    SciTech Connect

    Cubero, M.; Fernandez-Garcia, J. P.; Alvarez, M. A. G.; Lay, J. A.; Moro, A. M.; Acosta, L.; Martel, I.; Sanchez-Benitez, A. M.; Alcorta, M.; Borge, M. J. G.; Tengblad, O.; Buchmann, L.; Shotter, A.; Walden, P.; Diget, D. G.; Fulton, B.; Fynbo, H. O. U.; Galaviz, D.; Gomez-Camacho, J.; Mukha, I.

    2011-10-28

    We have studied the dynamical effects of the halo structure of {sup 11}Li on the scattering on heavy targets at energies around the Coulomb barrier. This experiment was performed at ISAC-II at TRIUMF with a world record in production of the post-accelerated {sup 11}Li beam. As part of this study we report here on the first measurement of the elastic cross section of the core nucleus, i.e. {sup 9}Li on {sup 208}Pb, at energies around the Coulomb barrier. A preliminary optical model analysis has been performed in order to extract a global optical potential to describe the measured angular distributions.

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

    PubMed

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

    2016-07-21

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

  5. Technical Barriers, Gaps, and Opportunities Related to Home Energy Upgrade Market Delivery

    SciTech Connect

    Bianchi, M. V. A.

    2011-11-01

    This report outlines the technical barriers, gaps, and opportunities that arise in executing home energy upgrade market delivery approaches, as identified through research conducted by the U.S. Department of Energy's Building America program. The objective of this report is to outline the technical1 barriers, gaps, and opportunities that arise in executing home energy upgrade market delivery approaches, as identified through research conducted by the U.S. Department of Energy's (DOE) Building America program. This information will be used to provide guidance for new research necessary to enable the success of the approaches. Investigation for this report was conducted via publications related to home energy upgrade market delivery approaches, and a series of interviews with subject matter experts (contractors, consultants, program managers, manufacturers, trade organization representatives, and real estate agents). These experts specified technical barriers and gaps, and offered suggestions for how the technical community might address them. The potential benefits of home energy upgrades are many and varied: reduced energy use and costs; improved comfort, durability, and safety; increased property value; and job creation. Nevertheless, home energy upgrades do not comprise a large part of the overall home improvement market. Residential energy efficiency is the most complex climate intervention option to deliver because the market failures are many and transaction costs are high (Climate Change Capital 2009). The key reasons that energy efficiency investment is not being delivered are: (1) The opportunity is highly fragmented; and (2) The energy efficiency assets are nonstatus, low-visibility investments that are not properly valued. There are significant barriers to mobilizing the investment in home energy upgrades, including the 'hassle factor' (the time and effort required to identify and secure improvement works), access to financing, and the opportunity cost of

  6. Adsorption-driven translocation of polymer chain into nanopores

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Neimark, Alexander V.

    2012-06-01

    The polymer translocation into nanopores is generally facilitated by external driving forces, such as electric or hydrodynamic fields, to compensate for entropic restrictions imposed by the confinement. We investigate the dynamics of translocation driven by polymer adsorption to the confining walls that is relevant to chromatographic separation of macromolecules. By using the self-consistent field theory, we study the passage of a chain trough a small opening from cis to trans compartments of spherical shape with adsorption potential applied in the trans compartment. The chain transfer is modeled as the Fokker-Plank diffusion along the free energy landscape of the translocation pass represented as a sum of the free energies of cis and trans parts of the chain tethered to the pore opening. We investigate how the chain length, the size of trans compartment, the magnitude of adsorption potential, and the extent of excluded volume interactions affect the translocation time and its distribution. Interplay of these factors brings about a variety of different translocation regimes. We show that excluded volume interactions within a certain range of adsorption potentials can cause a local minimum on the free energy landscape, which is absent for ideal chains. The adsorption potential always leads to the decrease of the free energy barrier, increasing the probability of successful translocation. However, the translocation time depends non-monotonically of the magnitude of adsorption potential. Our calculations predict the existence of the critical magnitude of adsorption potential, which separates favorable and unfavorable regimes of translocation.

  7. Adsorption-driven translocation of polymer chain into nanopores.

    PubMed

    Yang, Shuang; Neimark, Alexander V

    2012-06-01

    The polymer translocation into nanopores is generally facilitated by external driving forces, such as electric or hydrodynamic fields, to compensate for entropic restrictions imposed by the confinement. We investigate the dynamics of translocation driven by polymer adsorption to the confining walls that is relevant to chromatographic separation of macromolecules. By using the self-consistent field theory, we study the passage of a chain trough a small opening from cis to trans compartments of spherical shape with adsorption potential applied in the trans compartment. The chain transfer is modeled as the Fokker-Plank diffusion along the free energy landscape of the translocation pass represented as a sum of the free energies of cis and trans parts of the chain tethered to the pore opening. We investigate how the chain length, the size of trans compartment, the magnitude of adsorption potential, and the extent of excluded volume interactions affect the translocation time and its distribution. Interplay of these factors brings about a variety of different translocation regimes. We show that excluded volume interactions within a certain range of adsorption potentials can cause a local minimum on the free energy landscape, which is absent for ideal chains. The adsorption potential always leads to the decrease of the free energy barrier, increasing the probability of successful translocation. However, the translocation time depends non-monotonically of the magnitude of adsorption potential. Our calculations predict the existence of the critical magnitude of adsorption potential, which separates favorable and unfavorable regimes of translocation. PMID:22697566

  8. Potential of mean force calculation of the free energy of adsorption of Type I winter flounder antifreeze protein on ice

    NASA Astrophysics Data System (ADS)

    Battle, Keith; Alan Salter, E.; Wesley Edmunds, R.; Wierzbicki, Andrzej

    2010-04-01

    Antifreeze proteins (AFPs) are a unique class of proteins that inhibit ice growth without changing the melting point of ice. In this work, we study the detailed molecular mechanism of interactions between the hydrophobic side of the winter flounder (WF) AFP and two mutants, AAAA and SSSS, in which threonine residues are substituted by serines and alanines, respectively. Umbrella sampling molecular dynamics simulations of the separation of the proteins from the (2 0 1) surface in an explicit water box is carried out to calculate the potential of mean force free energies of adsorption using AMBER10i. We estimate wild-type WF's free energy of adsorption to ice to be about -12.0 kcal/mol. Gas-phase pseudopotential plane-wave calculations of methane adsorption onto select surfaces of ice are also carried out under periodic boundary conditions to address the possible enthalpic role of WF's methyl groups in binding. The contributions of hydrophobic residues to the free energy of adsorption are discussed.

  9. Overcoming barriers to residential conservation: do energy audits help

    SciTech Connect

    Hoffman, W.L.

    1982-12-01

    A study on the effects of energy audits on the pace and choice of household investment in energy-saving improvements in the home is reported. An evaluation based on the household's assessment of the usefulness of the audit which was provided for their home was performed. The number and types of recent conservation actions among audited and unaudited samples of households are compared. The audit's effect on household knowledge about the economically attractive options for their home and on the choice of recent improvements is assessed. Possible reasons are suggested for the weak effect of audits in stimulating activity and reorienting investment choices. (LEW)

  10. State Successes: Using Outreach and Eduction to Transcend Barriers to Wind Energy (Poster)

    SciTech Connect

    Kelly, M.; Flowers, L.

    2010-05-01

    Many states projected to contribute significantly to the United States' 20% wind energy by 2030 goal have not yet achieved a first wind farm, and many more have not yet hit the 100-MW mark. These states are struggling with basic barriers of the need for understanding of the wind resource; wind energy benefits and impacts; economic development, water, and carbon impacts; issues such as transmission, utility integration, siting, and wildlife; involvement of key constituents such as the electrical sector, the ag sector, and county commissioners; effective policy; and an educated public and an educated workforce. Other states have partially transcended these barriers and are encountering organized pushback; NIMBYism; siting problems such as zoning, permitting, and environmental issues; and interstate barriers such as transmission.

  11. Analysis of the barriers to renewable energy development on tribal lands

    NASA Astrophysics Data System (ADS)

    Jones, Thomas Elisha

    Native American lands have significant renewable energy resource potential that could serve to ensure energy security and a low carbon energy future for the benefit of tribes as well as the United States. Economic and energy development needs in Native American communities match the energy potential. A disproportionate amount of Native American households have no access to electricity, which is correlated with high poverty and unemployment rates. Despite the vast resources and need for energy, the potential for renewable energy development has not fully materialized. This research explores this subject through three separate articles: 1) a case study of the Navajo Nation that suggests economic viability is not the only significant factor for low adoption of renewable energy on Navajo lands; 2) an expert elicitation of tribal renewable energy experts of what they view as barriers to renewable energy development on tribal lands; and 3) a reevaluation of Native Nation Building Theory to include external forces and the role that inter-tribal collaboration plays with renewable energy development by Native nations. Major findings from this research suggests that 1) many Native nations lack the technical and legal capacity to develop renewable energy; 2) inter-tribal collaboration can provide opportunities for sharing resources and building technical, legal, and political capacity; and 3) financing and funding remains a considerable barrier to renewable energy development on tribal lands.

  12. Energy Savings Certificate Markets: Opportunities and Implementation Barriers

    SciTech Connect

    Friedman, B.; Bird, L.; Barbose, G.

    2009-07-01

    Early experiences with energy savings certificates (ESCs) have revealed their merits and the challenges associated with them. While in the United States ESC markets have yet to gain significant traction, lessons can be drawn from early experiences in the states of Connecticut and New York, as well as from established markets in Italy, France, and elsewhere. The staying power of European examples demonstrates that ESCs can help initiate more efficiency projects. This article compares ESCs with renewable energy certificates (RECs), looks at the unique opportunities and challenges they present, and reviews solutions and best practices demonstrated by early ESC markets. Three major potential ESC market types are also reviewed: compliance, voluntary, and carbon. Additionally, factors that will benefit ESC markets in the United States are examined: new state EEPS policies, public interest in tools to mitigate climate change, and the growing interest in a voluntary market for ESCs.

  13. Consistent energy barrier distributions in magnetic particle chains

    NASA Astrophysics Data System (ADS)

    Laslett, O.; Ruta, S.; Chantrell, R. W.; Barker, J.; Friedman, G.; Hovorka, O.

    2016-04-01

    We investigate long-time thermal activation behaviour in magnetic particle chains of variable length. Chains are modelled as Stoner-Wohlfarth particles coupled by dipolar interactions. Thermal activation is described as a hopping process over a multidimensional energy landscape using the discrete orientation model limit of the Landau-Lifshitz-Gilbert dynamics. The underlying master equation is solved by diagonalising the associated transition matrix, which allows the evaluation of distributions of time scales of intrinsic thermal activation modes and their energy representation. It is shown that as a result of the interaction dependence of these distributions, increasing the particle chain length can lead to acceleration or deceleration of the overall relaxation process depending on the initialisation procedure.

  14. Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

    PubMed

    Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

    2014-01-14

    The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T. PMID:24328531

  15. 11Li Breakup on 208 at energies around the Coulomb barrier.

    PubMed

    Fernández-García, J P; Cubero, M; Rodríguez-Gallardo, M; Acosta, L; Alcorta, M; Alvarez, M A G; Borge, M J G; Buchmann, L; Diget, C A; Falou, H A; Fulton, B R; Fynbo, H O U; Galaviz, D; Gómez-Camacho, J; Kanungo, R; Lay, J A; Madurga, M; Martel, I; Moro, A M; Mukha, I; Nilsson, T; Sánchez-Benítez, A M; Shotter, A; Tengblad, O; Walden, P

    2013-04-01

    The inclusive breakup for the (11)Li + (208)Pb reaction at energies around the Coulomb barrier has been measured for the first time. A sizable yield of (9)Li following the (11)Li dissociation has been observed, even at energies well below the Coulomb barrier. Using the first-order semiclassical perturbation theory of Coulomb excitation it is shown that the breakup probability data measured at small angles can be used to extract effective breakup energy as well as the slope of B(E1) distribution close to the threshold. Four-body continuum-discretized coupled-channels calculations, including both nuclear and Coulomb couplings between the target and projectile to all orders, reproduce the measured inclusive breakup cross sections and support the presence of a dipole resonance in the (11)Li continuum at low excitation energy. PMID:25166983

  16. Lack of an energy policy remains a major barrier

    SciTech Connect

    Owen, D.

    1991-03-01

    This paper reports that the war with Iraq provided a new dimension to the ongoing oil industry struggle to cope with oppressive government action and regulation. Coming as it did just before the administration was to announce guidelines for a long-awaited National Energy Strategy (NES), the war created a renewed and dramatic focus on the national energy security question. Now, numerous congressmen, senators and administration leaders are taking a fresh look at how the U.S. can extricate itself from excessive dependence on Middle East oil imports. For example, the planned free-trade agreement with Mexico could figure prominently in an alliance that would bring much more Mexican oil to the U.S. Meanwhile, the wild card is proposals to open up U.S. drilling offshore and in the Arctic National Wildlife Region (ANWR). Prior to hostilities, Middle East tensions brought on significant increases in the price of oil, and with it a large gain in oil company profits for fourth-quarter 1990. Result: talk in Congress of a new windfall profits tax.

  17. Universal Pinning Energy Barrier for Driven Domain Walls in Thin Ferromagnetic Films.

    PubMed

    Jeudy, V; Mougin, A; Bustingorry, S; Savero Torres, W; Gorchon, J; Kolton, A B; Lemaître, A; Jamet, J-P

    2016-07-29

    We report a comparative study of magnetic field driven domain wall motion in thin films made of different magnetic materials for a wide range of field and temperature. The full thermally activated creep motion, observed below the depinning threshold, is shown to be described by a unique universal energy barrier function. Our findings should be relevant for other systems whose dynamics can be modeled by elastic interfaces moving on disordered energy landscapes. PMID:27517790

  18. Probing the fusion of 7Li with 64Ni at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Shaikh, Md. Moin; Roy, Subinit; Rajbanshi, S.; Mukherjee, A.; Pradhan, M. K.; Basu, P.; Nanal, V.; Pal, S.; Shrivastava, A.; Saha, S.; Pillay, R. G.

    2016-04-01

    Background: The stable isotopes of Li, 6Li6 and 7Li, have two-body cluster structures of α +d and α +t with α -separation energies or breakup thresholds at 1.47 and 2.47 MeV, respectively. The weak binding of these projectiles introduces several new reaction channels not usually observed in the case of strongly bound projectiles. The impact of these breakup or breakup-like reaction channels on fusion, the dominant reaction process at near-barrier energies, with different target masses is of current interest. Purpose: Our purpose is to explore the fusion, at above and below the Coulmb barrier, of 7Li with 64Ni target in order to understand the effect of breakup or breakup-like processes with medium-mass target in comparison with 6Li, which has a lower breakup threshold. Measurement: The total fusion (TF) excitation of the weakly bound projectile 7Li with the medium-mass target 64Ni has been measured at the near-barrier energies (0.8 to 2 VB). The measurement was performed using the online characteristic γ -ray detection method. The complete fusion (CF) excitation function for the system was obtained using the x n -evaporation channels with the help of statistical model predictions. Results: At the above barrier energies CF cross sections exhibit an average suppression of about 6.5% compared to the one-dimensional barrier penetration model (1DBPM) predictions, while the model describes the measured TF cross section well. But below the barrier, both TF and CF show enhancements compared to 1DBPM predictions. Unlike 6Li, enhancement of CF for 7Li could not be explained by inelastic coupling alone. Conclusion: Whereas the σTF cross sections are almost the same for both the systems in the above barrier region, the suppression of σCF at above the barrier is less for the 7Li+64Ni system than for the 6+64Ni system. Also direct cluster transfer has been identified as the probable source for producing large enhancement in TF cross sections.

  19. Influence of the intercalated cations on the surface energy of montmorillonites: consequences for the morphology and gas barrier properties of polyethylene/montmorillonites nanocomposites.

    PubMed

    Picard, E; Gauthier, H; Gérard, J-F; Espuche, E

    2007-03-15

    Organically modified montmorillonites obtained by cation exchange from the same natural layered silicate were studied. The surface properties of the pristine and a series of organically modified clays were determined by inverse gas chromatography and the water adsorption mechanisms were studied by a gravimetric technique coupled with a microcalorimeter. A significant increase of the specific surface area, a decrease of the water adsorption, and a decrease of the dispersive component of the surface energy were observed when the sodium cations of the natural montmorillonite were exchanged for a quaternary ammonium. Slighter differences in surface properties were observed, on the other hand, between the different types of organically modified montmorillonites. Indeed, similar dispersive components of the surface energy were determined on the organoclays. Nevertheless, the specific surface area increased in the range 48-80 m(2)/g with increasing d-spacing values and the presence of specific groups attached to the quaternary ammonium, such as phenyl rings or hydroxyl groups, led to some specific behaviors, i.e., a more pronounced base character and a higher water adsorption at high activity, respectively. Differences in interlayer cation chain organization, denoted as crystallinity, were also observed as a function of the nature of the chains borne by the quaternary ammonium. In a later step, polyethylene-based nanocomposites were prepared with those organically modified montmorillonites. The clay dispersion and the barrier properties of the nanocomposites were discussed as a function of the montmorillonite characteristics and of the matrix/montmorillonite interactions expected from surface energy characterization. PMID:17222420

  20. Technological innovation in community housing development: Barriers to energy efficiency

    SciTech Connect

    Cavallo, J.D.

    1996-05-01

    Community housing developers produce affordable housing and jobs for many residents of low-income neighborhoods through the rehabilitation of existing single and multi-family buildings. Typically operating as small, not-for-profits or community-based organizations, the vast numbers of community housing developers creates high coordinating costs of operating jointly to acquire the shared learning needed to implement new techniques, such as those involving energy efficiency. This paper presents a model of technology adoption that suggests that new profitable technologies will be adopted only with low probability and that strategic interaction between potential adopters further reduces the likelihood of adoption. These features result from the ability of potential adopters to postpone the bearing the costs of adoption of new technologies and their ability to share the knowledge of others who have adopted new technologies. These features are particularly characteristic of community housing developers.

  1. Direct measurement of energy barriers on rough and heterogeneous solid surfaces

    SciTech Connect

    Lloyd, T.B.; LaGow, J.; Connelly, G.M.

    1996-12-31

    This paper will deal with the phenomenon of energy barriers to the spread of liquids on solids. These barriers often manifest themselves as a {open_quotes}pinning{close_quotes} of a sessile drop as liquid is added to it. That is, the volume of the drop increases, but the diameter does not. Thus the advancing contact angle ({theta}{sub a}) increases to a maximum. At the point where the hydrostatic pressure in the drop overcomes the {open_quotes}pinning{close_quotes} force the diameter suddenly increases and the drop relaxes to a metastable configuration which has a lower {theta}{sub a}. Energy barriers should be considered in many applications such as the spreading of liquid adhesives where thorough wetting is the goal. The interfacial forces involved are both long-range Lifshitz-van der Waals (LW) forces and short-range acid-base (AB) forces. The authors will describe how they measure the energy barriers on real surfaces directly and resolve them into their LW and AB components.

  2. Overcoming Codes and Standards Barriers to Innovations in Building Energy Efficiency

    SciTech Connect

    Cole, Pamala C.; Gilbride, Theresa L.

    2015-02-15

    In this journal article, the authors discuss approaches to overcoming building code barriers to energy-efficiency innovations in home construction. Building codes have been a highly motivational force for increasing the energy efficiency of new homes in the United States in recent years. But as quickly as the codes seem to be changing, new products are coming to the market at an even more rapid pace, sometimes offering approaches and construction techniques unthought of when the current code was first proposed, which might have been several years before its adoption by various jurisdictions. Due to this delay, the codes themselves can become barriers to innovations that might otherwise be helping to further increase the efficiency, comfort, health or durability of new homes. . The U.S. Department of Energy’s Building America, a program dedicated to improving the energy efficiency of America’s housing stock through research and education, is working with the U.S. housing industry through its research teams to help builders identify and remove code barriers to innovation in the home construction industry. The article addresses several approaches that builders use to achieve approval for innovative building techniques when code barriers appear to exist.

  3. Experimental Testing of Rockfall Barriers Designed for the Low Range of Impact Energy

    NASA Astrophysics Data System (ADS)

    Buzzi, O.; Spadari, M.; Giacomini, A.; Fityus, S.; Sloan, S. W.

    2013-07-01

    Most of the recent research on rockfall and the development of protective systems, such as flexible rockfall barriers, have been focused on medium to high levels of impacting energy. However, in many regions of the world, the rockfall hazard involves low levels of energy. This is particularly the case in New South Wales, Australia, because of the nature of the geological environments. The state Road and Traffic Authority (RTA) has designed various types of rockfall barriers, including some of low capacity, i.e. 35 kJ. The latter were tested indoors using a pendulum equipped with an automatic block release mechanism triggered by an optical beam. Another three systems were also tested, including two products designed by rockfall specialised companies and one modification of the initial design of the RTA. The research focused on the influence of the system's stiffness on the transmission of load to components of the barrier such as posts and cables. Not surprisingly, the more compliant the system, the less loaded the cables and posts. It was also found that removing the intermediate cables and placing the mesh downslope could reduce the stiffness of the system designed by the RTA. The paper concludes with some multi-scale considerations on the capacity of a barrier to absorb the energy based on experimental evidence.

  4. Prediction of binding free energy for adsorption of antimicrobial peptide lactoferricin B on a POPC membrane

    NASA Astrophysics Data System (ADS)

    Vivcharuk, Victor; Tomberli, Bruno; Tolokh, Igor S.; Gray, C. G.

    2008-03-01

    Molecular dynamics (MD) simulations are used to study the interaction of a zwitterionic palmitoyl-oleoyl-phosphatidylcholine (POPC) bilayer with the cationic antimicrobial peptide bovine lactoferricin (LFCinB) in a 100 mM NaCl solution at 310 K. The interaction of LFCinB with POPC is used as a model system for studying the details of membrane-peptide interactions, with the peptide selected because of its antimicrobial nature. Seventy-two 3 ns MD simulations, with six orientations of LFCinB at 12 different distances from a POPC membrane, are carried out to determine the potential of mean force (PMF) or free energy profile for the peptide as a function of the distance between LFCinB and the membrane surface. To calculate the PMF for this relatively large system a new variant of constrained MD and thermodynamic integration is developed. A simplified method for relating the PMF to the LFCinB-membrane binding free energy is described and used to predict a free energy of adsorption (or binding) of -1.05±0.39kcal/mol , and corresponding maximum binding force of about 20 pN, for LFCinB-POPC. The contributions of the ions-LFCinB and the water-LFCinB interactions to the PMF are discussed. The method developed will be a useful starting point for future work simulating peptides interacting with charged membranes and interactions involved in the penetration of membranes, features necessary to understand in order to rationally design peptides as potential alternatives to traditional antibiotics.

  5. The Analytical Parametrization of Fusion Barrier by Using the Skyrme Energy-Density Function Model

    NASA Astrophysics Data System (ADS)

    Zanganeh, V.; Mirzaei, M.; N., Wang

    2015-08-01

    Using the skyrme energy density formalism, a pocket formula is introduced for barrier heights and positions of 95 fusion reactions (48 ≤ ZP ZT ≤ 1520) with respect to the charge and mass numbers of the interacting nuclei. It is shown that the parameterized values of RB and VB are able to reproduce the corresponding experimental data with good accuracy. Moreover, the absolute errors of our formulas are less than those obtained using the analytical parametrization forms of the fusion barrier based on the proximity versions. The ability of the parameterized forms of the barrier heights and its positions to reproduce the experimental data of the fusion cross section have been analyzed using the Wong model.

  6. Current-induced changes of migration energy barriers in graphene and carbon nanotubes.

    PubMed

    Obodo, J T; Rungger, I; Sanvito, S; Schwingenschlögl, U

    2016-05-21

    An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative. PMID:27127889

  7. Role of neutron transfer and deformation effect in capture process at sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Scheid, W.; Zhang, H. Q.

    2012-12-01

    The roles of nuclear deformation and neutron transfer in sub-barrier capture process are studied within the quantum diffusion approach. The change of the deformations of colliding nuclei with neutron exchange can crucially influence the sub-barrier fusion. The sub-barrier capture reactions following the neutron pair transfer are used for the indirect study of neutron-neutron correlation in the surface region of nucleus. The strong surface enhancement of the neutron pairing in nuclei 48Ca, 64Ni, and 116,124,132Sn is demonstrated. Comparing the capture cross sections calculated without the breakup effect and experimental complete fusion cross sections, the breakup was analyzed in reactions with weakly bound projectiles 6,7,9Li and 9Be. A trend of a systematic behavior for the complete fusion suppression as a function of the target charge and bombarding energy is not achieved.

  8. Market barriers to energy efficiency: A critical reappraisal of the rationale for public policies to promote energy efficiency

    SciTech Connect

    Golove, W.H.; Eto, J.H.

    1996-03-01

    This report reviews current perspectives on market barriers to energy efficiency. Ratepayer-funded utility energy-efficiency programs are likely to change in scope, size, and nature as the deregulation process proceeds; the authors research focuses on understanding to what extent some form of future intervention may be warranted and how they might judge the success of particular interventions, especially those funded by ratepayers. They find that challenges to the existence of market barriers have, for the most part, failed to provide a testable alternative explanation for evidence suggesting that there is a substantial ``efficiency gap`` between a consumer`s actual investments in energy efficiency and those that appear to be in the consumer`s own interest. They then suggest that differences of opinion about the appropriateness of public policies stem not from disputes about whether market barriers exist, but from different perceptions of the magnitude of the barriers, and the efficacy and (possibly unintended) consequences of policies designed to overcome them. They conclude that there are compelling justifications for future energy-efficiency policies. Nevertheless, in order to succeed, they must be based on a sound understanding of the market problems they seek to correct and a realistic assessment of their likely efficacy. This understanding can only emerge from detailed investigations of the current operation of individual markets.

  9. Current-induced changes of migration energy barriers in graphene and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Obodo, J. T.; Rungger, I.; Sanvito, S.; Schwingenschlögl, U.

    2016-05-01

    An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative.An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR00534A

  10. Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage

    PubMed Central

    Xu, Fei; Tang, Zhiwei; Huang, Siqi; Chen, Luyi; Liang, Yeru; Mai, Weicong; Zhong, Hui; Fu, Ruowen; Wu, Dingcai

    2015-01-01

    Exceptionally large surface area and well-defined nanostructure are both critical in the field of nanoporous carbons for challenging energy and environmental issues. The pursuit of ultrahigh surface area while maintaining definite nanostructure remains a formidable challenge because extensive creation of pores will undoubtedly give rise to the damage of nanostructures, especially below 100 nm. Here we report that high surface area of up to 3,022 m2 g−1 can be achieved for hollow carbon nanospheres with an outer diameter of 69 nm by a simple carbonization procedure with carefully selected carbon precursors and carbonization conditions. The tailor-made pore structure of hollow carbon nanospheres enables target-oriented applications, as exemplified by their enhanced adsorption capability towards organic vapours, and electrochemical performances as electrodes for supercapacitors and sulphur host materials for lithium–sulphur batteries. The facile approach may open the doors for preparation of highly porous carbons with desired nanostructure for numerous applications. PMID:26072734

  11. Adsorption Refrigeration System

    SciTech Connect

    Wang, Kai; Vineyard, Edward Allan

    2011-01-01

    Adsorption refrigeration is an environmentally friendly cooling technology which could be driven by recovered waste heat or low-grade heat such as solar energy. In comparison with absorption system, an adsorption system has no problems such as corrosion at high temperature and salt crystallization. In comparison with vapor compression refrigeration system, it has the advantages of simple control, no moving parts and less noise. This paper introduces the basic theory of adsorption cycle as well as the advanced adsorption cycles such as heat and mass recovery cycle, thermal wave cycle and convection thermal wave cycle. The types, characteristics, advantages and drawbacks of different adsorbents used in adsorption refrigeration systems are also summarized. This article will increase the awareness of this emerging cooling technology among the HVAC engineers and help them select appropriate adsorption systems in energy-efficient building design.

  12. Calculation of energy barriers for magnetic vortices in sub-100 nm dots

    NASA Astrophysics Data System (ADS)

    Lapa, Pavel; King, Andrew; Roshchin, Igor V.

    2012-10-01

    In a magnetic vortex, the magnetization is curling in plane everywhere except the ``core,'' where it is out of plane. Interest in switching of magnetic vortices in nanodots is stimulated by their potential application for magnetic memories and nano-oscillators. By combining analytical and micromagnetic techniques, we calculated energy barriers for vortex switching in 20 nm-thick iron dots as a function of applied in-plane field and dot diameter. Using analytical formula for magnetization distribution in the vortex,footnotetextN. A. Usov and S. E. Peschany, J. Magn. Magn. Mater. 118, 290 (1992). we performed micromagnetic calculations of the dot energy for different vortex core positions. In contrast to the ``rigid body approximation,'' the core size and core shape in our calculations were varied to achieve the energy minimum for every core displacement. The energy barriers required for vortex nucleation and annihilation were calculated as a function of magnetic field. By comparing these barriers to the thermal energy kBT we obtained the temperature dependences of the vortex nucleation and annihilation fields in good agreement with the experiment.footnotetextR. K. Dumas et al., Appl. Phys. Lett. 91, 202501 (2007).

  13. Numerical Modelling of a Low-Energy Rockfall Barrier: New Insight into the Bullet Effect

    NASA Astrophysics Data System (ADS)

    Mentani, A.; Giacomini, A.; Buzzi, O.; Govoni, L.; Gottardi, G.; Fityus, S.

    2016-04-01

    This paper investigates the dynamic response of low energy, semi-rigid rockfall barriers. The study is based on a FE model that reproduces the geometry, components and connections of the existing systems that were previously tested at The University of Newcastle. The mechanical behaviour of the relevant barrier components was calibrated from simple mechanical tests and the response of the assembled system, i.e. 2 m high, 15 m long rockfall barrier, was validated against of full-scale tests results. Following a satisfactory validation of the model, further dynamic non-linear analyses were conducted to investigate the dependence of the full system performance to the size of impacting blocks. Interestingly, the total failure energy was found to evolve non-monotonically with block size because of dynamic effects that seem to prevail for impact speeds in the range of 15-20 m/s. The study also highlights the complex effects of adding intermediate longitudinal cables to the system. An improvement of the barrier performance is observed for the large blocks but the bullet effect is exacerbated for small blocks.

  14. Opportunities and barriers for a crop-based energy sector in Ontario

    NASA Astrophysics Data System (ADS)

    Klupfel, Ellen Joanne

    This study investigates the existing opportunities and barriers for expanding the crop-based energy sector in Ontario. The investigation takes place at a time when growing concerns about sustainability---environmental, social, and economic---are encouraging the exploration of alternatives to energy systems based on fossil fuels, and concerns around the future viability of rural communities are making agriculturally-based and rural-based energy production systems attractive to many. To explore opportunities and barriers for the crop-based energy sector, this thesis addresses the question: What is the political-economic context within which the crop-based energy sector operates in Ontario? Taking an institutional approach, the study involved 26 interviews with individuals whose organizations influence Ontario's crop-based energy sector (that includes the biofuels ethanol and biodiesel), developed a model outlining relationships between the crop-based energy sector and other sectors of the economy, as well as the state, and implemented a survey of Ontario Members of Provincial Parliament's perspectives on biofuels. This research examines the balance of power of knowledge, production, security, finance, and technology for Ontario's crop-based energy sector. The overall balance of power currently rests with the petroleum sector. Through force field analysis, the study also identifies the key opportunities and barriers for the growth and development of the biofuels sector. These opportunities include climate change and rural development agendas, and the barriers include the petroleum sector, cost of production, and some sectors of the state. A few overarching conclusions emerge from this research: (1) Change in Ontario's crop-based energy sector is driven foremost by political and economic forces; (2) Climate change is the most significant driving force for the development and expansion of Ontario's crop-based energy sector; (3) Production cost and resistance from the

  15. Calculating Transition Energy Barriers and Characterizing Activation States for Steps of Fusion.

    PubMed

    Ryham, Rolf J; Klotz, Thomas S; Yao, Lihan; Cohen, Fredric S

    2016-03-01

    We use continuum mechanics to calculate an entire least energy pathway of membrane fusion, from stalk formation, to pore creation, and through fusion pore enlargement. The model assumes that each structure in the pathway is axially symmetric. The static continuum stalk structure agrees quantitatively with experimental stalk architecture. Calculations show that in a stalk, the distal monolayer is stretched and the stored stretching energy is significantly less than the tilt energy of an unstretched distal monolayer. The string method is used to determine the energy of the transition barriers that separate intermediate states and the dynamics of two bilayers as they pass through them. Hemifusion requires a small amount of energy independently of lipid composition, while direct transition from a stalk to a fusion pore without a hemifusion intermediate is highly improbable. Hemifusion diaphragm expansion is spontaneous for distal monolayers containing at least two lipid components, given sufficiently negative diaphragm spontaneous curvature. Conversely, diaphragms formed from single-component distal monolayers do not expand without the continual injection of energy. We identify a diaphragm radius, below which central pore expansion is spontaneous. For larger diaphragms, prior studies have shown that pore expansion is not axisymmetric, and here our calculations supply an upper bound for the energy of the barrier against pore formation. The major energy-requiring deformations in the steps of fusion are: widening of a hydrophobic fissure in bilayers for stalk formation, splay within the expanding hemifusion diaphragm, and fissure widening initiating pore formation in a hemifusion diaphragm. PMID:26958888

  16. Free energy barriers for escape of water molecules from protein hydration layer.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2012-03-01

    Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these "slow" water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface. PMID:22288939

  17. Random free energy barrier hopping model for ac conduction in chalcogenide glasses

    NASA Astrophysics Data System (ADS)

    Murti, Ram; Tripathi, S. K.; Goyal, Navdeep; Prakash, Satya

    2016-03-01

    The random free energy barrier hopping model is proposed to explain the ac conductivity (σac) of chalcogenide glasses. The Coulomb correlation is consistently accounted for in the polarizability and defect distribution functions and the relaxation time is augmented to include the overlapping of hopping particle wave functions. It is observed that ac and dc conduction in chalcogenides are due to same mechanism and Meyer-Neldel (MN) rule is the consequence of temperature dependence of hopping barriers. The exponential parameter s is calculated and it is found that s is subjected to sample preparation and measurement conditions and its value can be less than or greater than one. The calculated results for a - Se, As2S3, As2Se3 and As2Te3 are found in close agreement with the experimental data. The bipolaron and single polaron hopping contributions dominates at lower and higher temperatures respectively and in addition to high energy optical phonons, low energy optical and high energy acoustic phonons also contribute to the hopping process. The variations of hopping distance with temperature is also studied. The estimated defect number density and static barrier heights are compared with other existing calculations.

  18. Energy Transfer of Excitons Between Quantum Wells Separated by a Wide Barrier

    SciTech Connect

    LYO,SUNGKWUN K.

    1999-12-06

    We present a microscopic theory of the excitonic Stokes and anti-Stokes energy transfer mechanisms between two widely separated unequal quantum wells with a large energy mismatch ({Delta}) at low temperatures (T). Exciton transfer through dipolar coupling, photon-exchange coupling and over-barrier ionization of the excitons through exciton-exciton Auger processes are examined. The energy transfer rate is calculated as a function of T and the center-to-center distance d between the two wells. The rates depend sensitively on T for plane-wave excitons. For located excitons, the rates depend on T only through the T-dependence of the localization radius.

  19. Systematical Behavior of Breakup Effects on Complete Fusion at Energies above the Coulomb Barrier

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Zhao, Wei-Juan; Gomes, P. R. S.; Zhao, En-Guang; Zhou, Shan-Gui

    We investigate the systematical behavior of the breakup effects on the complete fusion (CF) cross sections at energies above the Coulomb barrier. The CF cross sections are suppressed by the prompt breakup of the projectiles. This suppression effect, expressed as the ratio of the reduced fusion function and the universal fusion function (UFF), for reactions induced by the same projectile, is independent of the target and mainly determined by the lowest energy breakup channel of the projectile. There holds a good exponential relation between the suppression factor and the energy corresponding to the lowest breakup threshold.

  20. Formation of hyperdeformed states in capture reactions at sub-barrier energies

    SciTech Connect

    Zubov, A. S.; Antonenko, N. V.; Sargsyan, V. V.; Adamian, G. G.; Scheid, W.

    2010-09-15

    The high-spin hyperdeformed nuclear states treated as dinuclear or quasimolecular configurations are suggested to be directly populated in heavy ion collisions at sub-barrier energies. Tunneling through the Coulomb barrier is considered using the quantum diffusion approach based on the formalism of reduced density matrix. The reactions {sup 48}Ca+{sup 86}Kr,{sup 124}Sn,{sup 136}Xe,{sup 138}Ba,{sup 140}Ce, {sup 58}Ni+{sup 58}Ni, and {sup 40,48}Ca+{sup 40,48}Ca, are suggested for populating high-spin hyperdeformed states. The partial production and identification cross sections for the hyperdeformed states are calculated as the functions of bombarding energy.

  1. Nucleon exchange mechanism in heavy-ion collisions at near-barrier energies

    SciTech Connect

    Yilmaz, B.; Ayik, S.; Lacroix, D.

    2011-06-15

    Nucleon drift and diffusion mechanisms in central collisions of asymmetric heavy ions at near-barrier energies are investigated in the framework of a stochastic mean-field approach. Expressions for diffusion and drift coefficients for nucleon transfer deduced from the stochastic mean-field approach in the semiclassical approximation have similar forms familiar from the phenomenological nucleon exchange model. The variance of fragment mass distribution agrees with the empirical formula {sigma}{sub AA}{sup 2}(t)=N{sub exc}(t). The comparison with the time-dependent Hartree-Fock calculations shows that below barrier energies, the drift coefficient in the semiclassical approximation underestimates the mean number of nucleon transfer obtained in the quantal framework. Motion of the window in the dinuclear system has a significant effect on the nucleon transfer in asymmetric collisions.

  2. The quantum free energy barrier for hydrogen vacancy diffusion in Na3AlH6.

    PubMed

    Poma, Adolfo; Monteferrante, Michele; Bonella, Sara; Ciccotti, Giovanni

    2012-11-28

    The path integral single sweep method is used to assess quantum effects on the free energy barrier for hydrogen vacancy diffusion in a defective Na(3)AlH(6) crystal. This process has been investigated via experiments and simulations due to its potential relevance in the H release mechanism in sodium alanates, prototypical materials for solid state hydrogen storage. Previous computational studies, which used density functional methods for the electronic structure, were restricted to a classical treatment of the nuclear degrees of freedom. We show that, although they do not change the qualitative picture of the process, nuclear quantum effects reduce the free energy barrier height by about 18% with respect to the classical calculation improving agreement with available neutron scattering data. PMID:23064527

  3. Observation of the one- to six-neutron transfer reactions at sub-barrier energies

    SciTech Connect

    Jiang, C.L.; Rehm, K.E.; Gehring, J.

    1995-08-01

    It was suggested many years ago that when two heavy nuclei are in contact during a grazing collision, the transfer of several correlated neutron-pairs could occur. Despite considerable experimental effort, however, so far only cross sections for up to four-neutron transfers have been uniquely identified. The main difficulties in the study of multi-neutron transfer reactions are the small cross sections encountered at incident energies close to the barrier, and various experimental uncertainties which can complicate the analysis of these reactions. We have for the first time found evidence for multi-neutron transfer reactions covering the full sequence from one- to six-neutron transfer reactions at sub-barrier energies in the system {sup 58}Ni + {sup 100}Mo.

  4. Reaction Dynamics of Weakly-Bound Few-Body Nuclei at Energies Around the Coulomb Barrier

    NASA Astrophysics Data System (ADS)

    Boselli, Maddalena; Diaz-Torres, Alexis

    2016-03-01

    We present a quantum reaction approach that unambiguously quantifies the complete and incomplete fusion of weakly-bound few-body nuclei. Calculations carried out within a simple model for 6Li + 209Bi at energies near the Coulomb barrier show that converged probabilities for the total, complete and incomplete fusion as well as for the scattering process can be obtained with the time-dependent wave-packet dynamics.

  5. Barriers to Incorporating Climate Change Science into High School and Community College Energy Course Offerings

    NASA Astrophysics Data System (ADS)

    Howell, C.

    2013-05-01

    In reviewing studies evaluating trends in greenhouse gasses, weather, climate and/or ecosystems, it becomes apparent that climate change is a reality. It has also become evident that the energy sector accounts for most of the greenhouse gas emissions with worldwide emissions of carbon dioxide increasing by 31 percent from 1990 to 2005, higher than in the previous thousands of years. While energy courses and topics are presented in high school and community college classes the topic of Climate Change Science is not always a part of the conversation. During the summer of 2011 and 2012, research undergraduates conducted interviews with a total of 39 national community college and 8 high school instructors who participated in a two week Sustainable Energy Education Training (SEET) workshop. Interview questions addressed the barriers and opportunities to the incorporation of climate change as a dimension of an energy/renewable energy curriculum. Barriers found included: there is not enough instruction time to include it; some school administrators including community members do not recognize climate change issues; quality information about climate change geared to students is difficult to find; and, most climate change information is too scientific for most audiences. A Solution to some barriers included dialogue on sustainability as a common ground in recognizing environmental changes/concerns among educators, administrators and community members. Sustainability discussions are already supported in school business courses as well as in technical education. In conclusion, we cannot expect climate change to dissipate without humans making more informed energy and environmental choices. With global population growth producing greater emissions resulting in increased climate change, we must include the topic of climate change to students in high school and community college classrooms, preparing our next generation of leaders and workforce to be equipped to find solutions

  6. Barriers on the propagation of renewable energy sources and sustainable solid waste management practices in Greece.

    PubMed

    Boemi, Sn; Papadopoulos, Am; Karagiannidis, A; Kontogianni, S

    2010-11-01

    Renewable energy sources (RES), excluding large hydroelectric plants, currently produce 4.21% of total electricity production in Greece. Even when considering the additional production from large hydroelectric plants, which accounts for some 7.8%, the distance to be covered towards the objective of 20% electricity produced from RES by 2010 and respectively towards 20% of total energy production by 2020 is discouraging. The potential, however, does exist; unfortunately so do serious barriers. On the other hand, solid waste management (SWM) is an issue that generates continuously increasing interest due to the extra amounts of solid waste generated; the lack of existing disposal facilities with adequate infrastructure and integrated management plans, also often accompanied by legislative and institutional gaps. However, socio-economic and public awareness problems are still met in the planning and implementation of RES and SWM projects, together with the lack of a complete national cadastre and a spatial development master plan, specifying areas eligible for RES and SWM development. Specific barriers occur for individual RES and the on-going inclusion of waste-derived renewable energy in the examined palette further increases the complexity of the entire issue. The consolidated study of this broad set of barriers was a main task of the present study which was carried out within the frame of a Hellenic-Canadian research project; the main results will be discussed herein. PMID:20630941

  7. Sub-barrier fusion excitation function data and energy dependent Woods-Saxon potential

    NASA Astrophysics Data System (ADS)

    Gautam, Manjeet Singh

    2016-07-01

    This paper analyzed the role of intrinsic degrees of freedom of colliding nuclei in the enhancement of sub-barrier fusion cross-section data of various heavy ion fusion reactions. The influences of inelastic surface vibrations of colliding pairs are found to be dominant and their couplings result in the significantly larger fusion enhancement over the predictions of the one dimensional barrier penetration model at sub-barrier energies. The theoretical calculations are performed by using energy dependent Woods-Saxon potential model (EDWSP model) in conjunction with the one dimensional Wong formula. The effects of dominant intrinsic channels are entertained within framework of the coupled channel calculations obtained by using the code CCFULL. It is quite interesting to note that the energy dependence in Woods-Saxon potential simulates the effects of inelastic surface vibrational states of reactants wherein significantly larger value of diffuseness parameter ranging from a = 0.85 fm to a = 0.95 fm is required to address the observed fusion excitation function data of the various heavy ion fusion reactions.

  8. Shape of the hydrogen adsorption regions of MOF-5 and its impact on the hydrogen storage capacity

    NASA Astrophysics Data System (ADS)

    Cabria, I.; López, M. J.; Alonso, J. A.

    2008-11-01

    The adsorption of molecular hydrogen on a metal-organic framework (MOF) material, MOF-5, has been studied using the density-functional formalism. The calculated potential-energy surface shows that there are two main adsorption regions: both near the OZn4 oxide cores at the vertices of the cubic skeleton of MOF-5. The adsorption energies in those regions are between 100 and 130 meV/molecule. Those adsorption regions have the shape of long, wide, and deep connected trenches and passage of the molecule between regions needs to surpass small barriers of 30-50 meV. The shape of these regions, and not only the presence of metal atoms, explains the large storage capacity measured for MOF-5. The elongated shape explains why some authors have previously identified only one type of adsorption site, associated to the Zn oxide core, and others identified two or three sites. One should consider adsorption regions rather than adsorption sites. A third region of adsorption is near the benzenic rings of the MOF-5. We have also analyzed the possibility of dissociative chemisorption. The chemisorption energy with respect to two separated H atoms is 1.33 eV/H atom; but, since dissociating the free molecule costs 4.75 eV, the physisorbed H2 molecule is more stable than the dissociated chemisorbed state by about 2 eV. Dissociation of the adsorbed molecule costs less energy, but the dissociation barrier is still high.

  9. Parameterization of an interfacial force field for accurate representation of peptide adsorption free energy on high-density polyethylene

    PubMed Central

    Abramyan, Tigran M.; Snyder, James A.; Yancey, Jeremy A.; Thyparambil, Aby A.; Wei, Yang; Stuart, Steven J.; Latour, Robert A.

    2015-01-01

    Interfacial force field (IFF) parameters for use with the CHARMM force field have been developed for interactions between peptides and high-density polyethylene (HDPE). Parameterization of the IFF was performed to achieve agreement between experimental and calculated adsorption free energies of small TGTG–X–GTGT host–guest peptides (T = threonine, G = glycine, and X = variable amino-acid residue) on HDPE, with ±0.5 kcal/mol agreement. This IFF parameter set consists of tuned nonbonded parameters (i.e., partial charges and Lennard–Jones parameters) for use with an in-house-modified CHARMM molecular dynamic program that enables the use of an independent set of force field parameters to control molecular behavior at a solid–liquid interface. The R correlation coefficient between the simulated and experimental peptide adsorption free energies increased from 0.00 for the standard CHARMM force field parameters to 0.88 for the tuned IFF parameters. Subsequent studies are planned to apply the tuned IFF parameter set for the simulation of protein adsorption behavior on an HDPE surface for comparison with experimental values of adsorbed protein orientation and conformation. PMID:25818122

  10. Reaction Pathway and Free Energy Barrier for Reactivation of Dimethylphosphoryl-inhibited Human Acetylcholinesterase

    PubMed Central

    Liu, Junjun; Zhang, Yingkai; Zhan, Chang-Guo

    2009-01-01

    The dephosphorylation/reactivation mechanism and the corresponding free energy profile of dimethylphosphoryl-inhibited conjugate of human acetylcholinesterase (AChE) has been studied by performing first-principles quantum mechanical/molecular mechanical free energy (QM/MM-FE) calculations. Based on the QM/MM-FE results, for the favorable reaction pathway, the entire dephosphorylation/reactivation process consists of three reaction steps, including the nucleophilic water attack on the P atom, the spatial reorganization of the dimethylphosphoryl group, and the dissociation between the dimethylphosphoryl group and Ser203 of AChE. The overall free energy barrier for the entire dephosphorylation/reactivation reaction is found to be the free energy change from the initial reactant to the transition state associated with the spatial reorganization step, and the calculated overall free energy barrier (20.1 to 23.5 kcal/mol) is reasonably close to the experimentally-derived activation free energy of 22.3 kcal/mol. In addition, key amino acid residues and their specific roles in the reaction process have been identified. PMID:19924840

  11. Adsorption of polyiodobenzene molecules on the Pt(111) surface using van der Waals density functional theory

    NASA Astrophysics Data System (ADS)

    Johnston, Karen; Pekoz, Rengin; Donadio, Davide

    2016-02-01

    Adsorption of aromatic molecules on surfaces is widely studied due to applications in molecular electronics. In this work, the adsorption of iodobenzene molecules on the Pt(111) surface has been studied using density functional theory. Iodobenzene molecules, with various numbers of iodine atoms, have two non-dissociative adsorption minima. One structure exhibits chemisorption between the ring and the surface (short-range) and the other structure exhibits chemisorption between the iodine ions and the surface (long-range). Both structures have a strong van der Waals interaction with the surface. In general, the adsorption energy increases as the number of iodine atoms increases. The dissociated structure of monoiodobenzene was investigated, and the dissociation barrier and the barrier between the short- and long-range states were compared.

  12. The effect of ligand substitution and water co-adsorption on the adsorption dynamics and energy level matching of amino-phenyl acid dyes on TiO2.

    PubMed

    Manzhos, Sergei; Segawa, Hiroshi; Yamashita, Koichi

    2012-02-01

    We perform a comparative theoretical analysis of adsorption of dyes NK1 (2E,4E-2-cyano-5-(4-dimethylaminophenyl)penta-2,4-dienoic acid) and NK7 (2E,4E-2-cyano-5-(4-diphenylaminophenyl)penta-2,4-dienoic acid) on clean and water-covered anatase (101) surfaces of TiO(2). Ligand substitution away from the anchoring group changes the energy level matching between the dye's LUMO and the oxide's conduction band. Monodentate binding and bidentate binding configurations of the dyes to TiO(2) are found to have similar adsorption energies even though the injection from the bidentate mode is found to dominate. Water has a strong effect on adsorption, inducing deprotonation and affecting strongly and differently between the dyes the energy level matching, leading to a shut-off of the injection from NK7 of bidentate adsorption configuration. Ab initio molecular dynamics simulations show a strong effect of nuclear motion on energy levels, specifically, increasing the driving force for injection in the monodentate regime. PMID:22194034

  13. Anharmonic force field, vibrational energies, and barrier to inversion of SiH{sub 3}{sup -}

    SciTech Connect

    Aarset, Kirsten; Csaszar, Attila G.; Sibert, Edwin L. III; Allen, Wesley D.; Schaefer, Henry F. III; Klopper, Wim; Theoretical Chemistry Group, Debye Institute, Utrecht University, Padualaan 14, NL-3584 CH Utrecht, The Netherlands ; Noga, Jozef

    2000-03-01

    The full quartic force field of the ground electronic state of the silyl anion (SiH{sub 3}{sup -}) has been determined at the CCSD(T)-R12 level employing a [Si/H]=[16s11p6d5f/7s5p4d] basis set. The vibrational energy levels, using the quartic force field as a representation of the potential energy hypersurface around equilibrium, have been determined by vibrational perturbation theory carried out to second, fourth, and sixth order. The undetected vibrational fundamental for the umbrella mode, {nu}{sub 2}, is predicted to be 844 cm-1. High-quality ab initio quantum chemical methods, including higher-order coupled cluster (CC) and many-body perturbation (MP) theory with basis sets ranging from [Si/H] [5s4p2d/3s2p] to [8s7p6d5f4g3h/7s6p5d4f3g] have been employed to obtain the best possible value for the inversion barrier of the silyl anion. The rarely quantified effects of one- and two-particle relativistic terms, core correlation, and the diagonal Born-Oppenheimer correction (DBOC) have been included in the determination of the barrier for this model system. The final electronic (vibrationless) extrapolated barrier height of this study is 8351{+-}100 cm{sup -1}. (c) 2000 American Institute of Physics.

  14. Analytical energy-barrier-dependent Voc model for amorphous silicon solar cells

    NASA Astrophysics Data System (ADS)

    Castro-Carranza, A.; Nolasco, J. C.; Reininghaus, N.; Geißendörfer, S.; Vehse, M.; Parisi, J.; Gutowski, J.; Voss, T.

    2016-07-01

    We show that the open circuit voltage (Voc) in hydrogenated amorphous silicon (a-Si:H) solar cells can be described by an analytical energy-barrier-dependent equation, considering thermionic emission as the physical mechanism determining the recombination current. For this purpose, the current-voltage characteristics of two device structures, i.e., a-Si:H(n)/a-Si:H(i)/a-Si:H(p)/AZO p-i-n solar cells with different p-doping concentrations and a-Si:H(n)/a-Si:H(i)/AZO Schottky structures with different intrinsic layer thicknesses, were analyzed in dark and under illumination, respectively. The calculated barrier in the p-i-n devices is consistent with the difference between the work function of the p-layer and the conduction band edge of the i-layer at the interface in thermal equilibrium.

  15. Adsorption energy of small molecules on core-shell Fe@Au nanoparticles: tuning by shell thickness.

    PubMed

    Benoit, Magali; Tarrat, Nathalie; Morillo, Joseph

    2016-03-23

    The adsorption of several small molecules on different gold surfaces, Au(001), strained Au(001) and Au(001) epitaxied on Fe(001), has been characterized using density functional theory. The surface strain leads to a less energetically favourable adsorption for all studied molecules. Moreover, the presence of the iron substrate induces an additional decrease of the binding energy, for 1 and 2 Au monolayers. For carbon monoxide (CO), the structural and energetic variations with the number of Au monolayers deposited on Fe have been analyzed and correlated with the distance between the carbon atom and the gold surface. The effect of the subsurface layer has been evidenced for 1 and 2 monolayers. The other molecules show different quantitative behavior depending on the type of their interaction with the gold surface. However, the iron substrate weakens the interaction, either for the chemisorbed species or for the physisorbed species. 2 Au monolayers seem to be the best compromise to decrease the reactivity of the gold surface towards adsorption while preventing the Fe oxidation. PMID:26971708

  16. Can the Gibbs free energy of adsorption be predicted efficiently and accurately: an M05-2X DFT study.

    PubMed

    Michalkova, A; Gorb, L; Hill, F; Leszczynski, J

    2011-03-24

    This study presents new insight into the prediction of partitioning of organic compounds between a carbon surface (soot) and water, and it also sheds light on the sluggish desorption of interacting molecules from activated and nonactivated carbon surfaces. This paper provides details about the structure and interactions of benzene, polycyclic aromatic hydrocarbons, and aromatic nitrocompounds with a carbon surface modeled by coronene using a density functional theory approach along with the M05-2X functional. The adsorption was studied in vacuum and from water solution. The molecules studied are physisorbed on the carbon surface. While the intermolecular interactions of benzene and hydrocarbons are governed by dispersion forces, nitrocompounds are adsorbed also due to quite strong electrostatic interactions with all types of carbon surfaces. On the basis of these results, we conclude that the method of prediction presented in this study allows one to approach the experimental level of accuracy in predicting thermodynamic parameters of adsorption on a carbon surface from the gas phase. The empirical modification of the polarized continuum model leads also to a quantitative agreement with the experimental data for the Gibbs free energy values of the adsorption from water solution. PMID:21361266

  17. Linear solvation energy relationship for the adsorption of synthetic organic compounds on single-walled carbon nanotubes in water.

    PubMed

    Ding, H; Chen, C; Zhang, X

    2016-01-01

    The linear solvation energy relationship (LSER) was applied to predict the adsorption coefficient (K) of synthetic organic compounds (SOCs) on single-walled carbon nanotubes (SWCNTs). A total of 40 log K values were used to develop and validate the LSER model. The adsorption data for 34 SOCs were collected from 13 published articles and the other six were obtained in our experiment. The optimal model composed of four descriptors was developed by a stepwise multiple linear regression (MLR) method. The adjusted r(2) (r(2)adj) and root mean square error (RMSE) were 0.84 and 0.49, respectively, indicating good fitness. The leave-one-out cross-validation Q(2) ([Formula: see text]) was 0.79, suggesting the robustness of the model was satisfactory. The external Q(2) ([Formula: see text]) and RMSE (RMSEext) were 0.72 and 0.50, respectively, showing the model's strong predictive ability. Hydrogen bond donating interaction (bB) and cavity formation and dispersion interactions (vV) stood out as the two most influential factors controlling the adsorption of SOCs onto SWCNTs. The equilibrium concentration would affect the fitness and predictive ability of the model, while the coefficients varied slightly. PMID:26854726

  18. Fusion of Si28+Si28,30: Different trends at sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Montagnoli, G.; Stefanini, A. M.; Esbensen, H.; Jiang, C. L.; Corradi, L.; Courtin, S.; Fioretto, E.; Grebosz, J.; Haas, F.; Jia, H. M.; Mazzocco, M.; Michelagnoli, C.; Mijatović, T.; Montanari, D.; Parascandolo, C.; Scarlassara, F.; Strano, E.; Szilner, S.; Torresi, D.

    2014-10-01

    Background: The fusion excitation function of the system Si28+Si28 at energies near and below the Coulomb barrier is known only down to ≃15 mb. This precludes any information on both coupling effects on sub-barrier cross sections and the possible appearance of hindrance. For Si28+Si30 even if the fusion cross section is measured down to ≃50 μb, the evidence of hindrance is marginal. Both systems have positive fusion Q values. While Si28 has a deformed oblate shape, Si30 is spherical. Purpose: We investigate 1. the possible influence of the different structure of the two Si isotopes on the fusion excitation functions in the deep sub-barrier region and 2. whether hindrance exists in the Si+Si systems and whether it is strong enough to generate an S-factor maximum, thus allowing a comparison with lighter heavy-ion systems of astrophysical interest. Methods: Si28 beams from the XTU Tandem accelerator of the INFN Laboratori Nazionali di Legnaro were used. The setup was based on an electrostatic beam separator, and fusion evaporation residues (ER) were detected at very forward angles. Angular distributions of ER were measured. Results: Fusion cross sections of Si28+Si28 have been obtained down to ≃600 nb. The slope of the excitation function has a clear irregularity below the barrier, but no indication of a S-factor maximum is found. For Si28+Si30 the previous data have been confirmed and two smaller cross sections have been measured down to ≃4 μb. The trend of the S-factor reinforces the previous weak evidence of hindrance. Conclusions: The sub-barrier cross sections for Si28+Si28 are overestimated by coupled-channels calculations based on a standard Woods-Saxon potential, except for the lowest energies. Calculations using the M3Y+repulsion potential are adjusted to fit the Si28+Si28 and the existing Si30+Si30 data. An additional weak imaginary potential (probably simulating the effect of the oblate Si28 deformation) is required to fit the low-energy trend of

  19. Coarse-grained molecular dynamics study of membrane fusion: Curvature effects on free energy barriers along the stalk mechanism.

    PubMed

    Kawamoto, Shuhei; Klein, Michael L; Shinoda, Wataru

    2015-12-28

    The effects of membrane curvature on the free energy barrier for membrane fusion have been investigated using coarse-grained molecular dynamics (CG-MD) simulations, assuming that fusion takes place through a stalk intermediate. Free energy barriers were estimated for stalk formation as well as for fusion pore formation using the guiding potential method. Specifically, the three different geometries of two apposed membranes were considered: vesicle-vesicle, vesicle-planar, and planar-planar membranes. The free energy barriers for the resulting fusion were found to depend importantly on the fusing membrane geometries; the lowest barrier was obtained for vesicular membranes. Further, lipid sorting was observed in fusion of the mixed membranes of dimyristoyl phosphatidylcholine and dioleoyl phosphatidylethanolamine (DOPE). Specifically, DOPE molecules were found to assemble around the stalk to support the highly negative curved membrane surface. A consistent result for lipid sorting was observed when a simple continuum model (CM) was used, where the Helfrich energy and mixing entropy of the lipids were taken into account. However, the CM predicts a much higher free energy barrier than found using CG-MD. This discrepancy originates from the conformational changes of lipids, which were not considered in the CM. The results of the CG-MD simulations reveal that a large conformational change in the lipid takes place around the stalk region, which results in a reduction of free energy barriers along the stalk mechanism of membrane fusion. PMID:26723597

  20. Coarse-grained molecular dynamics study of membrane fusion: Curvature effects on free energy barriers along the stalk mechanism

    SciTech Connect

    Kawamoto, Shuhei; Shinoda, Wataru; Klein, Michael L.

    2015-12-28

    The effects of membrane curvature on the free energy barrier for membrane fusion have been investigated using coarse-grained molecular dynamics (CG-MD) simulations, assuming that fusion takes place through a stalk intermediate. Free energy barriers were estimated for stalk formation as well as for fusion pore formation using the guiding potential method. Specifically, the three different geometries of two apposed membranes were considered: vesicle–vesicle, vesicle–planar, and planar–planar membranes. The free energy barriers for the resulting fusion were found to depend importantly on the fusing membrane geometries; the lowest barrier was obtained for vesicular membranes. Further, lipid sorting was observed in fusion of the mixed membranes of dimyristoyl phosphatidylcholine and dioleoyl phosphatidylethanolamine (DOPE). Specifically, DOPE molecules were found to assemble around the stalk to support the highly negative curved membrane surface. A consistent result for lipid sorting was observed when a simple continuum model (CM) was used, where the Helfrich energy and mixing entropy of the lipids were taken into account. However, the CM predicts a much higher free energy barrier than found using CG-MD. This discrepancy originates from the conformational changes of lipids, which were not considered in the CM. The results of the CG-MD simulations reveal that a large conformational change in the lipid takes place around the stalk region, which results in a reduction of free energy barriers along the stalk mechanism of membrane fusion.

  1. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: the study of hydrophilic and hydrophobic microdomain.

    PubMed

    Zhou, Xiangyu; Wei, Junfu; Zhang, Huan; Liu, Kai; Wang, Han

    2014-05-30

    A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application. PMID:24721695

  2. Influence of strain on water adsorption and dissociation on rutile TiO2(110) surface.

    PubMed

    Yang, Long; Shu, Da-Jun; Li, Shao-Chun; Wang, Mu

    2016-06-01

    The influence of externally applied strain on water adsorption and dissociation on a defect-free rutile TiO2(110) surface is studied by using first-principles calculations. We found that while compressive strain makes water adsorption and dissociation less favorable, tensile strain increases the energy gain of water adsorption, and decreases the energy cost of water dissociation. Specifically, dissociative water becomes more stable than molecular water when an 8% tensile in-plane strain is applied. Moreover, the dissociation barrier decreases with increasing strain more rapidly for more isolated water. The rate of decrease of this barrier for nearly isolated water is 0.017 eV per 1% biaxial strain. This demonstrates that applying strain is a possible way to engineer the surface adsorption and dissociation of water on a TiO2(110) surface, and therefore engineer the relevant surface reactivity. PMID:27138099

  3. Relaxation times and energy barriers of rubbing-induced birefringence in glass-forming polymers

    NASA Astrophysics Data System (ADS)

    Shiu, K. P.; Qin, Zongyi; Yang, Z.

    2008-12-01

    The relaxations of rubbing-induced birefringence (RIB) in several glass-forming polymers, including polycarbonate and polystyrene (PS) derivatives with various modifications to the phenyl ring side group, are studied. Significant relaxations of RIB are observed at temperatures well below the glass transition temperature T g . The relaxation times span a wide range from ˜ 10 s to probably geological time scale. Physical aging effects are absent in the RIB relaxations. The model proposed for the interpretation of RIB in PS describes well the RIB relaxations in all the polymers investigated here. The energy barriers are of the order of a few hundred kJ/mol and decrease with decreasing temperature, in opposition to the trend of Vogel-Fulcher form for polymer segmental relaxations above T g . The relaxation behaviors of different polymers are qualitatively similar but somewhat different in quantitative details, such as in the values of the saturated birefringence, the shape of the initial barrier density distribution functions, the rates of barrier decrease with decreasing temperature, and the dependence of relaxation times on temperature and parameter ξ , etc. The RIB relaxations are different from any of the other relaxations below T g that have been reported in the literature, such as dielectric relaxations or optical probe relaxations. A microscopic model for the relaxations of RIB is much desired.

  4. Energy efficient engine, high pressure turbine thermal barrier coating. Support technology report

    NASA Technical Reports Server (NTRS)

    Duderstadt, E. C.; Agarwal, P.

    1983-01-01

    This report describes the work performed on a thermal barrier coating support technology task of the Energy Efficient Engine Component Development Program. A thermal barrier coating (TBC) system consisting of a Ni-Cr-Al-Y bond cost layer and ZrO2-Y2O3 ceramic layer was selected from eight candidate coating systems on the basis of laboratory tests. The selection was based on coating microstructure, crystallographic phase composition, tensile bond and bend test results, erosion and impact test results, furnace exposure, thermal cycle, and high velocity dynamic oxidation test results. Procedures were developed for applying the selected TBC to CF6-50, high pressure turbine blades and vanes. Coated HPT components were tested in three kinds of tests. Stage 1 blades were tested in a cascade cyclic test rig, Stage 2 blades were component high cycle fatigue tested to qualify thermal barrier coated blades for engine testing, and Stage 2 blades and Stage 1 and 2 vanes were run in factory engine tests. After completion of the 1000 cycle engine test, the TBC on the blades was in excellent condition over all of the platform and airfoil except at the leading edge above midspan on the suction side of the airfoil. The coating damage appeared to be caused by particle impingement; adjacent blades without TBC also showed evidence of particle impingement.

  5. Driven diffusion against electrostatic or effective energy barrier across α-hemolysin

    SciTech Connect

    Ansalone, Patrizio; Chinappi, Mauro; Rondoni, Lamberto; Cecconi, Fabio

    2015-10-21

    We analyze the translocation of a charged particle across an α-Hemolysin (αHL) pore in the framework of a driven diffusion over an extended energy barrier generated by the electrical charges of the αHL. A one-dimensional electrostatic potential is extracted from the full 3D solution of the Poisson’s equation. We characterize the particle transport under the action of a constant forcing by studying the statistics of the translocation time. We derive an analytical expression of translocation time average that compares well with the results from Brownian dynamic simulations of driven particles over the electrostatic potential. Moreover, we show that the translocation time distributions can be perfectly described by a simple theory which replaces the true barrier by an equivalent structureless square barrier. Remarkably, our approach maintains its accuracy also for low-applied voltage regimes where the usual inverse-Gaussian approximation fails. Finally, we discuss how the comparison between the simulated time distributions and their theoretical prediction results to be greatly simplified when using the notion of the empirical Laplace transform technique.

  6. Evolution of fusion hindrance for asymmetric systems at deep sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Shrivastava, A.; Mahata, K.; Pandit, S. K.; Nanal, V.; Ichikawa, T.; Hagino, K.; Navin, A.; Palshetkar, C. S.; Parkar, V. V.; Ramachandran, K.; Rout, P. C.; Kumar, Abhinav; Chatterjee, A.; Kailas, S.

    2016-04-01

    Measurements of fusion cross-sections of 7Li and 12C with 198Pt at deep sub-barrier energies are reported to unravel the role of the entrance channel in the occurrence of fusion hindrance. The onset of fusion hindrance has been clearly observed in 12C +198Pt system but not in 7Li +198Pt system, within the measured energy range. Emergence of the hindrance, moving from lighter (6,7Li) to heavier (12C, 16O) projectiles is explained employing a model that considers a gradual transition from a sudden to adiabatic regime at low energies. The model calculation reveals a weak effect of the damping of coupling to collective motion for the present systems as compared to that obtained for systems with heavier projectiles.

  7. Experimental study of the 13C+12C fusion reaction at deep sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Tudor, D.; Chilug, A. I.; Straticiuc, M.; Trache, L.; Chesneanu, D.; Toma, S.; Ghita, D. G.; Burducea, I.; Margineanu, R.; Pantelica, A.; Gomoiu, C.; Zhang, N. T.; Tang, X.; Li, Y. J.

    2016-04-01

    Heavy-ion fusion reactions between light nuclei such as carbon and oxygen isotopes have been studied because of their significance for a wide variety of stellar burning scenarios. One important stellar reaction is 12C+12C, but it is difficult to measure it in the Gamow window because of very low cross sections and several resonances occurring. Hints can be obtained from the study of 13C+12C reaction. We have measured this process by an activation method for energies down to Ecm=2.5 MeV using 13C beams from the Bucharest 3 MV tandetron and gamma-ray deactivation measurements in our low and ultralow background laboratories, the latter located in a salt mine about 100 km north of Bucharest. Results obtained so far are shown and discussed in connection with the possibility to go even further down in energy and with the interpretation of the reaction mechanism at such deep sub-barrier energies.

  8. Search for Monoenergetic Positron Emission from Heavy-Ion Collisions at Coulomb-Barrier Energies

    SciTech Connect

    Ahmad, I.; Back, B.B.; Betts, R.R.; Dunford, R.W.; Freer, M.; Happ, T.; Henderson, D.; Kutschera, W.; Last, J.; Lister, C.J.; Rhein, M.D.; Schiffer, J.P.; Wilt, P.; Wuosmaa, A.H.; Austin, S.M.; Kashy, E.; Maier, M.R.; Mercer, D.J.; Mikolas, D.; Winfield, J.S.; Yurkon, J.E.; Betts, R.R.; Conner, C.; Calaprice, F.P.; Young, A.; Chan, K.C.; Chishti, A.; Kaloskamis, N.I.; Xu, G.; Fox, J.D.; Roa, D.E.; Freedman, S.J.; Freer, M.; Gazes, S.B.; Schiffer, J.P.; Wolanski, M.R.; Hallin, A.L.; Liu, M.; Happ, T.; Rhein, M.D.; Perera, P.A.; Wolfs, F.L.; Trainor, T.A.

    1997-01-01

    Positron production in {sup 238}U+{sup 232}Th and {sup 238}U+{sup 181}Ta collisions near the Coulomb barrier has been studied. Earlier experiments reported narrow lines in the spectra of positrons, accumulated without the requirement of electrons detected in coincidence. No evidence of such structure is observed in the present data. The positron energy spectra are compared with estimates from dynamic atomic processes, and from internal pair conversion of electromagnetic transitions from the excited nuclei. {copyright} {ital 1997} {ital The American Physical Society}

  9. 7Be- and 8B-reaction dynamics at Coulomb barrier energies

    NASA Astrophysics Data System (ADS)

    Mazzocco, M.; Boiano, A.; Boiano, C.; La Commara, M.; Manea, C.; Parascandolo, C.; Pierroutsakou, D.; Signorini, C.; Strano, E.; Torresi, D.; Yamaguchi, H.; Kahl, D.; Acosta, L.; Di Meo, P.; Fernandez-Garcia, J. P.; Glodariu, T.; Grebosz, J.; Guglielmetti, A.; Imai, N.; Hirayama, Y.; Ishiyama, H.; Iwasa, N.; Jeong, S. C.; Jia, H. M.; Keeley, N.; Kim, Y. H.; Kimura, S.; Kubono, S.; Lay, J. A.; Lin, C. J.; Marquinez-Duran, G.; Martel, I.; Miyatake, H.; Mukai, M.; Nakao, T.; Nicoletto, M.; Pakou, A.; Rusek, K.; Sakaguchi, Y.; Sánchez-Benítez, A. M.; Sava, T.; Sgouros, O.; Stefanini, C.; Soramel, F.; Soukeras, V.; Stiliaris, E.; Stroe, L.; Teranishi, T.; Toniolo, N.; Wakabayashi, Y.; Watanabe, Y. X.; Yang, L.; Yang, Y. Y.

    2016-05-01

    We investigated the reaction dynamics induced by the Radioactive Ion Beams 7Be and 8B on a 208Pb target at energies around the Coulomb barrier. The two measurements are strongly interconnected, being 7Be (Sα = 1.586 MeV) the loosely bound core of the even more exotic 8B (Sp = 0.1375 MeV) nucleus. Here we summarize the present status of the data analysis for the measurement of the elastic scattering process for both reactions and the preliminary results for the optical model analysis of the collected data.

  10. Systematics of heavy-ion fusion hindrance at extreme sub-barrier energies

    SciTech Connect

    Jiang, C.L.; Back, B.B.; Esbensen, H.; Janssens, R.V.F.; Rehm, K.E.

    2006-01-15

    The recent discovery of hindrance in heavy-ion induced fusion reactions at extreme sub-barrier energies represents a challenge for theoretical models. Previously, it has been shown that in medium-heavy systems, the onset of fusion hindrance depends strongly on the ''stiffness'' of the nuclei in the entrance channel. In this work, we explore its dependence on the total mass and the Q-value of the fusing systems and find that the fusion hindrance depends in a systematic way on the entrance channel properties over a wide range of systems.

  11. Atomistic simulations of crystal-melt interfaces in a model binary alloy: Interfacial free energies, adsorption coefficients, and excess entropy

    NASA Astrophysics Data System (ADS)

    Becker, C. A.; Olmsted, D. L.; Asta, M.; Hoyt, J. J.; Foiles, S. M.

    2009-02-01

    Monte Carlo and molecular-dynamics simulations are employed in a study of the equilibrium structural and thermodynamic properties of crystal-melt interfaces in a model binary alloy system described by Lennard-Jones interatomic interactions with zero size mismatch, a ratio of interaction strengths equal to 0.75, and interspecies interactions given by Lorentz-Berthelot mixing rules. This alloy system features a simple lens-type solid-liquid phase diagram at zero pressure, with nearly ideal solution thermodynamics in the solid and liquid solution phases. Equilibrium density profiles are computed for (100)-oriented crystal-melt interfaces and are used to derive the magnitudes of the relative adsorption coefficients (Γi(j)) at six temperatures along the solidus/liquidus boundary. The values for Γ1(2) , the relative adsorption of the lower melting-point species (1) with respect to the higher melting point species (2), are found to vary monotonically with temperature, with values that are positive and in the range of a few atomic percent per interface site. By contrast, values of Γ2(1) display a much more complex temperature dependence with a large peak in the magnitude of the relative adsorption more than ten times larger than those found for Γ1(2) . The capillary fluctuation method is used to compute the temperature dependence of the magnitudes and anisotropies of the crystal-melt interfacial free energy (γ) . At all temperatures we obtain the ordering γ100>γ110>γ111 for the high-symmetry (100), (110), and (111) interface orientations. The values of γ monotonically decrease with decreasing temperature (i.e., increasing concentration of the lower melting-point species). Using the calculated temperature-dependent values of γ and Γ1(2) in the Gibbs adsorption theorem, we estimate that roughly 25% of the temperature dependence of γ for the alloys can be attributed to interface adsorption, while the remaining contribution arises from the relative excess entropy

  12. Barriers to Building Energy Efficiency (BEE) promotion: A transaction costs perspective

    NASA Astrophysics Data System (ADS)

    Qian Kun, Queena

    Worldwide, buildings account for a surprisingly high 40% of global energy consumption, and the resulting carbon footprint significantly exceeds that of all forms of transportation combined. Large and attractive opportunities exist to reduce buildings' energy use at lower costs and higher returns than in other sectors. This thesis analyzes the concerns of the market stakeholders, mainly real estate developers and end-users, in terms of transaction costs as they make decisions about investing in Building Energy Efficiency (BEE). It provides a detailed analysis of the current situation and future prospects for BEE adoption by the market's stakeholders. It delineates the market and lays out the economic and institutional barriers to the large-scale deployment of energy-efficient building techniques. The aim of this research is to investigate the barriers raised by transaction costs that hinder market stakeholders from investing in BEES. It explains interactions among stakeholders in general and in the specific case of Hong Kong as they consider transaction costs. It focuses on the influence of transaction costs on the decision-making of the stakeholders during the entire process of real estate development. The objectives are: 1) To establish an analytical framework for understanding the barriers to BEE investment with consideration of transaction costs; 2) To build a theoretical game model of decision making among the BEE market stakeholders; 3) To study the empirical data from questionnaire surveys of building designers and from focused interviews with real estate developers in Hong Kong; 4) To triangulate the study's empirical findings with those of the theoretical model and analytical framework. The study shows that a coherent institutional framework needs to be established to ensure that the design and implementation of BEE policies acknowledge the concerns of market stakeholders by taking transaction costs into consideration. Regulatory and incentive options

  13. Disintegration locations in 7Li→8Be transfer-triggered breakup at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Simpson, E. C.; Cook, K. J.; Luong, D. H.; Kalkal, Sunil; Carter, I. P.; Dasgupta, M.; Hinde, D. J.; Williams, E.

    2016-02-01

    Background: At above-barrier energies, complete fusion cross sections in collisions of light weakly bound nuclei with heavy target nuclei are suppressed when compared to well-bound nuclei. Breakup of the projectilelike nucleus was proposed to be the cause. In addition to direct breakup, breakup following transfer was shown to be substantial. Purpose: We investigate breakup in reactions with 7Li, triggered by sub-barrier proton pickup to unbound states in 8Be, which subsequently separate into two α particles. Method: Measurements of sub-barrier disintegration of 7Li on a 58Ni target were made using the Heavy Ion Accelerator Facility at the Australian National University. Combining the experimental results with classical simulations of post-breakup acceleration, we study the sensitivity of α -α energy and angle correlations to the proximity of disintegration to the target (proton donor) nucleus. Results: The simulations indicate that disintegration as the colliding nuclei approach each other leads to large angular separations θ12 of the α fragments. The detectors allow for a maximum opening angle of θ12=132∘ , such that the present experiment is largely insensitive to breakup occurring when the collision partners approach each other. The data are consistent with disintegration of (a) the 0+8Be ground state far from the targetlike nucleus, and (b) the 2+8Be resonance near the targetlike nucleus when the 8Be is receding from the targetlike nucleus. Conclusions: The present results shed light on the near-target component of transfer-induced breakup reactions. The distribution of events with respect to the opening angle of the α particles, and the orientation of their relative velocity with respect to the velocity of their center of mass, gives insights into their proximity to the target at the moment of breakup. Further measurements with larger angular coverage and more complete simulations are required to fully understand the influence of breakup on fusion.

  14. Adsorption and growth morphology of rare-earth metals on graphene studied by ab initio calculations and scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojie; Wang, C. Z.; Hupalo, M.; Yao, Y. X.; Tringides, M. C.; Lu, W. C.; Ho, K. M.

    2010-12-01

    Adsorption of rare-earth (RE) adatoms (Nd, Gd, Eu, and Yb) on graphene was studied by first-principles calculations based on the density-functional theory. The calculations show that the hollow site of graphene is the energetically favorable adsorption site for all the RE adatoms studied. The adsorption energies and diffusion barriers of Nd and Gd on graphene are found to be larger than those of Eu and Yb. Comparison with scanning tunneling microscopy experiments for Gd and Eu epitaxially grown on graphene confirms these calculated adsorption and barrier differences, since fractal-like islands are observed for Gd and flat-topped crystalline islands for Eu. The formation of flat Eu islands on graphene can be attributed to its low diffusion barrier and relatively larger ratio of adsorption energy to its bulk cohesive energy. The interactions between the Nd and Gd adatoms and graphene cause noticeable in-plane lattice distortions in the graphene layer. Adsorption of the RE adatoms on graphene also induces significant electric dipole and magnetic moments.

  15. Condensation on superhydrophobic surfaces: the role of local energy barriers and structure length scale.

    PubMed

    Enright, Ryan; Miljkovic, Nenad; Al-Obeidi, Ahmed; Thompson, Carl V; Wang, Evelyn N

    2012-10-01

    Water condensation on surfaces is a ubiquitous phase-change process that plays a crucial role in nature and across a range of industrial applications, including energy production, desalination, and environmental control. Nanotechnology has created opportunities to manipulate this process through the precise control of surface structure and chemistry, thus enabling the biomimicry of natural surfaces, such as the leaves of certain plant species, to realize superhydrophobic condensation. However, this "bottom-up" wetting process is inadequately described using typical global thermodynamic analyses and remains poorly understood. In this work, we elucidate, through imaging experiments on surfaces with structure length scales ranging from 100 nm to 10 μm and wetting physics, how local energy barriers are essential to understand non-equilibrium condensed droplet morphologies and demonstrate that overcoming these barriers via nucleation-mediated droplet-droplet interactions leads to the emergence of wetting states not predicted by scale-invariant global thermodynamic analysis. This mechanistic understanding offers insight into the role of surface-structure length scale, provides a quantitative basis for designing surfaces optimized for condensation in engineered systems, and promises insight into ice formation on surfaces that initiates with the condensation of subcooled water. PMID:22931378

  16. Electrical Characterization of High Energy Electron Irradiated Ni/4H-SiC Schottky Barrier Diodes

    NASA Astrophysics Data System (ADS)

    Paradzah, A. T.; Omotoso, E.; Legodi, M. J.; Auret, F. D.; Meyer, W. E.; Diale, M.

    2016-05-01

    The effect of high energy electron irradiation on Ni/4H-SiC Schottky barrier diodes was evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements at room temperature. Electron irradiation was achieved by using a radioactive strontium source with peak emission energy of 2.3 MeV. Irradiation was performed in fluence steps of 4.9 × 1013 cm-2 until a total fluence of 5.4 × 1014 cm-2 was reached. The Schottky barrier height determined from I-V measurements was not significantly changed by irradiation while that obtained from C-V measurements increased with irradiation. The ideality factor was obtained before irradiation as 1.05 and this value did not significantly change as a result of irradiation. The series resistance increased from 47 Ω before irradiation to 74 Ω after a total electron fluence of 5.4 × 1014 cm-2. The net donor concentration decreased with increasing irradiation fluence from 4.6 × 1014 cm-3 to 3.0 × 1014 cm-3 from which the carrier removal rate was calculated to be 0.37 cm-1.

  17. Potential energy barriers to ion transport within lipid bilayers. Studies with tetraphenylborate.

    PubMed Central

    Andersen, P S; Fuchs, M

    1975-01-01

    Tetraphenylborate-induced current transients were studied in lipid bilayers formed from bacterial phosphatidylethanolamine in decane. This ion movement was essentially confined to the membrane in terior during the current transients. Charge movement through the interior of the membrane during the current transients was studied as a function of the applied potential. The transferred charge approached an upper limit with increasing potential, which is interpreted to be the amount of charge due to tetraphenylborate ions absorbed into the boundary regions of the bilayer. A further analysis of the charge transfer as a function of potential indicates that the movement of tetraphenylborate ions is only influenced by a certain farction of the applied potential. For bacterial phosphatidylethanolamine bilayers the effective potential is 77 +/- 4% of the applied potential. The initial conductance and the time constant of the current transients were studied as a function of the applied potential using a Nernst-Planck electrodiffusion regime. It was found that an image-force potential energy barrier gave a good prediction of the observed behavior, provided that the effective potential was used in the calculations. We could not get a satisfactory prediction of the observed behavior with an Eyring rate theory model or a trapezoidal potential energy barrier. PMID:1148364

  18. Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier.

    PubMed

    Mökkönen, Harri; Ala-Nissila, Tapio; Jónsson, Hannes

    2016-09-01

    The recrossing correction to the transition state theory estimate of a thermal rate can be difficult to calculate when the energy barrier is flat. This problem arises, for example, in polymer escape if the polymer is long enough to stretch between the initial and final state energy wells while the polymer beads undergo diffusive motion back and forth over the barrier. We present an efficient method for evaluating the correction factor by constructing a sequence of hyperplanes starting at the transition state and calculating the probability that the system advances from one hyperplane to another towards the product. This is analogous to what is done in forward flux sampling except that there the hyperplane sequence starts at the initial state. The method is applied to the escape of polymers with up to 64 beads from a potential well. For high temperature, the results are compared with direct Langevin dynamics simulations as well as forward flux sampling and excellent agreement between the three rate estimates is found. The use of a sequence of hyperplanes in the evaluation of the recrossing correction speeds up the calculation by an order of magnitude as compared with the traditional approach. As the temperature is lowered, the direct Langevin dynamics simulations as well as the forward flux simulations become computationally too demanding, while the harmonic transition state theory estimate corrected for recrossings can be calculated without significant increase in the computational effort. PMID:27609008

  19. Electrical Characterization of High Energy Electron Irradiated Ni/4 H-SiC Schottky Barrier Diodes

    NASA Astrophysics Data System (ADS)

    Paradzah, A. T.; Omotoso, E.; Legodi, M. J.; Auret, F. D.; Meyer, W. E.; Diale, M.

    2016-08-01

    The effect of high energy electron irradiation on Ni/4 H-SiC Schottky barrier diodes was evaluated by current-voltage ( I- V) and capacitance-voltage ( C- V) measurements at room temperature. Electron irradiation was achieved by using a radioactive strontium source with peak emission energy of 2.3 MeV. Irradiation was performed in fluence steps of 4.9 × 1013 cm-2 until a total fluence of 5.4 × 1014 cm-2 was reached. The Schottky barrier height determined from I- V measurements was not significantly changed by irradiation while that obtained from C- V measurements increased with irradiation. The ideality factor was obtained before irradiation as 1.05 and this value did not significantly change as a result of irradiation. The series resistance increased from 47 Ω before irradiation to 74 Ω after a total electron fluence of 5.4 × 1014 cm-2. The net donor concentration decreased with increasing irradiation fluence from 4.6 × 1014 cm-3 to 3.0 × 1014 cm-3 from which the carrier removal rate was calculated to be 0.37 cm-1.

  20. Electrostatic energy barriers from dielectric membranes upon approach of translocating DNA molecules

    NASA Astrophysics Data System (ADS)

    Buyukdagli, Sahin; Ala-Nissila, T.

    2016-02-01

    We probe the electrostatic cost associated with the approach phase of DNA translocation events. Within an analytical theory at the Debye-Hückel level, we calculate the electrostatic energy of a rigid DNA molecule interacting with a dielectric membrane. For carbon or silicon based low permittivity neutral membranes, the DNA molecule experiences a repulsive energy barrier between 10 kBT and 100 kBT. In the case of engineered membranes with high dielectric permittivities, the membrane surface attracts the DNA with an energy of the same magnitude. Both the repulsive and attractive interactions result from image-charge effects and their magnitude survive even for the thinnest graphene-based membranes of size d ≈ 6 Å. For weakly charged membranes, the electrostatic energy is always attractive at large separation distances but switches to repulsive close to the membrane surface. We also characterise the polymer length dependence of the interaction energy. For specific values of the membrane charge density, low permittivity membranes repel short polymers but attract long polymers. Our results can be used to control the strong electrostatic energy of DNA-membrane interactions prior to translocation events by chemical engineering of the relevant system parameters.

  1. Effect of topographic barriers on the rates of available potential energy conversion of the oceans

    NASA Astrophysics Data System (ADS)

    Stewart, K. D.; Saenz, J. A.; Hogg, A. McC.; Hughes, G. O.; Griffiths, R. W.

    2014-04-01

    Determining the energy budget of the oceans requires evaluating the rates of available potential energy conversion in the circulation. Calculating these conversion rates depends upon the definition of an appropriate “reference” state of the density field, but this definition is complicated in the oceans by the presence of bottom topography. The trapping of dense fluid by topographic barriers means that there are multiple definitions for the reference state. The approach taken in this paper is to examine the sensitivity of the available potential energy budget to several methods for defining the reference state. The first method makes allowances for restrictions imposed on the flow by topography, however it is computationally intensive. The second method is proposed as an inexpensive alternative to the first. These new methods are used to evaluate the energy budget of a model overturning circulation maintained by surface buoyancy forcing. The results are compared with those obtained from two existing methods; one which employs an adiabatic resorting procedure ignoring topography, and one which uses a reference profile developed from the horizontal average of the density field. In our model, the rates of available potential energy conversion are insensitive to the reference state definition providing the reference state is developed from an adiabatic resorting of the domain. These results suggest that any of the adiabatic resorting methods proposed here would be sufficient to evaluate the rates of energy conversion in the ocean.

  2. Investigation of contribution of incomplete fusion in the total fusion process induced by 9Be on 181Ta target at near barrier energies

    NASA Astrophysics Data System (ADS)

    Kharab, Rajesh; Chahal, Rajiv; Kumar, Rajiv

    2016-02-01

    We have studied the relative contribution of incomplete fusion (ICF) and complete fusion (CF) in total fusion (TF) induced by 9Be on 181Ta target at energies in the vicinity of Coulomb barrier using classical dynamical model and Wong's formula in conjugation with energy dependent Woods-Saxon formula. It is found that at above barrier energies ICF contributes almost 30% in TF while at energies below the barrier qualitatively its contribution is much more than thirty percent.

  3. The {sup 6}He Optical Potential at energies around the Coulomb barrier

    SciTech Connect

    Fernandez-Garcia, J. P.; Alvarez, M. A. G.; Moro, A. M.

    2010-04-26

    We present an Optical Model (OM) study of {sup 6}He on {sup 208}Pb elastic scattering data, measured at laboratory energies around the Coulomb barrier (E{sub lab} = 14, 16, 18, 22, and 27 MeV)[1]. For the projectile-target bare interaction, we use the microscopic Sao Paulo Potential (SPP). This bare interaction is supplemented with a Coulomb Dipole Polarization (CDP) potential, as well as a diffuse complex Woods-Saxon potential. Four-body Continuum-Discretized-Coupled-Channels (CDCC) calculations have been performed in order to support the optical model analysis. We have also studied the alpha channel, which is the dominant reaction process. In the analysis of this channel, we compare the angular and energy distributions of the alpha particles measured at 22 MeV, with Distorted Wave Born Approximation (DWBA) calculations.

  4. Breakup threshold anomaly for the 8B + 58Ni system at near-Coulomb barrier energies

    NASA Astrophysics Data System (ADS)

    Gómez Camacho, A.; Aguilera, E. F.; Gomes, P. R. S.; Lubian, J.

    2011-09-01

    By using recent fusion cross section measurements for the system 8B + 58Ni, a simultaneous analysis of elastic scattering, fusion, and total reaction cross sections is performed for the weakly bound system 8B + 58Ni at energies close to the Coulomb barrier. The analysis is carried out with an optical potential with fusion and direct reaction parts (i.e., the nuclear polarization potential U is split into a volume part UF, which accounts for fusion reactions and a surface part UDR, responsible for direct reactions). The parameters of the Woods-Saxon potentials are determined by a χ2 analysis of the data. The presence of the threshold anomaly is investigated from the energy dependence of both the fusion and direct reaction parts of the polarization potential.

  5. Shell effects in damped collisions of Sr88 with Yb176 at the Coulomb barrier energy

    NASA Astrophysics Data System (ADS)

    Kozulin, E. M.; Knyazheva, G. N.; Dmitriev, S. N.; Itkis, I. M.; Itkis, M. G.; Loktev, T. A.; Novikov, K. V.; Baranov, A. N.; Trzaska, W. H.; Vardaci, E.; Heinz, S.; Beliuskina, O.; Khlebnikov, S. V.

    2014-01-01

    This work is a study of the influence of shell effects on the formation of binary fragments in damped collision. We have investigated binary reaction channels of the composite system with Z =108 produced in the reaction Sr88+176Yb at an energy slightly above the Bass barrier (Ec.m./EBass=1.03). Reaction products were detected by using the two-arm time-of-flight spectrometer CORSET at the K130 cyclotron of the Department of Physics, University of Jyväskylä. The mass-energy distribution of primary binary fragments has been measured. For targetlike fragments heavier than 190 u, which correspond to a mass transfer as large as twenty nucleons or more, an enhancement of the yields is observed. This striking result can be ascribed to the proton shells at Z =28 and 82 and implies the persistence of the shell effects in the formation of reaction fragments even for large mass transfers.

  6. Theoretical study of the elastic breakup of weakly bound nuclei at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Otomar, D. R.; Gomes, P. R. S.; Lubian, J.; Canto, L. F.; Hussein, M. S.

    2015-12-01

    We have performed continuum discretized coupled channel (CDCC) calculations for collisions of 7Li projectiles on 59Co,144Sm, and 208Pb targets at near-barrier energies, to assess the importance of the Coulomb and the nuclear couplings in the breakup of 7Li, as well as the Coulomb-nuclear interference. We have also investigated scaling laws, expressing the dependence of the cross sections on the charge and the mass of the target. This work is complementary to that previously reported by us on the breakup of 6Li. Here we explore the similarities and differences between the results for the two lithium isotopes. The relevance of the Coulomb dipole and quadrupole strengths at low energy for the two-cluster projectile is investigated in detail.

  7. The 6He Optical Potential at energies around the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Fernández-García, J. P.; Rodríguez-Gallardo, M.; Alvarez, M. A. G.; Moro, A. M.

    2010-04-01

    We present an Optical Model (OM) study of 6He on 208Pb elastic scattering data, measured at laboratory energies around the Coulomb barrier (Elab = 14, 16, 18, 22, and 27 MeV) [1]. For the projectile-target bare interaction, we use the microscopic São Paulo Potential (SPP). This bare interaction is supplemented with a Coulomb Dipole Polarization (CDP) potential, as well as a diffuse complex Woods-Saxon potential. Four-body Continuum-Discretized-Coupled-Channels (CDCC) calculations have been performed in order to support the optical model analysis. We have also studied the α channel, which is the dominant reaction process. In the analysis of this channel, we compare the angular and energy distributions of the α particles measured at 22 MeV, with Distorted Wave Born Approximation (DWBA) calculations.

  8. Permeation of low-Z atoms through carbon sheets: Density functional theory study on energy barriers and deformation effects

    SciTech Connect

    Huber, Stefan E. E-mail: Michael.probst@uibk.ac.at; Mauracher, Andreas; Probst, Michael E-mail: Michael.probst@uibk.ac.at

    2013-12-15

    Energetic and geometric aspects of the permeation of the atoms hydrogen to neon neutral atoms through graphene sheets are investigated by investigating the associated energy barriers and sheet deformations. Density functional theory calculations on cluster models, where graphene is modeled by planar polycyclic aromatic hydrocarbons (PAHs), provide the energies and geometries. Particularities of our systems, such as convergence of both energy barriers and deformation curves with increasing size of the PAHs, are discussed. Three different interaction regimes, adiabatic, planar and vertical, are investigated by enforcing different geometrical constraints. The adiabatic energy barriers range from 5 eV for hydrogen to 20 eV for neon. We find that the permeation of oxygen and carbon into graphene is facilitated by temporary chemical bonding while for other, in principle reactive atoms, it is not. We discuss implications of our results for modeling chemical sputtering of graphite.

  9. Final report. Renewable energy and energy efficiency in Mexico: Barriers and opportunities

    SciTech Connect

    Ashford, Mike

    2000-09-28

    The report describes the prospects for energy efficiency and greenhouse gas emissions reductions in Mexico, along with renewable energy potential. A methodology for developing emissions baselines is shown, in order to prepare project emissions reductions calculations. An application to the USIJI program was also prepared through this project, for a portfolio of energy efficiency projects.

  10. Calculation of energy-barrier lowering by incoherent switching in spin-transfer torque magnetoresistive random-access memory

    SciTech Connect

    Munira, Kamaram; Visscher, P. B.

    2015-05-07

    To make a useful spin-transfer torque magnetoresistive random-access memory (STT-MRAM) device, it is necessary to be able to calculate switching rates, which determine the error rates of the device. In a single-macrospin model, one can use a Fokker-Planck equation to obtain a low-current thermally activated rate ∝exp(−E{sub eff}/k{sub B}T). Here, the effective energy barrier E{sub eff} scales with the single-macrospin energy barrier KV, where K is the effective anisotropy energy density and V the volume. A long-standing paradox in this field is that the actual energy barrier appears to be much smaller than this. It has been suggested that incoherent motions may lower the barrier, but this has proved difficult to quantify. In the present paper, we show that the coherent precession has a magnetostatic instability, which allows quantitative estimation of the energy barrier and may resolve the paradox.

  11. Breakup and Elastic Scattering in the {sup 9}Be + {sup 144}Sm system at near barrier energies

    SciTech Connect

    Paes, B.; Garcia, V. N.; Lubian, J.; Gomes, P. R. S.; Padron, I.

    2010-05-21

    Breakup and elastic scattering in the Be + {sup 144}Sm system, at near barrier energies, are investigated. We calculate theoretically the non-capture breakup cross section by performing coupled reaction channel calculations. The energy dependence of the optical potential does not show the usual threshold anomaly found in tightly bound systems.

  12. Metals on graphene: correlation between adatom adsorption behavior and growth morphology

    SciTech Connect

    Liu, Xiaojie; Wang, Cai-Zhuang; Hupalo, Myron; Lu, Wencai; Tringides, Michael C.; Yao, Yongxin; Ho, Kai-Ming

    2012-05-19

    We present a systematic study of metal adatom adsorption on graphene by ab initio calculations. The calculations cover alkali metals, sp-simple metals, 3d and group 10 transition metals, noble metals, as well as rare earth metals. The correlation between the adatom adsorption properties and the growth morphology of the metals on graphene is also investigated. We show that the growth morphology is related to the ratio of the metal adsorption energy to its bulk cohesive energy (E(a)/E(c)) and the diffusion barrier (ΔE) of the metal adatom on graphene. Charge transfer, electric dipole and magnetic moments, and graphene lattice distortion induced by metal adsorption would also affect the growth morphologies of the metal islands. We also show that most of the metal nanostructures on graphene would be thermally stable against coarsening.

  13. A Review of Barriers to and Opportunities for the Integration of Renewable Energy in the Southeast

    SciTech Connect

    McConnell, Ben W; Hadley, Stanton W; Xu, Yan

    2011-08-01

    The objectives of this study were to prepare a summary report that examines the opportunities for and obstacles to the integration of renewable energy resources in the Southeast between now and the year 2030. The report, which is based on a review of existing literature regarding renewable resources in the Southeast, includes the following renewable energy resources: wind, solar, hydro, geothermal, biomass, and tidal. The evaluation was conducted by the Oak Ridge National Laboratory for the Energy Foundation and is a subjective review with limited detailed analysis. However, the report offers a best estimate of the magnitude, time frame, and cost of deployment of renewable resources in the Southeast based upon the literature reviewed and reasonable engineering and economic estimates. For the purposes of this report, the Southeast is defined as the states of Alabama, Arkansas, Florida, Georgia, Kentucky, Louisiana, Mississippi, North Carolina, South Carolina, Tennessee, Virginia, and West Virginia. In addition, some aspects of the report (wind and geothermal) also consider the extended Southeast, which includes Maryland, Missouri, Oklahoma, and Texas. A description of the existing base of renewable electricity installations in the region is given for each technology considered. Where available, the possible barriers and other considerations regarding renewable energy resources are listed in terms of availability, investment and maintenance costs, reliability, installation requirements, policies, and energy market. As stated above, the report is a comprehensive review of renewable energy resources in the southeastern region of United States based on a literature study that included information obtained from the Southern Bio-Power wiki, sources from the Energy Foundation, sources available to ORNL, and sources found during the review. The report consists of an executive summary, this introductory chapter describing report objectives, a chapter on analysis methods and

  14. Multilayer coatings for flexible high-barrier materials

    NASA Astrophysics Data System (ADS)

    Vaško, Karol; Noller, Klaus; Mikula, Milan; Amberg-Schwab, Sabine; Weber, Ulrike

    2009-06-01

    A multilayer, flexible, and transparent high-barrier system based on flexible plastic foils, polyethyleneterephthalate (PET) and ethylene-tetrafluoroethylene-copolymer (ETFE), combined with vacuum-deposited, inorganic SiOx layers and hybrid ORMOCER® varnish layers were prepared in different orders on a semiproduction level. Barrier properties of prepared systems, as water vapour transmission (WVTR) and oxygen transmission (OTR), were measured and studied in connection with surface energy, surface topography, and water vapour adsorption properties. Correlations among layers sequence, barrier properties, and other parameters are presented, including some basic principles of permeation of substances through multilayer barrier systems. A combination of several inorganic and hybrid varnish layers is necessary to achieve the technological demands from a barrier standpoint. It is easier to suppress the oxygen transport than the water transport, due to the additional active penetration of water through hydrogen bonds and silanol creations at oxide interfaces, capillary condensation, and swelling with high internal pressure, leading to new defects.

  15. Multilayer coatings for flexible high-barrier materials

    NASA Astrophysics Data System (ADS)

    Vaško, Karol; Noller, Klaus; Mikula, Milan; Amberg-Schwab, Sabine; Weber, Ulrike

    2009-06-01

    A multilayer, flexible, and transparent high-barrier system based on flexible plastic foils, polyethyleneterephthalate (PET) and ethylene-tetrafluoroethylene-copolymer (ETFE), combined with vacuum-deposited, inorganic SiOx layers and hybrid ORMOCER® varnish layers were prepared in different orders on a semiproduction level. Barrier properties of prepared systems, as water vapour transmission (WVTR) and oxygen transmission (OTR), were measured and studied in connection with surface energy, surface topography, and water vapour adsorption properties. Correlations among layers sequence, barrier properties, and other parameters are presented, including some basic principles of permeation of substances through multilayer barrier systems. A combination of several inorganic and hybrid varnish layers is necessary to achieve the technological demands from a barrier standpoint. It is easier to suppress the oxygen transport than the water transport, due to the additional active penetration of water through hydrogen bonds and silanol creations at oxide interfaces, capillary condensation, and swelling with high internal pressure, leading to new defects.

  16. Gas chromatographic determination of the interconversion energy barrier for dialkyl 2,3-pentadienedioate enantiomers.

    PubMed

    Mydlová, J; Krupcík, J; Májek, P; Skacáni, I; Jakubík, T; Sandra, P; Armstrong, D W

    2007-05-25

    The enantiomers of dialkyl 2,3-pentadienedioate undergo interconversion during gas chromatographic separation on chiral stationary phases. In this paper the on-column apparent interconversion kinetic and thermodynamic activation data were determined for dimethyl, diethyl, propylbutyl and dibutyl 2,3-pentadienedioate enantiomers by gas chromatographic separation of the racemic mixtures on a capillary column containing a polydimethylsiloxane stationary phase coupled to 2,3-di-O-methyl-6-O-tertbutyldimethylsilyl-beta-cyclodextrin. A deconvolution method was used to determine the individual enantiomer peak areas and retention times that are needed to calculate the interconversion rate constants and the energy barriers. The apparent rate constants and interconversion energy barriers decrease slightly with an increase in the alkyl chain length of the dialkyl 2,3-pentadienedioate esters. The optimum conformation of the dialkyl 2,3-pentadienedioate molecules, their separation selectivity factors and apparent interconversion enthalpy and entropy data changes with the alkyl chain length. The dependence of the apparent interconversion energy barrier (deltaG(app)(a-->b), deltaG(app)(b-->a)) on temperature was used to determine the apparent activation enthalpy (deltaH(app)(a-->b), deltaH(app)(b-->a)) and apparent entropy (deltaS(app)(a-->b), deltaS(app)(a-->b)) (where a denotes the first and b second eluted enantiomer). The comparison of the activation enthalpy and entropy (deltaS(app)(a-->b), deltaS(app)(a-->b)) indicated that the interconversion of dialkyl 2,3-pentadienedioate enantiomers on the HP-5+Chiraldex B-DM column series is an entropy driven process at 160 degrees C. Data obtained for dimethyl 2,3-pentadienedioate enantiomers on the HP-5+Chiraldex B-DM column series at 120 degrees C (deltaG(app)(a-->b) = 123.3 and deltaG(app)(b-->a) = 124.4 kJ mol(-1)) corresponds (at the 95% confidence interval) with the value of deltaG(#) = 128+/-1 kJ mol(-1) found at this

  17. The Ligand Shell as an Energy Barrier in Surface Reactions on Transition Metal Nanoparticles.

    PubMed

    Smith, Jeremy G; Jain, Prashant K

    2016-06-01

    Transition metal nanoparticles, including those employed in catalytic, electrocatalytic, and photocatalytic conversions, have surfaces that are typically coated with a layer of short or long-chain ligands. There is little systematic understanding of how much this ligand layer affects the reactivity of the underlying surface. We show for Ag nanoparticles that a surface-adsorbed thiol layer greatly impedes the kinetics of an ionic chemical reaction taking place on the Ag surface. The model reaction studied is the galvanic exchange of Ag with Au(3+) ions, the kinetics of which is measured on individual thiol-coated nanoparticles using in situ optical scattering spectroscopy. We observe a systematic lowering of the reactivity of the nanoparticle as the chain length of the thiol is increased, from which we deduce that the ligand layer serves as an energy barrier to the transport of incoming/outgoing reactive ions. This barrier effect can be decreased by light irradiation, resulting from weakened binding of the thiol layer to the metal surface. We find that the influence of the surface ligand layer on reactivity is much stronger than factors such as nanoparticle size, shape, or crystallinity. These findings provide improved understanding of the role of ligand or adsorbates in colloidal catalysis and photocatalysis and have important implications for the transport of reactants and ions to surfaces and for engineering the reactivity of nanoparticles using surface passivation. PMID:27152595

  18. Single-Chain Magnets Based on Octacyanotungstate with the Highest Energy Barriers for Cyanide Compounds

    NASA Astrophysics Data System (ADS)

    Wei, Rong-Min; Cao, Fan; Li, Jing; Yang, Li; Han, Yuan; Zhang, Xiu-Ling; Zhang, Zaichao; Wang, Xin-Yi; Song, You

    2016-04-01

    By introducing large counter cations as the spacer, two isolated 3, 3-ladder compounds, (Ph4P)[CoII(3-Mepy)2.7(H2O)0.3WV(CN)8]·0.6H2O (1) and (Ph4As)[CoII(3-Mepy)3WV(CN)8] (2, 3-Mepy = 3-methylpyridine), were synthesized and characterized. Static and dynamic magnetic characterizations reveal that compounds 1 and 2 both behave as the single-chain magnets (SCMs) with very high energy barriers: 252(9) K for 1 and 224(7) K for 2, respectively. These two compounds display the highest relaxation barriers for cyano-bridged SCMs and are preceded only by two cobalt(II)-radical compounds among all SCMs. Meanwhile, a large coercive field of 26.2 kOe (1) and 22.6 kOe (2) were observed at 1.8 K.

  19. Single-Chain Magnets Based on Octacyanotungstate with the Highest Energy Barriers for Cyanide Compounds

    PubMed Central

    Wei, Rong-Min; Cao, Fan; Li, Jing; Yang, Li; Han, Yuan; Zhang, Xiu-Ling; Zhang, Zaichao; Wang, Xin-Yi; Song, You

    2016-01-01

    By introducing large counter cations as the spacer, two isolated 3, 3-ladder compounds, (Ph4P)[CoII(3-Mepy)2.7(H2O)0.3WV(CN)8]·0.6H2O (1) and (Ph4As)[CoII(3-Mepy)3WV(CN)8] (2, 3-Mepy = 3-methylpyridine), were synthesized and characterized. Static and dynamic magnetic characterizations reveal that compounds 1 and 2 both behave as the single-chain magnets (SCMs) with very high energy barriers: 252(9) K for 1 and 224(7) K for 2, respectively. These two compounds display the highest relaxation barriers for cyano-bridged SCMs and are preceded only by two cobalt(II)-radical compounds among all SCMs. Meanwhile, a large coercive field of 26.2 kOe (1) and 22.6 kOe (2) were observed at 1.8 K. PMID:27071451

  20. Mechanisms and systematics of breakup in reactions of {sup 9}Be at near-barrier energies

    SciTech Connect

    Rafiei, R.; Rietz, R. du; Luong, D. H.; Hinde, D. J.; Dasgupta, M.; Evers, M.; Diaz-Torres, A.

    2010-02-15

    Below-barrier no-capture breakup measurements of the weakly bound {sup 9}Be nucleus, incident on targets ranging in atomic number from 62 to 83, have been carried out using a large-area high-resolution back-angle detector array. It is shown that the three-body reconstructed reaction Q-value and relative energy of the breakup fragments together reveal the full dynamics of the breakup mechanism, identifying all physical processes that lead to the breakup of the projectile-like nucleus. Contrasting with the simple expectation of direct breakup into the most energetically favored clusters, the data show that breakup following n-transfer dominates the total breakup yield. Breakup from long-lived states in the projectile-like nucleus, which on the reaction time scale may be considered stable, has been isolated from the prompt breakup yield. It has been shown that the prompt breakup probability essentially depends on the surface separation of the interacting nuclei. The measured prompt breakup probability functions for each target have been used together with a classical trajectory model to predict the above-barrier suppression of complete fusion. The suppression factor, expressed as the fraction of incomplete fusion, is nearly independent of target charge.

  1. Single-Chain Magnets Based on Octacyanotungstate with the Highest Energy Barriers for Cyanide Compounds.

    PubMed

    Wei, Rong-Min; Cao, Fan; Li, Jing; Yang, Li; Han, Yuan; Zhang, Xiu-Ling; Zhang, Zaichao; Wang, Xin-Yi; Song, You

    2016-01-01

    By introducing large counter cations as the spacer, two isolated 3, 3-ladder compounds, (Ph4P)[Co(II)(3-Mepy)2.7(H2O)0.3W(V)(CN)8]·0.6H2O (1) and (Ph4As)[Co(II)(3-Mepy)3W(V)(CN)8] (2, 3-Mepy = 3-methylpyridine), were synthesized and characterized. Static and dynamic magnetic characterizations reveal that compounds 1 and 2 both behave as the single-chain magnets (SCMs) with very high energy barriers: 252(9) K for 1 and 224(7) K for 2, respectively. These two compounds display the highest relaxation barriers for cyano-bridged SCMs and are preceded only by two cobalt(II)-radical compounds among all SCMs. Meanwhile, a large coercive field of 26.2 kOe (1) and 22.6 kOe (2) were observed at 1.8 K. PMID:27071451

  2. Adsorption of gases and vapors on nanoporous Ni2(4,4'-Bipyridine)3(NO3)4 metal-organic framework materials templated with methanol and ethanol: structural effects in adsorption kinetics.

    PubMed

    Fletcher, Ashleigh J; Cussen, Edmund J; Bradshaw, Darren; Rosseinsky, Matthew J; Thomas, K Mark

    2004-08-11

    Desolvation of Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2CH(3)OH and Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH give flexible metal-organic porous structures M and E, respectively, which have the same stoichiometry, but subtly different structures. This study combines measurements of the thermodynamics and kinetics of carbon dioxide, methanol, and ethanol sorption on adsorbents M and E over a range of temperatures with adsorbent structural characterization at different adsorbate (guest) loadings. The adsorption kinetics for methanol and ethanol adsorption on porous structure E obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. The corresponding adsorption kinetics for porous structure M follow a double exponential (DE) model, which is consistent with two different barriers for diffusion through the windows and along the pores in the structure. The former is a high-energy barrier due to the opening of the windows in the structure, required to allow adsorption to occur, while the latter is a lower-energy barrier for diffusion in the pore cavities. X-ray diffraction studies at various methanol and ethanol loadings showed that the host porous structures E and M underwent different scissoring motions, leading to an increase in unit cell volume with the space group remaining unchanged during adsorption. The results are discussed in terms of reversible adsorbate/adsorbent (host/guest) structural changes and the adsorption mechanism involving hydrogen-bonding interactions with specific surface sites for methanol and ethanol adsorption in relation to pore size and extent of filling. This paper contains the first evidence for individual kinetic barriers to diffusion through windows and pore cavities in flexible porous coordination polymer frameworks. PMID:15291578

  3. Assembly of single molecular magnets from dinuclear to 2D Dy-compounds with significant change of relaxation energy barriers.

    PubMed

    Chen, Zhi; Fang, Ming; Kang, Xiao-Min; Hou, Yin-Ling; Zhao, Bin

    2016-01-01

    A dinuclear Dy(III) compound (1) was structurally and magnetically characterized, displaying a single-molecule magnet (SMM) behavior with a relaxation energy barrier of 21(1) K. Interestingly, by only adding a suitable substituent on the ligand in , as an SMM building unit, can be further assembled into a two-dimensional (2D) framework (2), which possesses a typical SMM behavior and a high relaxation energy barrier of 68(2) K. The result implied that the assembly of an SMM can effectively tune the energy barrier. To our knowledge, a cluster-based SMM assembled into a new 2D framework with SMM behavior is seldom reported. PMID:26634233

  4. One-neutron stripping processes to excited states of the 6Li+96Zr reaction at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Hu, S. P.; Zhang, G. L.; Yang, J. C.; Zhang, H. Q.; Gomes, P. R. S.; Lubian, J.; Ferreira, J. L.; Wu, X. G.; Zhong, J.; He, C. Y.; Zheng, Y.; Li, C. B.; Li, G. S.; Qu, W. W.; Wang, F.; Zheng, L.; Yu, L.; Chen, Q. M.; Luo, P. W.; Li, H. W.; Wu, Y. H.; Zhou, W. K.; Zhu, B. J.; Sun, H. B.

    2016-01-01

    We report the measurement of one-neutron stripping to excited-state cross sections from the weakly bound projectile 6Li to the 96Zr target at near-barrier energies by the online γ -ray spectroscopy method. Transitions of the 97Zr nucleus were clearly identified by γ -γ coincidences. This cross section was found to be much smaller than the previously reported complete-fusion cross section for this system at energies above the barrier, whereas it becomes of the same magnitude around the Coulomb-barrier energy. No evidence of two-neutron transfer was found. We also performed coupled reaction channel calculations for the one-neutron stripping process. The calculation results are discussed.

  5. Surface anisotropy broadening of the energy barrier distribution in magnetic nanoparticles.

    PubMed

    Pérez, N; Guardia, P; Roca, A G; Morales, M P; Serna, C J; Iglesias, O; Bartolomé, F; García, L M; Batlle, X; Labarta, A

    2008-11-26

    The effect of surface anisotropy on the distribution of energy barriers in magnetic fine particles of nanometer size is discussed within the framework of the Tln(t/τ(0)) scaling approach. The comparison between the distributions of the anisotropy energy of the particle cores, calculated by multiplying the volume distribution by the core anisotropy, and of the total anisotropy energy, deduced by deriving the master curve of the magnetic relaxation with respect to the scaling variable Tln(t/τ(0)), enables the determination of the surface anisotropy as a function of the particle size. We show that the contribution of the particle surface to the total anisotropy energy can be well described by a size-independent value of the surface energy per unit area which permits the superimposition of the distributions corresponding to the particle core and effective anisotropy energies. The method is applied to a ferrofluid composed of non-interacting Fe(3-x)O(4) particles of 4.9 nm average size and x about 0.07. Even though the size distribution is quite narrow in this system, a relatively small value of the effective surface anisotropy constant K(s) = 2.9 × 10(-2) erg cm(-2) gives rise to a dramatic broadening of the total energy distribution. The reliability of the average value of the effective anisotropy constant, deduced from magnetic relaxation data, is verified by comparing it to that obtained from the analysis of the shift of the ac susceptibility peaks as a function of the frequency. PMID:21836285

  6. Role of electrostatic interactions in the adsorption kinetics of nanoparticles at fluid-fluid interfaces.

    PubMed

    Dugyala, Venkateshwar Rao; Muthukuru, Jyothi Sri; Mani, Ethayaraja; Basavaraj, Madivala G

    2016-02-21

    The adsorption of particles to the fluid-fluid interface is a key factor for the stabilization of fluid-fluid interfaces such as those found in emulsions, foams and bijels. However, for the formation of stable particle-laden interfaces, the particles must migrate to the interface from the bulk. Recent studies show that the adsorption of particles to the interface formed during emulsification is influenced by the surface charge of the particles. To further investigate this phenomenon, we study the effect of the surface charge of the particle on the adsorption kinetics of particles to the oil-water interface. By suspending a drop of aqueous dispersion of charge stabilized nanoparticles in decane, the adsorption dynamics of particles to the decane-water interface is studied using the dynamic surface tension measurements. When the particles are highly charged (low salt), a negligible change in the interface tension is observed indicating that almost no particles are adsorbed. These results show that the charged particles experience an energy barrier when they approach the interface. But when the particle surface charge is screened by the addition of monovalent salt, a significant reduction in surface tension is observed indicating the migration and adsorption of particles to the decane-water interface. We estimate the effective diffusivity of particles to the interface by analyzing the initial decay in the measured surface tension by considering particle laden drops containing different amounts of salt using the modified Ward and Tordai theory. This effective diffusivity is used to calculate the energy barrier for the adsorption of particles to the interface. The energy barrier from the analysis of dynamic surface tension data agrees well with the concept of image charge repulsion which inhibits the adsorption of highly charged particles to the interface. By considering various types of relevant interactions, we derive an analytical expression that qualitatively

  7. I. Gas adsorption properties and porosity of transition metal-based cyanogels. II. Novel energy transfer processes in organic light-emitting devices

    NASA Astrophysics Data System (ADS)

    Deshpande, Rahul Shrikant

    The gas adsorption properties and porosity of cyanide-bridged transition metal-based gels are investigated in the first part of this dissertation. The cyanide bridges, connecting two transition metal centers, are characteristic of these gels; hence, these gels are termed cyanogels. Aerogel versus xerogel structures have a profound effect, both, on the thermodynamics and kinetics of gas adsorption on these cyanogels. Carbon dioxide is selectively adsorbed on palladium-cobalt-based cyanogels; the adsorption is fully reversible on both types of gels discussed. The thermodynamics and kinetics of the gas adsorption processes on these gels are analyzed here. From the ease and reproducibility of the CO2 desorption and the associated enthalpy values, it is concluded that CO2 is physisorbed on these gels. Both the adsorption and desorption processes are first-order in the gels. Adsorption of carbon monoxide on the palladium-cobalt cyanogels is also investigated. Unlike CO 2 physisorption, carbon monoxide is chemisorbed on these gels. An uptake of CO brings about a profound change in the xerogel morphology. The palladium-cobalt-based aerogels possess both micro- and mesoporosity; the xerogels are predominantly microporous with a narrow microporosity. The aerogel surfaces are found to be fractal as analyzed by gas adsorption. Unlike the aerogels, the xerogels do not possess surface fractality. The mechanism of adsorption of different gases on these gels is analyzed based on the gel morphologies. These transition metal-based gels are promising for a variety of applications such as heterogeneous catalysts, gas filters and magnetic materials. The porosity of these gels can be exploited to make gel-embedded filters to separate mixtures of gases based on the their differential adsorption propensities. The reversible adsorption of CO2 can be harnessed practically by using these gels as CO2 storage reservoirs. In the second part of this dissertation, the first, balanced, white

  8. Why Density-Gradient Corrections Improve Atomization Energies and Barrier Heights

    NASA Astrophysics Data System (ADS)

    Perdew, John P.; Ernzerhof, Matthias; Zupan, Ales; Burke, Kieron

    While the Hartree-Fock (HF) approximation typically underestimates the strength of the chemical bond, the local spin density (LSD) approximation overestimates it. Thus LSD overbinds atoms in molecules, and underestimates the heights of energy barriers when the transition state is more highly bonded than the initial state. Generalized gradient approximations (GGA's), which incorporate density-gradient corrections to LSD, improve the agreement between calculated and measured energetics. This has been previously understood as a consequence of the fact that gradient corrections favor density inhomogeneity, which increases when a bond is stretched or broken. We show that gradient corrections also favor high density, which increases when a bond is compressed or formed, but that the inhomogeneity effect usually prevails. To quantify the discussion, we present a thermodynamic-like inequality which is satisfied when gradient corrections favor a process.

  9. Spectral and energy parameters of multiband barrier-discharge KrBr excilamps

    SciTech Connect

    Avdeev, S M; Erofeev, M V; Skakun, V S; Sosnin, E A; Suslov, A I; Tarasenko, V F; Schitz, D V

    2008-07-31

    The spectral and energy characteristics of multiband barrier-discharge coaxial KrBr excilamps are studied experimentally at pressures from a few tens of Torr to 0.4 atm. It is shown that an increase in the Br{sub 2} concentration reduces the emission intensity of KrBr* molecules with respect to the emission intensity of Br{sub 2}* molecules and reduces the total emission power of the excilamp. This can be explained by the nonradiative decay of exciplex KrBr* molecules caused by their quenching by molecular bromine. The emission power and efficiency in the Kr:Br{sub 2} = 400:1 mixture at a pressure of {approx}230 Torr and a discharge gap of 8.5 mm were 4.8 W and 2.4%, respectively. (laser applications and other topics in quantum electronics)

  10. Cross sections and barriers for nuclear fission induced by high-energy nucleons

    SciTech Connect

    Grudzevich, O. T.; Yavshits, S. G.

    2013-03-15

    The cross sections for the fission of {sup 232}Th, {sup 235,238}U, {sup 237}Np, and {sup 239}Pu target nuclei that was induced by 20- to 1000-MeV neutrons and protons were calculated. The respective calculations were based on the multiconfiguration-fission (MCFx) model, which was used to describe three basic stages of the interaction of high-energy nucleons with nuclei: direct processes (intranuclear cascade), equilibration of the emerging compound system, and the decay of the compound nucleus (statistical model). Fission barriers were calculated within the microscopic approach for isotopic chains formed by 15 to 20 nuclei of the required elements. The calculated fission cross sections were compared with available experimental data. It was shown that the input data set and the theoretical model used made it possible to predict satisfactorily cross section for nuclear fission induced by 20- to 1000-MeV nucleons.

  11. The free-energy barrier to hydride transfer across a dipalladium complex.

    PubMed

    Vanston, C R; Kearley, G J; Edwards, A J; Darwish, T A; de Souza, N R; Ramirez-Cuesta, A J; Gardiner, M G

    2015-01-01

    We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)2CH2}2Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique. PMID:25652724

  12. Threshold anomaly for the 7Be +58Ni system at near-Coulomb-barrier energies

    NASA Astrophysics Data System (ADS)

    Gómez Camacho, A.; Aguilera, E. F.

    2014-12-01

    By using recent fusion cross section measurements for the weakly bound system 7Be+58Ni around the Coulomb barrier, a simultaneous χ2 analysis of elastic scattering and fusion cross section data is performed. The analysis is carried out with optical polarization potentials for the fusion and direct reaction processes. That is, the nuclear polarization potential UN is split into a volume part UF which accounts for fusion reactions and a surface part UD R that is responsible for direct reactions. The parameters of fusion and direct reaction Woods-Saxon polarization potentials are determined by the analysis of the data. The presence of the threshold anomaly is investigated from the energy dependence of these polarization potentials. It is found that, contrary to other weakly bound systems, the 7Be+58Ni reaction presents the usual threshold anomaly.

  13. Fusion cross sections for the {sup 9}Be+{sup 124}Sn reaction at energies near the Coulomb barrier

    SciTech Connect

    Parkar, V. V.; Palit, R.; Sharma, Sushil K.; Naidu, B. S.; Santra, S.; Mahata, K.; Ramachandran, K.; Joshi, P. K.; Rath, P. K.; Trivedi, T.; Raghav, A.

    2010-11-15

    The complete and incomplete fusion cross sections for {sup 9}Be+{sup 124}Sn reaction have been deduced using the online {gamma}-ray measurement technique. Complete fusion at energies above the Coulomb barrier was found to be suppressed by {approx}28% compared to the coupled-channels calculations and is in agreement with the systematics of L. R. Gasques et al. [Phys. Rev. C 79, 034605 (2009)]. Study of the projectile dependence for fusion on a {sup 124}Sn target shows that, for {sup 9}Be nuclei, the enhancement at below-barrier energies is substantial compared to that of tightly bound nuclei.

  14. Triangular tessellation scheme for the adsorption free energy at the liquid-liquid interface: Towards nonconvex patterned colloids.

    PubMed

    de Graaf, Joost; Dijkstra, Marjolein; van Roij, René

    2009-11-01

    We present a numerical technique, namely, triangular tessellation, to calculate the free energy associated with the adsorption of a colloidal particle at a flat interface. The theory and numerical scheme presented here are sufficiently general to handle nonconvex patchy colloids with arbitrary surface patterns characterized by a wetting angle, e.g., amphiphilicity. We ignore interfacial deformation due to capillary, electrostatic, or gravitational forces, but the method can be extended to take such effects into account. It is verified that the numerical method presented is accurate and sufficiently stable to be applied to more general situations than presented in this paper. The merits of the tessellation method prove to outweigh those of traditionally used semianalytic approaches, especially when it comes to generality and applicability. PMID:20364983

  15. A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

    NASA Astrophysics Data System (ADS)

    Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

    2011-06-01

    The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

  16. Local environment dependance of the water diffusion energy barrier onto the (101) anatase surface

    NASA Astrophysics Data System (ADS)

    Agosta, Lorenzo; Gala, Fabrizio; Zollo, Giuseppe

    2016-06-01

    The adsorption properties of TiO2 surfaces with biological environments have shown to be very important for bio-compatibility properties. Interactions of biological molecules with inorganic materials in aqueous systems, are mediated by water molecules. Hence the understanding of the possible conformations that water molecules can assume on the inorganic surfaces it is very important. Many studies concerning the structural conformations of adsorbed water molecules on rutile and anatase, the most likely exposed surface phases, show that the first layer of adsorbed water molecules play a crucial role in mediating the structural and physical properties of the upper interacting environment layers. In this contest we performed a detailed analysis of the possible conformations of the first layer of water molecules adsorbed on the (101) TiO2 surface; total energy calculations and NEB techniques, in contest of the DFT theory, has been used to study the stability and the diffusion properties as a further insight of our previous studies about this topic.

  17. Influence of rotational energy barriers to the conformational search of protein loops in molecular dynamics and ranking the conformations.

    PubMed

    Tappura, K

    2001-08-15

    An adjustable-barrier dihedral angle potential was added as an extension to a novel, previously presented soft-core potential to study its contribution to the efficacy of the search of the conformational space in molecular dynamics. As opposed to the conventional soft-core potential functions, the leading principle in the design of the new soft-core potential, as well as of its extension, the soft-core and adjustable-barrier dihedral angle (SCADA) potential (referred as the SCADA potential), was to maintain the main equilibrium properties of the original force field. This qualifies the methods for a variety of a priori modeling problems without need for additional restraints typically required with the conventional soft-core potentials. In the present study, the different potential energy functions are applied to the problem of predicting loop conformations in proteins. Comparison of the performance of the soft-core and SCADA potential showed that the main hurdles for the efficient sampling of the conformational space of (loops in) proteins are related to the high-energy barriers caused by the Lennard-Jones and Coulombic energy terms, and not to the rotational barriers, although the conformational search can be further enhanced by lowering the rotational barriers of the dihedral angles. Finally, different evaluation methods were studied and a few promising criteria found to distinguish the near-native loop conformations from the wrong ones. PMID:11455590

  18. Hydrogen adsorption on palladium: a comparative theoretical study of different surfaces

    NASA Astrophysics Data System (ADS)

    Dong, W.; Ledentu, V.; Sautet, Ph.; Eichler, A.; Hafner, J.

    1998-08-01

    The interaction of atomic hydrogen with the Pd(111), Pd(100) and Pd(110) surfaces is studied by ab-initio density functional calculations within the generalized gradient approximation (GGA). For the three surfaces, we have determined the preferred adsorption sites, the adsorption structures, the work function changes and the surface diffusion barrier, including relaxation effects. This comparative study allows some common features to be seen, in particular in the adsorption energies and geometries for both surface and subsurface H-atoms, and some significant differences such as the surface diffusion and the dispersion of the H-induced surface state. The origin of these differences is explained by a detailed analysis of the electronic structures of both clean and hydrogen-covered surfaces. Our study leads to an interesting correlation between the hydrogen diffusion barrier and the surface roughness since it plays an important part in the catalytic activity of the respective surfaces.

  19. Elastic scattering of 17O+208Pb at energies near the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Torresi, D.; Strano, E.; Mazzocco, M.; Boiano, A.; Boiano, C.; Di Meo, P.; La Commara, M.; Manea, C.; Nicoletto, M.; Grebosz, J.; Guglielmetti, A.; Molini, P.; Parascandolo, C.; Pierroutsakou, D.; Signorini, C.; Soramel, F.; Toniolo, N.; Filipescu, D.; Gheorghe, A.; Glodariu, T.; Jeong, S.; Kim, Y. H.; Lay, J. A.; Miyatake, H.; Pakou, A.; Sgouros, O.; Soukeras, V.; Stroe, L.; Vitturi, A.; Watanabe, Y.; Zerva, K.

    2016-05-01

    Within the frame of the commissioning of a new experimental apparatus EXPADES we undertook the measurement of the elastic scattering angular distribution for the system 17O+208Pb at energy around the Coulomb barrier. The reaction dynamics induced by loosely bound Radioactive Ion Beams is currently being extensively studied [4]. In particular the study of the elastic scattering process allows to obtain direct information on the total reaction cross section of the exotic nuclei. In order to understand the effect of the low binding energy on the reaction mechanism it is important to compare radioactive weakly bound nuclei with stable strongly-bound nuclei. In this framework the study of the 17O+208Pb elastic scattering can be considered to be complementary to a previous measurement of the total reaction cross section for the system 17F+208Pb at energies of 86, 90.4 MeV [5, 6]. The data will be compared with those obtained for the neighboring systems 16,18O+208Pb and others available in literature.

  20. Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

    NASA Astrophysics Data System (ADS)

    Markovits, A.; Paniagua, J. C.; López, N.; Minot, C.; Illas, F.

    2003-03-01

    Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

  1. Changes in the size of the apparent surface area and adsorption energy of the rye roots by low pH and the presence of aluminium ions induced

    NASA Astrophysics Data System (ADS)

    Szatanik-Kloc, Alicja

    2016-07-01

    The plant reactions on Al-stress include i.a. change of the surface area of the roots, which in the physicochemistry of plants characterizes the transport of water and ions through the root. The object of this study is the specific surface area of the roots of plants which are tolerant to aluminium, such as rye. Plants of rye were grown in a nutrient solution for 14 days at pH 4.5 in the presence of Al3+ ions of concentration 10, 20, and 40 mg dm-3. The control plants were grown continuously at pH 7 or pH 4.5 without Al3+. The apparent surface area and adsorption energy of the plants roots were determined from water vapour adsorption - desorption data. The apparent surface area of roots growing in the aluminium was (with respect to control) statistically significantly lower. There were no statistically significant differences in the apparent surface area of the roots which grew in pH 7, pH 4.5 without Al3+. The average water vapour adsorption energy of the root surface, under stress conditions decreased. In the roots grown in the presence of Al+3, there was a slight decrease in high energy adsorption centres and an increase in the amount of low-energy centres.

  2. The role of vdW interactions in coverage dependent adsorption energies of atomic adsorbates on Pt(111) and Pd(111)

    NASA Astrophysics Data System (ADS)

    Thirumalai, Hari; Kitchin, John R.

    2016-08-01

    Adsorption, a fundamental process in heterogeneous catalysis is known to be dependent on the adsorbate-adsorbate and surface-adsorbate bonds. van der Waals (vdW) interactions are one of the types of interactions that have not been examined thoroughly as a function of adsorbate coverage. In this work we quantify the vdW interactions for atomic adsorbates on late transition metal surfaces, and determine how these long range forces affect the coverage dependent adsorption energies. We calculate the adsorption energies of carbon, nitrogen, oxygen, sulfur, fluorine, bromine and chlorine species on Pt(111) and Pd(111) at coverages ranging from 1/4 to 1 ML using the BEEF-vdW functional. We observe that adsorption energies remain coverage dependent, and this coverage dependence is shown to be statistically significant. vdW interactions are found to be coverage dependent, but more significantly, they are found to be dependent on molecular properties such as adsorbate size, and consequently, correlate with the adsorbate effective nuclear charge. We observe that these interactions account for a reduction in the binding energy of the system, due to the destabilizing attractive interactions between the adsorbates which weaken its bond with the surface.

  3. Nucleation and interfacial adsorption in ternary systems.

    PubMed

    Philippe, T

    2015-03-01

    Nucleation is studied in incompressible ternary fluids by examining the topology of the overall landscape of the energy surface. Minimum free energy paths for nucleation (MFEPs) of a single nucleus in an infinite matrix are computed with the string method in the framework of the continuum theory of nucleation for the regular solution. Properties of the critical nucleus are compared with the predictions of the classical nucleation theory. MFEPs are found to exhibit complex nucleation pathways with non-monotonic variations of compositions in the interfacial region, specifically adsorption of a component. In the symmetric regular solution, the minority component is found to segregate at the interface during nucleation with a concomitant depletion of the nucleus core, resulting in unpredicted partition of the non-selective component. Despite increasing the gradient energy, such inhomogeneity in composition is shown to lower the nucleation barrier. PMID:25747088

  4. Hyperosmolar opening of the blood-brain barrier in the energy-depleted rat brain. Part 1. Permeability studies

    SciTech Connect

    Greenwood, J.; Luthert, P.J.; Pratt, O.E.; Lantos, P.L.

    1988-02-01

    A simple saline perfusion system was used to investigate the effects of hyperosmolar solutions of arabinose and mannitol upon the permeability of the blood-brain barrier. The small, polar molecule (/sup 14/C)mannitol and the larger, visual marker Evans blue were used as indicators of barrier integrity in the perfused energy-depleted brain. One-minute perfusion of hyperosmolar solutions consistently opened the barrier suggesting that the mechanism of osmotic barrier opening is independent of energy-producing metabolism. The accumulation of radiolabel in the brain was expressed as the ratio of tissue to perfusate radioactivity (Rt/Rp) and, for cerebrum, this increased from a control value of 0.0022 +/- 0.0007 (mean +/- SEM; n = 4) to a value of 0.0124 +/- 0.0008 (n = 4) following 0.9 M arabinose and to 0.0495 +/- 0.0072 (n = 4) following 1.8 M arabinose. There was a significant reduction of water content of hyperosmolar perfused brains. These findings support the hypothesis that osmotic barrier opening is the result of the passive shrinkage of endothelial cells and the surrounding tissue.

  5. On the hydrogen adsorption and dissociation on Cu surfaces and nanorows

    NASA Astrophysics Data System (ADS)

    Álvarez-Falcón, Leny; Viñes, Francesc; Notario-Estévez, Almudena; Illas, Francesc

    2016-04-01

    Here we present a thorough density functional theory study, including and excluding dispersive forces interaction description, on the adsorption and dissociation of H2 molecule on the low-index Miller Cu (111), (100), and (110) surfaces and two different surface Cu nanorows, all displaying a different number of surface nearest neighbors, nn. The computational setup has been optimized granting an accuracy below 0.04 eV. Surface and nanorow energies-for which a new methodology to extract them is presented- are found to follow the nn number. However, the adsorption strength is found not to. Thus, the adsorption energies seem to be governed by a particular orbital ↔ band interaction rather than by the simple nn surface saturation. The van der Waals (vdW) forces are found to play a key role in the adsorption of H2, and merely an energetic adjustment on chemisorbed H adatoms. Neither clear trends are observed for H2 and H adsorption energies, and H2 dissociation energy with respect nn, and nor Brønsted-Evans-Polanyi, making H2 adsorption and dissociation a trend outlier compared to other cases. H2 is found to adsorb and dissociate on Cu(100) surface. On the Cu(111) surface, the rather small H2 adsorption energy would prevent H2 dissociation, regardless if it is thermodynamically driven. On Cu(110) surface, the H2 dissociation process would be endothermic and achievable if adsorption energy is released on surpassing the dissociation energy barrier. On low-coordinated sites on Cu nanorows, vdW plays a key role in the H2 dissociation process, which otherwise is found to be endothermic. Indeed, dispersive forces turn the process markedly exothermic. Nanoparticle Cu systems must display Cu(100) surfaces or facets in order to dissociate H2, vital in many hydrogenation processes.

  6. Imaging the radical channel in acetaldehyde photodissociation: Competing mechanisms at energies close to the triplet exit barrier

    SciTech Connect

    Amaral, G. A.; Arregui, A.; Rodriguez, J. D.; Banares, L.; Rubio-Lago, L.

    2010-08-14

    The photodissociation of acetaldehyde in the radical channel has been studied at wavelengths between 315 and 325 nm using the velocity-map imaging technique. Upon one-photon absorption at 315 nm, the molecule is excited to the first singlet excited state S{sub 1}, which, in turn, undergoes intersystem crossing to the first excited triplet state T{sub 1}. On the triplet surface, the molecule dissociates into CH{sub 3} and HCO radicals with large kinetic energy release (KER), in accordance with the well characterized exit barrier on T{sub 1}. However, at longer wavelengths (>320 nm), which correspond to excitation energies just below the triplet barrier, a sudden change in KER is observed. At these photolysis wavelengths, there is not enough energy to surpass the exit barrier on the triplet state, which leaves the possibility of unimolecular dissociation on S{sub 0} after internal conversion from S{sub 1}. We have characterized the fragments' KER at these wavelengths, as well as determined the energy partitioning for the radical fragments. A new accurate estimate of the barrier height on T{sub 1} is presented.

  7. Adsorption and interaction energy of π ethene on Pt(1 1 1) and Pt alloys: A detailed analysis of vibrational, energetic and electronic properties

    NASA Astrophysics Data System (ADS)

    Haubrich, J.; Becker, C.; Wandelt, K.

    2009-06-01

    We present a detailed analysis of the electronic and geometric bonding properties of the model alkene ethene on different mono- and bimetallic surfaces to establish the difference between adsorption energy and interaction energy and to elucidate the chemical character of a single platinum atom in different chemical environments. The adsorption of ethene on Pt(1 1 1) at 100 K leads to two adsorption states, which are commonly described as being of di- σ-type (bidentate, μ 2η 2) and π-type (monodentate, μ 1η 2). While the later is the minority species on Pt(1 1 1) it is of larger abundance on the platinum alloys. We have chosen π-bonded ethene for our study since it can be found on Pt(1 1 1), the Pt 3Sn and Pt 2Sn surface alloys, and Cu 3Pt(1 1 1). Density functional theory calculations of the adsorption structures, site and decomposed densities of states, as well as partial charge densities in conjunction with vibrational spectroscopy show that the bonding, i.e. the interaction energy, of the π ethene is only weakly influenced by alloying. Even in a copper matrix - as in the case of Cu 3Pt(1 1 1) - the bonding platinum atom essentially keeps its chemical identity and the interaction energy is reduced by only 14% compared to Pt(1 1 1). This observation suggests that bonding on surfaces is a strongly localized phenomenon. However, the adsorption energy decreases significantly due to alloying, which is attributed to the varying local relaxation of the different metal surfaces.

  8. Influence of hydrodynamic energy on Holocene reef flat accretion, Great Barrier Reef

    NASA Astrophysics Data System (ADS)

    Dechnik, Belinda; Webster, Jody M.; Nothdurft, Luke; Webb, Gregory E.; Zhao, Jian-xin; Duce, Stephanie; Braga, Juan C.; Harris, Daniel L.; Vila-Concejo, Ana; Puotinen, Marji

    2016-01-01

    The response of platform reefs to sea-level stabilization over the past 6 ka is well established for the Great Barrier Reef (GBR), with reefs typically accreting laterally from windward to leeward. However, these observations are based on few cores spread across reef zones and may not accurately reflect a reef's true accretional response to the Holocene stillstand. We present a new record of reef accretion based on 49 U/Th ages from Heron and One Tree reefs in conjunction with re-analyzed data from 14 reefs across the GBR. We demonstrate that hydrodynamic energy is the main driver of accretional direction; exposed reefs accreted primarily lagoon-ward while protected reefs accreted seawards, contrary to the traditional growth model in the GBR. Lateral accretion rates varied from 86.3 m/ka-42.4 m/ka on the exposed One Tree windward reef and 68.35 m/ka-15.7 m/ka on the protected leeward Heron reef, suggesting that wind/wave energy is not a dominant control on lateral accretion rates. This represents the most comprehensive statement of lateral accretion direction and rates from the mid-outer platform reefs of the GBR, confirming great variability in reef flat growth both within and between reef margins over the last 6 ka, and highlighting the need for closely-spaced transects.

  9. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    PubMed Central

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  10. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    PubMed

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  11. One-neutron stripping from 9Be to 181Ta, 169Tm, 187Re and at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Fang, Y. D.; Gomes, P. R. S.; Lubian, J.; Ferreira, J. L.; Mendes Junior, D. R.; Zhou, X. H.; Liu, M. L.; Zhang, N. T.; Zhang, Y. H.; Li, G. S.; Wang, J. G.; Guo, S.; Qiang, Y. H.; Gao, B. S.; Zheng, Y.; Lei, X. G.; Wang, Z. G.

    2016-03-01

    We report the measurement of one-neutron stripping of 9Be to the 181Ta, 187Re and nuclei, in the range from subbarrier to above-barrier energies. The activation technique was used, with the detection of off-line γ rays. The results show that the transfer cross sections for the three systems investigated are very similar and are much larger than the corresponding fusion cross sections at subbarrier energies, whereas fusion predominates at energies above the barrier. Data are in good agreement with our coupled reaction channel calculations. We also investigate the ratio, as a function of energy, between experimental transfer and fusion cross sections. The role of transfer couplings on the fusion excitation functions is also discussed.

  12. Multinucleon transfer in O,1816,19F+208Pb reactions at energies near the fusion barrier

    NASA Astrophysics Data System (ADS)

    Rafferty, D. C.; Dasgupta, M.; Hinde, D. J.; Simenel, C.; Simpson, E. C.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; McNeil, S. D.; Ramachandran, K.; Vo-Phuoc, K.; Wakhle, A.

    2016-08-01

    Background: Nuclear reactions are complex, involving collisions between composite systems where many-body dynamics determines outcomes. Successful models have been developed to explain particular reaction outcomes in distinct energy and mass regimes, but a unifying picture remains elusive. The irreversible transfer of kinetic energy from the relative motion of the collision partners to their internal states, as is known to occur in deep inelastic collisions, has yet to be successfully incorporated explicitly into fully quantal reaction models. The influence of these processes on fusion is not yet quantitatively understood. Purpose: To investigate the population of high excitation energies in transfer reactions at sub-barrier energies, which are precursors to deep inelastic processes, and their dependence on the internuclear separation. Methods: Transfer probabilities and excitation energy spectra have been measured in collisions of O,1816,19F+208Pb , at various energies below and around the fusion barrier, by detecting the backscattered projectile-like fragments in a Δ E -E telescope. Results: The relative yields of different transfer outcomes are strongly driven by Q values, but change with the internuclear separation. In 16O+208Pb , single nucleon transfer dominates, with a strong contribution from -2 p transfer close to the Coulomb barrier, though this channel becomes less significant in relation to the -2 p 2 n transfer channel at larger separations. For 18O+208Pb , the -2 p 2 n channel is the dominant charge transfer mode at all separations. In the reactions with 19F,-3 p 2 n transfer is significant close to the barrier, but falls off rapidly with energy. Multinucleon transfer processes are shown to lead to high excitation energies (up to ˜15 MeV), which is distinct from single nucleon transfer modes which predominantly populate states at low excitation energy. Conclusions: Kinetic energy is transferred into internal excitations following transfer, with this

  13. Transportation Energy Futures Series. Non-Cost Barriers to Consumer Adoption of New Light-Duty Vehicle Technologies

    SciTech Connect

    Stephens, Thomas

    2013-03-01

    Consumer preferences are key to the adoption of new vehicle technologies. Barriers to consumer adoption include price and other obstacles, such as limited driving range and charging infrastructure; unfamiliarity with the technology and uncertainty about direct benefits; limited makes and models with the technology; reputation or perception of the technology; standardization issues; and regulations. For each of these non-cost barriers, this report estimates an effective cost and summarizes underlying influences on consumer preferences, approximate magnitude and relative severity, and assesses potential actions, based on a comprehensive literature review. While the report concludes that non-cost barriers are significant, effective cost and potential market share are very uncertain. Policies and programs including opportunities for drivers to test drive advanced vehicles, general public outreach and information programs, incentives for providing charging and fueling infrastructure, and development of technology standards were examined for their ability to address barriers, but little quantitative data exists on the effectiveness of these measures. This is one in a series of reports produced as a result of the Transportation Energy Futures project, a Department of Energy-sponsored multi-agency effort to pinpoint underexplored strategies for reducing GHGs and petroleum dependence related to transportation. View all reports on the TEF Web page, http://www.eere.energy.gov/analysis/transportationenergyfutures/index.html.

  14. Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

    PubMed

    Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

    2016-01-14

    In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested. PMID:26661060

  15. Localized Opto-Mechanical Control of Protein Adsorption onto Carbon Nanotubes

    PubMed Central

    O'Dell, Dakota; Serey, Xavier; Kang, Pilgyu; Erickson, David

    2014-01-01

    Chemical reactions can be described by an energy diagram along a reaction coordinate in which an activation barrier limits the rate at which reactants can be transformed into products. This reaction impedance can be overcome by reducing the magnitude of the barrier through the use of catalysis, increasing the thermal energy of the system, or through macroscopic mechanical processes. Here, we demonstrate direct molecular-scale control of a reaction through the precise application of opto-mechanical work. The method uses optical gradient forces generated in the evanescent field surrounding hybrid photonic-plasmonic structures to drive an otherwise unlikely adsorption reaction between proteins and carbon nanotubes. The adsorption of immunoglobulins on carbon nanotubes is used as a model reaction and investigated with an extended DLVO theory. The technique is also used to force a Förster resonance energy transfer between fluorophores on mismatched immunoglobulin proteins and is expected to lead to novel forms of chemical synthesis. PMID:25330911

  16. Irreversible adsorption-driven assembly of nanoparticles at fluid interfaces revealed by a dynamic surface tension probe.

    PubMed

    Bizmark, Navid; Ioannidis, Marios A; Henneke, Dale E

    2014-01-28

    Adsorption-driven self-assembly of nanoparticles at fluid interfaces is a promising bottom-up approach for the preparation of advanced functional materials and devices. Full realization of its potential requires quantitative understanding of the parameters controlling the self-assembly, the structure of nanoparticles at the interface, the barrier properties of the assembly, and the rate of particle attachment. We argue that models of dynamic surface or interfacial tension (DST) appropriate for molecular species break down when the adsorption energy greatly exceeds the mean energy of thermal fluctuations and validate alternative models extending the application of generalized random sequential adsorption theory to nanoparticle adsorption at fluid interfaces. Using a model colloidal system of hydrophobic, charge-stabilized ethyl cellulose nanoparticles at neutral pH, we demonstrate the potential of DST measurements to reveal information on the energy of adsorption, the adsorption rate constant, and the energy of particle-interface interaction at different degrees of nanoparticle coverage of the interface. These findings have significant implications for the quantitative description of nanoparticle adsorption at fluid interfaces. PMID:24397479

  17. Adsorption of methylchloride on Si(100) from first principles

    NASA Astrophysics Data System (ADS)

    Romero, Aldo H.; Sbraccia, Carlo; Silvestrelli, Pier Luigi; Ancilotto, Francesco

    2003-07-01

    The chemisorption of methylchloride (CH3Cl) on Si(100) is studied from first principles. We find that, among a number of possible adsorption configurations, the lowest-energy structure is one in which the methylchloride molecule is dissociated into CH3 and Cl fragments which are bound to the two Si atoms of the same surface dimer. Our calculations show that dissociative chemisorption of methylchloride on Si(100) may proceed along different reaction paths characterized by different energy barriers that the system must overcome: some dissociation processes are mediated by a molecular precursor state and, at least in one case, we find that the dissociation process is nonactivated, in agreement with recent experimental findings. We have also generated, for many possible adsorption structures, theoretical scanning tunneling microscopy images which could facilitate the interpretation of experimental measurements.

  18. Protein misfolding occurs by slow diffusion across multiple barriers in a rough energy landscape

    PubMed Central

    Yu, Hao; Dee, Derek R.; Liu, Xia; Brigley, Angela M.; Sosova, Iveta; Woodside, Michael T.

    2015-01-01

    The timescale for the microscopic dynamics of proteins during conformational transitions is set by the intrachain diffusion coefficient, D. Despite the central role of protein misfolding and aggregation in many diseases, it has proven challenging to measure D for these processes because of their heterogeneity. We used single-molecule force spectroscopy to overcome these challenges and determine D for misfolding of the prion protein PrP. Observing directly the misfolding of individual dimers into minimal aggregates, we reconstructed the energy landscape governing nonnative structure formation. Remarkably, rather than displaying multiple pathways, as typically expected for aggregation, PrP dimers were funneled into a thermodynamically stable misfolded state along a single pathway containing several intermediates, one of which blocked native folding. Using Kramers’ rate theory, D was found to be 1,000-fold slower for misfolding than for native folding, reflecting local roughening of the misfolding landscape, likely due to increased internal friction. The slow diffusion also led to much longer transit times for barrier crossing, allowing transition paths to be observed directly for the first time to our knowledge. These results open a new window onto the microscopic mechanisms governing protein misfolding. PMID:26109573

  19. Internal rotation barrier of the XH3sbnd YH3 (X, Y = C or Si) molecules. An energy decomposition analysis study

    NASA Astrophysics Data System (ADS)

    Chang, Xin; Su, Peifeng; Wu, Wei

    2014-08-01

    In this paper, the barriers of the internal rotation in ethane, methylsilane, and disilane are investigated by the generalized Kohn-Sham based energy decomposition analysis (GKS-EDA) scheme (P. Su, et al. J. Phys. Chem A 118 (2014) 2531). The rotation barriers and the inter-conversion energies from the three geometrical variation processes are decomposed into the electrostatic, exchange-repulsion, polarization, correlation and geometrical relaxation terms. It is concluded that the rotation barriers of the three molecules are all dominated by exchange-repulsion (Pauli repulsion). The geometry relaxation does not make a difference to the origin of the barrier.

  20. Numerical determination of the interfacial energy and nucleation barrier of curved solid-liquid interfaces in binary systems

    NASA Astrophysics Data System (ADS)

    Kundin, Julia; Choudhary, Muhammad Ajmal

    2016-07-01

    The phase-field crystal (PFC) technique is a widely used approach for modeling crystal growth phenomena with atomistic resolution on mesoscopic time scales. We use a two-dimensional PFC model for a binary system based on the work of Elder et al. [Phys. Rev. B 75, 064107 (2007), 10.1103/PhysRevB.75.064107] to study the effect of the curved, diffuse solid-liquid interface on the interfacial energy as well as the nucleation barrier. The calculation of the interfacial energy and the nucleation barrier certainly depends on the proper definition of the solid-liquid dividing surface and the corresponding nucleus size. We define the position of the sharp interface at which the interfacial energy is to be evaluated by using the concept of equimolar dividing surface (re) and the minimization of the interfacial energy (rs). The comparison of the results based on both radii shows that the difference re-rs is always positive and has a limit for large cluster sizes which is comparable to the Tolman length. Furthermore, we found the real nucleation barrier for small cluster sizes, which is defined as a function of the radius rs, and compared it with the classical nucleation theory. The simulation results also show that the extracted interfacial energy as function of both radii is independent of system size, and this dependence can be reasonably described by the nonclassical Tolman formula with a positive Tolman length.

  1. Spectral Modeling of Residual Stress and Stored Elastic Strain Energy in Thermal Barrier Coatings

    SciTech Connect

    Donegan, Sean; Rolett, Anthony

    2013-12-31

    Solutions to the thermoelastic problem are important for characterizing the response under temperature change of refractory systems. This work extends a spectral fast Fourier transform (FFT) technique to analyze the thermoelastic behavior of thermal barrier coatings (TBCs), with the intent of probing the local origins of failure in TBCs. The thermoelastic FFT (teFFT) approach allows for the characterization of local thermal residual stress and strain fields, which constitute the origins of failure in TBC systems. A technique based on statistical extreme value theory known as peaks-over-threshold (POT) is developed to quantify the extreme values ("hot spots") of stored elastic strain energy (i.e., elastic energy density, or EED). The resolution dependence of the teFFT method is assessed through a sensitivity study of the extreme values in EED. The sensitivity study is performed both for the local (point-by-point) eld distributions as well as the grain scale eld distributions. A convergence behavior to a particular distribution shape is demonstrated for the local elds. The grain scale fields are shown to exhibit a possible convergence to a maximum level of EED. To apply the teFFT method to TBC systems, 3D synthetic microstructures are created to approximate actual TBC microstructures. The morphology of the grains in each constituent layer as well as the texture is controlled. A variety of TBC materials, including industry standard materials and potential future materials, are analyzed using the teFFT. The resulting hot spots are quantified using the POT approach. A correlation between hot spots in EED and interface rumpling between constituent layers is demonstrated, particularly for the interface between the bond coat (BC) and the thermally grown oxide (TGO) layer.

  2. Transportation Energy Futures Series: Non-Cost Barriers to Consumer Adoption of New Light-Duty Vehicle Technologies

    SciTech Connect

    Stephens, T.

    2013-03-01

    Consumer preferences are key to the adoption of new vehicle technologies. Barriers to consumer adoption include price and other obstacles, such as limited driving range and charging infrastructure; unfamiliarity with the technology and uncertainty about direct benefits; limited makes and models with the technology; reputation or perception of the technology; standardization issues; and regulations. For each of these non-cost barriers, this report estimates an effective cost and summarizes underlying influences on consumer preferences, approximate magnitude and relative severity, and assesses potential actions, based on a comprehensive literature review. While the report concludes that non-cost barriers are significant, effective cost and potential market share are very uncertain. Policies and programs including opportunities for drivers to test drive advanced vehicles, general public outreach and information programs, incentives for providing charging and fueling infrastructure, and development of technology standards were examined for their ability to address barriers, but little quantitative data exists on the effectiveness of these measures. This is one in a series of reports produced as a result of the Transportation Energy Futures project, a Department of Energy-sponsored multi-agency effort to pinpoint underexplored strategies for reducing GHGs and petroleum dependence related to transportation.

  3. The effect of breakup of 6Li on elastic scattering and fusion with 28Si at near barrier energies

    NASA Astrophysics Data System (ADS)

    Sinha, Mandira; Roy, Subinit; Basu, P.; Majumdar, H.

    2016-01-01

    Elastic scattering angular distributions for 6Li+28Si system were measured at Elab = 16, 21MeV and analyzed along with the existing data from the previous measurements in the energy range of Elab = 7.5 - 27MeV. The measured cross-sections and the existing data, forming a set of angular distributions over a range of E/Vb = 0.9 - 3.23, were analyzed using the phenomenological optical model potential (OMP). Three different sets of potential parameters were used. The energy dependence of the real and the imaginary potential strengths were, subsequently, extracted at the radius of sensitivity (Rav) for the system. Continuum Discretized Coupled Channel (CDCC) calculation was performed to explore the contribution of projectile break-up (BU) on the observed energy dependence of the effective potential for elastic scattering of 6Li from 28Si. The energy variation of the strength of the real potential with continuum coupling was found to agree with the energy dependence of the same extracted from the (OMP) analysis at energies around the barrier. But the behavior of the imaginary strength appeared to be different. The calculated fusion cross-sections, including the effect of BU, clearly overestimated the measured fusion excitation function data in the below and near barrier energies but compared well with the data at higher energies.

  4. SCC-DFTB Energy Barriers for Single and Double Proton Transfer Processes in the Model Molecular Systems Malonaldehyde and Porphycene

    SciTech Connect

    Walewski, L.; Krachtus, D; Fischer, S.; Smith, Jeremy C; Bala, P.; Lesyng, B.

    2005-09-01

    Self-consistent charge-density functional tight-binding SCC-DFTB is a computationally efficient method applicable to large (bio)molecular systems in which (bio)chemical reactions may occur. Among these reactions are proton transfer processes. This method, along with more advanced ab initio techniques, is applied in this study to compute intramolecular barriers for single and double proton transfer processes in the model systems, malonaldehyde and porphycene, respectively. SCC-DFTB is compared with experimental data and higher-level ab initio calculations. For malonaldehyde, the SCC-DFTB barrier height is 3.1 kcal/mol in vacuo and 4.2 kcal/mol in water solution. In the case of porphycene, the minimum energy pathways for double intramolecular proton transfer were determined using the conjugate peak refinement (CPR) method. Six isomers of porphycene were ordered according to energy. The only energetically allowed pathway was found to connect two symmetrical trans states via an unstable cis-A isomer. The SCC-DFTB barrier heights are 11.1 kcal/mol for the trans-cis-A process, and 7.4 kcal/mol for the reverse cis-A-trans one with the energy difference of 3.7 kcal/mol between the trans- and cis-A states. The method provides satisfactory energy results when compared with reference ab initio and experimental data.

  5. Simulations about self-absorption of tritium in titanium tritide and the energy deposition in a silicon Schottky barrier diode.

    PubMed

    Li, Hao; Liu, Yebing; Hu, Rui; Yang, Yuqing; Wang, Guanquan; Zhong, Zhengkun; Luo, Shunzhong

    2012-11-01

    Simulations on the self-absorption of tritium electrons in titanium tritide films and the energy deposition in a silicon Schottky barrier diode are carried out using the Geant4 radiation transport toolkit. Energy consumed in each part of the Schottky radiovoltaic battery is simulated to give a clue about how to make the battery work better. The power and energy-conversion efficiency of the tritium silicon Schottky radiovoltaic battery in an optimized design are simulated. Good consistency with experiments is obtained. PMID:22935439

  6. Fabrication of Low Adsorption Energy Ni-Mo Cluster Cocatalyst in Metal-Organic Frameworks for Visible Photocatalytic Hydrogen Evolution.

    PubMed

    Zhen, Wenlong; Gao, Haibo; Tian, Bin; Ma, Jiantai; Lu, Gongxuan

    2016-05-01

    An effective cocatalyst is crucial for enhancing the visible photocatalytic performance of the hydrogen generation reaction. By using density-functional theory (DFT) and frontier molecular orbital (FMO) theory calculation analysis, the hydrogen adsorption free energy (ΔGH) of Ni-Mo alloy (458 kJ·mol(-1)) is found to be lower than that of Ni itself (537 kJ·mol(-1)). Inspired by these results, the novel, highly efficient cocatalyst NiMo@MIL-101 for photocatalysis of the hydrogen evolution reaction (HER) was fabricated using the double solvents method (DSM). In contrast with Ni@MIL-101 and Mo@MIL-101, NiMo@MIL-101 exhibited an excellent photocatalytic performance (740.2 μmol·h(-1) for HER), stability, and high apparent quantum efficiency (75.7%) under 520 nm illumination at pH 7. The NiMo@MIL-101 catalyst also showed a higher transient photocurrent, lower overpotential (-0.51 V), and longer fluorescence lifetime (1.57 ns). The results uncover the dependence of the photocatalytic activity of HER on the ΔGH of Ni-Mo (MoNi4) alloy nanoclusters, i.e., lower ΔGH corresponding to higher HER activity for the first time. The NiMo@MIL-101 catalyst could be a promising candidate to replace precious-metal catalysts of the HER. PMID:27070204

  7. Adsorption of Iodine and Potassium on Bi2Sr2CaCu2O8+δ Investigated by Low Energy Alkali Ion Scattering

    SciTech Connect

    Gu, G.D.; Gann, R.D.; Cao, J.X.; Wu, R.Q.; Wen, J.; Xu, Z.; Gu, G.D.; Yarmoff, J.A.

    2010-01-01

    The adsorption of K and I on the surface of the high-T{sub c} cuprate BSCCO-2212 is investigated with low-energy (0.8 to 2 keV) Na{sup +} ion scattering and density functional theory (DFT). Samples were cleaved in ultrahigh vacuum and charge-resolved spectra of the scattered ions were collected with time-of-flight. The spectra contain a single peak representing Na scattered from Bi, as the clean surfaces are terminated by BiO. The neutralization of scattered Na depends on the local potential above the target site, and the angular dependence indicates that the clean surface has an inhomogeneous potential. Neutralization is dependent on the coverage of I, but independent of K adsorption. DFT suggests high-symmetry sites for the adsorption of both I and K, and that the potential above the Bi sites is altered by I by an amount consistent with the experimental findings, while the potential is not affected by K adsorption. DFT also enables an experimental determination of the 'freezing distance,' which is the effective point beyond which charge exchange does not occur, to be 1.6 {+-} 0.1 {angstrom} from the outermost Bi layer.

  8. A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier

    NASA Astrophysics Data System (ADS)

    Rechkemmer, Yvonne; Breitgoff, Frauke D.; van der Meer, Margarethe; Atanasov, Mihail; Hakl, Michael; Orlita, Milan; Neugebauer, Petr; Neese, Frank; Sarkar, Biprajit; van Slageren, Joris

    2016-02-01

    Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials.

  9. A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier

    PubMed Central

    Rechkemmer, Yvonne; Breitgoff, Frauke D.; van der Meer, Margarethe; Atanasov, Mihail; Hakl, Michael; Orlita, Milan; Neugebauer, Petr; Sarkar, Biprajit; van Slageren, Joris

    2016-01-01

    Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials. PMID:26883902

  10. A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier.

    PubMed

    Rechkemmer, Yvonne; Breitgoff, Frauke D; van der Meer, Margarethe; Atanasov, Mihail; Hakl, Michael; Orlita, Milan; Neugebauer, Petr; Neese, Frank; Sarkar, Biprajit; van Slageren, Joris

    2016-01-01

    Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials. PMID:26883902

  11. Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Aurab; Bouhali, Othmane; Mousseau, Normand; Becquart, Charlotte S.; El-Mellouhi, Fedwa

    2016-08-01

    Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, C-insertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from

  12. Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

    PubMed

    Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

    2013-02-01

    The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk. PMID:23646573

  13. Improvement of pesticide adsorption capacity of cellulose fibre by high-energy irradiation-initiated grafting of glycidyl methacrylate

    NASA Astrophysics Data System (ADS)

    Takács, Erzsébet; Wojnárovits, László; Koczog Horváth, Éva; Fekete, Tamás; Borsa, Judit

    2012-09-01

    Cellulose as a renewable raw material was used for preparation of adsorbent of organic impurities in wastewater treatment. Hydrophobic surface of cellulose substrate was developed by grafting glycidyl methacrylate in simultaneous grafting using gamma irradiation initiation. Water uptake of cellulose significantly decreased while adsorption of phenol and a pesticide molecule (2,4-dichlorophenoxyacetic acid: 2,4-D) increased upon grafting. Adsorption equilibrium data fitted the Freundlich isotherm for both solutes.

  14. Differential adsorption of CHON isomers at interstellar grain surfaces

    NASA Astrophysics Data System (ADS)

    Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

    2015-06-01

    Context. The CHON generic chemical formula covers different isomers such as isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC); the first three have been identified in a large variety of environments in the interstellar medium (ISM). Several phenomena could be at the origin of the observed abundances, such as different pathways of formation and destruction involving gas phase reactions with different possible activation barriers and/or surface processes depending on the local temperature and the nature of the support. Aims: The scope of this article is to shed some light on the interaction of the CHON isomers with interstellar grains as a function of the nature of the surface and to determine the corresponding adsorption energies in order to find whether this phenomenon could play a role in the abundances observed in the ISM. Methods: The question was addressed by means of numerical simulations using first principle periodic density functional theory (DFT) to represent the grain support as a solid of infinite dimension. Results: Regardless of the nature of the model surface (water ice, graphene, silica), two different classes of isomers were identified: weakly bound (HNCO and HCNO) and strongly bound (HOCN and HONC), with the adsorption energies of the latter group being about twice those of the former. The range of the adsorption energies is (from highest to lowest) HOCN > HONC > HNCO > HCNO. They are totally disconnected from the relative stabilities, which range from HNCO > HOCN > HCNO > HONC. Conclusions: The possibility of hydrogen bonding is the discriminating factor in the trapping of CHON species on grain surfaces. Whatever the environment, differential adsorption is effective and its contribution to the molecular abundances should not be ignored. The theoretical adsorption energies provided here could be profitably used for a more realistic modeling of molecule-surfaces interactions.

  15. EFFECTS OF NUCLEAR INDUCED BREAKUP ON THE FUSION OF 6Li+12C AND 6He+12C SYSTEMS AROUND BARRIER ENERGIES

    NASA Astrophysics Data System (ADS)

    Duhan, Sukhvinder S.; Singh, Manjeet; Kharab, Rajesh

    2012-06-01

    We have studied the effects of nuclear induced breakup channel coupling on the fusion cross-section for 6Li+12C and 6He+12C systems in the near barrier energy regime using the dynamic polarization potential (DPP) approach. It has been found that there is enhancement in the fusion cross-section with respect to standard one-dimensional barrier penetration model in the below barrier energy regime while at energies above the barrier there is suppression of fusion cross-section with respect to simple barrier penetration model is observed. The agreement between data and predictions for 6Li+12C system improves significantly as a result of the inclusion of nuclear induced DPP.

  16. Market and behavioral barriers to energy efficiency: A preliminary evaluation of the case for tariff financing in California

    SciTech Connect

    Fujita, K. Sydny

    2011-06-23

    Consumers regularly forgo purchases of high efficiency appliances that appear to be cost effective at a reasonable rate of return. While some argue that this is a true revelation of preferences for appliance features, this 'efficiency gap' can be largely explained by a combination of market and behavioral failures that reduce consumers ability to evaluate the relative value of appliances and skew preferences toward initial cost savings, undervaluing future reductions in operating costs. These failures and barriers include externalities of energy use, imperfect competition between manufacturers, asymmetric information, bounded rationality, split incentives, and transaction costs (Golove 1996). Recognizing the social benefit of energy conservation, several major methods are used by policymakers to ensure that efficient appliances are purchased: minimum efficiency standards, Energy Star labeling, and rebates and tax credits. There is no single market for energy services; there are hundreds of uses, thousands of intermediaries, and millions of users, and likewise, no single appropriate government intervention (Golove 1996). Complementary approaches must be implemented, considering policy and institutional limitations. In this paper, I first lay out the rationale for government intervention by addressing the market and behavioral failures and barriers that arise in the context of residential energy efficiency. I then consider the ways in which some of these failures and barriers are addressed through major federal programs and state and utility level programs that leverage them, as well as identifying barriers that are not addressed by currently implemented programs. Heterogeneity of consumers, lack of financing options, and split incentives of landlords and tenants contribute significantly to the under-adoption of efficient appliances. To quantify the size of the market most affected by these barriers, I estimate the number of appliances, and in particular the number

  17. Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)-Water Interface

    SciTech Connect

    Kerisit, Sebastien N.; Zarzycki, Piotr P.; Rosso, Kevin M.

    2015-04-30

    The interaction of Fe(II) with ferric oxide/oxyhydroxide phases is central to the biogeochemical redox chemistry of iron. Molecular simulation techniques were employed to determine the mechanisms and quantify the rates of Fe(II) oxidative adsorption at the hematite (001)-water interface. Molecular dynamics potential of mean force calculations of Fe(II) adsorbing on the hematite surface revealed the presence of three free energy minima corresponding to Fe(II) adsorbed in an outersphere complex, a monodentate innersphere complex, and a tridentate innersphere complex. The free energy barrier for adsorption from the outersphere position to the monodentate innersphere site was calculated to be similar to the activation enthalpy for water exchange around aqueous Fe(II). Adsorption at both innersphere sites was predicted to be unfavorable unless accompanied by release of protons. Molecular dynamics umbrella sampling simulations and ab initio cluster calculations were performed to determine the rates of electron transfer from Fe(II) adsorbed as an innersphere and outersphere complex. The electron transfer rates were calculated to range from 10^-4 to 10^2 s-1, depending on the adsorption site and the potential parameter set, and were generally slower than those obtained in the bulk hematite lattice. The most reliable estimate of the rate of electron transfer from Fe(II) adsorbed as an outersphere complex to lattice Fe(III) was commensurate with the rate of adsorption as an innersphere complex suggesting that adsorption does not necessarily need to precede oxidation.

  18. Complementing the adsorption energies of CO2, H2S and NO2 to h-BN sheets by doping with carbon

    NASA Astrophysics Data System (ADS)

    Sagynbaeva, Myskal; Hussain, Tanveer; Panigrahi, Puspamitra; Johansson, Borje; Ahuja, Rajeev

    2015-03-01

    We predict the adsorption proficiency of hexagonal boron nitride (h-BN) sheets to toxic gas molecules like CO2, H2S and NO2 on the basis of first-principles density functional theory calculations. The computed energies predict the pristine h-BN sheet to have very little affinity towards the mentioned gas molecules. However, while doping C at the N site of the h-BN sheet brings a significant enhancement to the estimated adsorption energies, doping C at B site of the sheet is found to be energetically not so favorable. To have a higher coverage effect, the concentration of C doping on the h-BN sheet is further increased which resulted in upsurging the adsorption energies for the mentioned gas molecules. Among the three, CO2, H2S are found to be physisorbed to the C-doped h-BN sheets, where as the C-doped sheets are found to have strong affinity towards NO2 gas molecules.

  19. Tunneling in Al/Al2 O3 /Al junctions and its direct link with energy gap and tunneling time across the barrier

    NASA Astrophysics Data System (ADS)

    Patino, Edgar; Kelkar, Neelima

    Quantum tunneling has been widely used in order to investigate the density of states of the materials across the barrier and magnetoresistance in magnetic tunnel junctions (MTJs). In spite of the possible applications there is no clear understanding of the barrier parameters as a function of temperature. Measurements of current-voltage (I-V) characteristics of a high quality Al/Al2O3/Al junction at temperatures ranging from 3.5 K to 300 K have been used to extract the barrier properties. Fitting results using Simmons' model led to a constant value of barrier width s ~20.8 Å and a continuous increase in the barrier height with decreasing temperature. The latter is used to determine the energy band gap temperature dependence and average phonon frequency ω = 2.05 × 1013 sec-1 in Al2O3. Finally from the experimentally extracted barrier height and width parameters we calculate the tunneling time for a solid state tunnel junction. The order of magnitude of this time corresponds to the one obtained in sophisticated experiments.The barrier parameters are used to extract the temperature dependent dwell times in tunneling (τD = 3.6 × 10-16 sec at mid-barrier energies) and locate resonances above the barrier.

  20. Nuclear rainbow in the 16O + 27AL system: The role of couplings at energies far above the barrier

    NASA Astrophysics Data System (ADS)

    Pereira, D.; Linares, R.; Oliveira, J. R. B.; Lubian, J.; Chamon, L. C.; Gomes, P. R. S.; Cunsolo, A.; Cappuzzello, F.; Cavallaro, M.; Carbone, D.; Foti, A.

    2012-04-01

    High precision elastic and inelastic angular distributions have been measured for the 16O + 27Al system at a beam energy of 100 MeV. The data analysis confirms a rainbow formation as already predicted by parameter-free Coupled Channel calculations. It also helps to reveal the crucial role of inelastic couplings in the rainbow formation for heavier systems even at energies far above the Coulomb barrier. This feature, well known in atomic/molecular scattering, is experimentally studied for the first time in Nuclear Physics.

  1. Adsorption and dissociation of molecular hydrogen on the (0001) surface of double hexagonal close packed americium

    NASA Astrophysics Data System (ADS)

    Dholabhai, P. P.; Ray, A. K.

    2009-01-01

    Hydrogen molecule adsorption on the (0001) surface of double hexagonal packed americium has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals method (FP-L/APW+lo). Weak molecular hydrogen adsorptions were observed. Adsorption energies were optimized with respect to the distance of the adsorbates from the surface for three approach positions at three adsorption sites, namely t1 (one-fold top), b2 (two-fold bridge), and h3 (three-fold hollow) sites. Adsorption energies were computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at the fully relativistic level (with spin-orbit coupling SOC). The most stable configuration corresponds to a horizontal adsorption with the molecular approach being perpendicular to a lattice vector. The surface coverage is equivalent to one-fourth of a monolayer (ML), with the adsorption energies at the NSOC and SOC theoretical levels being 0.0997 eV and 0.1022 eV, respectively. The respective distance of the hydrogen molecule from the surface and hydrogen-hydrogen distance was found to be 2.645 Å and 0.789 Å, respectively. The work functions decreased and the net magnetic moments remained almost unchanged in all cases compared with the corresponding quantities of bare dhcp Am (0001) surface. The adsorbate-substrate interactions have been analyzed in detail using the partial charges inside the muffin-tin spheres, difference charge density distributions, and the local density of states. The effects of adsorption on the Am 5f electron localization-delocalization characteristics have been discussed. Reaction barrier for the dissociation of hydrogen molecule has been presented.

  2. Atomic and Molecular Adsorption on Re(0001)

    SciTech Connect

    Hahn, Konstanze; Mavrikakis, Manos

    2014-02-01

    Using periodic, self-consistent density functional theory calculations, the adsorption of several atomic (H, S, N, O and C) and molecular (CO2, N2, NH3, HCN, CO and NO) species and molecular fragments (NH2, NH, CN, CNH2, HNO, NOH, CH3, CH2, CH and OH) on the (0001) facet of rhenium at a coverage of 0.25 ML has been studied. Preferred binding sites with their corresponding binding energy and deformation energy of the surface, as well as an estimated diffusion barrier of each species have been determined. Atomic species and molecular fragments tend to bind to threefold sites, whereas molecular species tend to bind to top sites. The binding strength, with respect to the corresponding gas phase species and in increasing order for all species studied, is: CO2 < N2 < NH3 < CO < CH3 < HCN < NO < H < NH2 < OH < CH2 < CNH2 < CN < HNO < NH < NOH < S < N < O < CH < C. The vibrational frequencies of all species in their most energetically favorable adsorbed configuration have been calculated. Finally, the thermochemistry of adsorption and decomposition of NO, NO + H, NH3, N2, CO2, CO and CH4 on Re(0001) has been analyzed.

  3. Examination of the influence of transfer channels on the barrier height distribution: Scattering of 20Ne on 58Ni,60Ni, and 61Ni at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Trzcińska, A.; Piasecki, E.; Amar, A.; Czarnacki, W.; Keeley, N.; Kisieliński, M.; Kliczewski, S.; Kowalczyk, M.; Lommel, B.; Mutterer, M.; Siudak, R.; Stolarz, A.; Strojek, I.; Tiourin, G.; Trzaska, W. H.

    2016-05-01

    Background: It was suggested that the shape of the barrier height distribution can be determined not only by strong reaction channels (collective excitations) but also by weak channels such as transfers and/or noncollective excitations. Purpose: The study of the barrier height distributions for the 20Ne+58,60,61Ni systems requires information on transfer cross sections at near-barrier energies. Methods: A measurement of the cross sections for various transfer channels at a backward angle (142 degrees), at a near-barrier energy was performed. Identification of products was based on time-of-flight and Δ E -E methods. A measurement of the angular distribution of α stripping in the 20Ne+61Ni system was performed using a gas Δ E -E telescope. Results: For all three systems studied: 20Ne+58Ni ,60Ni, and 61Ni total (sum of all transfer channels) cross sections are similar and dominated by α stripping. Conclusions: The results, as well as coupled reaction channel calculations, suggest that transfer is not responsible for smoothing the barrier height distribution in 20Ne+61Ni , supporting the hypothesis that barrier distribution shapes are influenced by noncollective excitations.

  4. Atomic and molecular adsorption on Au(111)

    SciTech Connect

    Santiago-Rodríguez, Yohaselly; Herron, Jeffrey A.; Curet-Arana, María C.; Mavrikakis, Manos

    2014-09-01

    Periodic self-consistent density functional theory (DFT-GGA) calculations were used to study the adsorption of several atomic species, molecular species and molecular fragments on the Au(111) surface with a coverage of 1/4 monolayer (ML). Binding geometries, binding energies, and diffusion barriers were calculated for 27 species. Furthermore, we calculated the surface deformation energy associated with the binding events. The binding strength for all the analyzed species can be ordered as follows: NH3 < NO < CO < CH3 < HCO < NH2 < COOH < OH < HCOO < CNH2 < H < N < NH < NOH < COH < Cl,< HCO3 < CH2 < CN b HNO < O < F < S < C < CH. Although the atomic species preferred to bind at the three-fold fcc site, no tendency was observed in site preference for the molecular species and fragments. The intramolecular and adsorbate-surface vibrational frequencies were calculated for all the adsorbates on their most energetically stable adsorption site. Most of the theoretical binding energies and frequencies agreed with experimental values reported in the literature. In general, the values obtained with the PW91 functional are more accurate than RPBE in reproducing these experimental binding energies. The energies of the adsorbed species were used to calculate the thermochemical potential energy surfaces for decomposition of CO, NO, N2, NH3 and CH4, oxidation of CO, and hydrogenation of CO, CO2 and NO, giving insight into the thermochemistry of these reactions on gold nanoparticles. These potential energy surfaces demonstrated that: the decomposition of species is not energetically favorable on Au(111); the desorption of NH3, NO and CO are more favorable than their decomposition; the oxidation of CO and hydrogenation of CO and NO on Au(111) to form HCO and HNO, respectively, are also thermodynamically favorable.

  5. Intermediate-band photosensitive device with quantum dots embedded in energy fence barrier

    DOEpatents

    Forrest, Stephen R.; Wei, Guodan

    2010-07-06

    A plurality of layers of a first semiconductor material and a plurality of dots-in-a-fence barriers disposed in a stack between a first electrode and a second electrode. Each dots-in-a-fence barrier consists essentially of a plurality of quantum dots of a second semiconductor material embedded between and in direct contact with two layers of a third semiconductor material. Wave functions of the quantum dots overlap as at least one intermediate band. The layers of the third semiconductor material are arranged as tunneling barriers to require a first electron and/or a first hole in a layer of the first material to perform quantum mechanical tunneling to reach the second material within a respective quantum dot, and to require a second electron and/or a second hole in a layer of the first semiconductor material to perform quantum mechanical tunneling to reach another layer of the first semiconductor material.

  6. A computational study on the energetics and mechanisms for the dissociative adsorption of SiHx(x = 1-4) on W(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Lin, Y. H.; Raghunath, P.; Lin, M. C.

    2016-01-01

    The adsorption and dissociation mechanisms of SiHx(x = 1-4) species on W(1 1 1) surface have been investigated by using the periodic density functional theory with the projector-augmented wave approach. The adsorption of all the species on four surface sites: top (T), bridge (B), shallow (S), and deep (D) sites have been analyzed. For SiH4 on a top site, T-SiH4(a), it is more stable with an adsorption energy of 2.6 kcal/mol. For SiH3, the 3-fold shallow site is most favorable with adsorption energy of 46.0 kcal/mol. For SiH2, its adsorption on a bridge site is most stable with 73.0 kcal/mol binding energy, whereas for SiH and Si the most stable adsorption configurations are on 3-fold deep sites with very high adsorption energies, 111.8 and 134.7 kcal/mol, respectively. The potential energy surfaces for the dissociative adsorption of all SiHx species on the W(1 1 1) surface have been constructed using the CINEB method. The barriers for H-atom migration from SiHx(a) to its neighboring W atoms, preferentially on B-sites, were predicted to be 0.4, 1.0, 4.5 and, 8.0 kcal/mol, respectively, for x = 4, 3, 2, and 1, respectively. The adsorption energy of the H atom on a bridge site on the clean W(1 1 1) surface was predicted to be 65.9 kcal/mol, which was found to be slightly affected by the co-adsorption of SiHx-1 within ± 1 kcal/mol.

  7. Numerical determination of the interfacial energy and nucleation barrier of curved solid-liquid interfaces in binary systems.

    PubMed

    Kundin, Julia; Choudhary, Muhammad Ajmal

    2016-07-01

    The phase-field crystal (PFC) technique is a widely used approach for modeling crystal growth phenomena with atomistic resolution on mesoscopic time scales. We use a two-dimensional PFC model for a binary system based on the work of Elder et al. [Phys. Rev. B 75, 064107 (2007)PRBMDO1098-012110.1103/PhysRevB.75.064107] to study the effect of the curved, diffuse solid-liquid interface on the interfacial energy as well as the nucleation barrier. The calculation of the interfacial energy and the nucleation barrier certainly depends on the proper definition of the solid-liquid dividing surface and the corresponding nucleus size. We define the position of the sharp interface at which the interfacial energy is to be evaluated by using the concept of equimolar dividing surface (r^{e}) and the minimization of the interfacial energy (r^{s}). The comparison of the results based on both radii shows that the difference r^{e}-r^{s} is always positive and has a limit for large cluster sizes which is comparable to the Tolman length. Furthermore, we found the real nucleation barrier for small cluster sizes, which is defined as a function of the radius r^{s}, and compared it with the classical nucleation theory. The simulation results also show that the extracted interfacial energy as function of both radii is independent of system size, and this dependence can be reasonably described by the nonclassical Tolman formula with a positive Tolman length. PMID:27575196

  8. Global versus local adsorption selectivity

    NASA Astrophysics Data System (ADS)

    Pauzat, Françoise; Marloie, Gael; Markovits, Alexis; Ellinger, Yves

    2015-10-01

    The origin of the enantiomeric excess found in the amino acids present in the organic matter of carbonaceous meteorites is still unclear. Selective adsorption of one of the two enantiomers existing after a racemic formation could be part of the answer. Hereafter we report a comparative study of the adsorption of the R and S enantiomers of α-alanine and lactic acid on the hydroxylated { } chiral surface of α-quartz using numerical simulation techniques. Structurally different adsorption sites were found with opposite R versus S selectivity for the same molecule-surface couple, raising the problem of whether to consider adsorption as a local property or as a global response characteristic of the whole surface. To deal with the second term of this alternative, a statistical approach was designed, based on the occurrence of each adsorption site whose energy was calculated using first principle periodic density functional theory. It was found that R-alanine and S-lactic acid are the enantiomers preferentially adsorbed, even if the adsorption process on the quartz { } surface stays with a disappointingly poor enantio-selectivity. Nevertheless, it highlighted the important point that considering adsorption as a global property changes perspectives in the search for more efficient enantio-selective supports and more generally changes the way to apprehend adsorption processes in astro-chemistry/biology.

  9. Applying Risk Science and Stakeholder Engagement to Overcome Environmental Barriers to Marine and Hydrokinetic Energy Projects

    SciTech Connect

    Copping, Andrea E.; Anderson, Richard M.; Van Cleve, Frances B.

    2010-09-20

    The production of electricity from the moving waters of the ocean has the potential to be a viable addition to the portfolio of renewable energy sources worldwide. The marine and hydrokinetic (MHK) industry faces many hurdles, including technology development, challenges of offshore deployments, and financing; however, the barrier most commonly identified by industry, regulators, and stakeholders is the uncertainty surrounding potential environmental effects of devices placed in the water and the permitting processes associated with real or potential impacts. Regulatory processes are not well positioned to judge the severity of harm due to turbines or wave generators. Risks from MHK devices to endangered or protected animals in coastal waters and rivers, as well as the habitats that support them, are poorly understood. This uncertainty raises concerns about catastrophic interactions between spinning turbine blades or slack mooring lines and marine mammals, birds and fish. In order to accelerate the deployment of tidal and wave devices, there is a need to sort through the extensive list of potential interactions that may cause harm to marine organisms and ecosystems, to set priorities for regulatory triggers, and to direct future research. Identifying the risk of MHK technology components on specific marine organisms and ecosystem components can separate perceived from real risk-relevant interactions. Scientists from Pacific Northwest National Laboratory (PNNL) are developing an Environmental Risk Evaluation System (ERES) to assess environmental effects associated with MHK technologies and projects through a systematic analytical process, with specific input from key stakeholder groups. The array of stakeholders interested in the development of MHK is broad, segmenting into those whose involvement is essential for the success of the MHK project, those that are influential, and those that are interested. PNNL and their partners have engaged these groups, gaining

  10. Effective coordination as a predictor of adsorption energies: A model study of NO on Rh(100) and Rh/MgO(100) surfaces

    SciTech Connect

    Pushpa, Raghani; Gironcoli, Stefano de; Narasimhan, Shobhana

    2009-04-15

    We have studied the adsorption of NO, and the coadsorption of N and O, on four physical and hypothetical systems: unstrained and strained Rh(100) surfaces and monolayers of Rh atoms on strained and unstrained MgO(100) surfaces. We find that as we go from Rh(100) to Rh/Mg0(100), via the other two hypothetical systems, the effective coordination progressively decreases, the d band narrows and its center shifts closer to the Fermi level, and the strength of adsorption and coadsorption increases. Both the strain and the presence of the oxide substrate contribute significantly to this. However, charge transfer is found to play a negligible role due to a canceling out between donation and back-donation processes. Our results suggest that lowering the effective coordination of Rh catalysts by strain, roughening, or the use of inert substrates might lower activation energies for the dissociation of NO.

  11. Toward understanding the nature of internal rotation barriers with a new energy partition scheme: ethane and n-butane.

    PubMed

    Liu, Shubin; Govind, Niranjan

    2008-07-24

    On the basis of an alternative energy partition scheme where density-based quantification of the steric effect was proposed [Liu, S. B. J. Chem. Phys. 2007, 126, 244103], the origin of the internal rotation barrier between the eclipsed and staggered conformers of ethane and n-butane is systematically investigated in this work. Within the new scheme, the total electronic energy is decomposed into three independent components, steric, electrostatic, and fermionic quantum. The steric energy defined in this way is repulsive, exclusive, and extensive and intrinsically linked to Bader's atoms in molecules approach. Two kinds of differences, adiabatic (with optimal structure) and vertical (with fixed geometry), are considered for the molecules in this work. We find that in the adiabatic case the eclipsed conformer possesses a larger steric repulsion than the staggered conformer for both molecules, but in the vertical cases the staggered conformer retains a larger steric repulsion. For ethane, a linear relationship between the total energy difference and the fermionic quantum energy difference is discovered. This linear relationship, however, does not hold for n-butane, whose behaviors in energy component differences are found to be more complicated. The impact of basis set and density functional choices on energy components from the new energy partition scheme has been investigated, as has its comparison with another definition of the steric effect in the literature in terms of the natural bond orbital analysis through the Pauli Exclusion Principle. In addition, profiles of conceptual density functional theory reactivity indices as a function of dihedral angle changes have been examined. Put together, these results suggest that the new energy partition scheme provides insights from a different perspective of internal rotation barriers. PMID:18563887

  12. Hindrance of complete fusion in the {sup 8}Li+{sup 208}Pb system at above-barrier energies

    SciTech Connect

    Aguilera, E. F.; Martinez-Quiroz, E.; Rosales, P.; Kolata, J. J.; DeYoung, P. A.; Peaslee, G. F.; Mears, P.; Guess, C.; Becchetti, F. D.; Lupton, J. H.; Chen, Yu

    2009-10-15

    The {sup 211,212}At yields resulting from the interaction of the radioactive projectile {sup 8}Li with a {sup 208}Pb target have been measured at energies between 3 and 8.5 MeV above the Coulomb barrier. They are signatures for fusion of the whole charge but not necessarily the whole mass of the projectile, so they are included in a corresponding operational definition of complete fusion. Within this definition, a fusion suppression factor of 0.70{+-}0.02 (stat.) {+-}0.04 (syst.) is deduced from a comparison to a one-dimensional barrier-penetration-model calculation using parameters extrapolated from values for {sup 6,7}Li+{sup 209}Bi and {sup 9}Be+{sup 208}Pb taken from the literature. Possible incomplete fusion processes are discussed and the results are fitted with a phenomenological model assuming breakup prior to fusion followed by capture of a {sup 7}Li fragment.

  13. Ordering of Self-Diffusion Barrier Energies on Pt(110)-1x2

    SciTech Connect

    Feibelman, Peter J.

    1999-06-01

    Bond-counting arguments, supported by ab-initio calculations, predict a lower barrier for "leapfrog" diffusion of Pt addimers on Pt(llO)-lx2 than for adatom dif- fusion or addimer dissociation. This conflicts with experiment, possibly signaling contaminant influence.

  14. OVERVIEW OF THE U.S. DEPARTMENT OF ENERGY AND NUCLEAR REGULATORY COMMISSION PERFORMANCE ASSESSMENT APPROACHES: CEMENTITIOUS BARRIERS PARTNERSHIP

    SciTech Connect

    Langton, C.; Burns, H.

    2009-05-29

    Engineered barriers including cementitious barriers are used at sites disposing or contaminated with low-level radioactive waste to enhance performance of the natural environment with respect to controlling the potential spread of contaminants. Drivers for using cementitious barriers include: high radionuclide inventory, radionuclide characteristics (e.g., long half-live, high mobility due to chemical form/speciation, waste matrix properties, shallow water table, and humid climate that provides water for leaching the waste). This document comprises the first in a series of reports being prepared for the Cementitious Barriers Partnership. The document is divided into two parts which provide a summary of: (1) existing experience in the assessment of performance of cementitious materials used for radioactive waste management and disposal and (2) sensitivity and uncertainty analysis approaches that have been applied for assessments. Each chapter is organized into five parts: Introduction, Regulatory Considerations, Specific Examples, Summary of Modeling Approaches and Conclusions and Needs. The objective of the report is to provide perspective on the state of the practice for conducting assessments for facilities involving cementitious barriers and to identify opportunities for improvements to the existing approaches. Examples are provided in two contexts: (1) performance assessments conducted for waste disposal facilities and (2) performance assessment-like analyses (e.g., risk assessments) conducted under other regulatory regimes. The introductory sections of each section provide a perspective on the purpose of performance assessments and different roles of cementitious materials for radioactive waste management. Significant experience with assessments of cementitious materials associated with radioactive waste disposal concepts exists in the US Department of Energy Complex and the commercial nuclear sector. Recently, the desire to close legacy facilities has created

  15. Thermodynamics of downhill folding: multi-probe analysis of PDD, a protein that folds over a marginal free energy barrier.

    PubMed

    Naganathan, Athi N; Muñoz, Victor

    2014-07-31

    Downhill folding proteins fold in microseconds by crossing a very low or no free energy barrier (<3 RT), and exhibit a complex unfolding behavior in equilibrium. Such unfolding complexity is due to the weak thermodynamic coupling that exists between the various structural segments of these proteins, and it is manifested in unfolding curves that differ depending on the structural probe employed to monitor the process. Probe-dependent unfolding has important practical implications because it permits one to investigate the folding energy landscape in detail using multiprobe thermodynamic experiments. This type of thermodynamic behavior has been investigated in depth on the protein BBL, an example of extreme (one-state) downhill folding in which there is no free energy barrier at any condition, including the denaturation midpoint. However, an open question is, to what extent is such thermodynamic behavior observed on less extreme downhill folders? Here we perform a multiprobe spectroscopic characterization of the microsecond folder PDD, a structural and functional homologue of BBL that folds within the downhill regime, but is not an example of one-state downhill folding; rather at the denaturation midpoint PDD folds by crossing an incipient free energy barrier. Model-free analysis of the unfolding curves from four different spectroscopic probes together with differential scanning calorimetry reveals a dispersion of ∼9 K in the apparent melting temperature and also marked differences in unfolding broadness (from ∼50 to ∼130 kJ mol(-1) when analyzed with a two-state model), confirming that such properties are also observed on less extreme downhill folders. We subsequently perform a global quantitative analysis of the unfolding data of PDD using the same ME statistical mechanical model that was used before for the BBL domain. The analysis shows that this simple model captures all of the features observed on the unfolding of PDD (i.e., the intensity and temperature

  16. Equilibrium and kinetics studies of arsenate adsorption by FePO(4).

    PubMed

    Hamayun, M; Mahmood, T; Naeem, A; Muska, M; Din, S U; Waseem, M

    2014-03-01

    The present work is focusing on removal of arsenate from aqueous solution using FePO4. The equilibrium study regarding the removal of arsenic by FePO4 was carried out at 298, 308, 318 and 328K. Langmuir parameters were found to increase with the increase in temperature indicating that the adsorption is favorable at high temperature. Kinetic study of arsenate adsorption on FePO4 was also carried out at different temperatures and at pH 6 and 8. Different kinetic models were used to the kinetic data amongst which pseudo second order model was best fitted. The mechanism of the adsorption kinetics was investigated by employing intraparticle diffusion and Richenberg models. The energy of activation (Ea) was found to be 30 and 35.52kJmol(-1) at pH 6 and pH 8, respectively, suggesting chemisorption nature of the adsorption process. The negative entropic values of activation signified the existence of entropy barrier while the positive ΔG(#) values indicated the existence of energy barrier to be crossed over for the occurrence of a chemical reaction. Both the spectroscopic studies and increase in equilibrium pH reveal the anion exchange removal of arsenate from aqueous solution to the solid surface. PMID:24280053

  17. Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

    SciTech Connect

    Mussard, Bastien; Reinhardt, Peter; Toulouse, Julien; Ángyán, János G.

    2015-04-21

    We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Szabo and Ostlund [J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism, provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse et al., J. Chem. Phys. 135, 084119 (2011)], this works confirms range-separated RPAx-SO2 as a promising method for general chemical applications.

  18. Validation and divergence of the activation energy barrier crossing transition at the AOT/lecithin reverse micellar interface.

    PubMed

    Narayanan, S Shankara; Sinha, Sudarson Sekhar; Sarkar, Rupa; Pal, Samir Kumar

    2008-03-13

    In this report, the validity and divergence of the activation energy barrier crossing model for the bound to free type water transition at the interface of the AOT/lecithin mixed reverse micelle (RM) has been investigated for the first time in a wide range of temperatures by time-resolved solvation of fluorophores. Here, picosecond-resolved solvation dynamics of two fluorescent probes, ANS (1-anilino-8-naphthalenesulfonic acid, ammonium salt) and Coumarin 500 (C-500), in the mixed RM have been carefully examined at 293, 313, 328, and 343 K. Using the dynamic light scattering (DLS) technique, the size of the mixed RMs at different temperatures was found to have an insignificant change. The solvation process at the reverse micellar interface has been found to be the activation energy barrier crossing type, in which interface-bound type water molecules get converted into free type water molecules. The activation energies, Ea, calculated for ANS and C-500 are 7.4 and 3.9 kcal mol(-1), respectively, which are in good agreement with that obtained by molecular dynamics simulation studies. However, deviation from the regular Arrhenius type behavior was observed for ANS around 343 K, which has been attributed to the spatial heterogeneity of the probe environments. Time-resolved fluorescence anisotropy decay of the probes has indicated the existence of the dyes in a range of locations in RM. With the increase in temperature, the overall anisotropy decay becomes faster revealing the lability of the microenvironment at elevated temperatures. PMID:18281975

  19. Efficient sampling over rough energy landscapes with high barriers: A combination of metadynamics with integrated tempering sampling.

    PubMed

    Yang, Y Isaac; Zhang, Jun; Che, Xing; Yang, Lijiang; Gao, Yi Qin

    2016-03-01

    In order to efficiently overcome high free energy barriers embedded in a complex energy landscape and calculate overall thermodynamics properties using molecular dynamics simulations, we developed and implemented a sampling strategy by combining the metadynamics with (selective) integrated tempering sampling (ITS/SITS) method. The dominant local minima on the potential energy surface (PES) are partially exalted by accumulating history-dependent potentials as in metadynamics, and the sampling over the entire PES is further enhanced by ITS/SITS. With this hybrid method, the simulated system can be rapidly driven across the dominant barrier along selected collective coordinates. Then, ITS/SITS ensures a fast convergence of the sampling over the entire PES and an efficient calculation of the overall thermodynamic properties of the simulation system. To test the accuracy and efficiency of this method, we first benchmarked this method in the calculation of ϕ - ψ distribution of alanine dipeptide in explicit solvent. We further applied it to examine the design of template molecules for aromatic meta-C-H activation in solutions and investigate solution conformations of the nonapeptide Bradykinin involving slow cis-trans isomerizations of three proline residues. PMID:26957155

  20. Development of facile property calculation model for adsorption chillers based on equilibrium adsorption cycle

    NASA Astrophysics Data System (ADS)

    Yano, Masato; Hirose, Kenji; Yoshikawa, Minoru; Thermal management technology Team

    Facile property calculation model for adsorption chillers was developed based on equilibrium adsorption cycles. Adsorption chillers are one of promising systems that can use heat energy efficiently because adsorption chillers can generate cooling energy using relatively low temperature heat energy. Properties of adsorption chillers are determined by heat source temperatures, adsorption/desorption properties of adsorbent, and kinetics such as heat transfer rate and adsorption/desorption rate etc. In our model, dependence of adsorption chiller properties on heat source temperatures was represented using approximated equilibrium adsorption cycles instead of solving conventional time-dependent differential equations for temperature changes. In addition to equilibrium cycle calculations, we calculated time constants for temperature changes as functions of heat source temperatures, which represent differences between equilibrium cycles and real cycles that stemmed from kinetic adsorption processes. We found that the present approximated equilibrium model could calculate properties of adsorption chillers (driving energies, cooling energies, and COP etc.) under various driving conditions quickly and accurately within average errors of 6% compared to experimental data.

  1. Systematic study of suppression of complete fusion in reactions involving weakly bound nuclei at energies above the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Zhao, Wei-Juan; Diaz-Torres, Alexis; Zhao, En-Guang; Zhou, Shan-Gui

    2016-01-01

    Complete fusion excitation functions of reactions involving breakup are studied by using the empirical coupled-channel (ECC) model with breakup effects considered. An exponential function with two parameters is adopted to describe the prompt-breakup probability in the ECC model. These two parameters are fixed by fitting the measured prompt-breakup probability or the complete fusion cross sections. The suppression of complete fusion at energies above the Coulomb barrier is studied by comparing the data with the predictions from the ECC model without the breakup channel considered. The results show that the suppression of complete fusion is roughly independent of the target for the reactions involving the same projectile.

  2. Energy barriers for bit-encoding states based on 360° domain walls in ultrathin ferromagnetic nanorings

    NASA Astrophysics Data System (ADS)

    Muratov, C. B.; Osipov, V. V.; Vanden-Eijnden, E.

    2015-05-01

    A numerical thermal stability study of the bit-encoding states in a proposed multi-level magnetic storage element based on an ultrathin ferromagnetic nanoring is presented. The material parameters and the ring dimensions for which there are five distinct metastable magnetization configurations separated by energy barriers exceeding 50kBT at room temperature are identified. The results are obtained, using the string method for the study of rare events to locate the transition states separating the metastable states and to identify the most likely thermally activated pathways.

  3. Elastic Scattering Of {sup 6,7}Li+{sup 80}Se At Near And Above Barrier Energies

    SciTech Connect

    Fimiani, L.; Marti, G. V.; Capurro, O. A.; Barbara, E. de; Testoni, J. E.; Zalazar, L.; Arazi, A.; Cardona, M. A.; Carnelli, P.; Figueira, J. M.; Hojman, D.; Martinez Heimann, D.; Negri, A. E.; Pacheco, A. J.; Fernandez Niello, J. O.

    2010-08-04

    In this work we propose to study the elastic scattering of the weakly bound projectiles {sup 6,7}Li on an intermediate mass target {sup 80}Se. From the experimental results presented here, precise angular distributions at energies below, around and above the nominal Coulomb barriers of the systems were obtained. The final goal of our work is to determine the characteristic parameters of the optical potential and use them to address the question of whether the usual threshold anomaly or the breakup threshold anomaly are present or not in these systems.

  4. Bulk-barrier transistor

    NASA Astrophysics Data System (ADS)

    Mader, H.; Mueller, R.; Beinvogl, W.

    1983-10-01

    Experimental and theoretical results are presented on a bulk-barrier transistor (BBT). In this device the charge-carrier transportation is determined by an energy barrier, which is located inside a semiconductor. The barrier is the result of a space-charge region in a three-layered n-p-n or p-n-p structure with a very thin middle layer. The height of the energy barrier, which is adjustable by technological parameters, can be controlled by an external voltage.

  5. Method of local increments for the calculation of adsorption energies of atoms and small molecules on solid surfaces. 2. CO/MgO(001).

    PubMed

    Staemmler, Volker

    2011-06-30

    The method of local increments is used in connection with an embedded cluster approach and wave function based quantum chemical ab initio methods to describe the adsorption of a single CO molecule on the MgO(001) surface. The first step in this approach is a conventional Hartree-Fock calculation. The occupied orbitals are then localized by means of the Foster-Boys localization procedure, and the full system is decomposed into several "subunits" that consist of the orbitals localized at the CO molecule and at the Mg and O atoms of the MgO cluster. The correlation energy is expanded into a series of local n-body increments that are evaluated separately and independently. In this way, big savings in computer time can be achieved because (a) the treatment of a large system is replaced with a series of much faster calculations for small subsystems and (b) the big basis sets necessary for describing dispersion effects are only needed for the atoms in the respective subsystem while all other atoms can be treated by medium size Hartree-Fock type basis sets. The coupled electron pair approach, CEPA, an approximate coupled cluster method, is used to calculate the correlation energies of the various subsystems. For the vertical adsorption of CO on top a Mg atom of the MgO(001) surface with the C atom toward Mg, the individual one- and two-body increments are calculated as functions of the CO-MgO separation and a full potential energy curve is constructed from them. A very shallow minimum with an adsorption energy of 0.016 eV at a Mg-C distance of 3.04 Å is found at the Hartree-Fock level, while inclusion of correlation (dispersion) effects shortens the Mg-C distance to 2.59 Å and yields a much larger adsorption energy of 0.124 eV. This is in very good agreement with the best experimental value of 0.14 eV. The basis set superposition error, BSSE, was fully corrected for by the counterpoise method and the bonding mechanism was analyzed at the Hartree-Fock level by means of

  6. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  7. A seven-degree-of-freedom, time-dependent quantum dynamics study on the energy efficiency in surmounting the central energy barrier of the OH + CH{sub 3} → O + CH{sub 4} reaction

    SciTech Connect

    Yan, Pengxiu; Wang, Yuping; Li, Yida; Wang, Dunyou

    2015-04-28

    A time-dependent, quantum reaction dynamics calculation with seven degrees of freedom was carried out to study the energy efficiency in surmounting the approximate center energy barrier of OH + CH{sub 3}. The calculation shows the OH vibration excitations greatly enhance the reactivity, whereas the vibrational excitations of CH{sub 3} and the rotational excitations hinder the reactivity. On the basis of equal amount of total energy, although this reaction has a slight early barrier, it is the OH vibrational energy that is the dominate force in promoting the reactivity, not the translational energy. The studies on both the forward O + CH{sub 4} and reverse OH + CH{sub 3} reactions demonstrate, for these central barrier reactions, a small change of the barrier location can significantly change the energy efficacy roles on the reactivity. The calculated rate constants agree with the experimental data.

  8. Detection of the adsorption of water monolayers through the ion oscillation frequency in the magnesium oxide lattice by means of low energy electron diffraction

    NASA Astrophysics Data System (ADS)

    Guevara-Bertsch, M.; Ramírez-Hidalgo, G.; Chavarría-Sibaja, A.; Avendaño, E.; Araya-Pochet, J. A.; Herrera-Sancho, O. A.

    2016-03-01

    We investigate the variation of the oscillation frequency of the Mg2+ and O2- ions in the magnesium oxide lattice due to the interactions of the surface with water monolayers by means of Low Energy Electron Diffraction. Our key result is a new technique to determine the adsorbate vibrations produced by the water monolayers on the surface lattice as a consequence of their change in the surface Debye temperature and its chemical shift. The latter was systematically investigated for different annealing times and for a constant external thermal perturbation in the range of 110-300 K in order to accomplish adsorption or desorption of water monolayers in the surface lattice.

  9. Modeling of Peptide Adsorption Interactions with a Poly(lactic acid) Surface

    PubMed Central

    O'Brien, C. P.; Stuart, S. J.; Bruce, D. A.; Latour, R. A.

    2009-01-01

    The biocompatibility of implanted materials and devices is governed by the conformation, orientation, and composition of the layer of proteins that adsorb to the surface of the material immediately upon implantation, so an understanding of this adsorbed protein layer is essential to the rigorous and methodical design of implant materials. In this study, novel molecular dynamics techniques were employed in order to determine the change in free energy for the adsorption of a solvated nine-residue peptide (GGGG-K-GGGG) to a crystalline polylactide surface in an effort to elucidate the fundamental mechanisms that govern protein adsorption. This system, like many others, involves two distinct types of sampling problems: a spatial sampling problem, which arises due to entropic effects creating barriers in the free energy profile, and a conformational sampling problem, which occurs due to barriers in the potential energy landscape. In a two-step process that addresses each sampling problem in turn, the technique of biased replica exchange molecular dynamics was refined and applied in order to overcome these sampling problems and, using the information available at the atomic level of detail afforded by molecular simulation, both quantify and characterize the interactions between the peptide and a relevant biomaterial surface. The results from these simulations predict a fairly strong adsorption response with an adsorption free energy of -2.5 ± 0.6 kcal/mol (mean ±95% confidence interval), with adsorption primarily due to hydrophobic interactions between the nonpolar groups of the peptide and the PLA surface. As part of a larger and ongoing effort involving both simulation and experimental investigations, this work contributes to the goal of transforming the engineering of biomaterials from one dominated by trial-and-error to one which is guided by an atomic-level understanding of the interactions that occur at the tissue-biomaterial interface. PMID:19360943

  10. Surface free energies and elemental surface compositions of human enamel after application of commercially available mouthrinses and adsorption of salivary constituents.

    PubMed

    Perdok, J F; Van Der Mei, H C; Busscher, H J; Genet, M J; Rouxhet, P G

    1990-01-01

    The adsorption of active agents from six commercially available mouthrinses to ground and polished enamel, with and without adsorbed salivary constituents, was monitored by contact angle measurements and X-ray Photoelectron Spectroscopy (XPS). Human enamel samples were treated with mouthrinses containing chlorhexidine (Peridex), stannous fluoride/amine fluoride (Meridol), thymol/benzoic acid (Listerine), sanguinarine (Veadent), sodium fluoride (Prodent), or cetylpyridinium chloride (Merocet). XPS indicated a sizeable adsorption of both active and non-active components for all products. After treatment, all enamel surface free energies increased except for the stannous fluoride/amine fluoride containing mouthrinse. It is suggested that non-active components in the products cause an increase in surface free energy. Despite this thermodynamically unfavorable increase in surface free energy, all rinses have plaque reducing effects, indicating that this unfavorable surface characteristic is overruled by the antibacterial properties of the components. Replacement of non-active components by less adsorbing surfactants could increase the efficiency of the products tested. PMID:2090159

  11. High-Resolution Electron Energy Loss Studies of Oxygen, Hydrogen, Nitrogen, Nitric Oxide, and Nitrous Oxide Adsorption on Germanium Surfaces.

    NASA Astrophysics Data System (ADS)

    Entringer, Anthony G.

    The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting

  12. A theoretical study of water adsorption and decomposition on low-index spinel ZnGa2O4 surfaces: correlation between surface structure and photocatalytic properties.

    PubMed

    Jia, Chuanyi; Fan, Weiliu; Yang, Fei; Zhao, Xian; Sun, Honggang; Li, Pan; Liu, Li

    2013-06-11

    Water adsorption and decomposition on stoichiometrically perfect and oxygen vacancy containing ZnGa2O4 (100), (110), and (111) surfaces were investigated through periodic density functional theory (DFT) calculations. The results demonstrated that water adsorption and decomposition are surface-structure-sensitive processes. On a stoichiometrically perfect surface, the most stable molecular adsorption that could take place involved the generation of hydrogen bonds. For dissociative adsorption, the adsorption energy of the (111) surface was more than 4 times the energies of the other two surfaces, indicating it to be the best surface for water decomposition. A detailed comparison of these three surfaces showed that the primary reason for this observation was the special electronic state of the (111) surface. When water dissociated on the (111) surface, the special Ga3c-4s and 4p hybridization states at the Fermi level had an obvious downshift to the lower energies. This large energy gain greatly promoted the dissociation of water. Because the generation of O(3c) vacancy defects on the (100) and (110) surfaces could increase the stability of the dissociative adsorption states with few changes to the energy barrier, this type of defect would make the decomposition of water molecules more favorable. However, for the (111) surface, the generation of vacancy defects could decrease the stability of the dissociative adsorption states and significantly increase their energy barriers. Therefore, the decomposition of water molecules on the oxygen vacancy defective (111) surface would be less favorable than the perfect (111) surface. These findings on the decomposition of H2O on the ZnGa2O4 surfaces can be used toward the synthesis of water-splitting catalysts. PMID:23682995

  13. Phosphate adsorption on lanthanum loaded biochar.

    PubMed

    Wang, Zhanghong; Shen, Dekui; Shen, Fei; Li, Tianyu

    2016-05-01

    To attain a low-cost and high-efficient phosphate adsorbent, lanthanum (La) loaded biochar (La-BC) prepared by a chemical precipitation method was developed. La-BC and its pristine biochar (CK-BC) were comparatively characterized using zeta potential, BET surface area, scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The adsorption ability and the mechanisms during adsorption process for the La-BC samples were also investigated. La loaded on the surface of biochar can be termed as La-composites (such as LaOOH, LaONO3 and La(OH)3), leading to the decrease of negative charge and surface area of biochar. La-BC exhibited the high adsorption capacity to phosphate compared to CK-BC. Adsorption isotherm and adsorption kinetic studies showed that the Langmuir isotherm and second order model could well describe the adsorption process of La-BC, indicating that the adsorption was dominated by a homogeneous and chemical process. The calculated maximum adsorption capacity was as high as 46.37 mg g(-1) (computed in P). Thermodynamic analysis revealed that the adsorption was spontaneous and endothermic. SEM, XRD, XPS and FT-IR analysis suggested that the multi-adsorption mechanisms including precipitation, ligand exchange and complexation interactions can be evidenced during the phosphate adsorption process by La-composites in La-BC. PMID:26871732

  14. Through-thickness determination of phase composition and residual stresses in thermall barrier coatings using high- energy x-rays.

    SciTech Connect

    Weyant, , C. M.; Almer, J. D.; Faber, K. T.; Stony Brook Univ.

    2009-01-01

    High-energy X-rays were used to determine the local phase composition and residual stresses through the thickness of as-sprayed and heat-treated plasma-sprayed thermal barrier coatings consisting of a NiCoCrAlY bond coat and an yttria-stabilized zirconia (YSZ) topcoat produced with through-thickness segmentation cracks. The as-sprayed residual stresses reflected the combined influence of quenching stresses from the plasma spray process, thermal expansion mismatch between the topcoat, bond coat and substrate, and stress relief from the segmentation cracks. Heat treatments led to the formation of a thermally grown oxide (TGO) which was in compression in the plane, as well as relief of quenching stresses and development of a stress gradient in the YSZ topcoat. The high-energy X-ray technique used in this study revealed the effects that TGO and segmentation cracks have on the in-plane stress state of the entire coating.

  15. Hindrance of heavy-ion fusion at extreme sub-barrier energies in open-shell colliding systems

    NASA Astrophysics Data System (ADS)

    Jiang, C. L.; Rehm, K. E.; Esbensen, H.; Janssens, R. V.; Back, B. B.; Davids, C. N.; Greene, J. P.; Henderson, D. J.; Lister, C. J.; Pardo, R. C.; Pennington, T.; Peterson, D.; Seweryniak, D.; Shumard, B.; Sinha, S.; Tang, X. D.; Tanihata, I.; Zhu, S.; Collon, P.; Kurtz, S.; Paul, M.

    2005-04-01

    The excitation function for the fusion-evaporation reaction 64Ni+100Mo has been measured down to a cross section of ˜5 nb. Extensive coupled-channels calculations have been performed, which cannot reproduce the steep falloff of the excitation function at extreme sub-barrier energies. Thus, this system exhibits a hindrance for fusion, a phenomenon that has been discovered only recently. In the S-factor representation introduced to quantify the hindrance, a maximum is observed at Es=120.6MeV, which corresponds to 90% of the reference energy Erefs, a value expected from systematics of closed-shell systems. A systematic analysis of Ni-induced fusion reactions leading to compound nuclei with mass A=100-200 is presented in order to explore a possible dependence of fusion hindrance on nuclear structure.

  16. Protein diffusion and long-term adsorption states at charged solid surfaces.

    PubMed

    Kubiak-Ossowska, Karina; Mulheran, Paul A

    2012-11-01

    The diffusion pathways of lysozyme adsorbed to a model charged ionic surface are studied using fully atomistic steered molecular dynamics simulation. The simulations start from existing protein adsorption trajectories, where it has been found that one particular residue, Arg128 at the N,C-terminal face, plays a crucial role in anchoring the lysozyme to the surface [Langmuir 2010 , 26 , 15954 - 15965]. We first investigate the desorption pathway for the protein by pulling the Arg128 side chain away from the surface in the normal direction, and its subsequent readsorption, before studying diffusion pathways by pulling the Arg128 side chain parallel to the surface. We find that the orientation of this side chain plays a decisive role in the diffusion process. Initially, it is oriented normal to the surface, aligning in the electrostatic field of the surface during the adsorption process, but after resorption it lies parallel to the surface, being unable to return to its original orientation due to geometric constraints arising from structured water layers at the surface. Diffusion from this alternative adsorption state has a lower energy barrier of ∼0.9 eV, associated with breaking hydrogen bonds along the pathway, in reasonable agreement with the barrier inferred from previous experimental observation of lysozyme surface clustering. These results show the importance of studying protein diffusion alongside adsorption to gain full insight into the formation of protein clusters and films, essential steps in the future development of functionalized surfaces. PMID:23062108

  17. First-principles study of oxygen adsorption and diffusion on the UN(001) surface

    NASA Astrophysics Data System (ADS)

    Nie, J. L.; Ao, L.; Zu, X. T.; Huang, H.; Liu, K. Z.

    2015-12-01

    First-principles calculations have been performed to study the interaction of oxygen with UN(001) surface. The molecule oxygen was found to dissociate spontaneously on all considered adsorption sites on the surface. Atomic oxygen (O) preferred to adsorb on a hollow site or the top of uranium ions, which were energetically degenerate. Adsorption on top of nitrogen (N) ion was found to be unstable which may be attributed to the repulsion of negatively charged O with the N anions. In comparison with those on α-U(001)surface at the same coverage, the adsorption of O on UN(001) surface was found to be less stable, being about 0.7 eV higher in adsorption energy. The diffusion barrier for O on the surface was found to be ∼0.5 eV, similar to those of α-U(001)surface. The penetration of O into the substrate was difficult with a high barrier of 2.86 eV. Analysis on the density of states (DOS) has shown that the adsorbed oxygen has strong chemical interaction with surface ions, characterized by the hybridization of O 2p states with N 2p and U 6d, U 5f states.

  18. Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide.

    PubMed

    Sun, Xiaoli; Wang, Zhiguo; Fu, Y Q

    2015-01-01

    Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristine MoS2. The presence of defects causes that the Li is strongly bound to the monolayer MoS2 with adsorption energies in the range between 2.81 and 3.80 eV. The donation of Li 2s electron to the defects causes an enhancement of adsorption of Li on the monolayer MoS2. At the same time, the presence of defects does not apparently affect the diffusion of Li, and the energy barriers are in the range of 0.25-0.42 eV. The presence of the defects can enhance the energy storage capacity, suggesting that the monolayer MoS2 with defects is a suitable anode material for the Li-ion batteries. PMID:26692345

  19. Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide

    PubMed Central

    Sun, Xiaoli; Wang, Zhiguo; Fu, Y. Q.

    2015-01-01

    Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristine MoS2. The presence of defects causes that the Li is strongly bound to the monolayer MoS2 with adsorption energies in the range between 2.81 and 3.80 eV. The donation of Li 2s electron to the defects causes an enhancement of adsorption of Li on the monolayer MoS2. At the same time, the presence of defects does not apparently affect the diffusion of Li, and the energy barriers are in the range of 0.25–0.42 eV. The presence of the defects can enhance the energy storage capacity, suggesting that the monolayer MoS2 with defects is a suitable anode material for the Li-ion batteries. PMID:26692345

  20. Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide

    NASA Astrophysics Data System (ADS)

    Sun, Xiaoli; Wang, Zhiguo; Fu, Y. Q.

    2015-12-01

    Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristine MoS2. The presence of defects causes that the Li is strongly bound to the monolayer MoS2 with adsorption energies in the range between 2.81 and 3.80 eV. The donation of Li 2s electron to the defects causes an enhancement of adsorption of Li on the monolayer MoS2. At the same time, the presence of defects does not apparently affect the diffusion of Li, and the energy barriers are in the range of 0.25-0.42 eV. The presence of the defects can enhance the energy storage capacity, suggesting that the monolayer MoS2 with defects is a suitable anode material for the Li-ion batteries.

  1. First principles study of nanoscale mechanism of oxygen adsorption on lanthanum zirconate surfaces

    NASA Astrophysics Data System (ADS)

    Guo, Xingye; Wu, Linmin; Zhang, Yi; Jung, Yeon-Gil; Li, Li; Knapp, James; Zhang, Jing

    2016-09-01

    Lanthanum zirconate (La2Zr2O7) is a rare-earth pyrochlore material, which has been proposed as a promising thermal barrier coating (TBC) material due to its low thermal conductivity and high temperature phase stability. At elevated temperatures, degradation of La2Zr2O7 may occur due to adsorption of oxygen (O2) on La2Zr2O7 surfaces. This paper investigates nanoscale mechanism of O2 adsorption on La2Zr2O7 coating surfaces using the density functional theory (DFT) calculations. La2Zr2O7 surface energies on (001), (011) and (111) planes are calculated. The surface free energy of (011) plane is lower than those of (001) and (111) planes. On (001), (011) and (111) planes of La2Zr2O7, the lowest adsorption energy occurs at 4-fold site, bridge site, and 3-fold-FCC site, respectively. Among all calculated cases, the lowest adsorption energy site is 3-fold-FCC on (111) plane, which is confirmed by the Bader charge transfer analyses. Charge density difference analyses show that the 3-fold-FCC site on (111) surface has the largest charge density, suggesting the strongest interaction between O2 and La2Zr2O7 surface.

  2. Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface.

    PubMed

    Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

    2013-12-14

    The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials. PMID:24329077

  3. Adsorption and diffusion of hydrogen on Pd(211) and Pd(111): Results from first-principles electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Hong, Sampyo; Rahman, Talat S.

    2007-04-01

    We have carried out first-principles calculations of H adsorption on Pd(211) using density-functional theory with the generalized gradient approximation in the plane-wave basis to find out that the most preferred is the threefold hollow site on the terrace of Pd(211) with an adsorption energy of 0.52eV : the hcp and fcc sites being almost energetically equally favorable. For subsurface H adsorption on Pd(211), the octahedral site with an adsorption energy of 0.19eV is slightly more favorable than the tetrahedral site (0.18eV) . Our calculated activation energy barrier for H to diffuse from the preferred surface site to the subsurface one on Pd(211) is 0.33eV , as compared with 0.41eV on Pd(111). Thus, there is an enhancement of the probability of finding subsurface hydrogen in Pd(211). Additionally, we find the diffusion barriers for H on the terraces of Pd(211) to be 0.11eV , while that along the step edge to be only 0.05eV and that within the second layer (subsurface) to be 0.15eV .

  4. Adsorption and dehydrogenation mechanism of methane on clean and oxygen-covered Pd (1 0 0) surfaces: A DFT study

    NASA Astrophysics Data System (ADS)

    Jiang, Zhao; Wang, Bin; Fang, Tao

    2014-11-01

    Using density functional theory (DFT) together with periodic slab models, the adsorption and dehydrogenation mechanisms of methane on clean and oxygen-covered Pd (1 0 0) surfaces have been studied systematically. Different adsorption geometries were investigated for CH4 and related intermediates (CH3, CH2, CH, C, H, O and OH). It was found that CH4 and CH3 prefer to adsorb on the top site, CH2 and OH are favorable on the bridge site, while CH, C, O and H species adsorb preferentially on the hollow site. In addition, this work identified the stable co-adsorption configurations for the relevant co-adsorption groups. It was concluded that the effect of co-adsorbed oxygen atom tends to weaken the adsorbate-substrate interaction on the Pd (1 0 0) surface. Finally, transition states, energy barriers and reaction energies were determined to confirm the mechanism of dehydrogenation of CH4 on clean and oxygen-covered Pd (1 0 0) surfaces. The existence of oxygen atom increases the energy barriers obviously and inhibits the dissociation of CHx (x = 1, 2 and 4) except for CH3 group.

  5. Diffusion barriers

    NASA Technical Reports Server (NTRS)

    Nicolet, M. A.

    1983-01-01

    The choice of the metallic film for the contact to a semiconductor device is discussed. One way to try to stabilize a contact is by interposing a thin film of a material that has low diffusivity for the atoms in question. This thin film application is known as a diffusion barrier. Three types of barriers can be distinguished. The stuffed barrier derives its low atomic diffusivity to impurities that concentrate along the extended defects of a polycrystalline layer. Sacrificial barriers exploit the fact that some (elemental) thin films react in a laterally uniform and reproducible fashion. Sacrificial barriers have the advantage that the point of their failure is predictable. Passive barriers are those most closely approximating an ideal barrier. The most-studied case is that of sputtered TiN films. Stuffed barriers may be viewed as passive barriers whose low diffusivity material extends along the defects of the polycrystalline host.

  6. Republic of Korea Reduction of Financing Barriers for Energy Savings Performance Contracts

    SciTech Connect

    Howard, D. L.

    2005-11-01

    This paper discusses the findings developed for strengthening the role of performance contracting in improving energy efficiency in the Republic of Korea. The U.S. Environmental Protection Agency (EPA) sponsored development of this paper by the National Renewable Energy Laboratory (NREL), as a part of the Korean-U.S. Climate Technology Partnerships (CTP) program. The results and recommendations outlined in this paper together with other efforts are designed to assist other countries striving to improve their efficient use of energy.

  7. First-principles calculations of the indigo encapsulation and adsorption by MgO nanotubes

    SciTech Connect

    Sánchez-Ochoa, F. Cocoletzi, Gregorio H.; Canto, Gabriel I.; Takeuchi, Noboru

    2014-06-07

    We have performed ab-initio calculations to investigate the structural and electronic properties of (m,m) chiral magnesium oxide nanotubes, (m,m)MgONTs, to explore the encapsulation, inclusion, and adsorption of dyes (organic molecules) such as Indigo (IND). Studies start by determining the structural parameters of the MgO nanotubes with different diameters and the IND. The indigo encapsulation into the MgONT is studied considering four (m,m) chiralities which yield 4 different NT diameters. In the endohedral functionalization, the indigo is within the NT at a tilt angle as in previous theoretical studies of organic molecules inside carbon and boron-nitride nanotubes. Results show that the encapsulation is a strong exothermic process with the m = 6 case exhibiting the largest encapsulation energy. It is also explored the indigo adsorption on the NT surface in the parallel and perpendicular configurations. The perpendicular configuration of the IND adsorption on the (8,8)MgONT exhibits the largest energy. The indigo inclusion within the NTs meets a potential barrier when m < 6, however this barrier diminishes as the index increases. Additionally, we have determined the total density of states (DOS), partial DOS, electron charge redistributions, and the highest occupied molecular orbital–lowest unoccupied molecular orbital levels for the NTs with m = 6. Very strong binding energies and electron charge transfer from the IND to NTs is present in the atomic structures.

  8. First-principles calculations of the indigo encapsulation and adsorption by MgO nanotubes

    NASA Astrophysics Data System (ADS)

    Sánchez-Ochoa, F.; Cocoletzi, Gregorio H.; Canto, Gabriel I.; Takeuchi, Noboru

    2014-06-01

    We have performed ab-initio calculations to investigate the structural and electronic properties of (m,m) chiral magnesium oxide nanotubes, (m,m)MgONTs, to explore the encapsulation, inclusion, and adsorption of dyes (organic molecules) such as Indigo (IND). Studies start by determining the structural parameters of the MgO nanotubes with different diameters and the IND. The indigo encapsulation into the MgONT is studied considering four (m,m) chiralities which yield 4 different NT diameters. In the endohedral functionalization, the indigo is within the NT at a tilt angle as in previous theoretical studies of organic molecules inside carbon and boron-nitride nanotubes. Results show that the encapsulation is a strong exothermic process with the m = 6 case exhibiting the largest encapsulation energy. It is also explored the indigo adsorption on the NT surface in the parallel and perpendicular configurations. The perpendicular configuration of the IND adsorption on the (8,8)MgONT exhibits the largest energy. The indigo inclusion within the NTs meets a potential barrier when m < 6, however this barrier diminishes as the index increases. Additionally, we have determined the total density of states (DOS), partial DOS, electron charge redistributions, and the highest occupied molecular orbital-lowest unoccupied molecular orbital levels for the NTs with m = 6. Very strong binding energies and electron charge transfer from the IND to NTs is present in the atomic structures.

  9. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations.

    PubMed

    Wang, Xinye; Huang, Yaji; Pan, Zhigang; Wang, Yongxing; Liu, Changqi

    2015-09-15

    Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl2 molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl2. Considering the energy barriers, it is easy for PbO and PbCl2 to adsorb on Al surfaces but difficult to escape. The high energy barriers of de-HCl process cause the difficulties of PbCl2 to form PbO·Al2O3·2SiO2 with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent. PMID:25880048

  10. Depositional response to seagrass mortality along a low-energy, barrier-island coast: west-central Florida

    SciTech Connect

    Evans, M.W.; Hine, A.C.; David, R.A.; Belknap, D.F.

    1985-01-01

    Analysis of aerial photographs and surficial sediment samples from the northern islands of the west-central barrier system of Florida indicates that: (1) seagrass beds in the nearshore zone have controlled onshore/longshore sand transport, and (2) resulting sedimentary accumulations within nearshore seagrass beds make differentiation of nearshore and backbarrier facies difficult. Between 1957 and 1973, an extensive seagrass community occupying the nearshore zone off Anclote Key disappeared, thus allowing the sudden and rapid onshore and longshore transport of sand. The 1000 year old barrier island lengthened 30% by recurved spit growth in this very short period of time. Although there are not direct observations, four possible causes of seagrass mortality have been postulated, and of these overgrazing as a result of the accelerated population growth of sea urchins (Lytechinus variegatus) seems to be the most likely cause. Because of the ability of seagrasses to trap fine-grained sediments, contribute organic matter, and provide for low-energy, sheltered, molluscan biocoenosis, there is little depositional difference between these nearshore and backbarrier/lagoonal facies. This work indicates that the development and destruction of benthic floral communities should be considered as a process that generates or accentuates episodicity/cyclicity in the sedimentary record. Additionally, such changes in these communities should be expected to present a blurred distinction between certain types of coastal sedimentary facies.

  11. High-energy electron-energy spectra of atoms undergoing tunneling and barrier-suppression ionization by superintense linearly polarized laser radiation

    SciTech Connect

    Krainov, V.P.; Sofronov, A.V.

    2004-01-01

    The high-energy electron-energy spectra of atoms and atomic ions undergoing direct tunneling or barrier-suppression ionization by superintense linearly polarized femtosecond laser pulse are derived. The Landau-Dykhne adiabatic approximation is used. The new result is the simple analytic expression for the electron momentum spectrum along the polarization axis and along the other directions in the case of the relativistic quiver electron energies. The contribution from the direct tunneling ionization exceeds the contribution from the ionization occurring in the rescattering processes. The energy spectrum is independent of the laser frequency and of the nonrelativistic ionization potential of the atom (atomic ion) considered. The conclusions have been made that (1) the drift electron energy along the polarization axis is much greater than in other directions. (2) the energy distribution depends on the sign of the electron drift momentum along the propagation of laser radiation, and (3) the electron drift energy is the nonrelativistic quantity even when the quiver electron energy has high ultrarelativistic values.

  12. Additive effects on the energy barrier for synaptic vesicle fusion cause supralinear effects on the vesicle fusion rate

    PubMed Central

    Schotten, Sebastiaan; Meijer, Marieke; Walter, Alexander Matthias; Huson, Vincent; Mamer, Lauren; Kalogreades, Lawrence; ter Veer, Mirelle; Ruiter, Marvin; Brose, Nils; Rosenmund, Christian

    2015-01-01

    The energy required to fuse synaptic vesicles with the plasma membrane (‘activation energy’) is considered a major determinant in synaptic efficacy. From reaction rate theory, we predict that a class of modulations exists, which utilize linear modulation of the energy barrier for fusion to achieve supralinear effects on the fusion rate. To test this prediction experimentally, we developed a method to assess the number of releasable vesicles, rate constants for vesicle priming, unpriming, and fusion, and the activation energy for fusion by fitting a vesicle state model to synaptic responses induced by hypertonic solutions. We show that complexinI/II deficiency or phorbol ester stimulation indeed affects responses to hypertonic solution in a supralinear manner. An additive vs multiplicative relationship between activation energy and fusion rate provides a novel explanation for previously observed non-linear effects of genetic/pharmacological perturbations on synaptic transmission and a novel interpretation of the cooperative nature of Ca2+-dependent release. DOI: http://dx.doi.org/10.7554/eLife.05531.001 PMID:25871846

  13. Entrance Channel Mass Asymmetry Effects in Sub-Barrier Fusion Dynamics by Using Energy Dependent Woods-Saxon Potential

    NASA Astrophysics Data System (ADS)

    Manjeet Singh, Gautam

    2015-12-01

    The present article highlights the inconsistency of static Woods-Saxon potential and the applicability of energy dependent Woods-Saxon potential to explore the fusion dynamics of {}4822Ti+58,60,6428Ni, {}4622Ti+{}6428Ni,{}5022Ti+{}6028Ni, and {}199F+9341Nb reactions leading to formation of different Sn-isotopes via different entrance channels. Theoretical calculations based upon one-dimensional Wong formula obtained by using static Woods-Saxon potential unable to provide proper explanation for sub-barrier fusion enhancement of these projectile-target combinations. However, the predictions of one-dimensional Wong formula based upon energy dependent Woods-Saxon potential model (EDWSP model) accurately describe the observed fusion dynamics of these systems wherein the significantly larger value of diffuseness parameter ranging from a = 0.85 fm to a = 0.97 fm is required to address the experimental data in whole range of energy. Therefore, the energy dependence in nucleus-nucleus potential simulates the influence of the nuclear structure degrees of freedom of the colliding pairs. Supported by Dr. D.S. Kothari Post-Doctoral Fellowship Scheme sponsored by University Grants Commission (UGC), New Delhi, India

  14. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies

    DOE PAGESBeta

    Srinivasan, Sriram Goverapet; Shivaramaiah, Radha; Kent, Paul R. C.; Stack, Andrew G.; Navrotsky, Alexandra; Riman, Richard; Anderko, Andre; Bryantsev, Vyacheslav S.

    2016-07-11

    Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La bastnsite is isomorphic to themore » structure of Ce bastnasite belonging to the P2c space group, while the Inorganic Crystal Structure Database structure in the P2m space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La bastnasite to support these theoretical findings. Six different surfaces are studied by DFT, namely [100], [0001], [101], [102], [104] and [112]. Among these, the [100] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La bastnasite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [100] and [0001] facets, chiseled at its ends by the [101] and [102] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnasite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of the bastnasite water interface and designing

  15. Nucleon-nucleon correlations in heavy ion transfer reactions: Recent investigations at energies far below the Coulomb barrier

    SciTech Connect

    Corradi, Lorenzo

    2015-10-15

    Excitation functions of one- and two-neutron transfer channels have been measured for the {sup 96}Zr+{sup 40}Ca and {sup 116}Sn+{sup 60}Ni systems at bombarding energies ranging from the Coulomb barrier to ∼25% below. Target-like recoils have been identified in A, Z and velocity with the large solid angle magnetic spectrometer PRISMA. The experimental transfer probabilities have been compared, in absolute values and in slope, with semiclassical microscopic calculations which incorporate nucleon-nucleon pairing correlations. For the first time in a heavy ion collision, one was able to provide a consistent description of one and two neutron transfer reactions by incorporating, in the reaction mechanism, all known structure information of entrance and exit channels nuclei. In particular, there is no need to introduce any enhancement factor for the description of two neutron transfer, of course very important are the correlations induced by the pairing interaction.

  16. Total and partial capture cross sections in reactions with deformed nuclei at energies near and below the Coulomb barrier

    SciTech Connect

    Kuzyakin, R. A. Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.

    2013-06-15

    Within the quantum diffusion approach, the capture of a projectile nucleus by a target nucleus is studied at bombarding energies above and below the Coulomb barrier. The effects of deformation of interacting nuclei and neutron transfer between them on the total and partial capture cross sections and the mean angular momentum of the captured system are studied. The results obtained for the {sup 16}O + {sup 112}Cd, {sup 152}Sm, and {sup 184}W; {sup 19}F +{sup 175}Lu; {sup 28}Si +{sup 94,100}Mo and {sup 154}Sm; {sup 40}Ca +{sup 96}Zr; {sup 48}Ca+ {sup 90}Zr; and {sup 64}Ni +{sup 58,64}Ni, {sup 92,96}Zr, and {sup 100}Mo reactions are in good agreement with available experimental data.

  17. Total and partial capture cross sections in reactions with deformed nuclei at energies near and below the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Kuzyakin, R. A.; Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.

    2013-06-01

    Within the quantum diffusion approach, the capture of a projectile nucleus by a target nucleus is studied at bombarding energies above and below the Coulomb barrier. The effects of deformation of interacting nuclei and neutron transfer between them on the total and partial capture cross sections and the mean angular momentum of the captured system are studied. The results obtained for the 16O + 112Cd, 152Sm, and 184W; 19F +175Lu; 28Si +94,100Mo and 154Sm; 40Ca +96Zr; 48Ca+ 90Zr; and 64Ni +58,64Ni, 92,96Zr, and 100Mo reactions are in good agreement with available experimental data.

  18. π adsorption of ethene on to the {111} surface of copper. A periodic ab initio study of the effect of k-point sampling on the energy, atomic and electronic structure

    NASA Astrophysics Data System (ADS)

    Watson, G. W.; Wells, R. P. K.; Willock, D. J.; Hutchings, G. J.

    2000-07-01

    The adsorption of ethene on the {111} surface of copper has been studied by using density functional theory calculations with gradient corrections. The surface is described by a periodic (3×3) slab, three layers thick, with ethene adsorbed on one side. The energy of the adsorption shows great sensitivity to the k-point sampling employed, with single k-point calculations overestimating the binding by over 800% when compared with a calculation converged with respect to the k-point sampling. In addition, the structure of the adsorbed molecule is considerably distorted, which is in contradiction with conclusions drawn from the experimental vibrational frequencies. Calculations that are converged with respect to the k-point sampling indicate a much weaker interaction between the molecule and the surface, with adsorption energies of 11.1 and 10.9 kJ mol -1 for atop-h and atop-b, respectively. This weaker interaction leads to a geometry for the adsorbed molecule that is close to the gas-phase ethene structure, in agreement with the vibrational frequencies. We have proposed a model of molecular adsorption that is a balance between attraction, resulting from localised bond formation, and repulsion, due to interaction between the extended electronic states and the molecule's electron density. If the extended electronic states are underestimated, as in cluster or low k-point calculations, the repulsion is underestimated. This results in stronger bonding to the surface and overestimation of the adsorption energy.

  19. Characterization of volatile organic compound adsorption on multiwall carbon nanotubes under different levels of relative humidity using linear solvation energy relationship.

    PubMed

    Li, Mei-Syue; Wu, Siang Chen; Shih, Yang-Hsin

    2016-09-01

    Multiwall carbon nanotubes (MWCNTs) have been used as an adsorbent for evaluating the gas/solid partitioning of selected volatile organic compounds (VOCs). In this study, 15 VOCs were probed to determine their gas/solid partitioning coefficient (LogKd) using inverse gas chromatography at different relative humidity (RH) levels. Interactions between MWCNTs and VOCs were analyzed by regressing the observed LogKd with the linear solvation energy relationship (LSER). The results demonstrate that the MWCNT carbonyl and carboxyl groups provide high adsorption capacity for the VOCs (LogKd 3.72-5.24g/kg/g/L) because of the π-/n-electron pair interactions and hydrogen-bond acidity. The increasing RH gradually decreased the LogKd and shifted the interactions to dipolarity/polarizability, hydrogen-bond basicity, and cavity formation. The derived LSER equations provided adequate fits of LogKd, which is useful for VOC-removal processes and fate prediction of VOC contaminants by MWCNT adsorption in the environment. PMID:27152974

  20. Exploring the interfacial structure of protein adsorbates and the kinetics of protein adsorption: an in situ high-energy X-ray reflectivity study.

    PubMed

    Evers, Florian; Shokuie, Kaveh; Paulus, Michael; Sternemann, Christian; Czeslik, Claus; Tolan, Metin

    2008-09-16

    The high energy X-ray reflectivity technique has been applied to study the interfacial structure of protein adsorbates and protein adsorption kinetics in situ. For this purpose, the adsorption of lysozyme at the hydrophilic silica-water interface has been chosen as a model system. The structure of adsorbed lysozyme layers was probed for various aqueous solution conditions. The effect of solution pH and lysozyme concentration on the interfacial structure was measured. Monolayer formation was observed for all cases except for the highest concentration. The adsorbed protein layers consist of adsorbed lysozyme molecules with side-on or end-on orientation. By means of time-dependent X-ray reflectivity scans, the time-evolution of adsorbed proteins was monitored as well. The results of this study demonstrate the capabilities of in situ X-ray reflectivity experiments on protein adsorbates. The great advantages of this method are the broad wave vector range available and the high time resolution. PMID:18715021

  1. Wave energies and wave-induced longshore currents in an unstructured-grid model - circulation in front of barrier islands

    NASA Astrophysics Data System (ADS)

    Jörg-Olaf Wolff, , Prof. _., Dr.; Grashorn, Sebastian, , Dr.; Lettmann, Karsten A., , Dr.; Badewien, Thomas H., , Dr.; Stanev, Emil V., Prof. _., Dr.

    2015-04-01

    An unstructured-grid model (FVCOM) coupled to a wave model (FVCOM-SWAVE) is used to investigate the hydrodynamic and wave energy conditions during a moderate and a storm situation in the southern North Sea. Two different setups are presented. One setup covers the whole North Sea with moderately increased grid resolution at the coast, whereas the other comprises a very high resolution East Frisian Wadden Sea setup, one-way coupled to the coarser North Sea model. The results of both model setups are validated, compared to each other and analysed with a focus on longshore currents and wave energy. The results show that during storm conditions strong wave-induced longshore currents occur in front of the barrier islands of the East Frisian Wadden Sea, resulting in total current speeds up to 2 m/s. This effect is especially pronounced in the high-resolution setup. The wave-current interaction also influences the sea surface elevation by raising the water level in the tidal basins. Calculated wave energies show large differences between moderate wind and storm conditions with time-averaged values up to 200 kW/m. The numerical results indicate that wave-current coupling, albeit numerically expensive, cannot be ignored because it plays an important role in almost all near coastal transport phenomena (sediments, contaminants, bacteria, etc.).

  2. Ab initio study of silane and disilane adsorption on Si(100)-(2x1) surface

    NASA Astrophysics Data System (ADS)

    Huang, Min; Randall, John; Chabal, Yves J.; Wallace, Robert M.; Cho, Kyeongjae

    2010-03-01

    Silane (SiH4) and disilane (Si2H6) are common precursors for the growth of Si and SiO2 thin films for microelectronic and photovoltaic devices. The adsorption of silane and disilane on Si(100)-(2x1) surface, which are important steps in the growth of Si films in atomic layer epitaxy (ALE), were investigated using density functional theory calculations. The silane molecule dissociates on the Si surface at the intra-dimer site with barrier energy of 0.22 eV. We investigate both Si-Si bond cleavage and Si-H bond cleavage mechanisms for adsorption of Si2H6 on Si (100) surface. A Si-H bond cleavage mechanism was found to be more favored than Si-Si bond cleavage mechanism due to the lower barrier energy of 0.04 eV. The lower barrier energy for Si2H6 dissociation than that of SiH4 agrees well with the experimental results showing that Si2H6 has higher sticking coefficient than SiH4 on Si surface at 300K. The vibration frequencies of Si2H5, SiH3, SiH2, SiH resulting from dissociation of silane and disilane were calculated and compared with experimental results available. The simulation results will facilitate the controlled ALE for atomically precise manufacturing applications.

  3. Adsorption and plasma-catalytic oxidation of acetone over zeolite-supported silver catalyst

    NASA Astrophysics Data System (ADS)

    Trinh, Quang Hung; Sanjeeva Gandhi, M.; Mok, Young Sun

    2015-01-01

    The abatement of acetone using a combination of non-thermal plasma, catalysis and adsorption was investigated in a dielectric barrier discharge plasma reactor packed with silver-coated zeolite pellets serving as both adsorbent and catalyst. The removal of acetone in this reactor system was carried out by cyclic operation comprising two repetitive steps, namely, adsorption followed by plasma-catalytic oxidation. The effects of the zeolite-supported silver catalyst on the reduction of unwanted ozone emission and the behavior for the formation of gaseous byproducts were examined. The experimental results showed that the zeolite-supported catalyst had a high acetone adsorption capacity of 1.07 mmol g-1 at 25 °C. Acetone with a concentration of 300 ppm was removed from the gas stream and enriched on the zeolite surface during the adsorption step of the cyclic process (100 min). In the succeeding step, the adsorbed acetone was plasma-catalytically treated under oxygen-flowing atmosphere to recover the adsorption capability of the surface. The plasma-catalytic oxidation of the acetone adsorbed in the previous 100 min adsorption step was completed in 15 min. The abatement of acetone by the cyclic adsorption and plasma-catalytic oxidation process was able to increase the performance of the reactor with respect to the energy efficiency, compared to the case of continuous plasma-catalytic treatment. The use of the zeolite-supported silver catalyst largely decreased the emission of unreacted ozone and increased the amount of gaseous byproducts such as carbon oxides and aldehydes due to the enhanced oxidation of the adsorbed acetone and intermediates.

  4. Energy dependence of the optical potentials for the 9Be +208Pb and 9Be +209Bi systems at near-Coulomb-barrier energies

    NASA Astrophysics Data System (ADS)

    Gómez Camacho, A.; Yu, N.; Zhang, H. Q.; Gomes, P. R. S.; Jia, H. M.; Lubian, J.; Lin, C. J.

    2015-04-01

    We analyze the energy dependence of the interacting optical potential, at near barrier energies, for two systems involving the weakly bound projectile 9Be and the heavy 208Pb and 209Bi targets, by the simultaneous fit of elastic scattering angular distributions and fusion excitation functions. The approach used consists of dividing the optical potential into two parts. A short-range potential VF+i WF that is responsible for fusion, and a superficial potential VDR+i WDR for direct reactions. It is found, for both systems studied, that the fusion imaginary potential WF presents the usual threshold anomaly (TA) observed in tightly bound systems, whereas the direct reaction imaginary potential WDR shows a breakup threshold anomaly (BTA) behavior. Both potentials satisfy the dispersion relation. The direct reaction polarization potential predominates over the fusion potential and so a net overall behavior is found to follow the BTA phenomenon.

  5. Elastic scattering for the system {sup 6}Li+p at near barrier energies with MAGNEX

    SciTech Connect

    Soukeras, V.; Pakou, A.; Sgouros, O.; Cappuzzello, F.; Bondi, M.; Nicolosi, D.; Acosta, L.; Marquinez-Duran, G.; Martel, I.; Agodi, C.; Carbone, D.; Cavallaro, M.; Cunsolo, A.; Di Pietro, A.; Fernández-García, J. P.; Figuera, P.; Fisichella, M.; Alamanos, N.; De Napoli, M.; Foti, A.; and others

    2015-02-24

    Elastic scattering measurements have been performed for the {sup 6}Li+p system in inverse kinematics at the energies of 16, 20, 25 and 29 MeV. The heavy ejectile was detected by the large acceptance MAGNEX spectrometer at the Laboratori Nazionali del Sud (LNS) in Catania, in the angular range between ∼2{sup 0} and 12{sup 0} in the laboratory system, giving us the possibility to span almost a full angular range in the center of mass system. Results will be presented and discussed for one of the energies.

  6. High Penetration of Renewable Energy in the Transportation Sector: Scenarios, Barriers, and Enablers; Preprint

    SciTech Connect

    Vimmerstedt, L.; Brown, A.; Heath, G.; Mai, T.; Ruth, M.; Melaina, M.; Simpkins, T.; Steward, D.; Warner, E.; Bertram, K.; Plotkin, S.; Patel, D.; Stephens, T.; Vyas, A.

    2012-06-01

    Transportation accounts for 71% of U.S. petroleum use and 33% of its greenhouse gases emissions. Pathways toward reduced greenhouse gas emissions and petroleum dependence in the transportation sector have been analyzed in considerable detail, but with some limitations. To add to this knowledge, the U.S. Department of Energy has launched a study focused on underexplored greenhouse-gas-abatement and oil-savings opportunities related to transportation. This Transportation Energy Futures study analyzes specific issues and associated key questions to strengthen the existing knowledge base and help cultivate partnerships among federal agencies, state and local governments, and industry.

  7. Water adsorption and dissociation on Ni(110): How is it different from its close packed counterparts?

    SciTech Connect

    Seenivasan, H.; Tiwari, Ashwani K.

    2014-05-07

    Water adsorption and dissociation on Ni(110) surface is studied in detail and compared with its close packed counterparts using density functional theory calculations. Water adsorption occurs on the top site as found on Ni(100) and Ni(111) but the adsorption is stronger on Ni(110). H and OH preferably adsorb on the short bridge sites (brgshort) opposed to hollow sites on (100) and (111) surfaces. Energy barriers for water molecule dissociation on Ni(110) as obtained from the transition state (TS) calculations were low compared to other Ni low indexed surfaces. TS geometries at different positions of the lattice coordinate, Q, were obtained to study the effect of surface temperature on dissociation of H{sub 2}O molecules. These calculations revealed that second layer atoms were also involved in the TS. Dissociation probabilities are obtained using a semi-classical approximation by sampling Q for a Boltzmann distribution at different temperatures. Results showed that the increasing surface temperature significantly increases the dissociation probabilities at lower energies and saturates near the barrier for dissociation. Although the contribution from both top and second layers is similar at low surface temperatures, motion of top layer atoms contribute more towards dissociation probability at higher surface temperatures. Dissociation probabilities obtained are more than one order of magnitude higher than that on Ni(100) and Ni(111) surfaces suggesting Ni(110) to be more reactive among the low indexed Ni surfaces.

  8. Comparisons between adsorption and diffusion of alkali, alkaline earth metal atoms on silicene and those on silicane: Insight from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Bo, Xu; Huan-Sheng, Lu; Bo, Liu; Gang, Liu; Mu-Sheng, Wu; Chuying, Ouyang

    2016-06-01

    The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory. Silicane is staler against the metal adatoms than silicene. Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene. Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed. However, the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate. Combining the adsorption energy with the diffusion energy barriers, it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage. In order to avoid forming a metal cluster, we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane. Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials. Project supported by the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20152ACB21014, 20151BAB202006, and 20142BAB212002) and the Fund from the Jiangxi Provincial Educational Committee, China (Grant No. GJJ14254). Bo Xu is also supported by the Oversea Returned Project from the Ministry of Education, China.

  9. Constraining the Symmetry Energy:. a Journey in the Isospin Physics from Coulomb Barrier to Deconfinement

    NASA Astrophysics Data System (ADS)

    di Toro, M.; Colonna, M.; Greco, V.; Ferini, G.; Rizzo, C.; Rizzo, J.; Baran, V.; Gaitanos, T.; Prassa, V.; Wolter, H. H.; Zielinska-Pfabe, M.

    Heavy Ion Collisions (HIC) represent a unique tool to probe the in-medium nuclear interaction in regions away from saturation. In this work we present a selection of reaction observables in dissipative collisions particularly sensitive to the isovector part of the interaction, i.e.to the symmetry term of the nuclear Equation of State (EoS). At low energies the behavior of the symmetry energy around saturation influences dissipation and fragment production mechanisms. We will first discuss the recently observed Dynamical Dipole Radiation, due to a collective neutron-proton oscillation during the charge equilibration in fusion and deep-inelastic collisions. Important Iso - EOS are stressed. Reactions induced by unstable 132Sn beams appear to be very promising tools to test the sub-saturation Isovector EoS. New Isospin sensitive observables are also presented for deep-inelastic, fragmentation collisions and Isospin equilibration measurements (Imbalance Ratios). The high density symmetry term can be derived from isospin effects on heavy ion reactions at relativistic energies (few AGeV range), that can even allow a "direct" study of the covariant structure of the isovector interaction in the hadron medium. Rather sensitive observables are proposed from collective flows and from pion/kaon production. The possibility of the transition to a mixed hadron-quark phase, at high baryon and isospin density, is finally suggested. Some signatures could come from an expected "neutron trapping" effect. The importance of studying violent collisions with radioactive beams from low to relativistic energies is finally stressed.

  10. The role of couplings in nuclear rainbow formation at energies far above the barrier

    SciTech Connect

    Pereira, D.; Linares, R.; and others

    2012-10-20

    A study of the {sup 16}O+{sup 28}Si elastic and inelastic scattering is presented in the framework of Coupled Channel theory. The Sao Paulo Potential is used in the angular distribution calculations and compared with the existing data at 75 MeV bombarding energy. A nuclear rainbow pattern is predicted and becomes more clear above 100 MeV.

  11. Edge energy transport barrier and turbulence in the I-mode regime on Alcator C-Moda)

    NASA Astrophysics Data System (ADS)

    Hubbard, A. E.; Whyte, D. G.; Churchill, R. M.; Cziegler, I.; Dominguez, A.; Golfinopoulos, T.; Hughes, J. W.; Rice, J. E.; Bespamyatnov, I.; Greenwald, M. J.; Howard, N.; Lipschultz, B.; Marmar, E. S.; Reinke, M. L.; Rowan, W. L.; Terry, J. L.

    2011-05-01

    We report extended studies of the I-mode regime [Whyte et al., Nucl. Fusion 50, 105005 (2010)] obtained in the Alcator C-Mod tokamak [Marmar et al., Fusion Sci. Technol. 51(3), 3261 (2007)]. This regime, usually accessed with unfavorable ion B × ∇B drift, features an edge thermal transport barrier without a strong particle transport barrier. Steady I-modes have now been obtained with favorable B × ∇B drift, by using specific plasma shapes, as well as with unfavorable drift over a wider range of shapes and plasma parameters. With favorable drift, power thresholds are close to the standard scaling for L-H transitions, while with unfavorable drift they are ˜ 1.5-3 times higher, increasing with Ip. Global energy confinement in both drift configurations is comparable to H-mode scalings, while density profiles and impurity confinement are close to those in L-mode. Transport analysis of the edge region shows a decrease in edge χeff, by typically a factor of 3, between L- and I-mode. The decrease correlates with a drop in mid-frequency fluctuations (f ˜ 50-150 kHz) observed on both density and magnetics diagnostics. Edge fluctuations at higher frequencies often increase above L-mode levels, peaking at f ˜ 250 kHz. This weakly coherent mode is clearest and has narrowest width (Δf/f ˜ 0.45) at low q95 and high Tped, up to 1 keV. The Er well in I-mode is intermediate between L- and H-mode and is dominated by the diamagnetic contribution in the impurity radial force balance, without the Vpol shear typical of H-modes.

  12. Fusion cross section of 12C+13C at sub-barrier energies

    NASA Astrophysics Data System (ADS)

    Zhang, N. T.; Tang, X. D.; Chen, H.; Chesneanu, D.; Straticiuc, M.; Trache, L.; Burducea, I.; Li, K. A.; Li, Y. J.; Ghita, D. G.; Margineanu, R.; Pantelica, A.; Gomoiu, C.

    2016-02-01

    In the recent work at Notre Dame, correlations between three carbon isotope fusion systems have been studied and it is found that the fusion cross sections of 12C+13Cand 13C+13C provide an upper limit on the fusion cross section of the astrophysically important 12C+12C reaction.The aim of this work is to continue such research by measuring the fusion cross section of the 12C+13C reaction to lower energies. In this experiment, the off-line activity measurement was performed in the ultra-low background laboratory 12C+13C and the fusion cross section for has been determined in the energy range of Ec.m. =2.5-6.8 MeV. Comparison between this work and several models is also presented.

  13. Angular anisotropy of photofission of even-even nuclei at above-barrier energies

    SciTech Connect

    Rudnikov, V.E.; Smirenkin, G.N.; Soldatov, A.S.; Juhasz, S.

    1988-09-01

    Results of measurements are presented for angular distributions of photofission fragments of /sup 232/Th and /sup 234//sup ,//sup 236//sup ,//sup 238/U by bremsstrahlung ..gamma.. rays in the maximum energy range of E/sub max/ = 6--10 MeV. The observed angular anisotropy of photofission is discussed as a function of E/sub max/ and the nucleon composition of the nucleus.

  14. Potential Energy Surfaces of Oxygen Vacancies in Rutile TiO2: Configuration Coordinate and Migration Barrier Schemes

    NASA Astrophysics Data System (ADS)

    Kazempour, Ali

    2013-09-01

    Applying the screened hybrid functional Heyd-Scuseria-Ernzerhof (HSE) method, we studied the polaronic degree of freedom of different charged oxygen vacancies Vo in rutile TiO2. The HSE method not only corrects the band gap, but also allows for correct polaron localization. Due to the important role of phonon in oxygen vacancy associated levels in the gap, we calculated configuration coordinate (CC) potential energy surfaces for all charged Vo's. Our calculated CC diagrams with effective impression on host states, show significant improvement of electron-lattice interaction compared to semi(local) DFT methods. The obtained values of stokes shifts for sequential transitions of charged vacancies agree well with experimental evidences which confirm Ti3+ centers are responsible for photoluminescence. In addition, we explored the effect of polaron localization on diffusive mechanism of Vo along most open [001] direction. Calculated values of migration barriers for V o2+ are found to be in quantitative agreement with experimental migration energy [E. Iguchi and K. Yajima, J. Phys. Soc. Jpn.32 (1971) 1415] of 2.4 eV. These results highlight the small polaronic behavior of Vo's and is consistent with studies suggest the polaronic hopping model for electron transport of n-type conductivity in reduced TiO2 [J.-F. Baumard and F. Gervais, Phys. Rev. B15 (1977) 2316-2323].

  15. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    DOE PAGESBeta

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom inmore » the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).« less

  16. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).

  17. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-28

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)

  18. /sup 64/Ni +/sup 92/Zr fission yields at energies close to the Coulomb barrier

    SciTech Connect

    Wolfs, F.L.H.; Janssens, R.V.F.; Holzmann, R.; Khoo, T.L.; Ma, W.C.; Sanders, S.J.

    1989-03-01

    Fission yields for the /sup 64/Ni+/sup 92/Zr reaction at laboratory energies between 240 and 300 MeV have been measured. ''Elastic scattering'' angular distributions were also obtained and used to deduce the generalized total reaction cross sections. The competition between fission and light-particle evaporation from the compound nucleus is well reproduced by statistical-model calculations. However, the calculated neutron multiplicities for this reaction are larger than those previously measured. Possible reasons for this discrepancy are discussed.

  19. Electrical swing adsorption gas storage and delivery system

    DOEpatents

    Judkins, Roddie R.; Burchell, Timothy D.

    1999-01-01

    Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided.

  20. Electrical swing adsorption gas storage and delivery system

    DOEpatents

    Judkins, R.R.; Burchell, T.D.

    1999-06-15

    Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided. 5 figs.

  1. The energy barrier in singlet fission can be overcome through coherent coupling and entropic gain

    NASA Astrophysics Data System (ADS)

    Chan, Wai-Lun; Ligges, Manuel; Zhu, X.-Y.

    2012-10-01

    One strategy to improve solar-cell efficiency is to generate two excited electrons from just one photon through singlet fission, which is the conversion of a singlet (S1) into two triplet (T1) excitons. For efficient singlet fission it is believed that the cumulative energy of the triplet states should be no more than that of S1. However, molecular analogues that satisfy this energetic requirement do not show appreciable singlet fission, whereas crystalline tetracene displays endothermic singlet fission with near-unity quantum yield. Here we probe singlet fission in tetracene by directly following the intermediate multiexciton (ME) state. The ME state is isoenergetic with 2 × T1, but fission is not activated thermally. Rather, an S1 ⇔ ME superposition formed through a quantum-coherent process allows access to the higher-energy ME. We attribute entropic gain in crystalline tetracene as the driving force for the subsequent decay of S1 ⇔ ME into 2 × T1, which leads to a high singlet-fission yield.

  2. Experimental evidence for a fusion enhancement in 19O+12C at near barrier energies

    NASA Astrophysics Data System (ADS)

    Singh, Varinderjit; Steinbach, T. K.; Vadas, J.; Wiggins, B. B.; Hudan, S.; Desouza, R. T.; Baby, L. T.; Tripathi, V.; Kuvin, S. A.; Wiedenhover, I.; Umar, A. S.; Oberacker, V. E.

    2016-03-01

    Fusion of neutron-rich light nuclei in the outer crust of an accreting neutron star has been proposed as responsible for triggering X-ray super-bursts. The underlying hypothesis in this proposition is that the fusion of neutron-rich nuclei is enhanced as compared to stable nuclei. To investigate this hypothesis, an experiment has been performed to measure the fusion excitation function for 18O and 19O nuclei incident on a 12C target. A beam of 19O was produced by the 18O(d,p) reaction at Florida State University and separated using the RESOLUT mass spectrometer. The resulting 19O beam bombarded a 100 μg/cm2 12C target at an intensity of 2-4 x 104p/s. Evaporation residues resulting from the de-excitation of the fusion product were distinguished by measuring their energy and time-of-flight. Evaporation residues were detected with high efficiency by measuring them in the angular range 4.4° <=θlab <= 11.7°. The fusion cross-section has been measured down to 170 mb level. As compared to 18O+12C the fusion cross-section for 19O+12C is enhanced by approximately a factor of 3 times at the lowest energy measured. The measured excitation function will be compared with theoretical calculations. Supported by the US DOE under Grant No. DEFG02-88ER-40404.

  3. The impact of the competitive adsorption of ions at surface sites on surface free energies and surface forces

    NASA Astrophysics Data System (ADS)

    Parsons, Drew F.; Salis, Andrea

    2015-04-01

    The relationship between surface charge and surface potential at the solid-liquid interface is often determined by a charge regulation process, the chemisorption of a potential determining ion such as H+. A subtle ion-specific effect can be observed when other ions compete with the primary potential determining ion to bind to a surface site. Site competition may involve alternative ions competing for a first binding site, e.g., metals ions competing with H+ to bind to a negatively charged oxide or carboxyl site. Second-binding sites with site competition may also be found, including amphoteric OH2+ sites, or anion binding to amine groups. In this work, a general theoretical model is developed to describe the competitive adsorption of ions at surface sites. Applied to the calculation of forces, the theory predicts a 20% increase in repulsion between titania surfaces in 1 mM NaCl, and a 25% reduction in repulsion between silica surfaces in 0.1M NaCl compared to calculations neglecting ion site competition.

  4. The impact of the competitive adsorption of ions at surface sites on surface free energies and surface forces.

    PubMed

    Parsons, Drew F; Salis, Andrea

    2015-04-01

    The relationship between surface charge and surface potential at the solid-liquid interface is often determined by a charge regulation process, the chemisorption of a potential determining ion such as H(+). A subtle ion-specific effect can be observed when other ions compete with the primary potential determining ion to bind to a surface site. Site competition may involve alternative ions competing for a first binding site, e.g., metals ions competing with H(+) to bind to a negatively charged oxide or carboxyl site. Second-binding sites with site competition may also be found, including amphoteric OH2 (+) sites, or anion binding to amine groups. In this work, a general theoretical model is developed to describe the competitive adsorption of ions at surface sites. Applied to the calculation of forces, the theory predicts a 20% increase in repulsion between titania surfaces in 1 mM NaCl, and a 25% reduction in repulsion between silica surfaces in 0.1M NaCl compared to calculations neglecting ion site competition. PMID:25854258

  5. Energy-Efficient Phase-Change Memory with Graphene as a Thermal Barrier.

    PubMed

    Ahn, Chiyui; Fong, Scott W; Kim, Yongsung; Lee, Seunghyun; Sood, Aditya; Neumann, Christopher M; Asheghi, Mehdi; Goodson, Kenneth E; Pop, Eric; Wong, H-S Philip

    2015-10-14

    Phase-change memory (PCM) is an important class of data storage, yet lowering the programming current of individual devices is known to be a significant challenge. Here we improve the energy-efficiency of PCM by placing a graphene layer at the interface between the phase-change material, Ge2Sb2Te5 (GST), and the bottom electrode (W) heater. Graphene-PCM (G-PCM) devices have ∼40% lower RESET current compared to control devices without the graphene. This is attributed to the graphene as an added interfacial thermal resistance which helps confine the generated heat inside the active PCM volume. The G-PCM achieves programming up to 10(5) cycles, and the graphene could further enhance the PCM endurance by limiting atomic migration or material segregation at the bottom electrode interface. PMID:26308280

  6. Multinucleon transfer study in 206Pb(18O,x ) at energies above the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Sonika, Roy, B. J.; Parmar, A.; Pal, U. K.; Kumawat, H.; Jha, V.; Pandit, S. K.; Parkar, V. V.; Ramachandran, K.; Mahata, K.; Pal, A.; Santra, S.; Mohanty, A. K.; Sekizawa, K.

    2015-08-01

    Single- and multi-nucleon transfer reactions, namely, 206Pb(18O,20O), 206Pb(18O,19O), 206Pb(18O,17O), 206Pb(18O,16O), 206Pb(18O,18N), 206Pb(18O,17N), 206Pb(18O,16N), 206Pb(18O,15N), 206Pb(18O,14N), 206Pb(18O,16C), 206Pb(18O,15C), 206Pb(18O,14C), 206Pb(18O,13C), 206Pb(18O,12C), 206Pb(18O,12B), 206Pb(18O,11B), 206Pb(18O,10B), 206Pb(18O,10Be), and 206Pb(18O,9Be), have been studied at an incident 18O energy of 139 MeV. The total kinetic energy loss (TKEL) spectrum and angular distribution of reaction products have been measured. The Q value and angle integrated cross sections are deduced. Angular distributions for the elastically scattered 18O particles are also measured. Fully microscopic time-dependent Hartree-Fock (TDHF) calculations, based on the independent single-nucleon transfer mode, have been carried out and are compared with experimental data of multinucleon transfer reactions. The TDHF calculations provide reasonable agreement with the experimental data for cases where one- and two-nucleon transfer is involved; the discrepancy is large for multinucleon transfer reactions. The effect of particle evaporation on the production cross sections has been studied. Inclusion of particle evaporation effects, though improving the results, could not reproduce the measured cross sections. Possible origins of these discrepancies are discussed.

  7. Production of unknown neutron-rich isotopes in 238U collisions at near-barrier energy

    NASA Astrophysics Data System (ADS)

    Zhao, Kai; Li, Zhuxia; Zhang, Yingxun; Wang, Ning; Li, Qingfeng; Shen, Caiwan; Wang, Yongjia; Wu, Xizhen

    2016-08-01

    The production cross sections for primary and residual fragments with charge number from Z =70 to 120 produced in the collision of 238U at 7.0 MeV/nucleon are calculated by the improved quantum molecular dynamics (ImQMD) model incorporated with the statistical evaporation model (hivap code). The calculation results predict that about 60 unknown neutron-rich isotopes from elements Ra (Z =88 ) to Db (Z =105 ) can be produced with the production cross sections above the lower bound of 10-8 mb in this reaction. And almost all of the unknown neutron-rich isotopes are emitted at the laboratory angles θlab≤60°. Two cases, i.e., the production of the unknown uranium isotopes with A ≥244 and that of rutherfordium with A ≥269 , are investigated to understand the production mechanism of unknown neutron-rich isotopes. It is found that for the former case the collision time between two uranium nuclei is shorter and the primary fragments producing the residues have smaller excitation energies of ≤30 MeV and the outgoing angles of those residues cover a range of 30°-60°. For the latter case, a longer collision time is needed for a large number of nucleons being transferred and thus it results in higher excitation energies and smaller outgoing angles of primary fragments, and eventually results in a very small production cross section for the residues of Rf with A ≥269 which have a small interval of outgoing angles of θlab=40°-50°.

  8. Vehicle barrier

    DOEpatents

    Hirsh, Robert A.

    1991-01-01

    A vehicle security barrier which can be conveniently placed across a gate opening as well as readily removed from the gate opening to allow for easy passage. The security barrier includes a barrier gate in the form of a cable/gate member in combination with laterally attached pipe sections fixed by way of the cable to the gate member and lateral, security fixed vertical pipe posts. The security barrier of the present invention provides for the use of cable restraints across gate openings to provide necessary security while at the same time allowing for quick opening and closing of the gate areas without compromising security.

  9. Free Energy Barriers for the N-Terminal Asparagine to Succinimide Conversion: Quantum Molecular Dynamics Simulations for the Fully Solvated Model.

    PubMed

    Kaliman, Ilya; Nemukhin, Alexander; Varfolomeev, Sergei

    2010-01-12

    Deamidation of asparagine residues represents one of the main routes for the post-translational modification of protein sequences. We computed the estimates of the free energy barriers for three stages of the deamidation process, deprotonation, cyclization, and deamination, of the conversion of asparagine to the succinimide intermediate within the fully solvated model with explicit water molecules. The Born-Oppenheimer molecular dynamics in the Gaussian and Plane Wave (GPW) approximation as implemented in the CP2K quantum chemistry package was utilized to sample the configurational space. By applying the metadynamics technique, the estimates of the free energy barriers were obtained for three separated stages of the reaction. In agreement with the experimental kinetic measurements, the estimated activation barriers do not exceed 21 kcal/mol. We demonstrate that the use of fully solvated models is the critical issue in theoretical studies of these reactions. We also conclude that more extensive sampling is necessary to obtain full free energy profiles and accurate barriers for the reaction stages. PMID:26614331

  10. Simultaneous escaping of explicit and hidden free energy barriers: application of the orthogonal space random walk strategy in generalized ensemble based conformational sampling.

    PubMed

    Zheng, Lianqing; Chen, Mengen; Yang, Wei

    2009-06-21

    To overcome the pseudoergodicity problem, conformational sampling can be accelerated via generalized ensemble methods, e.g., through the realization of random walks along prechosen collective variables, such as spatial order parameters, energy scaling parameters, or even system temperatures or pressures, etc. As usually observed, in generalized ensemble simulations, hidden barriers are likely to exist in the space perpendicular to the collective variable direction and these residual free energy barriers could greatly abolish the sampling efficiency. This sampling issue is particularly severe when the collective variable is defined in a low-dimension subset of the target system; then the "Hamiltonian lagging" problem, which reveals the fact that necessary structural relaxation falls behind the move of the collective variable, may be likely to occur. To overcome this problem in equilibrium conformational sampling, we adopted the orthogonal space random walk (OSRW) strategy, which was originally developed in the context of free energy simulation [L. Zheng, M. Chen, and W. Yang, Proc. Natl. Acad. Sci. U.S.A. 105, 20227 (2008)]. Thereby, generalized ensemble simulations can simultaneously escape both the explicit barriers along the collective variable direction and the hidden barriers that are strongly coupled with the collective variable move. As demonstrated in our model studies, the present OSRW based generalized ensemble treatments show improved sampling capability over the corresponding classical generalized ensemble treatments. PMID:19548709

  11. Physiology and immunology of mucosal barriers in catfish (Ictalurus spp.)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mucosal barriers of catfish (Ictalurus spp.) constitute the first line of defense against pathogen invasion while simultaneously carrying out a diverse array of other critical physiological processes, including nutrient adsorption, osmoregulation, waste excretion, and environmental sensing. Catf...

  12. Measurement of the fusion excitation function for 19O + 12C at near barrier energies

    NASA Astrophysics Data System (ADS)

    Singh, Varinderjit; Steinbach, T. K.; Vadas, J.; Wiggins, B. B.; Hudan, S.; Desouza, R. T.; Baby, L. T.; Tripathi, V.; Kuvin, S. A.; Wiedenhover, I.

    2015-10-01

    Fusion of neutron-rich light nuclei in the outer crust of an accreting neutron star has been proposed as responsible for triggering X-ray super-bursts. The underlying hypothesis in this proposition is that the fusion of neutron-rich nuclei is enhanced as compared to stable nuclei. To investigate this hypothesis, an experiment has been performed to measure the fusion excitation function for 18O and 19O nuclei incident on a 12C target. A beam of 19O was produced by the 18O(d,p) reaction at Florida State University and separated using the RESOLUT mass spectrometer. The resulting 19O beam bombarded a 100 μg/cm2 12C target at an intensity of 2-4 × 103 p/s. Evaporation residues resulting from the de-excitation of the fusion product were distinguished by measuring their energy and time-of-flight. Using silicon detectors, micro-channel plate detectors, and an ionization chamber, evaporation residues were detected in the angular range θlab <= 23° with high efficiency. Initial experimental results including measurement of the fusion cross-section to approximately the 100 mb level will be presented. The measured excitation function will be compared to theoretical predictions. Supported by the US DOE under Grand No. DEFG02-88ER-40404.

  13. Static and dynamic deformation effects in the fusion cross section of light heavy ions at sub-barrier energies

    SciTech Connect

    Hussein, M.S.; Canto, L.F.; Donangelo, R.

    1980-02-01

    The static and dynamic deformation effects on the sub-barrier fusion cross section of light heavy ions are investigated by performing a coupled channel calculation for the system /sup 12/C+/sup 16/O. It is found that dynamic effects are negligible whereas static effects could be important, and they appear to show up partly through absorption under the barrier.

  14. DFT modelling of hydrogen sulphide adsorption on α-Cr2O3 (0001) surface

    NASA Astrophysics Data System (ADS)

    Maldonado, Frank; Stashans, Arvids

    2016-05-01

    Density functional theory has been used to predict properties of hydrogen sulphide, H2S, adsorption on the α-Cr2O3 (0001) surface. Five energetically most favourable adsorption configurations have been selected for the study. Our work reveals adsorption geometries as well as discusses electronic and magnetic properties of the adsorbate on chromium oxide surface. It is shown that two different adsorption types, namely molecular adsorption and dissociative adsorption, can take place leading to two sets of adsorption energies. The most favourable arrangement is found to correspond to the case of dissociative adsorption with molecular hydrogen forming OH group at the α-Cr2O3 (0001) surface.

  15. Examples of Department of Energy Successes for Remediation of Contaminated Groundwater: Permeable Reactive Barrier and Dynamic Underground Stripping ASTD Projects

    SciTech Connect

    Purdy, C.; Gerdes, K.; Aljayoushi, J.; Kaback, D.; Ivory, T.

    2002-02-27

    Since 1998, the Department of Energy's (DOE) Office of Environmental Management has funded the Accelerated Site Technology Deployment (ASTD) Program to expedite deployment of alternative technologies that can save time and money for the environmental cleanup at DOE sites across the nation. The ASTD program has accelerated more than one hundred deployments of new technologies under 76 projects that focus on a broad spectrum of EM problems. More than 25 environmental restoration projects have been initiated to solve the following types of problems: characterization of the subsurface using chemical, radiological, geophysical, and statistical methods; treatment of groundwater contaminated with DNAPLs, metals, or radionuclides; and other projects such as landfill covers, purge water management systems, and treatment of explosives-contaminated soils. One of the major goals of the ASTD Program is to deploy a new technology or process at multiple DOE sites. ASTD projects are encouraged to identify subsequent deployments at other sites. Some of the projects that have successfully deployed technologies at multiple sites focusing on cleanup of contaminated groundwater include: Permeable Reactive Barriers (Monticello, Rocky Flats, and Kansas City), treating uranium and organics in groundwater; and Dynamic Underground Stripping (Portsmouth, and Savannah River), thermally treating DNAPL source zones. Each year more and more new technologies and approaches are being used at DOE sites due to the ASTD program. DOE sites are sharing their successes and communicating lessons learned so that the new technologies can replace the baseline or standard approaches at DOE sites, thus expediting cleanup and saving money.

  16. Vibrational analysis on the revised potential energy curve of the low-barrier hydrogen bond in photoactive yellow protein.

    PubMed

    Kanematsu, Yusuke; Kamikubo, Hironari; Kataoka, Mikio; Tachikawa, Masanori

    2016-01-01

    Photoactive yellow protein (PYP) has a characteristic hydrogen bond (H bond) between p-coumaric acid chromophore and Glu46, whose OH bond length has been observed to be 1.21 Å by the neutron diffraction technique [Proc. Natl. Acad. Sci. 106, 440-4]. Although it has been expected that such a drastic elongation of the OH bond could be caused by the quantum effect of the hydrogen nucleus, previous theoretical computations including the nuclear quantum effect have so far underestimated the bond length by more than 0.07 Å. To elucidate the origin of the difference, we performed a vibrational analysis of the H bond on potential energy curve with O…O distance of 2.47 Å on the equilibrium structure, and that with O…O distance of 2.56 Å on the experimental crystal structure. While the vibrationally averaged OH bond length for equilibrium structure was underestimated, the corresponding value for crystal structure was in reasonable agreement with the corresponding experimental values. The elongation of the O…O distance by the quantum mechanical or thermal fluctuation would be indispensable for the formation of a low-barrier hydrogen bond in PYP. PMID:27274362

  17. Vibrational analysis on the revised potential energy curve of the low-barrier hydrogen bond in photoactive yellow protein

    PubMed Central

    Kanematsu, Yusuke; Kamikubo, Hironari; Kataoka, Mikio; Tachikawa, Masanori

    2015-01-01

    Photoactive yellow protein (PYP) has a characteristic hydrogen bond (H bond) between p-coumaric acid chromophore and Glu46, whose OH bond length has been observed to be 1.21 Å by the neutron diffraction technique [Proc. Natl. Acad. Sci. 106, 440–4]. Although it has been expected that such a drastic elongation of the OH bond could be caused by the quantum effect of the hydrogen nucleus, previous theoretical computations including the nuclear quantum effect have so far underestimated the bond length by more than 0.07 Å. To elucidate the origin of the difference, we performed a vibrational analysis of the H bond on potential energy curve with O…O distance of 2.47 Å on the equilibrium structure, and that with O…O distance of 2.56 Å on the experimental crystal structure. While the vibrationally averaged OH bond length for equilibrium structure was underestimated, the corresponding value for crystal structure was in reasonable agreement with the corresponding experimental values. The elongation of the O…O distance by the quantum mechanical or thermal fluctuation would be indispensable for the formation of a low-barrier hydrogen bond in PYP. PMID:27274362

  18. A salen-type Dy4 single-molecule magnet with an enhanced energy barrier and its analogues.

    PubMed

    Luan, Fang; Yan, Pengfei; Zhu, Jing; Liu, Tianqi; Zou, Xiaoyan; Li, Guangming

    2015-03-01

    Four isomorphic tetranuclear lanthanide complexes, namely [Ln4(L)2(HL)2(NO3)2(OH)2](NO3)2·4H2O (Ln = Dy (1); Tb (2); Ho (3); Er (4)), constructed using hexadentate salen-type ligand N,N'-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine, have been isolated. X-ray crystallographic analysis reveals that all of the complexes 1-4 are of discrete tetranuclear structure with a unique {Ln4O8} core in which four lanthanide ions are coplanar in a rhombic frame. There are two crystallographically unequivalent lanthanide ions, that is the Ln1(III) ion which is nine-coordinated in a monocapped square-antiprismatic geometry of the C(4v) point group and the Ln2(III) ion which is eight-coordinated in a distorted bicapped trigonal-prismatic geometry of the C(2v) point group. Magnetic analysis reveals that complex 1 exhibits two slow magnetic relaxations with the highest energy barrier among the reported tetranuclear salen-type dysprosium SMMs. This further extends the available SMMs of salen-type lanthanide complexes. PMID:25619145

  19. First-principles molecular dynamics simulations of condensed-phase V-type nerve agent reaction pathways and energy barriers.

    PubMed

    Gee, Richard H; Kuo, I-Feng W; Chinn, Sarah C; Raber, Ellen

    2012-03-14

    Computational studies of condensed-phase chemical reactions are challenging in part because of complexities in understanding the effects of the solvent environment on the reacting chemical species. Such studies are further complicated due to the demanding computational resources required to implement high-level ab initio quantum chemical methods when considering the solvent explicitly. Here, we use first-principles molecular dynamics simulations to examine condensed-phase decontamination reactions of V-type nerve agents in an explicit aqueous solvent. Our results include a detailed study of hydrolysis, base-hydrolysis, and nucleophilic oxidation of both VX and R-VX, as well as their protonated counterparts (i.e., VXH(+) and R-VXH(+)). The decontamination mechanisms and chemical reaction energy barriers, as determined from our simulations, are found to be in good agreement with experiment. The results demonstrate the applicability of using such simulations to assist in understanding new decontamination technologies or other applications that require computational screening of condensed-phase chemical reaction mechanisms. PMID:22298156

  20. Power law size-distributed heterogeneity explains colloid retention on soda lime glass in the presence of energy barriers.

    PubMed

    Pazmino, Eddy; Trauscht, Jacob; Dame, Brittany; Johnson, William P

    2014-05-20

    This article concerns reading the nanoscale heterogeneity thought responsible for colloid retention on surfaces in the presence of energy barriers (unfavorable attachment conditions). We back out this heterogeneity on glass surfaces by comparing mechanistic simulations incorporating discrete heterogeneity with colloid deposition experiments performed across a comprehensive set of experimental conditions. Original data is presented for attachment to soda lime glass for three colloid sizes (0.25, 1.1, and 1.95 μm microspheres) under a variety of ionic strengths and fluid velocities in an impinging jet system. A comparison of mechanistic particle trajectory simulations incorporating discrete surface heterogeneity represented by nanoscale zones of positive charge (heterodomains) indicates that a power law size distribution of heterodomains ranging in size from 120 to 60 nm in radius was able to explain the observed retention for all conditions examined. In contrast, uniform and random placement of single-sized heterodomains failed to capture experimentally observed colloid retention across the range of conditions examined. PMID:24773424

  1. Evaluation of the energy barrier for failure of Au atomic contact based on temperature dependent current-voltage characteristics.

    PubMed

    Aiba, Akira; Kaneko, Satoshi; Fujii, Shintaro; Nishino, Tomoaki; Kiguchi, Manabu

    2016-08-01

    We investigated the mechanical stability of single gold atomic contacts at an applied bias voltage of 0-1 V using a nano-fabricated mechanically controllable break junction technique at 300-400 K under ambient conditions. The single atomic contact shows the quantized conductance (G0 = 2e(2)/h) and can carry considerably large current, which results in the current-induced failure of the contact. The contact failure behaviour under the applied bias conditions was studied by statistical analysis of the current-voltage (I-V) curves of the single Au contacts. We demonstrated that, at the elevated temperature of 300-400 K, the current-induced local heating effect is negligibly small and current-induced forces in the contact are responsible for the observed failure of the single gold contacts under the high bias voltage conditions (>0.4 V). Furthermore, based on the temperature dependence of the contact failure behaviour in the I-V curves, the energy barrier of the contact-failure was evaluated to be ca. 0.1 V. PMID:27427285

  2. Adsorption and dissociation of oxygen molecules on Si(111)-(7×7) surface

    SciTech Connect

    Niu, Chun-Yao; Wang, Jian-Tao

    2013-11-21

    The adsorption and dissociation of O{sub 2} molecules on Si(111)-(7×7) surface have been studied by first-principles calculations. Our results show that all the O{sub 2} molecular species adsorbed on Si(111)-(7×7) surface are unstable and dissociate into atomic species with a small energy barrier about 0.1 eV. The single O{sub 2} molecule adsorption tends to form an ins×2 or a new metastable ins×2* structure on the Si adatom sites and the further coming O{sub 2} molecules adsorb on those structures to produce an ad-ins×3 structure. The ad-ins×3 structure is indeed highly stable and kinetically limited for diving into the subsurface layer to form the ins×3-tri structure by a large barrier of 1.3 eV. Unlike the previous views, we find that all the ad-ins, ins×2, and ad-ins×3 structures show bright images, while the ins×2*, ins×3, and ins×3-tri structures show dark images. The proposed oxidation pathways and simulated scanning tunneling microscope images account well for the experimental results and resolve the long-standing confusion and issue about the adsorption and reaction of O{sub 2} molecules on Si(111) surface.

  3. First-principles calculations of NO and NO2 adsorption on a spinel ZnGaAlO4(100) surface

    NASA Astrophysics Data System (ADS)

    Xiang, Chao; Tan, Honglin; Lu, Jiansheng; Yu, Lan; Song, Peng; Zeng, Chunhua; Zhang, Defeng; Tao, Shigang

    2014-07-01

    Density functional theory (DFT) has been used to investigate the properties of NO and NO2 adsorption on a ZnGaAlO4(100) surface. The calculation results show that the minimum surface energy is 2.3073 J m-2. The configuration of NO adsorbed on the surface is more stable through an N-down orientation due to the strong hybridization between d states and the NO-π orbital. In particular, NO approaches Zn via its N side with an adsorption energy of -23.50 kcal mol-1, while the comparable value is -44.19 kcal mol-1 for NO2 adsorbed at Zn, suggesting a higher degree of adsorption stability. In addition, substitution of Al with Ga is responsible for the most stable mode of NO2 adsorption with a binding energy of -53.40 kcal mol-1. This demonstrates that the process of desorption of NO2 is thermodynamically feasible. NO2 adsorbed on the surface is activated, showing that the adsorption can directly lead to a dissociation of NO2. Moreover, the process of dissociation of NO2 adsorbed at Ga is favored due to a lower energy barrier of activation.

  4. Effects of van der Waals interaction on nanoparticle adsorption

    NASA Astrophysics Data System (ADS)

    Poddar, Nitun; Amar, Jacques

    2014-03-01

    The results of molecular dynamics (MD) simulations carried out using an all-atom model in order to understand the structure, diffusion, and binding of dodecanethiol (DDT)-coated Au nanoparticles (NPs) at the toluene-air interface are presented. We find that due to the strong attraction between DDT and toluene, the NP lies mainly below the interface. As a result, the coefficient for diffusion along the interface is close to the Stokes-Einstein prediction for 3D bulk diffusion. We also find that, due to the small ratio of ligand length to NP diameter, there is little spontaneous asymmetry in the NP coating. We have also used our MD results along with analytical expressions for the van der Waals (VdW) interactions to estimate corrections to the adsorption energy for DDT-coated Au NPs at the toluene-vapor interface as well as for alkanethiol-coated NPs at the water-vapor interface. In both cases, we find that the core-solvent interaction may significantly reduce the binding energy. We also find that the competition between this interaction and short-range attraction to the interface leads to well-defined activation barriers for interfacial desorption as well as for NP adsorption from the solvent. This work was supported by NSF Grant No. CHE-1012896.

  5. Hydrogen adsorption on functionalized nanoporous activated carbons.

    PubMed

    Zhao, X B; Xiao, B; Fletcher, A J; Thomas, K M

    2005-05-12

    There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions. PMID:16852056

  6. Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

    NASA Astrophysics Data System (ADS)

    Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk

    2016-04-01

    The adsorption, diffusion, and dissociation of pyridine, C5H5N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom. The origin of the diffusion pathway is discussed in terms of the C2-Pt π-bond being stronger than the corresponding CN-Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).

  7. Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory.

    PubMed

    Kolsbjerg, Esben L; Groves, Michael N; Hammer, Bjørk

    2016-04-28

    The adsorption, diffusion, and dissociation of pyridine, C5H5N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom. The origin of the diffusion pathway is discussed in terms of the C2-Pt π-bond being stronger than the corresponding CN-Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111). PMID:27131536

  8. 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.

  9. The influence of the textural properties of activated carbons on acetaminophen adsorption at different temperatures.

    PubMed

    Galhetas, Margarida; Andrade, Marta A; Mestre, Ana S; Kangni-foli, Ekoé; Villa de Brito, Maria J; Pinto, Moisés L; Lopes, Helena; Carvalho, Ana P

    2015-05-14

    The influence of temperature (20-40 °C) on the acetaminophen adsorption onto activated carbons with different textures was studied. Different temperature dependences, not explained by kinetic effects, were observed for carbons with different micropore size distribution patterns: adsorption capacity increased for pine gasification residues (Pi-fa) derived carbons and decreased for sisal based materials. No significant variation was seen for carbon CP. The species identified by (1)H NMR spectroscopy on the back-extraction solution proved that during the adsorption process exist the conditions required to promote the formation of acetaminophen oligomers which have constrained access to the narrow microporosity. The rotation energy of the dihedral angle between monomers (estimated by electronic DFT methods) showed that conformations in the planar form are less stable than the non-planar conformation (energy barrier of 70 and 23 kJ mol(-1)), but have critical dimensions similar to the monomer and can access most of the micropore volume. The enthalpy change of the overall process showed that the energy gain of the system (endothermic) for Pi-fa samples (≈40 kJ mol(-1)) was enough to allow a change in the dimer, or even a larger oligomer, conformation to the planar form. This will permit adsorption in the narrow micropores, thus explaining the uptake increase with temperature. Non-continuous micropore size distributions centered at pore widths close to the critical dimensions of the planar form seem to be crucial for a positive evolution of the adsorption capacity with temperature. PMID:25898008

  10. Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

    PubMed Central

    Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

    2009-01-01

    Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

  11. The dissociative adsorption of silane and disilane on Si(100)-(2×1)

    NASA Astrophysics Data System (ADS)

    Shi, J.; Tok, E. S.; Kang, H. Chuan

    2007-10-01

    We investigate the dissociative adsorption of silane and disilane on Si(100)-(2×1) using pseudopotential planewave density functional theory calculations. These are important steps in the growth of silicon films. Although silane has been studied computationally in some detail previously, we find physisorbed precursor states for the intradimer and interdimer channels. The silane energetics calculated here are in good agreement with experimental data and previous theoretical estimates and provide us with a useful reference point for our disilane calculations. Disilane has not been studied as intensively as silane. We investigate both silicon-silicon bond cleavage and silicon-hydrogen bond cleavage mechanisms, and for each we investigate intradimer, interdimer, and inter-row channels. As in the case of silane, we also find precursor states in the adsorption path in agreement with molecular beam experiments. The qualitative picture that emerges is that adsorption takes place through a weakly bound precursor state with a transition state to chemisorption that is low lying in energy relative to the gas phase. This is in good agreement with experimental data. However, the calculated energetics are only in fair agreement with experiments, with our transition state to chemisorption being about 0.02eV above the gas phase while experimentally it is estimated to be approximately 0.28eV below the gas phase. This suggests that accurate theoretical characterization of these weakly bound precursor states and the adsorption barriers requires further computational work.

  12. The dissociative adsorption of silane and disilane on Si(100)-(2 x 1).

    PubMed

    Shi, J; Tok, E S; Kang, H Chuan

    2007-10-28

    We investigate the dissociative adsorption of silane and disilane on Si(100)-(2 x 1) using pseudopotential planewave density functional theory calculations. These are important steps in the growth of silicon films. Although silane has been studied computationally in some detail previously, we find physisorbed precursor states for the intradimer and interdimer channels. The silane energetics calculated here are in good agreement with experimental data and previous theoretical estimates and provide us with a useful reference point for our disilane calculations. Disilane has not been studied as intensively as silane. We investigate both silicon-silicon bond cleavage and silicon-hydrogen bond cleavage mechanisms, and for each we investigate intradimer, interdimer, and inter-row channels. As in the case of silane, we also find precursor states in the adsorption path in agreement with molecular beam experiments. The qualitative picture that emerges is that adsorption takes place through a weakly bound precursor state with a transition state to chemisorption that is low lying in energy relative to the gas phase. This is in good agreement with experimental data. However, the calculated energetics are only in fair agreement with experiments, with our transition state to chemisorption being about 0.02 eV above the gas phase while experimentally it is estimated to be approximately 0.28 eV below the gas phase. This suggests that accurate theoretical characterization of these weakly bound precursor states and the adsorption barriers requires further computational work. PMID:17979377

  13. Al atom on MoO3(010) surface: adsorption and penetration using density functional theory.

    PubMed

    Wu, Hong-Zhang; Bandaru, Sateesh; Wang, Da; Liu, Jin; Lau, Woon Ming; Wang, Zhenling; Li, Li-Li

    2016-03-14

    Interfacial issues, such as the interfacial structure and the interdiffusion of atoms at the interface, are fundamental to the understanding of the ignition and reaction mechanisms of nanothermites. This study employs first-principle density functional theory to model Al/MoO3 by placing an Al adatom onto a unit cell of a MoO3(010) slab, and to probe the initiation of interfacial interactions of Al/MoO3 nanothermite by tracking the adsorption and subsurface-penetration of the Al adatom. The calculations show that the Al adatom can spontaneously go through the topmost atomic plane (TAP) of MoO3(010) and reach the 4-fold hollow adsorption-site located below the TAP, with this subsurface adsorption configuration being the most preferred one among all plausible adsorption configurations. Two other plausible configurations place the Al adatom at two bridge sites located above the TAP of MoO3(010) but the Al adatom can easily penetrate below this TAP to a relatively more stable adsorption configuration, with a small energy barrier of merely 0.2 eV. The evidence of subsurface penetration of Al implies that Al/MoO3 likely has an interface with intermixing of Al, Mo and O atoms. These results provide new insights on the interfacial interactions of Al/MoO3 and the ignition/combustion mechanisms of Al/MoO3 nanothermites. PMID:26899169

  14. Adsorption and dissociation of O 2 on CuCl(1 1 1) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Liu, Hongyan; Wang, Baojun; Ren, Jun; Li, Zhong

    2011-10-01

    The adsorption and dissociation of O 2 on CuCl(1 1 1) surface have been systematically studied by the density functional theory (DFT) slab calculations. Different kinds of possible modes of atomic O and molecular O 2 adsorbed on CuCl(1 1 1) surface and possible dissociation pathways are identified, and the optimized geometry, adsorption energy, vibrational frequency and Mulliken charge are obtained. The calculated results show that the favorable adsorption occurs at hollow site for O atom, and molecular O 2 lying flatly on the surface with one O atom binding with top Cu atom is the most stable adsorption configuration. The O-O stretching vibrational frequencies are significantly red-shifted, and the charges transferred from CuCl to oxygen. Upon O 2 adsorption, the oxygen species adsorbed on CuCl(1 1 1) surface mainly shows the characteristic of the superoxo (O 2-), which primarily contributes to improving the catalytic activity of CuCl, meanwhile, a small quantity of O 2 dissociation into atomic O also occur, which need to overcome very large activation barrier. Our results can provide some microscopic information for the catalytic mechanism of DMC synthesis over CuCl catalyst from oxidative carbonylation of methanol.

  15. Adsorption and dissociation of H2O on the (001) surface of uranium mononitride: energetics and mechanism from first-principles investigation.

    PubMed

    Bo, Tao; Lan, Jian-Hui; Zhang, Yu-Juan; Zhao, Yao-Lin; He, Chao-Hui; Chai, Zhi-Fang; Shi, Wei-Qun

    2016-05-21

    The interfacial interaction of uranium mononitride (UN) with water from the environment unavoidably leads to corrosion of nuclear fuels, which affects a lot of processes in the nuclear fuel cycle. In this work, the microscopic adsorption behaviors of water on the UN(001) surface as well as water dissociation and accompanying H2 formation mechanisms have been investigated on the basis of DFT+U calculations and ab initio atomistic thermodynamics. For adsorption of one H2O monomer, the predicted adsorption energies are -0.88, -2.07, and -2.07 eV for the most stable molecular, partially dissociative, and completely dissociative adsorption, respectively. According to our calculations, a water molecule dissociates into OH and H species via three pathways with small energy barriers of 0.78, 0.72, and 0.85 eV, respectively. With the aid of the neighboring H atom, H2 formation through the reaction of H* + OH* can easily occur via two pathways with energy barriers of 0.61 and 0.36 eV, respectively. The molecular adsorption of water shows a slight coverage dependence on the surface while this dependence becomes obvious for partially dissociative adsorption as the water coverage increases from 1/4 to 1 ML. In addition, based on the "ab initio atomistic thermodynamic" simulations, increasing H2O partial pressure will enhance the stability of the adsorbed system and water coverage, while increasing temperature will decrease the H2O coverage. We found that the UN(001) surface reacts easily with H2O at room temperature, leading to dissolution and corrosion of the UN fuel materials. PMID:27118421

  16. Investigation of the energy barrier to the rotation of amide CN bonds in ACE inhibitors by NMR, dynamic HPLC and DFT.

    PubMed

    Bouabdallah, S; Ben Dhia, M T; Driss, M R; Touil, S

    2016-09-01

    The isomerizations of Enalapril, Perindopril, Enalaprilat and Lisinopril have been investigated using NMR spectroscopic, dynamic chromatographic, unified equation and DFT theoretical calculations. The thermodynamic parameters (ΔH, ΔS and ΔG) were determined by varying the temperature in the NMR experiments. At the coalescence temperature, we can evaluate the isomerization barrier to the rotation (ΔG(≠)) around the amide bond. Using dynamics chromatography and an unified equation introduced by Trap, we can determine isomerization rate constants and Gibbs activation energies. Molecular mechanics calculations also provided evidence for the presence of low energy conformers for the ACE due to restricted amide rotation. With the value of barriers (ΔE) between them of the order of (20kJmol(-1)), which is in agreement with the dynamic NMR results and DFT calculations. PMID:27344631

  17. Method and apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; TeGrotenhuis, Ward E.; Drost, Kevin; Vishwanathan, Vilayanur V.

    2004-06-08

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. In another aspect, the apparatus or methods utilize heat exchange channels of varying lengths that have volumes controlled to provide equal heat fluxes. Methods of fuel cell startup are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  18. Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

    2003-10-07

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  19. Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

    2005-12-13

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  20. Ab initio studies on the adsorption and implantation of Al and Fe to nitride materials

    NASA Astrophysics Data System (ADS)

    Riedl, H.; Zálešák, J.; Arndt, M.; Polcik, P.; Holec, D.; Mayrhofer, P. H.

    2015-09-01

    The formation of transfer material products on coated cutting and forming tools is a major failure mechanism leading to various sorts of wear. To describe the atomistic processes behind the formation of transfer materials, we use ab initio to study the adsorption energy as well as the implantation barrier of Al and Fe atoms for (001)-oriented surfaces of TiN, Ti0.50Al0.50N, Ti0.90Si0.10N, CrN, and Cr0.90Si0.10N. The interactions between additional atoms and nitride-surfaces are described for pure adhesion, considering no additional stresses, and for the implantation barrier. The latter, we simplified to the stress required to implant Al and Fe into sub-surface regions of the nitride material. The adsorption energies exhibit pronounced extrema at high-symmetry positions and are generally highest at nitrogen sites. Here, the binary nitrides are comparable to their ternary counterparts and the average adhesive energy is higher (more negative) on CrN than TiN based systems. Contrary, the implantation barrier for Al and Fe atoms is higher for the ternary systems Ti0.50Al0.50N, Ti0.90Si0.10N, and Cr0.90Si0.10N than for their binary counterparts TiN and CrN. Based on our results, we can conclude that TiN based systems outperform CrN based systems with respect to pure adhesion, while the Si-containing ternaries exhibit higher implantation barriers for Al and Fe atoms. The data obtained are important to understand the atomistic interaction of metal atoms with nitride-based materials, which is valid not just for machining operations but also for any combination such as interfaces between coatings and substrates or multilayer and phase arrangements themselves.

  1. The Effects of a High-Energy Diet on Hippocampal Function and Blood-Brain Barrier Integrity in the Rat

    PubMed Central

    Kanoski, Scott E.; Zhang, Yanshu; Zheng, Wei; Davidson, Terry L.

    2016-01-01

    Cognitive impairment and Alzheimer’s Disease are linked with intake of a Western Diet, characterized by high levels of saturated fats and simple carbohydrates. In rats, these dietary components have been shown to disrupt hippocampal-dependent learning and memory processes, particularly those involving spatial memory. Using a rat model, the present research assessed the degree to which consumption of a high-energy (HE) diet, similar to those found in modern Western cultures, produces a selective impairment in hippocampal function as opposed to a more global cognitive disruption. Learning and memory performance was examined following 90-days consumption of an HE-diet in three nonspatial discrimination learning problems that differed with respect to their dependence on the integrity of the hippocampus. The results showed that consumption of the HE-diet impaired performance in a hippocampal-dependent feature negative discrimination problem relative to chow-fed controls, whereas performance was spared on two discrimination problems that do not rely on the hippocampus. To explore the mechanism whereby consuming HE-diets impairs cognitive function, we investigated the effect of HE-diets on the integrity of the blood-brain barrier (BBB). We found that HE-diet consumption produced a decrease in mRNA expression of tight junction proteins, particularly Claudin-5 and -12, in the choroid plexus and the BBB. Consequently, an increased blood-to-brain permeability of sodium fluorescein was observed in the hippocampus, but not in the striatum and prefrontal cortex following HE-diet access. There results indicate that hippocampal function may be particularly vulnerable to disruption by HE-diets, and this disruption may be related to impaired BBB integrity. PMID:20413889

  2. Oxygen adsorption at noble metal/TiO2 junctions

    NASA Astrophysics Data System (ADS)

    Hossein-Babaei, F.; Alaei-Sheini, Navid; Lajvardi, Mehdi M.

    2016-03-01

    Electric conduction in titanium dioxide is known to be oxygen sensitive and the conductivity of a TiO2 ceramic body is determined mainly by the concentration of its naturally occurring oxygen vacancy. Recently, fabrications and electronic features of a number of noble metal/TiO2-based electronic devices, such as solar cells, UV detectors, gas sensors and memristive devices have been demonstrated. Here, we investigate the effect of oxygen adsorption at the noble metal/TiO2 junction in such devices, and show the potentials of these junctions in chemical sensor fabrication. The polycrystalline, poly-phase TiO2 layers are grown by the selective and controlled oxidation of titanium thin films vacuum deposited on silica substrates. Noble metal thin films are deposited on the oxide layers by physical vapor deposition. Current-voltage (I-V) diagrams of the fabricated devices are studied for Ag/, Au/, and Pt/TiO2 samples. The raw samples show no junction energy barrier. After a thermal annealing in air at 250° C, I-V diagrams change drastically. The annealed samples demonstrate highly non-linear I-V indicating the formation of high Schottky energy barriers at the noble metal/TiO2 junctions. The phenomenon is described based on the effect of the oxygen atoms adsorbed at the junction.

  3. Overcoming Rapid Inactivation of Lung Surfactant: Analogies Between Competitive Adsorption and Colloid Stability

    PubMed Central

    Zasadzinski, Joseph A.; Stenger, Patrick C.; Shieh, Ian; Dhar, Prajnaparamita

    2009-01-01

    Lung surfactant (LS) is a mixture of lipids and proteins that line the alveolar air-liquid interface, lowering the interfacial tension to levels that make breathing possible. In acute respiratory distress syndrome (ARDS), inactivation of LS is believed to play an important role in the development and severity of the disease. This review examines the competitive adsorption of LS and surface-active contaminants, such as serum proteins, present in the alveolar fluids of ARDS patients, and how this competitive adsorption can cause normal amounts of otherwise normal LS to be ineffective in lowering the interfacial tension. LS and serum proteins compete for the air-water interface when both are present in solution either in the alveolar fluids or in a Langmuir trough. Equilibrium favors LS as it has the lower equilibrium surface pressure, but the smaller proteins are kinetically favored over multi-micron LS bilayer aggregates by faster diffusion. If albumin reaches the interface, it creates an energy barrier to subsequent LS adsorption that slows or prevents the adsorption of the necessary amounts of LS required to lower surface tension. This process can be understood in terms of classic colloid stability theory in which an energy barrier to diffusion stabilizes colloidal suspensions against aggregation. This analogy provides qualitative and quantitative predictions regarding the origin of surfactant inactivation. An important corollary is that any additive that promotes colloid coagulation, such as increased electrolyte concentration, multivalent ions, hydrophilic non-adsorbing polymers such as PEG, dextran, etc. or polyelectrolytes such as chitosan, added to LS, also promotes LS adsorption in the presence of serum proteins and helps reverse surfactant inactivation. The theory provides quantitative tools to determine the optimal concentration of these additives and suggests that multiple additives may have a synergistic effect. A variety of physical and chemical

  4. Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni2(4,4'-bipyridine)3(NO3)4: guest modification of host sorption behavior.

    PubMed

    Fletcher, A J; Cussen, E J; Prior, T J; Rosseinsky, M J; Kepert, C J; Thomas, K M

    2001-10-17

    This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a

  5. Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

    PubMed

    Shih, Yang-hsin; Li, Mei-syue

    2008-06-15

    Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals. PMID:17980962

  6. Barriers and opportunities for improving energy efficiency in the social housing sector: Case study of E4C's Division of Housing and Mental Health

    NASA Astrophysics Data System (ADS)

    Marchand-Smith, Patrick

    Energy efficiency improvements in the social housing sector have the potential to produce a range of environmental and social benefits. These improvements can be produced through retrofits that deliver energy savings or new construction built to a high standard of energetic efficiency. However, implementation of these approaches is hindered by economic and organizational constraints affecting the agencies that provide society with social housing and the governments that support the provision of these services. This thesis builds on the work of other researchers studying these constraints by supplying an in-depth case study from Alberta and a discussion based on its findings. The case study focuses on E4C, a social service agency with several housing projects. Overall, findings matched important themes identified in the academic literature. The in-depth nature of the case study added additional insight to many of these themes. Most barriers are economic in nature and related to a lack of sufficient funding or the up-front costs of energy-saving retrofits. The recommendations presented are based on consideration of the multiple barriers and opportunities faced. Most of these require a considerable investment of time on the part of agencies and would be followed up by capital investments to implement energy-saving changes. Therefore it is important to note that the most significant barrier is commitment, which is one of E4C's central values. This thesis showed that commitment cannot exceed capacity to act. Greater commitment on the part of governments, agencies or society at large could have significant impacts in improving the energy efficiency of buildings in the Albertan, and Canadian, social housing sector.

  7. Ab initio calculations of stationary points on the benzene-Ar and p-difluorobenzene-Ar potential energy surfaces: barriers to bound orbiting states

    NASA Astrophysics Data System (ADS)

    Moulds, Rebecca J.; Buntine, Mark A.; Lawrance, Warren D.

    2004-09-01

    The potential energy surfaces of the van der Waals complexes benzene-Ar and p-difluorobenzene-Ar have been investigated at the second-order Møller-Plesset (MP2) level of theory with the aug-cc-pVDZ basis set. Calculations were performed with unconstrained geometry optimization for all stationary points. This study has been performed to elucidate the nature of a conflict between experimental results from dispersed fluorescence and velocity map imaging (VMI). The inconsistency is that spectra for levels of p-difluorobenzene-Ar and -Kr below the dissociation thresholds determined by VMI show bands where free p-difluorobenzene emits, suggesting that dissociation is occurring. We proposed that the bands observed in the dispersed fluorescence spectra are due to emission from states in which the rare gas atom orbits the aromatic chromophore; these states are populated by intramolecular vibrational redistribution from the initially excited level [S. M. Bellm, R. J. Moulds, and W. D. Lawrance, J. Chem. Phys. 115, 10709 (2001)]. To test this proposition, stationary points have been located on both the benzene-Ar and p-difluorobenzene-Ar potential energy surfaces (PESs) to determine the barriers to this orbiting motion. Comparison with previous single point CCSD(T) calculations of the benzene-Ar PES has been used to determine the amount by which the barriers are overestimated at the MP2 level. As there is little difference in the comparable regions of the benzene-Ar and p-difluorobenzene-Ar PESs, the overestimation is expected to be similar for p-difluorobenzene-Ar. Allowing for this overestimation gives the barrier to movement of the Ar atom around the pDFB ring via the valley between the H atoms as ⩽204 cm-1 in S0 (including zero point energy). From the estimated change upon electronic excitation, the corresponding barrier in S1 is estimated to be ⩽225 cm-1. This barrier is less than the 240 cm-1 energy of 302¯, the vibrational level for which the anomalous "free p

  8. Atom and Amine Adsorption on Flat and Stepped Gold Surfaces & Structure, Stability and Spin Ordering in Manganese Sulfide Clusters

    NASA Astrophysics Data System (ADS)

    Lewoczko, April D.

    In part I, we investigate gold catalysis in the chemistry of organonitrogen compounds. We examine the adsorption of oxygen, nitrogen and sulfur atoms on the gold (111), (100) and (211) surfaces using density functional theory (DFT). Sulfur atoms bind most strongly, followed by oxygen and nitrogen atoms with stronger adsorption for greater coordination to the surface. We see a trend of stronger adsorption to undercoordinated gold, but find it is non-universal with the adsorption strength trend: (111) > (211) > (100). We consider the diffusion of oxygen, nitrogen and sulfur adatoms and find facile long-range diffusion of oxygen atoms on the (100) surface. Lastly, we compare the adsorption of methylamine on gold to that of a selection of alkylamines, methanol and methanethiol. In each case, the ontop site is preferred with stronger adsorption at low coordinated gold. At oxygen atom coverages of 0.125 -- 0.25 ML on Au (111), we find cooperative adsorption of methylamine and oxygen atoms. Energetic costs for adsorbate tilt from the surface normal and rotation about the gold-nitrogen bond are calculated. While methylamine rotation is barrierless on the (111) and (211) surfaces, it has a low energetic barrier for the 0.125 ML and 0.25 ML O atom pre-covered Au (111) surfaces. In part II, we interpret the experimental mass spectrum of small gas phase manganese sulfide clusters using DFT and elucidate the role of ionicity and spin ordering in sizes with special stability, i.e. magic clusters. We first consider nine low lying minima (MnS)6 structures and reveal antiferromagnetic (AFM) spin ordering with a ˜0.1 eV/pair AFM energy benefit and a ˜0.1 A shrinkage of average Mn-Mn distances over clusters with ferromagnetic (FM) spin ordering. We calculate energetic barriers for interconversion between the two lowest lying (MnS)6 isomers and predict an elevated cluster melting temperature due to increased configurational entropy in a pre-melted state. Second, we demonstrate the

  9. One- and two-nucleon transfer in the {sup 28} Si+{sup 68}Zn system at energies below the Coulomb barrier

    SciTech Connect

    Kataria, D.O.; Sinha, A.K.; Das, J.J.; Madhavan, N.; Sugathan, P.; Baby, L.T.; Mazumdar, I.; Singh, R.; Baba, C.V.; Agarwal, Y.K.; Vinodkumar, A.M.; Varier, K.M.

    1997-10-01

    Excitation functions for one- and two-nucleon transfer in {sup 28}Si + {sup 68}Zn system have been measured at energies below the Coulomb barrier. The experiment was carried out by detecting the forward recoiling targetlike nuclei using the recoil mass separator, HIRA. With a pulsed beam, the time-of-flight of the recoils was measured and used to resolve the M/q ambiguity. This enabled the determination of the two-nucleon transfer yields. The role of one- and two-nucleon transfer in the sub-barrier fusion cross-section enhancement has been investigated. It turns out that the coupling of the positive Q-value two-neutron transfer channel results in a significant contribution to the enhancement. Coupling to both the transfer and the inelastic channels is able to explain the observed enhancement. {copyright} {ital 1997} {ital The American Physical Society}

  10. ARSENIC TREATMENT BY ADSORPTIVE TECHNOLOGY

    EPA Science Inventory

    Presentation will discuss the removal of arsenic from drinking water using the adsorptive media treatment process. Fundamental information is provided on the design and operation of adsorptive media technology including the selection of the adsorptive media. The information cites...

  11. Evaluation of the isosteric heat of adsorption at zero coverage for hydrogen on activated carbons

    NASA Astrophysics Data System (ADS)

    Dohnke, E.; Beckner, M.; Romanos, J.; Olsen, R.; Wexler, C.; Pfeifer, P.

    2011-03-01

    Activated carbons made from corn cob show promise as materials for high-capacity hydrogen storage. As part of our characterization of these materials, we are interested in learning how different production methods affect the adsorption energies. In this talk, we will show how hydrogen adsorption isotherms may be used to calculate these adsorption energies at zero coverage using Henry's law. We will additionally discuss differences between the binding energy and the isosteric heat of adsorption by applying this analysis at different temperatures.

  12. A Simple Adsorption Experiment

    ERIC Educational Resources Information Center

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

    The study of adsorption phenomenon is one of the most relevant and traditional physical chemistry experiments performed by chemistry undergraduate students in laboratory courses. In this article, we describe an easy, inexpensive, and straightforward way to experimentally determine adsorption isotherms using pieces of filter paper as the adsorbent…

  13. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules.

    PubMed

    DePalma, Joseph W; Wang, Jian; Wexler, Anthony S; Johnston, Murray V

    2015-11-12

    Quantum chemical calculations were employed to model the interactions of the [(NH4(+))4(HSO4(-))4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of this cluster and a carboxylic acid, aldehyde, or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient [(NH4(+))4(SO4(-))4]cluster is able to adsorb an oxygenated organic molecule. While adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is less so, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ∼1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules. PMID:26488562

  14. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    SciTech Connect

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH4+)4(HSO4-)4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH4+)4(SO4-)4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.

  15. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    DOE PAGESBeta

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH4+)4(HSO4-)4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH4+)4(SO4-)4] cluster, is able to adsorb an oxygenated organic molecule.more » Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  16. Identifying perceived barriers and benefits to reducing energy consumption in an affordable housing complex using the Community-Based Social Marketing model

    NASA Astrophysics Data System (ADS)

    Reaves, Daniel

    Energy production and consumption has a negative impact on both environmental and human health. Energy consumption can be directly impacted by human behavior, especially in the residential sector. As a result, this sector has been studied significantly; however, energy reducing behavior change research focusing on the affordable housing sector has not been studied thoroughly to date. This study seeks to implement the first two phases of the Community Based Social Marketing (CBSM) framework in an affordable housing setting. The goals were to identify the optimal behaviors for energy reduction based on phase one survey results and to identify the perceived benefits and barriers associated with those behaviors. Additionally, this study identified nuances in the CBSM process that researchers should take into consideration when implementing CBSM in an affordable housing environment.

  17. Nanoporous chalcogenides for adsorption and gas separation.

    PubMed

    Ori, Guido; Massobrio, Carlo; Pradel, Annie; Ribes, Michel; Coasne, Benoit

    2016-05-21

    The adsorption and gas separation properties of amorphous porous chalcogenides such as GeS2 are investigated using statistical mechanics molecular simulation. Using a realistic molecular model of such amorphous adsorbents, we show that they can be used efficiently to separate different gases relevant to environmental and energy applications (H2, CO2, CH4, N2). In addition to shedding light on the microscopic adsorption mechanisms, we show that coadsorption in this novel class of porous materials can be described using the ideal adsorbed solution theory (IAST). Such a simple thermodynamic model, which allows avoiding complex coadsorption measurements, describes the adsorption of mixture from pure component adsorption isotherms. Our results, which are found to be in good agreement with available experimental data, paves the way for the design of gas separation membranes using the large family of porous chalcogenides. PMID:27126718

  18. How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?

    PubMed

    Mardirossian, Narbe; Head-Gordon, Martin

    2016-09-13

    The 14 Minnesota density functionals published between the years 2005 and early 2016 are benchmarked on a comprehensive database of 4986 data points (84 data sets) involving molecules composed of main-group elements. The database includes noncovalent interactions, isomerization energies, thermochemistry, and barrier heights, as well as equilibrium bond lengths and equilibrium binding energies of noncovalent dimers. Additionally, the sensitivity of the Minnesota density functionals to the choice of basis set and integration grid is explored for both noncovalent interactions and thermochemistry. Overall, the main strength of the hybrid Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., M06-2X), barrier heights (e.g., M08-HX, M08-SO, MN15), and systems heavily characterized by self-interaction error (e.g., M06-2X, M08-HX, M08-SO, MN15), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-2X is recommended from the 10 hybrid Minnesota functionals). Similarly, the main strength of the local Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., MN15-L), barrier heights (e.g., MN12-L), and systems heavily characterized by self-interaction error (e.g., MN12-L and MN15-L), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-L is clearly the best from the four local Minnesota functionals). As an overall guide, M06-2X and MN15 are perhaps the most broadly useful hybrid Minnesota functionals, while M06-L and MN15-L are perhaps the most broadly useful local Minnesota functionals, although each has different strengths and weaknesses. PMID:27537680

  19. Measuring the Fusion Cross-Section of 18,19 O + 12 C with Low-Intensity Beams at Energies Near and Below the Coulomb Barrier

    NASA Astrophysics Data System (ADS)

    Steinbach, Tracy; Vadas, Justin; Schmidt, Jon; Singh, Varinderjit; Hudan, Sylvie; Desouza, Romualdo; Baby, Lagy; Kuvin, Sean; Wiedenhover, Ingo; Umar, Sait; Oberacker, Volker

    2015-04-01

    Fusion of neutron-rich light nuclei has been proposed as a heat source that triggers an X-ray superburst in the crust of an accreting neutron star. To investigate this hypothesis the total fusion cross-section for beams of low-intensity, neutron-rich nuclei (<105 ions/s) on light targets has been measured at energies near and below the Coulomb barrier. Evaporation residues, resulting from the fusion of oxygen and 12 C nuclei, were identified by their energy and Time-of-flight. Using this technique, the fusion excitation function was measured in the sub-barrier domain down to the 2 mb level. Comparison of the measured fusion excitation function with the predictions of a density constrained TDHF model reveals that the experimental data exhibit a smaller decrease in cross-section with decreasing energy than is theoretically predicted. This difference can be interpreted as a larger tunneling probability for the experimental data as compared to the theoretical predictions. To determine if this difference increases in magnitude with decreasing incident energy improvements have been implemented to enable measurement of the fusion cross-section to an even lower level. Supported by the US DOE under Grand No. DEFG02-88ER-40404.

  20. An accurate full-dimensional potential energy surface for H-Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption.

    PubMed

    Janke, Svenja M; Auerbach, Daniel J; Wodtke, Alec M; Kandratsenka, Alexander

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab. PMID:26429033

  1. An accurate full-dimensional potential energy surface for H–Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption

    SciTech Connect

    Janke, Svenja M.; Auerbach, Daniel J.; Kandratsenka, Alexander; Wodtke, Alec M.

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H–Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  2. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

    SciTech Connect

    Erikat, I. A.; Hamad, B. A.

    2013-11-07

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

  3. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface.

    PubMed

    Erikat, I A; Hamad, B A

    2013-11-01

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir-C and Ir-Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule. PMID:24206318

  4. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

    NASA Astrophysics Data System (ADS)

    Erikat, I. A.; Hamad, B. A.

    2013-11-01

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir-C and Ir-Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

  5. Language barriers

    PubMed Central

    Ngwakongnwi, Emmanuel; Hemmelgarn, Brenda R.; Musto, Richard; King-Shier, Kathryn M.; Quan, Hude

    2012-01-01

    Abstract Objective To assess use of regular medical doctors (RMDs), as well as awareness and use of telephone health lines or telehealth services, by official language minorities (OLMs) in Canada. Design Analysis of data from the 2006 postcensal survey on the vitality of OLMs. Setting Canada. Participants In total, 7691 English speakers in Quebec and 12 376 French speakers outside Quebec, grouped into those who experienced language barriers and those with no language barriers. Main outcome measures Health services utilization (HSU) by the presence of language barriers; HSU measures included having an RMD, use of an RMD’s services, and awareness of and use of telephone health lines or telehealth services. Multivariable models examined the associations between HSU and language barriers. Results After adjusting for age and sex, English speakers residing in Quebec with limited proficiency in French were less likely to have RMDs (adjusted odds ratio [AOR] 0.66, 95% CI 0.50 to 0.87) and to use the services of their RMDs (AOR 0.65, 95% CI 0.50 to 0.86), but were more likely to be aware of the existence of (AOR 1.50, 95% CI 1.16 to 1.93) and to use (AOR 1.43, 95% CI 0.97 to 2.11) telephone health lines or telehealth services. This pattern of having and using RMDs and telehealth services was not observed for French speakers residing outside of Quebec. Conclusion Overall we found variation in HSU among the language barrier populations, with lower use observed in Quebec. Age older than 45 years, male sex, being married or in common-law relationships, and higher income were associated with having RMDs for OLMs. PMID:23242902

  6. Kinetic energy barriers on the GaN(0001) surface: A nucleation study by scanning tunneling microscopy

    SciTech Connect

    Zheng Hao; Xie, M. H.; Wu, H. S.; Xue, Q. K.

    2008-01-15

    Island nucleation of GaN on its (0001) surface is studied by scanning tunneling microscopy. A comparison is made between surfaces with and without excess Ga and among surfaces with different excess Ga coverages. Evidence is provided for the change of step characteristics of GaN(0001) by excess Ga adlayers, where the Ehrlich-Schwoebel effect is seen to be mediated by excess Ga coverage. For single Ga adlayer covered GaN(0001) surfaces, nucleation island densities are evaluated, which are used to derive the kinetic barriers of adatom diffusion on a terrace. A barrier of less than 1 eV is obtained for the system, and the Ga adlayers make GaN growth surfactant mediated.

  7. Theoretical study of the geometries and decomposition energies of CO₂ on Al₁₂X: doping effect of Al₁₂X.

    PubMed

    Zhao, Jian-Ying; Zhao, Feng-Qi; Xu, Si-Yu; Ju, Xue-Hai

    2014-03-01

    The adsorption and decomposition of CO₂ molecule on X-centered icosahedronal Al₁₂X clusters (doping atom X=Al, Be, Zn, Fe, Ni, Cu, B, C, Si, P) were investigated by the DFT methods of PW91 and PWC. Adsorption energies, chemisorption energies and energy barriers of physic- and chemisorptions for CO₂ were determined. It was found that the doping atoms and spin states have important influences on the Al₁₂X geometries, electronic properties and energies of the adsorption processes. CO₂ chemisorption on the Al₁₂C cluster is energetically and kinetically unfavorable. CO₂ decomposition on the metallic doping Al₁₂X (X=Fe, Ni, Cu) clusters has relatively low energy barriers. On contrary, the barriers are large when X=B, C, Si and P. The energy barriers for CO₂ chemisorption and decomposition on the Al₁₂Fe cluster are 5.23 kJ/mol and 38.53 kJ/mol, respectively. These values are the lowest among all the clusters being discussed. The adsorption and decomposition of CO₂ on the Al₁₂X cluster can be tuned by X doping. PMID:24361849

  8. CO adsorption on the Ni2Pb/Ni(1 1 1) surface alloy: A DFT study

    NASA Astrophysics Data System (ADS)

    Kośmider, K.; Kucharczyk, R.; Jurczyszyn, L.

    2013-02-01

    Structural and electronic properties of the Pb/Ni(1 1 1) overlayer and the Ni2Pb/Ni(1 1 1) surface alloy have been investigated within a DFT-PBE approach in order to determine its reactivity towards adsorption of CO molecules. This work has been motivated by a photoemission study of CO adsorption on Pb/Ni(1 1 1) surface phases [V. Matolín et al., Phys. Rev. B 74 (2006) 075416] indicating that Pb adatoms inhibit CO adsorption in a purely geometrical way by site blocking at Ni(1 1 1), whereas surface alloying has a poisoning effect of the Ni-CO bond weakening. In general, our DFT computations confirm experimental findings for the Pb/Ni(1 1 1) overlayer, as the very high activation barrier of about 2 eV due to the presence of Pb adatoms makes the CO chemisorption virtually impossible. For the Ni2Pb/Ni(1 1 1) surface alloy, we show that CO can bind to Ni atoms in the on-top position, and this process occurs to be exothermic with the energy gain of 0.35 eV per CO molecule. Dramatic reduction of the computed adsorption energy with respect to the pure Ni(1 1 1) substrate is in apparent agreement with experiment. However, it follows from our simulations that the CO adsorption process is accompanied by a substantial rearrangement of Ni atoms within the Ni2Pb surface alloy layer. Taking into account the associated deformation energy in the overall energetic balance yields nearly the same interaction energy between the CO molecules and the Ni atoms for the alloyed and the pure Ni(1 1 1) substrate, so the Ni-CO bond appears not to be weakened. The experimentally observed suppression of CO adsorption upon the alloy formation can be explained by a notable increase of the activation barrier for CO chemisorption from about 0.1 eV for the pure Ni(1 1 1) to roughly 0.5 eV for the Ni2Pb/Ni(1 1 1) surface alloy, affecting the corresponding reaction rate.

  9. Quasihomogeneous nucleation of amyloid beta yields numerical bounds for the critical radius, the surface tension, and the free energy barrier for nucleus formation

    NASA Astrophysics Data System (ADS)

    Garai, K.; Sahoo, B.; Sengupta, P.; Maiti, S.

    2008-01-01

    Amyloid aggregates are believed to grow through a nucleation mediated pathway, but important aggregation parameters, such as the nucleation radius, the surface tension of the aggregate, and the free energy barrier toward aggregation, have remained difficult to measure. Homogeneous nucleation theory, if applicable, can directly relate these parameters to measurable quantities. We employ fluorescence correlation spectroscopy to measure the particle size distribution in an aggregating solution of Alzheimer's amyloid beta molecule (Aβ1-40) and analyze the data from a homogeneous nucleation theory perspective. We observe a reproducible saturation concentration and a critical dependence of various aspects of the aggregation process on this saturation concentration, which supports the applicability of the nucleation theory to Aβ aggregation. The measured size distributions show a valley between two peaks ranging from 5to50nm, which defines a boundary for the value of the nucleation radius. By carefully controlling the conditions to inhibit heterogeneous nucleation, we can hold off nucleation in a 25 times supersaturated solution for at least up to 3h at room temperature. This quasi-homogeneous kinetics implies that at room temperature, the surface energy of the Aβ /water interface is ⩾4.8mJ/m2, the free energy barrier to nucleation (at 25 times supersaturation) is ⩾1.93×10-19J, and the number of monomers in the nucleus is ⩾29.

  10. Polarization Energies at Organic-Organic Interfaces: Impact on the Charge Separation Barrier at Donor-Acceptor Interfaces in Organic Solar Cells.

    PubMed

    Ryno, Sean M; Fu, Yao-Tsung; Risko, Chad; Brédas, Jean-Luc

    2016-06-22

    We probe the energetic landscape at a model pentacene/fullerene (C60) interface to investigate the interactions between positive and negative charges, which are critical to the processes of charge separation and recombination in organic solar cells. Using a polarizable force field, we find that polarization energy, i.e., the stabilization a charge feels due to its environment, is larger at the interface than in the bulk for both a positive and a negative charge. The combination of the charge being more stabilized at the interface and the Coulomb attraction between the charges results in a barrier to charge separation at the pentacene/C60 interface that can be in excess of 0.7 eV for static configurations of the donor and acceptor locations. However, the impact of molecular motions, i.e., the dynamics, at the interface at room temperature results in a distribution of polarization energies and in charge separation barriers that can be significantly reduced. The dynamic nature of the interface is thus critical, with the polarization energy distributions indicating that sites along the interface shift in time between favorable and unfavorable configurations for charge separation. PMID:27244215

  11. Simultaneous optical model analysis of elastic scattering, fusion, and breakup for the Be9+Sm144 system at near-barrier energies

    NASA Astrophysics Data System (ADS)

    Gómez Camacho, A.; Gomes, P. R. S.; Lubian, J.; Padrón, I.

    2008-05-01

    A simultaneous optical model calculation of elastic scattering, complete fusion, and breakup cross sections for energies around the Coulomb barrier is presented for reactions involving the weakly bound projectile Be9 on the medium size target Sm144. In the calculations, the nuclear polarization potential U is split into a volume part UF, which is responsible for fusion reactions, and a surface part UDR, which accounts for direct reactions. A simultaneous χ2 analysis of elastic and complete fusion data shows that the extracted optical potential parameters of the real VF and imaginary WF parts of UF and the corresponding parts VDR and WDR of UDR satisfy separately the dispersion relation. Energy-dependent forms for the fusion and direct reaction potentials indicate that, at the strong absorption radius, the direct reaction potentials dominate over the fusion potentials. Moreover, the imaginary direct reaction potential results in a rather smooth function of E around the barrier energy. These findings show that the threshold anomaly, usually present in reactions with tightly bound projectiles, is not exhibited for the system Be9+Sm144. Within this formalism, the effect of breakup reactions on complete fusion is studied by turning on and off the potentials responsible for breakup reactions.

  12. Unusual dissociative adsorption of H2 over stoichiometric MgO thin film supported on molybdenum

    NASA Astrophysics Data System (ADS)

    Song, Zhenjun; Xu, Hu

    2016-03-01

    The dissociation of a hydrogen molecule on perfect MgO(0 0 1) films deposited on Mo(0 0 1) surface is investigated systematically using periodic density-functional theory (DFT) method. The unusual adsorption behavior of heterolytic dissociative hydrogen molecule at neighboring surface oxygen and surface magnesium, is clarified here. To our knowledge, this heterolytic dissociative state has never been found before on bulk MgO(0 0 1) or metal supported perfect MgO(0 0 1) surfaces (without low coordination sites). The results confirm that, in all cases, the heterolytic dissociation is much more favorable that homolytic dissociation both energetically and kinetically. The energy differences between two dissociative states are very large, in the range of 1.1 eV-1.5 eV for Mo supported 1 ML-3 ML oxide films, which inhibits, to a great extent, the homolytic dissociation in the respect of reaction thermodynamics. The energy barriers of heterolytic dissociation are about 0.5 eV, much lower that the barrier of homolytic dissociation. The transformation reaction on thick films will be more endothermic. Passing through heterolytic dissociation state has significantly lowered the reaction heat and the energy barrier for obtaining homolytic dissociative structure, which makes the homolytic splitting of H2 easier on 2 ML oxide films. The results provide a useful strategy for enhancing the reactivity of the nonreducible metal oxide.

  13. Investigation of Neutron-Rich Osmium Isotopes in the Reaction 136Xe+208Pb at the Energies Close to Coulomb Barrier

    NASA Astrophysics Data System (ADS)

    Novikov, K.; Kozulin, E.; Dmitriev, S.; Greenlees, P.; Hannape, F.; Itkis, I. M.; Khlebnikov, S.; Knyazheva, G.; Loktev, T.; Maurer, J.; di Nitto, A.; Pakarinen, J.; Ruotsalainen, P.; Sandzelius, M.; Sorri, J.; Trzaska, W. H.; Vardaci, E.; Zagrebaev, V.

    2013-06-01

    At the present time, a great interest is paid to the research of the properties of atomic nuclei (isotopes) located far from the beta stability line. Neutron-rich osmium isotopes of multi-nucleon transfer reactions investigated in this work. The reaction 136Xe+208Pb with energy near Coulomb barrier is used for production osmium isotopes. The CORSAR-V setup was created in framework of our investigations. Method of separation volatile reaction products from non-volatile products was realized from experimental setup. The fist experimental results were obtained at this time.

  14. Superheavy nuclei and fission barriers

    NASA Astrophysics Data System (ADS)

    Lu, Bing-Nan; Zhao, Jie; Zhao, En-Guang; Zhou, Shan-Gui

    In this chapter, we will present relativistic mean field (RMF) description of heavy and superheavy nuclei (SHN). We will discuss the shell structure and magic numbers in the mass region of SHN, binding energies and α decay Q values, shapes of ground states and potential energy surfaces and fission barriers. We particularly focus on the multidimensionally-constrained covariant density functional theories (CDFT) and the applications of CDFT to the study of exotic nuclear shapes and fission barriers.

  15. Hybrid adsorptive membrane reactor

    DOEpatents

    Tsotsis, Theodore T.; Sahimi, Muhammad; Fayyaz-Najafi, Babak; Harale, Aadesh; Park, Byoung-Gi; Liu, Paul K. T.

    2011-03-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  16. Hybrid adsorptive membrane reactor

    NASA Technical Reports Server (NTRS)

    Tsotsis, Theodore T. (Inventor); Sahimi, Muhammad (Inventor); Fayyaz-Najafi, Babak (Inventor); Harale, Aadesh (Inventor); Park, Byoung-Gi (Inventor); Liu, Paul K. T. (Inventor)

    2011-01-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  18. The Oklahoma Field Test: Air-conditioning electricity savings from standard energy conservation measures, radiant barriers, and high-efficiency window air conditioners

    SciTech Connect

    Ternes, M.P.; Levins, W.P.

    1992-08-01

    A field test Involving 104 houses was performed in Tulsa, Oklahoma, to measure the air-conditioning electricity consumption of low-income houses equipped with window air conditioners, the reduction in this electricity consumption attributed to the installation of energy conservation measures (ECMS) as typically installed under the Oklahoma Weatherization Assistance Program (WAP), and the reduction achieved by the replacement of low-efficiency window air conditioners with high-efficiency units and the installation of attic radiant barriers. Air-conditioning electricity consumption and indoor temperature were monitored weekly during the pre-weatherization period (June to September 1988) and post-weatherization period (May to September 1989). House energy consumption models and regression analyses were used to normalize the air-conditioning electricity savings to average outdoor temperature conditions and the pre-weatherization indoor temperature of each house. The following conclusions were drawn from the study: (1) programs directed at reducing air-conditioning electricity consumption should be targeted at clients with high consumption to improve cost effectiveness; (2) replacing low-efficiency air conditioners with high-efficiency units should be considered an option in a weatherization program directed at reducing air-conditioning electricity consumption; (3) ECMs currently being installed under the Oklahoma WAP (chosen based on effectiveness at reducing space-heating energy consumption) should continue to be justified based on their space-heating energy savings potential only; and (4) attic radiant barriers should not be included in the Oklahoma WAP if alternatives with verified savings are available or until further testing demonstrates energy savings or other benefits in this typo of housing.

  19. Methylamine adsorption and decomposition on B12N12 nanocage: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Nurazar, Roghaye

    2014-08-01

    Density functional theory calculations are performed to investigate the adsorption and decomposition of methylamine (CH3NH2) on the surface of a B12N12 fullerene-like nanocage. Two adsorption types and two reaction channels are identified. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3NH2. The pathways of CH3NH2 decomposition via bond scission of the Csbnd N and Nsbnd H bonds are examined. The results indicate that Nsbnd H bond scission is the most favorable pathway on the B12N12 surface. The side reaction that generates CH3 and NH2 fragments is endothermic by 15.6 kcal/mol with an energy-barrier height of 81.5 kcal/mol. For the CH3NH2 decomposition on the B12N12 surface, the rate-determining step appears to be as the following reaction: CH3NH → CH3N + H.

  20. Adsorption of Ar on individual carbon nanotubes, graphene, and graphite

    NASA Astrophysics Data System (ADS)

    Dzyubenko, Boris; Kahn, Joshua; Vilches, Oscar; Cobden, David

    2015-03-01

    We compare and contrast results of adsorption measurements of Ar on single-walled carbon nanotubes, graphene, and graphite. Adsorption isotherms on individual suspended nanotubes were obtained using both the mechanical resonance frequency shift (sensitive to mass adsorption) and the electrical conductance. Isotherms on graphene mounted on hexagonal boron nitride were obtained using only the conductance. New volumetric adsorption isotherms on bulk exfoliated graphite were also obtained, paying special attention to the very low coverage region (less than 2% of a monolayer). This allowed us to compare the degree of heterogeneity on the three substrate types, the binding energies, and the van der Waals 2D parameters. Research supported by NSF DMR 1206208.

  1. C sbnd N rotational barrier, MP4 and CCSD(T) energies of formohydrazide and formohydroxamic acid and vibrational spectral analysis of the hydrazide

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.

    2009-02-01

    The C sbnd N internal rotations in formohydrazide OHC sbnd NH sbnd NH 2 and formohydroxamic acid OHC sbnd NH sbnd OH were investigated at the B3LYP/6-311+G** and MP2/6-311+G** levels of theory. The C sbnd N rotational barrier in the molecules was calculated to be about 28-30 kcal/mol. The energies of the molecules were calculated at the B3LYP, MP2, MP4(SDTQ) and CCSD(T) levels of theory with both 6-311G** and 6-311+G** basis sets. From the calculations at all the levels formohydroxamic acid was predicted to exist predominantly in a non-planar near- cis conformation at ambient temperature. From all the calculations formohydrazide was predicted to have a planar cis-syn (C dbnd O and N sbnd N bonds eclipse each other and NH 2 moiety is syn to C sbnd N bond) conformation as the lowest energy structure. The NH 2 inversion barrier in formohydrazide was predicted to be about 5-7 kcal/mol. The vibrational frequencies of the cis-syn formohydrazide were computed at the B3LYP/6-311+G** level and normal coordinate calculations were carried out. Complete vibrational assignments were made on the basis of normal coordinate analyses and experimental infrared and Raman data of the molecule.

  2. Influence of chlorine substitution on intramolecular hydrogen bond energy and ESIPT barrier: Experimental and theoretical measurements on the photophysics of 3,5-dichlorosalicylic acid

    NASA Astrophysics Data System (ADS)

    Paul, Bijan Kumar; Samanta, Anuva; Guchhait, Nikhil

    2010-08-01

    The effect of chlorine atom on the intramolecular hydrogen bond strength and excited state proton transfer barrier in pharmaceutically important chloro-substituted derivative of salicylic acid viz., 3,5-dichlorosalicylic acid (3,5DCSA) has been explored through steady-state absorption, emission and time-resolved fluorescence spectroscopy. Stokes shifted emission band with negligible solvent polarity dependency corresponds to the spectroscopic signature of excited state intramolecular proton transfer (ESIPT) reaction. The spectral signature was compared with its parent molecule salicylic acid (SA) and 5-chlorosalicylic acid (5ClSA). Quantum chemical calculations by ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods have been fruitfully employed to correlate experimental findings. Calculated S0 and S1 states potential energy surfaces across the proton transfer co-ordinate substantiates the experimental evidence for the occurrence of ESIPT process and negates the ground state intramolecular proton transfer (GSIPT) reaction. Weakening of intramolecular hydrogen bond (IMHB) energy and subsequent enhancement of barrier to ESIPT reaction in 3,5DCSA as compared to SA and 5ClSA appears to be a reflection of conjugate impact of electron withdrawing inductive and electron donating resonance effects of chlorine substitutions depending on its location on the aromatic benzene nucleus.

  3. Mapping the Surface Adsorption Forces of Nanomaterials in Biological Systems

    PubMed Central

    Xia, Xin R.; Monteiro-Riviere, Nancy A.; Mathur, Sanjay; Song, Xuefeng; Xiao, Lisong; Oldenberg, Steven J.; Fadeel, Bengt; Riviere, Jim E.

    2011-01-01

    The biological surface adsorption index (BSAI) is a novel approach to characterize surface adsorption energy of nanomaterials that is the primary force behind nanoparticle aggregation, protein corona formation, and other complex interactions of nanomaterials within biological systems. Five quantitative nanodescriptors were obtained to represent the surface adsorption forces (hydrophobicity, hydrogen bond, polarity/polarizability, and lone-pair electrons) of the nanomaterial interaction with biological components. We have mapped the surface adsorption forces over 16 different nanomaterials. When the five-dimensional information of the nanodescriptors was reduced to two dimensions, the 16 nanomaterials were classified into distinct clusters according their surface adsorption properties. BSAI nanodescriptors are intrinsic properties of nanomaterials useful for quantitative structure–activity relationship (QSAR) model development. This is the first success in quantitative characterization of the surface adsorption forces of nanomaterials in biological conditions, which could open a quantitative avenue in predictive nanomedicine development, risk assessment, and safety evaluation of nanomaterials. PMID:21999618

  4. Adsorption of aqueous copper on peanut hulls

    NASA Astrophysics Data System (ADS)

    Davis, Kanika Octavia

    A method was established for measuring the adsorption of Cu(II) from aqueous solution to unmodified and modified peanut hulls at constant temperature and pH. Modification of the hulls was performed by oxidation with alkaline hydrogen peroxide. During the modification process, the hydrogen peroxide solubilizes the lignin component, making the surface more porous which increases the availability of binding sites, while simultaneously oxidizing the cellulose. The oxidation of alcohol groups creates more binding sites by creating functional groups such as COO-, which increases chelation to metal ions. Fourier transform infrared spectroscopy confirms delignification of the peanut hulls by the disappearance of carboxyl peaks of the modified hulls, which were originally produced from the lignin content. Although, oxidation is not fully confirmed, it is not ruled out because the expected carboxylate peak (1680 cm-1) maybe overshadowed by a broad peak due to OH bending of water adsorbed to the hulls. Hulls adsorbed copper from solutions in the concentration range of 50-1000 ppm of CuCl2. Concentrations of pre- and post-adsorption solutions were determined using inductively coupled plasma optical emission spectroscopy. The adsorption isotherms were fit to known two and three-parameter models, evaluated and the binding mechanism was inferred. Maximum surface coverage was 3.5 +/- 0.6 mg Cu2+ /g hull for unmodified hulls and 11 +/- 1 mg Cu2+/g hull for modified hulls. The adsorption for the hulls is best described by the Langmuir model, suggesting monolayer, homogeneous adsorption. With a free energy of adsorption of 10.5 +/- 0.9 kJ/mol for unmodified hulls and 14.5 +/-0.4 kJ/mol for modified hulls, the process is categorized as chemisorption for both types of hulls. The adsorption for both hulls is also described by the Redlich-Peterson model, giving beta nearer to 1 than 0, which further suggests homogeneous adsorption described by the Langmuir model. After rinsing the hulls

  5. Substrate-induced structures of bismuth adsorption on graphene: a first principles study.

    PubMed

    Lin, Shih-Yang; Chang, Shen-Lin; Chen, Hsin-Hsien; Su, Shu-Hsuan; Huang, Jung-Chun; Lin, Ming-Fa

    2016-07-28

    The geometric and electronic properties of Bi-adsorbed monolayer graphene, enriched by the strong effect of a substrate, are investigated by first-principles calculations. The six-layered substrate, corrugated buffer layer, and slightly deformed monolayer graphene are all simulated. Adatom arrangements are thoroughly studied by analyzing the ground-state energies, bismuth adsorption energies, and Bi-Bi interaction energies of different adatom heights, inter-adatom distance, adsorption sites, and hexagonal positions. A hexagonal array of Bi atoms is dominated by the interactions between the buffer layer and the monolayer graphene. An increase in temperature can overcome a ∼50 meV energy barrier and induce triangular and rectangular nanoclusters. The most stable and metastable structures agree with the scanning tunneling microscopy measurements. The density of states exhibits a finite value at the Fermi level, a dip at ∼-0.2 eV, and a peak at ∼-0.6 eV, as observed in the experimental measurements of the tunneling conductance. PMID:27354143

  6. Adsorption and solvation of ethanol at the water liquid-vapor interface: a molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Wilson, M. A.; Pohorille, A.

    1997-01-01

    The free energy profiles of methanol and ethanol at the water liquid-vapor interface at 310K were calculated using molecular dynamics computer simulations. Both alcohols exhibit a pronounced free energy minimum at the interface and, therefore, have positive adsorption at this interface. The surface excess was computed from the Gibbs adsorption isotherm and was found to be in good agreement with experimental results. Neither compound exhibits a free energy barrier between the bulk and the surface adsorbed state. Scattering calculations of ethanol molecules from a gas phase thermal distribution indicate that the mass accommodation coefficient is 0.98, and the molecules become thermalized within 10 ps of striking the interface. It was determined that the formation of the solvation structure around the ethanol molecule at the interface is not the rate-determining step in its uptake into water droplets. The motion of an ethanol molecule in a water lamella was followed for 30 ns. The time evolution of the probability distribution of finding an ethanol molecule that was initially located at the interface is very well described by the diffusion equation on the free energy surface.

  7. Density functional theory study of adsorption and dissociation of HfCl4 and H2O on Ge /Si(100)-(2×1): Initial stage of atomic layer deposition of HfO2 on SiGe surface

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Lu, Hong-Liang; Zhang, David Wei; Xu, Min; Ren, Jie; Zhang, Jian-Yun; Wang, Ji-Tao; Wang, Li-Kang

    2005-04-01

    We have investigated adsorption and dissociation of water and HfCl4 on Ge /Si(100)-(2×1) surface with density functional theory. The Si-Ge heterodimer and Ge-Ge homodimer are employed to represent the Si1-xGex surface. The activation energy for adsorption of water on Ge-Ge homodimer is much higher than that on Si-Ge heterodimer. No net activation barrier exists during the adsorption of HfCl4 on both SiGe surface dimers. The differences in the potential energy surface between reactions on Si-Ge and Ge-Ge dimers are due to different bond strengths. It should also be noticed that the activation energy for HfCl4 is quite flat, thus HfCl4 adsorbs and dissociates on Ge /Si(100)-(2×1) easily.

  8. Adsorption of nicotine from aqueous solution onto hydrophobic zeolite type USY

    NASA Astrophysics Data System (ADS)

    Lazarevic, Natasa; Adnadjevic, Borivoj; Jovanovic, Jelena

    2011-07-01

    The isothermal adsorption of nicotine from an aqueous solution onto zeolite type USY was investigated. The adsorption isotherms of nicotine onto the zeolite at different temperatures ranging from 298 to 322 K were determined. It was found that the adsorption isotherms can be described by the model of Freundlich adsorption isotherm. Based on the adsorption isotherms the changes of adsorption heat, free energy and entropy with adsorption degree were determined. The determined decrease of adsorption heat with adsorption degree can be explained by the presence of the adsorption centers of different energy and concentration on interface of zeolite-nicotine solution. It was found that the probability function of density distribution of the heat of adsorption (DDF) has exponential form. It was concluded that the possibility of fitting the adsorption isotherms of nicotine onto the zeolite by Freundlich adsorption isotherm was a direct consequence of that. The determined increase in entropy with the increase in adsorption degree can be explained with the change of phase state of adsorbed nicotine.

  9. Development of Simultaneous Corrosion Barrier and Optimized Microstructure in FeCrAl Heat-Resistant Alloy for Energy Applications. Part 1: The Protective Scale

    NASA Astrophysics Data System (ADS)

    Pimentel, G.; Aranda, M. M.; Chao, J.; González-Carrasco, J. L.; Capdevila, C.

    2015-09-01

    Coarse-grained Fe-based oxide dispersion-strengthened (ODS) steels are a class of advanced materials for combined cycle gas turbine systems to deal with operating temperatures and pressures of around 1100°C and 15-30 bar in aggressive environments, which would increase biomass energy conversion efficiencies up to 45% and above. This two-part paper reports the possibility of the development of simultaneous corrosion barrier and optimized microstructure in a FeCrAl heat-resistant alloy for energy applications. The first part reports the mechanism of generating a dense, self-healing α-alumina layer by thermal oxidation, during a heat treatment that leads to a coarse-grained microstructure with a potential value for high-temperature creep resistance in a FeCrAl ODS ferritic alloy, which will be described in more detail in the second part.

  10. Overcoming Barriers.

    PubMed

    Neal-Boylan, Leslie; Schmidt, Kari L

    2015-01-01

    Dr. Neal-Boylan's program of scholarship has always focused on nurse workforce issues. She recently published two books related to how nurses work. One (The Nurse's Reality Gap: Overcoming Barriers Between Academic Achievement and Clinical Success; Neal-Boylan, 2013) focused on the experience of new graduates from baccalaureate, master's, and doctoral programs. The second book, The Nurse's Reality Shift: Using Our History to Transform Our Future (Neal-Boylan, 2014), focuses on the problems nursing continues to face throughout our history and has failed to correct. PMID:26200309

  11. Methanol adsorption on the clean CeO₂(111) surface: A density functional theory study

    SciTech Connect

    Mei, Donghai; Deskins, N. Aaron; Dupuis, Michel; Ge, Qingfeng

    2007-07-19

    Molecular and dissociative adsorption of methanol at various sites on the stoichiometric CeO₂(111) surface have been studied using density functional theory periodic calculations. At 0.25 monolayer (ML) coverage, the dissociative adsorption with an adsorption energy of 0.55 eV is slightly favored. The most stable state is the dissociative adsorption of methanol via C-H bond breaking, forming a coadsorbed hydroxymethyl group and hydrogen adatom on two separate O₃C surface sites. The strongest molecular adsorption occurs through an O-Ce₇subC connection with an adsorption energy of 0.48 eV. At methanol coverage of 0.5 ML, the dissociative adsorption and the molecular adsorption became competitive. The adsorption energy per methanol molecule for both adsorption modes falls into a narrow range of 0.46-0.55 eV. As methanol coverage increases beyond 0.5 ML, the molecular adsorption becomes more energetically favorable than the dissociative adsorption because of the attractive hydrogen bonding between coadsorbed methanol molecules. At full monolayer, the adsorption energy of molecular adsorption is 0.40 eV per molecule while the adsorption energy for total dissociative adsorption of methanol is only 0.17 eV. The results at different methanol coverages indicate that methanol can adsorb on a defect-free CeO₂(111) surface, which are also consistent with experimental observations. This research was performed using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory, which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Computing time was made available under a Computational Grand Challenge “Computational Catalysis”. This work also financially supported by the Laboratory Directed Research and Development project of PNNL.

  12. Fusion barrier distribution described by above-barrier resonances

    NASA Astrophysics Data System (ADS)

    Sahu, B.; Agarwalla, S. K.; Shastry, C. S.

    2003-01-01

    We have constructed an analytically solvable, smooth, short-ranged, realistic and composite barrier potential with parameters controlling the flatness at the top, the range and the asymmetry of the barrier. When certain condition on flatness is obeyed, the transmission coefficient (T) across this barrier is found to be oscillatory in the above-barrier region of energy representing above-barrier resonances (ABR). Using this T with proper dependence on angular momentum, we estimate the results of fusion cross section σ f and the distribution function {d2(Eσ f) }/{dE 2} in the cases of two best studied examples namely 16O +144Sm and 16O +208Pb systems. On comparison with the corresponding experimental data we find good explanations of these fusion data. The asymmetry in the composite barrier addresses the problem of sub-barrier enhancement of σ f data. On the other hand, for the first time, the oscillatory structure in the results of {d2(Eσ f) }/{dE 2} is proved to be the manifestation of ABR sustained by the composite barrier by virtue of its flatness at the top.

  13. Bonneville Power Administration and the Industrial Technologies Program Leverage Support to Overcome Energy Efficiency Barriers in the Northwest

    SciTech Connect

    2010-06-18

    Through its Energy Smart Industrial program, BPA is informing and assisting utilities and industries to have a better understanding of the benefits that come from participating in energy-savings programs. Read about how BPA is encouraging energy efficiency projects through its utilities.

  14. Barrier Formation

    PubMed Central

    Lyaruu, D.M.; Medina, J.F.; Sarvide, S.; Bervoets, T.J.M.; Everts, V.; DenBesten, P.; Smith, C.E.; Bronckers, A.L.J.J.

    2014-01-01

    Enamel fluorosis is an irreversible structural enamel defect following exposure to supraoptimal levels of fluoride during amelogenesis. We hypothesized that fluorosis is associated with excess release of protons during formation of hypermineralized lines in the mineralizing enamel matrix. We tested this concept by analyzing fluorotic enamel defects in wild-type mice and mice deficient in anion exchanger-2a,b (Ae2a,b), a transmembrane protein in maturation ameloblasts that exchanges extracellular Cl− for bicarbonate. Defects were more pronounced in fluorotic Ae2a,b−/− mice than in fluorotic heterozygous or wild-type mice. Phenotypes included a hypermineralized surface, extensive subsurface hypomineralization, and multiple hypermineralized lines in deeper enamel. Mineral content decreased in all fluoride-exposed and Ae2a,b−/− mice and was strongly correlated with Cl−. Exposure of enamel surfaces underlying maturation-stage ameloblasts to pH indicator dyes suggested the presence of diffusion barriers in fluorotic enamel. These results support the concept that fluoride stimulates hypermineralization at the mineralization front. This causes increased release of protons, which ameloblasts respond to by secreting more bicarbonates at the expense of Cl− levels in enamel. The fluoride-induced hypermineralized lines may form barriers that impede diffusion of proteins and mineral ions into the subsurface layers, thereby delaying biomineralization and causing retention of enamel matrix proteins. PMID:24170372

  15. Effective interactions in multisite cells for adsorption in microporous materials

    NASA Astrophysics Data System (ADS)

    Demontis, Pierfranco; Pazzona, Federico G.; Suffritti, Giuseppe B.

    2009-04-01

    Local, discrete models of self-interacting multisite adsorption cells have been shown to be able to provide a coarse-grained representation of equilibrium properties of small molecules adsorbed in nanoporous materials at the mesoscopic scale. In the present work we show how the essential statistical properties of a host cell of structured sites with multiple adsorption energies and particle-particle interactions (that is the partition function, the average energy, and the average number of guests close to the windows connecting the cell to its surroundings) can be reproduced by a less-structured cell with two occupancy-dependent adsorption energy levels.

  16. A theoretical study of nitric oxide adsorption and dissociation on copper-exchanged zeolites SSZ-13 and SAPO-34: the impact of framework acid-base properties.

    PubMed

    Uzunova, Ellie L; Mikosch, Hans

    2016-04-28

    The adsorption of nitric oxide as dinitrosyls and the deNOx proton-mediated reaction mechanism are assessed using electronic structure methods and transition state theory. Dinitrosyls bind to copper cations either via a N-atom or via an O-atom, with N-binding being more stable. In their ground states, dinitrosyls reach a planar configuration with the metal cation. The two nitric oxide molecules are kept together in O-bonded dinitrosyls by the N-N bond and the adsorption complex obtains a cyclic planar structure, while N-bonded dinitrosyls have out-of-plane conformations with low energy barriers. An asymmetric structure ZCu(ON)(NO) with one N-bonded nitrosyl and the other O-bonded is of the lowest stability. The cyclic hyponitrite ZCu(ON)2 adsorption complex undergoes O-N bond breaking upon protonation of one oxygen atom and this lowers the energy barrier of the first reaction step of nitric oxide dissociation to yield N2O and a hydroxylated copper site ZCu(OH) by 45 kJ mol(-1) for Cu-SAPO-34 and by 46 kJ mol(-1) for Cu-SSZ-13. The more stable N-bonded dinitrosyl ZCu(NO)2 provides less favorable reaction which passes through the asymmetric ZCu(ON)(NO) intermediate structure. Brønsted acid sites facilitate the reversal of one nitrosyl group. The role of proton transfer from a Brønsted acid site to dinitrosyls is not limited to the initial step of facilitating the N-O bond cleavage, but it also contributes to the stabilization of intermediate oxygen species formed at the copper site as hydroxide ZCu(OH) and hydroperoxide, ZCuOOH. Without protonation, the unstable ZCuO intermediate causes structural deformation with strongly lengthened T-O bonds in the framework. The rate determining step is N2O decomposition to N2 and O2, whether starting with a ZCu(NO)2 or a ZCu(ON)2 adsorption complex, and Cu-SSZ-13 has a clear advantage with an energy barrier of 195 kJ mol(-1)vs. 265 kJ mol(-1) for Cu-SAPO-34. In the final step the Brønsted acid site is restored by proton

  17. Binary association complexes of LiH, BeH/sub 2/, and BH/sub 3/. Relative isomer stabilities and barrier heights for their interconversion: energy barriers in the dimerization reactions

    SciTech Connect

    DeFrees, D.J.; Raghavachari, K.; Schlegel, H.B.; Pople, J.A.; Schleyer, P.v.R.

    1987-03-26

    Ab initio molecular orbital theory has been used to study the six compounds Li/sub 2/H/sub 2/, LiBeH/sub 3/, LiBH/sub 4/, Be/sub 2/H/sub 4/, BeBH/sub 5/, and B/sub 2/H/sub 6/. Geometry optimizations and vibrational analysis at the HF/6-31G* level indicate Li--(H)/sub 2/--Li (D/sub 2h/), Li--(H)/sub 2/--BeH (C/sub 2v/), Li--(H)/sub 3/--BH (C/sub 3v/), HBe--(H)/sub 2/--BeH (D/sub 2h/), HBe--(H)/sub 3/--BH (C/sub 3v/), and H/sub 2/B--(H)/sub 2/--BH/sub 2/ (D/sub 2h/) to the most stable forms. Inclusion of electron correlation corrections at the MP4/6-31G** level does not alter these conclusions. Other isomers were also examined in detail, and it was found that the potential energy surfaces for the species are generally flat. Activation energies for isomer interconversion and hydrogen scrambling reactions are generally less than 10 kcal mol/sup -1/. Examination of the HF/3-21 G potential surfaces indicates that there is no activation energy for the dimerization of LiH or BeH/sub 2/. The same is true for the dimerization of BH/sub 3/ at the correlated MP26-31G* level, although a small barrier is found on the HF/6-31G* surface. Enthalpies of complexation at 298 K from separate LiH, BeH/sub 2/, and BH/sub 3/ fragments, ..delta..H/sup 0//sub 298/, computed by using the HF/6-31G* harmonic frequencies and the MP4/6-31G** electronic energies are as follows: Li/sub 2/H/sub 2/, -45.9; LiBeH/sub 3/, -43.6; LiBH/sub 4/, -60.1; Be/sub 2/H/sub 4/, -30.5; BeBH/sub 5/, -45.7; B/sub 2/H/sub 6/, -36.0 kcal mol/sup -1/.

  18. Unusual adsorption site behavior in PCN-14 metal-organic framework predicted from Monte Carlo simulation.

    PubMed

    Lucena, Sebastião M P; Mileo, Paulo G M; Silvino, Pedro F G; Cavalcante, Célio L

    2011-12-01

    The adsorption equilibrium of methane in PCN-14 was simulated by the Monte Carlo technique in the grand canonical ensemble. A new force field was proposed for the methane/PCN-14 system, and the temperature dependence of the molecular siting was investigated. A detailed study of the statistics of the center of mass and potential energy showed a surprising site behavior with no energy barriers between weak and strong sites, allowing open metal sites to guide methane molecules to other neighboring sites. Moreover, this study showed that a model assuming weakly adsorbing open metal clusters in PCN-14, densely populated only at low temperatures (below 150 K), can explain published experimental data. These results also explain previously observed discrepancies between neutron diffraction experiments and Monte Carlo simulations. PMID:22044392

  19. A first-principles study of sodium adsorption and diffusion on phosphorene.

    PubMed

    Liu, Xiao; Wen, Yanwei; Chen, Zhengzheng; Shan, Bin; Chen, Rong

    2015-07-01

    The structural, electronic, electrochemical as well as diffusion properties of Na doped phosphorene have been investigated based on first-principles calculations. The strong binding energy between Na and phosphorene indicates that Na could be stabilized on the surface of phosphorene without clustering. By comparing the adsorption of Na atoms on one side and on both sides of phosphorene, it has been found that Na-Na exhibits strong repulsion at the Na-Na distance of less than 4.35 Å. The Na intercalation capacity is estimated to be 324 mA h g(-1) and the calculated discharge curve indicates quite a low Na(+)/Na voltage of phosphorene. Moreover, the diffusion energy barrier of Na atoms on the phosphorene surface at both low and high Na concentrations is as low as 40-63 meV, which implies the high mobility of Na during the charge/discharge process. PMID:26051226

  20. On the adsorption and formation of Pt dimers on the CeO2(111) surface

    NASA Astrophysics Data System (ADS)

    Bruix, Albert; Nazari, Fariba; Neyman, Konstantin M.; Illas, Francesc

    2011-12-01

    The direct adsorption of Pt2 dimers on CeO2(111) and their formation from isolated adsorbed Pt atoms have been studied using periodic slab model calculations based on density functional theory and including the so-called on-site Hubbard parameter (GGA + U). In the most stable configuration Pt2 is found to be almost parallel to the surface; the electronic ground state is closed shell and there is no evidence of charge transfer towards or from the surface. The formation of Pt2 from two single adsorbed Pt atoms involves a rather small energy barrier of ˜0.10 eV only. On the contrary, dissociation of adsorbed Pt2 requires to overcome a considerable barrier of ˜1.43 eV. This indicates that once Pt2 is formed it will remain on the surface, thus likely triggering the growth of larger supported Pt particles.

  1. Ammonia Production Using Pressure Swing Adsorption

    SciTech Connect

    2009-02-01

    This factsheet describes a research project whose overall objective is to develop and demonstrate a technically feasible and commercially viable system that integrates reaction to produce ammonia along with recovery of the products by adsorption separation methods and significantly decrease the energy requirement in ammonia production.

  2. Quantum chemical ab initio prediction of proton exchange barriers between CH4 and different H-zeolites.

    PubMed

    Tuma, Christian; Sauer, Joachim

    2015-09-14

    A hybrid MP2:DFT (second-order Møller-Plesset perturbation theory-density functional theory) method that combines MP2 calculations for cluster models with DFT calculations for the full periodic structure is used to localize minima and transition structures for proton jumps at different Brønsted sites in different frameworks (chabazite, faujasite, ferrierite, and ZSM-5) and at different crystallographic positions of a given framework. The MP2 limit for the periodic structures is obtained by extrapolating the results of a series of cluster models of increasing size. A coupled-cluster (CCSD(T)) correction to MP2 energies is calculated for cluster models consisting of three tetrahedra. For the adsorption energies, this difference is small, between 0.1 and 0.9 kJ/mol, but for the intrinsic proton exchange barriers, this difference makes a significant (10.85 ± 0.25 kJ/mol) and almost constant contribution across different systems. The total values of the adsorption energies vary between 22 and 34 kJ/mol, whereas the total proton exchange energy barriers fall in the narrow range of 152-156 kJ/mol. After adding nuclear motion contributions (harmonic approximation, 298 K), intrinsic enthalpy barriers between 134 and 141 kJ/mol and apparent energy barriers between 105 and 118 kJ/mol are predicted for the different sites examined for the different frameworks. These predictions are consistent with experimental results available for faujasite, ferrierite, and ZSM-5. PMID:26374003

  3. Quantum chemical ab initio prediction of proton exchange barriers between CH{sub 4} and different H-zeolites

    SciTech Connect

    Tuma, Christian; Sauer, Joachim

    2015-09-14

    A hybrid MP2:DFT (second-order Møller–Plesset perturbation theory–density functional theory) method that combines MP2 calculations for cluster models with DFT calculations for the full periodic structure is used to localize minima and transition structures for proton jumps at different Brønsted sites in different frameworks (chabazite, faujasite, ferrierite, and ZSM-5) and at different crystallographic positions of a given framework. The MP2 limit for the periodic structures is obtained by extrapolating the results of a series of cluster models of increasing size. A coupled-cluster (CCSD(T)) correction to MP2 energies is calculated for cluster models consisting of three tetrahedra. For the adsorption energies, this difference is small, between 0.1 and 0.9 kJ/mol, but for the intrinsic proton exchange barriers, this difference makes a significant (10.85 ± 0.25 kJ/mol) and almost constant contribution across different systems. The total values of the adsorption energies vary between 22 and 34 kJ/mol, whereas the total proton exchange energy barriers fall in the narrow range of 152–156 kJ/mol. After adding nuclear motion contributions (harmonic approximation, 298 K), intrinsic enthalpy barriers between 134 and 141 kJ/mol and apparent energy barriers between 105 and 118 kJ/mol are predicted for the different sites examined for the different frameworks. These predictions are consistent with experimental results available for faujasite, ferrierite, and ZSM-5.

  4. Surface rheology of saponin adsorption layers.

    PubMed

    Stanimirova, R; Marinova, K; Tcholakova, S; Denkov, N D; Stoyanov, S; Pelan, E

    2011-10-18

    Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3

  5. O2 adsorption on AunRh n = 1-5 neutral and charged clusters

    NASA Astrophysics Data System (ADS)

    Buendía, Fernando; Beltrán, Marcela R.

    2016-04-01

    Theoretical evidence is presented for the molecular and dissociative adsorption of O2 on free AunRh neutral, anionic and cationic clusters with 1 to 5 gold atoms, indicating that the stabilization of the activated di-oxygen species is a key factor for the unusual catalytic activities of Au-based catalysts. The structure, stability, for both molecular and dissociative O2 adsorption on AunRh n = 1-5 clusters has been investigated using density-functional theory. To find the transition states, the minimum energy paths have been explored for a few clusters. In general, lower values for the activation energy have been found when compared with the barriers that occur on pure Aun based clusters. The higher binding energies in the AuRh mix favor oxygen dissociation among any other possible reaction paths. The anionic clusters being the most reactive of all. The molecular bonding mechanism to these complexes involves charge transfer to the oxygen molecule with a concomitant activation of the O-O bond to a superoxo-like state. The characteristic planar structures of both pure gold and AuRh clusters prevail for most of the cases here studied. The odd-even characteristic catalytic activation of pure gold clusters is not observed once even a single rhodium atom has been added to the cluster.

  6. Studies of H2O on beta-AgI surfaces - An effective pair potential model. [molecular adsorption for ice nucleation

    NASA Technical Reports Server (NTRS)

    Hale, B. N.; Kiefer, J.

    1980-01-01

    The adsorption of a water molecule on surfaces of beta-AgI, the hexagonal crystal believed to be primarily responsible for the ice-nucleating properties of AgI, is studied on the basis of an effective pair potential model. The water molecule is represented by a rigid point charge ST-2 model and the AgI substrate by an array of point atoms, and maximal binding energy surfaces and optimal H2O configurations are generated for the water molecule adsorbed on the rigid and unrelaxed basal and prism faces. Modeling of H2O adsorption above a two-layer ledge, an iodine vacancy and an H2O molecule trapped in the vacancy indicates that H2O adsorption is favored at interstitial sites where no substrate atoms lie directly below. The prism face is found to attract the water molecule more strongly and provide larger energy barriers to surface diffusion than basal face sites, with the ideal basal faces providing hexagonal patterns of adsorption sites for the H2O with preferred dipole moments aligned.

  7. The Adsorption of Polyelectrolytes on Hydroxyapatite Crystals.

    PubMed

    Tsortos; Nancollas

    1999-01-01

    The adsorption of two polyelectrolytes, poly-L-Glutamate and poly-L-Aspartate, on hydroxyapatite (HAP) crystals was studied both experimentally and theoretically. Langmuir adsorption isotherms were obtained for both these molecules, with binding constants K = 6 x 10(6) and 3 x 10(6) M-1, respectively, at 37.0 degreesC, pH 7.4, and 0.15 M ionic strength. A theoretical analysis of the data, based on a model proposed by Hesselink, suggested a "train-loop" type of adsorption with non-electrostatic energy terms 3.51 and 4.76 (kT) for poly-L-Glu and poly-L-Asp, respectively. Copyright 1999 Academic Press. PMID:9878142

  8. Adsorption of gases on carbon molecular sieves

    SciTech Connect

    Vyas, S.N.; Patwardhan, S.R.; Vijayalakshmi, S. . Dept. of Chemical Engineering); Ganesh, K.S. )

    1994-12-01

    Adsorption on carbon molecular sieves (CMS) prepared by coke deposition has become an interesting area of adsorption due to its microporous nature and favorable separation factor on size and shape selectivity basis for many gaseous systems. In the present work CMS was synthesized from coconut shell through three major steps, namely, carbonization, activation, and coke deposition by hydrocarbon cracking. The crushed, washed, and sieved granules of coconut shell (particle size 2--3 mm) were pretreated with sodium silicate solution and oven-dried at 150 C to create the inorganic sites necessary for coke deposition. Carbonization and activation of the dried granules were carried out at 800 C, for 30 min each. The activated char thus produced was subjected to hydrocarbon cracking at 600 C for periods varying from 30 to 180 min. The product samples were characterized in terms of adsorption isotherm, kinetic adsorption curve, surface area, pore volume, pore size distribution, and characteristic energy for adsorption by using O[sub 2], N[sub 2], C[sub 2]H[sub 2], CO[sub 2], C[sub 3]H[sub 6], and CH[sub 4].

  9. Barrier infrared detector

    NASA Technical Reports Server (NTRS)

    Ting, David Z. (Inventor); Khoshakhlagh, Arezou (Inventor); Soibel, Alexander (Inventor); Hill, Cory J. (Inventor); Gunapala, Sarath D. (Inventor)

    2012-01-01

    A superlattice-based infrared absorber and the matching electron-blocking and hole-blocking unipolar barriers, absorbers and barriers with graded band gaps, high-performance infrared detectors, and methods of manufacturing such devices are provided herein. The infrared absorber material is made from a superlattice (periodic structure) where each period consists of two or more layers of InAs, InSb, InSbAs, or InGaAs. The layer widths and alloy compositions are chosen to yield the desired energy band gap, absorption strength, and strain balance for the particular application. Furthermore, the periodicity of the superlattice can be "chirped" (varied) to create a material with a graded or varying energy band gap. The superlattice based barrier infrared detectors described and demonstrated herein have spectral ranges covering the entire 3-5 micron atmospheric transmission window, excellent dark current characteristics operating at least 150K, high yield, and have the potential for high-operability, high-uniformity focal plane arrays.

  10. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    SciTech Connect

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  11. Reactions with Weakly Bound Nuclei, at near Barrier Energies, and the Breakup and Transfer Influences on the Fusion and Elastic Scattering

    NASA Astrophysics Data System (ADS)

    Gomes, P. R. S.; Lubian, J.; Canto, L. F.; Otomar, D. R.; Junior, D. R. Mendes; de Faria, P. N.; Linares, R.; Sigaud, L.; Rangel, J.; Ferreira, J. L.; Ferioli, E.; Paes, B.; Cardozo, E. N.; Cortes, M. R.; Ermamatov, M. J.; Lotti, P.; Hussein, M. S.

    2016-03-01

    We present a brief review of the reaction mechanisms involved in collisions of weakly bound projectiles with tightly bound targets, at near-barrier energies. We discuss systematic behaviors of the data, with emphasis in fusion, breakup, nucleon transfer and elastic scattering. The dependence of the breakup cross section on the charge and mass of the target is discussed, and the influence of the breakup channel on complete fusion is investigated. For this purpose, we compare reduced fusion cross sections with a benchmark universal curve. The behaviors observed in the comparisons are explained in terms of polarization potentials and of nucleon transfer followed by breakup. The influence of the breakup process on elastic scattering is also discussed. Some apparent contradictions between results of different authors are explained and some perspectives of the field are presented.

  12. The impact of energy barrier height on border traps in the metal insulator semicondoctor gate stacks on III–V semiconductors

    NASA Astrophysics Data System (ADS)

    Yoshida, Shinichi; Taniguchi, Satoshi; Minari, Hideki; Lin, Dennis; Ivanov, Tsvetan; Watanabe, Heiji; Nakazawa, Masashi; Collaert, Nadine; Thean, Aaron

    2016-08-01

    We investigated the effect of a thin interfacial layer (IL) made of silicon or germanium between high-k dielectrics and III–V semiconductors on the frequency dispersion of the capacitance–voltage (C–V) curves in detail. We demonstrated experimentally that the frequency dispersion at accumulation voltage is strongly dependent on the energy barrier height (ΦB) between high-k dielectrics and semiconductors. It was revealed that the improvement of frequency dispersion for n-type III–V semiconductors with IL is attributed to the increase in ΦB realized by inserting Ge IL. Moreover, the border trap density did not necessarily decrease with IL through the assessment of border trap density using a distributed bulk-oxide trap model. Finally, we proved that it is important to increase ΦB to suppress the carrier exchange and improve high-k/III–V gate stack reliability.

  13. Revealing highly unbalanced energy barriers in the extension and contraction of the muscle-like motion of a [c2]daisy chain.

    PubMed

    Zhao, Yan-Ling; Zhang, Rui-Qin; Minot, Christian; Hermann, Klaus; Van Hove, Michel A

    2015-07-28

    Nanoscale muscle-like materials have aroused great interest as they may provide controllable mechanical operations by artificial actuations. Molecular designs to achieve the desired motion at the macroscopic scale in experiments require atomic level understanding. By systematic quantum chemical and molecular dynamics calculations we reveal that the length change is not only due to the linear telescoping from the dibenzo[24]crown-8 recognition at two docking stations but also the folding/unfolding of two bulky stoppers. The extension and contraction processes of a [c2]daisy chain under acidic vs. basic conditions are exothermic but need to cross very different energy barriers, being at least double the height under acidic compared to basic conditions, hindering balanced cyclic motions at moderate excitation. Our result suggests that to realize the desired muscle-like motion one should adopt sufficiently high external excitation, using for example reasonably high temperature and further optimizing the solution used. PMID:26096825

  14. Structural anisotropy of cyanido-bridged {CoW} single-molecule magnets induced by bidentate ligands: towards the rational enhancement of an energy barrier.

    PubMed

    Chorazy, Szymon; Rams, Michał; Hoczek, Anna; Czarnecki, Bernard; Sieklucka, Barbara; Ohkoshi, Shin-Ichi; Podgajny, Robert

    2016-04-01

    Pentadecanuclear {Co[W(V)(CN)8]6} clusters were combined with bidentate 2,2'-bipyridine N,N'-dioxide (2,2'-bpdo) ligands resulting in two distinct molecules, {Co9W6(2,2'-bpdo)7} (cluster A) and {Co9W6(2,2'-bpdo)6} (cluster B), capped by seven and six 2,2'-bpdo ligands, respectively. They crystallize within a single {Co9W6(2,2'-bpdo)7}·{Co9W6(2,2'-bpdo)6}·solvent (1) supramolecular network, and reveal single-molecule magnet behaviour with an enhanced energy barrier, a ΔE/kB of 30.0(8) K, which was tentatively ascribed to seven-capped axially deformed cluster A. PMID:26933695

  15. PLATYPUS: A code for reaction dynamics of weakly-bound nuclei at near-barrier energies within a classical dynamical model

    NASA Astrophysics Data System (ADS)

    Diaz-Torres, Alexis

    2011-04-01

    A self-contained Fortran-90 program based on a three-dimensional classical dynamical reaction model with stochastic breakup is presented, which is a useful tool for quantifying complete and incomplete fusion, and breakup in reactions induced by weakly-bound two-body projectiles near the Coulomb barrier. The code calculates (i) integrated complete and incomplete fusion cross sections and their angular momentum distribution, (ii) the excitation energy distribution of the primary incomplete-fusion products, (iii) the asymptotic angular distribution of the incomplete-fusion products and the surviving breakup fragments, and (iv) breakup observables, such as angle, kinetic energy and relative energy distributions. Program summaryProgram title: PLATYPUS Catalogue identifier: AEIG_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEIG_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 332 342 No. of bytes in distributed program, including test data, etc.: 344 124 Distribution format: tar.gz Programming language: Fortran-90 Computer: Any Unix/Linux workstation or PC with a Fortran-90 compiler Operating system: Linux or Unix RAM: 10 MB Classification: 16.9, 17.7, 17.8, 17.11 Nature of problem: The program calculates a wide range of observables in reactions induced by weakly-bound two-body nuclei near the Coulomb barrier. These include integrated complete and incomplete fusion cross sections and their spin distribution, as well as breakup observables (e.g. the angle, kinetic energy, and relative energy distributions of the fragments). Solution method: All the observables are calculated using a three-dimensional classical dynamical model combined with the Monte Carlo sampling of probability-density distributions. See Refs. [1,2] for further details. Restrictions: The

  16. Adsorption of hydrogen on boron-doped graphene: A first-principles prediction

    SciTech Connect

    Zhou, Yungang; Zu, Xiaotao T.; Gao, Fei; Nie, JL; Xiao, H. Y.

    2009-01-01

    The doping effects of boron on the atomic adsorption of hydrogen on graphene have been investigated using density functional theory calculations. The hydrogen adsorption energies and electronic structures have been considered for pristine and B-doped graphene with the adsorption of hydrogen on top of carbon or boron atom. It is found that the B-doping forms an electron-deficient structure, and decreases the hydrogen adsorption energy dramatically. For the adsorption of hydrogen on top of other sites, similar results also have been found. These results indicate that the hydrogen storage capacity is improved by the doping of B atom.

  17. New Adsorption Methods.

    ERIC Educational Resources Information Center

    Wankat, Phillip C.

    1984-01-01

    Discusses a simple method for following the movement of a solute in an adsorption or ion exchange system. This movement is used to study a variety of operational methods, including continuous flow and pulsed flow counter-current operations and simulated counter-current systems. Effect of changing thermodynamic variables is also considered. (JM)

  18. Circularly polarized antennas for active holographic imaging through barriers

    SciTech Connect

    McMakin, Douglas L; Severtsen, Ronald H; Lechelt, Wayne M; Prince, James M

    2011-07-26

    Circularly-polarized antennas and their methods of use for active holographic imaging through barriers. The antennas are dielectrically loaded to optimally match the dielectric constant of the barrier through which images are to be produced. The dielectric loading helps to remove barrier-front surface reflections and to couple electromagnetic energy into the barrier.

  19. Over the Barrier in Wave Mechanics.

    ERIC Educational Resources Information Center

    Burge, E. J.

    1984-01-01

    Discusses the transmission of incident energies at a one-dimensional square barrier when energies are greater than the barrier height and the region accommodates a whole number of half wavelengths of psi. Describes sketching the probability density curve, physical interpretation, and special cases. An appendix develops the mathematics in greater…

  20. Density functional study of the cysteine adsorption on Au nanoclusters

    NASA Astrophysics Data System (ADS)

    Pérez, L. A.; López-Lozano, X.; Garzón, I. L.

    2009-04-01

    The adsorption of the cysteine amino acid (H-SCβH2-CαH-NH2-COOH) on the Au55 cluster is investigated through density functional theory calculations. Two isomers, with icosahedral (Ih) and chiral (C1) geometries, of the Au55 cluster are used to calculate the adsorption energy of the cysteine on different facets of these isomers. Results, only involving the S(thiolate)-Au bonding show that the higher adsorption energies are obtained when the sulfur atom is bonded to an asymmetrical bridge site at the facet containing Au atoms with the lowest coordination of the C1 cluster isomer.

  1. Synthetic Eelgrass Oil Barrier

    NASA Astrophysics Data System (ADS)

    Curtis, T. G.

    2013-05-01

    surface of filaments because the physical, van der Waals, forces, the basis for their adhesion to the surface, are weak and act over only a short distance. SE can be deployed in a fashion similar to a demersal fishing "longline". Oil can be "caught" by replacing baited hooks and snoods with closely spaced filaments of EMA. Adsorption of floating oil requires the filaments be long enough to reach the surface, and float, as eelgrass at low tide, on the surface for some distance. Laying multiple, parallel, lines of SE offshore, makes it possible to recover each, one at a time, and replace it without breeching the barrier to oil that they form. As EMA is tough and elastic, with a large surface area to volume ratio, by virtue of being formed as an open-cell foam, considerable oil is adsorbed and can be recovered by squeezing the oil out of the filaments. Lines of SE can be redeployed and do not have to be discarded.

  2. Electron-Beam-Induced Deposition as a Technique for Analysis of Precursor Molecule Diffusion Barriers and Prefactors.

    PubMed

    Cullen, Jared; Lobo, Charlene J; Ford, Michael J; Toth, Milos

    2015-09-30

    Electron-beam-induced deposition (EBID) is a direct-write chemical vapor deposition technique in which an electron beam is used for precursor dissociation. Here we show that Arrhenius analysis of the deposition rates of nanostructures grown by EBID can be used to deduce the diffusion energies and corresponding preexponential factors of EBID precursor molecules. We explain the limitations of this approach, define growth conditions needed to minimize errors, and explain why the errors increase systematically as EBID parameters diverge from ideal growth conditions. Under suitable deposition conditions, EBID can be used as a localized technique for analysis of adsorption barriers and prefactors. PMID:26340502

  3. A Density Functional Theory Study of Formaldehyde Adsorption on Ceria

    SciTech Connect

    Mei, Donghai; Deskins, N. Aaron; Dupuis, Michel

    2007-11-01

    Molecular adsorption of formaldehyde on the stoichiometric CeO2(111) and CeO2(110) surfaces was studied using periodic density functional theory. Two adsorption modes (strong chemisorbed and weak physisorbed) were identified on both surfaces. This is consistent with recent experimental observations. On the (111) surface, formaldehyde strongly chemisorbs with an adsorption energy of 0.86 eV to form a dioxymethylene-like structure, in which a surface O lifts from the surface to bind with the C of formaldehyde. A weak physisorbed state with adsorption energy of 0.28 eV was found with the O of formaldehyde interacting with a surface Ce. On the (110) surface, dioxymethyelene formation was also observed, with an adsorption energy of 1.31 eV. The weakly adsorbed state of formaldehyde on the (110) surface was energetically comparable to the weak adsorption state on the (111) surface, but adsorption occurred through a formaldehyde C and surface O interaction. Analysis of the local density of states and charge density differences after adsorption shows that strong covalent bonding occurs between the C of formaldehyde and surface O when dioxymethylene forms. Calculated vibrational frequencies also confirm dioxymethylene formation. Our results also show that as the coverage increases, the adsorption of formaldehyde on the (111) surface becomes weak, but is nearly unaffected on the (110) surface. This work was supported by a Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL). The computations were performed using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory, which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington. Computing time was made under a Computational Grand Challenge “Computational Catalysis”. Part of the computing time was also granted by the National Energy Research Scientific Computing

  4. Effect of nitrogen doping of graphene oxide on hydrogen and hydroxyl adsorption

    NASA Astrophysics Data System (ADS)

    Min, Byeong June; Jeong, Hae Kyung

    2014-05-01

    We investigate how nitrogen-doping affects the hydrogen (H) and the hydroxyl (OH) adsorption on graphene oxide (GO) and on nitrogen-doped GO (NGO) via pseudopotential plane wave density functional calculations within the local spin density approximation. We find that the nitrogendoping brings about drastic changes in the hydrogen and the hydroxyl adsorption energetics, but its effects depend sensitively on the nitrogen configuration in NGO. The H and the OH adsorption energies are comparable only for pyrrolic NGO. In GO and quarternary NGO, the H adsorption energy is greater than the OH adsorption energy while the trend is reversed in pyridinic NGO. Also, the OH adsorption process is less affected by nitrogen-doping than the H adsorption is.

  5. Field study of moisture damage in walls insulated without a vapor barrier. Final report for the Oregon Department of Energy

    SciTech Connect

    Tsongas, G.A.

    1980-05-01

    Considerable uncertainty has existed over whether or not wall insulation installed without a vapor barrier causes an increased risk of moisture damage (wood decay) within walls. This report describes the results of one of the first major studies in the country aimed at finding out if such a moisture problem really exists. The exterior walls of a total of 96 homes in Portland, Oregon were opened, of which 70 had retrofitted insulation and 26 were uninsulated and were a control group. The types of insulation included urea-formaldehyde foam (44), mineral wool (16), and cellulose (10). In each opened wall cavity the moisture content of wood was measured and insulation and wood samples were taken for laboratory analysis of moisture content and for the determination of the presence of absence of decay fungi. Foam shrinkage was also measured. To evaluate the possible influence of the relative air tightness of the homes, fan depressurization tests were run using a door blower unit. The field and laboratory test results indicating the lack of a moisture damage problem in existing homes with wood siding in climates similar to that of western Oregon are described along with results of a statistical analysis of the data. Related problems of interest to homeowners and insulation installers are noted. The standard operating procedures used throughout the study are discussed, including the home selection process, quantitative and qualitative techniques used to identify wall locations with the highest moisture content, wall opening and data/sample collection methodology, laboratory analysis of samples, data processing and analysis, and applicability of the results. Recommendations for furutre tests are made. Finally, the potential and desirability for future retrofitting of wall insulation is explored.

  6. Adsorption of water vapor by homoionic montmorillonites: Heats of adsorption and desorption

    SciTech Connect

    Dios Cancela, G.; Huertas, F.J.; Romero Taboada, E.; Sanchez-Rasero, F.; Hernandez Laguna, A.

    1997-01-15

    Adsorption isotherms for water vapor, basal spacing, and immersion heats and water desorption heats of Li{sup +}, Na{sup +}, Mg{sup 2+}, Ca{sup 2+}, Cu{sup 2+}, and Fe{sup 3+} montmorillonite are measured at various relative humidities (r.h.). The amount of water adsorbed as a function of r.h. is found to increase gradually, whereas basal spacing increases and the adsorption heat decreases in steps. The water desorption heat also decreases in steps. The entropy of adsorbed water appears to be negative with respect to the entropy of liquid water. A theoretical model is proposed to describe the hydration process of Li{sup +}, Na{sup +}, Mg{sup 2+}, Ca{sup 2+}, Cu{sup 2+}, and Fe{sup 3+} montmorillonites. The experimental adsorption heats are found to have a direct relationship with the sum of the hydration energy of the cations plus expansion energy.

  7. The Oklahoma Field Test: Air-Conditioning Electricity Savings from Standard Energy Conservation Measures, Radiant Barriers, and High-Efficiency Window Air Conditioners

    SciTech Connect

    Ternes, M.P.

    1992-01-01

    A field test involving 104 houses was performed in Tulsa, Oklahoma, to measure the air-conditioning electricity consumption of low-income houses equipped with window air conditioners, the reduction in this electricity consumption attributed to the installation of energy conservation measures (ECMs) as typically installed under the Oklahoma Weatherization Assistance Program (WAP), and the reduction achieved by the replacement of low-efficiency window air conditioners with high-efficiency units and the installation of attic radiant barriers. Air-conditioning electricity consumption and indoor temperature were monitored weekly during the pre-weatherization period (June to September 1988) and post-weatherization period (May to September 1989). House energy consumption models and regression analyses were used to normalize the air-conditioning electricity savings to average outdoor temperature conditions and the pre-weatherization indoor temperature of each house. The average measured pre-weatherization air-conditioning electricity consumption was 1664 kWh/year ($119/year). Ten percent of the houses used less than 250 kWh/year, while another 10% used more than 3000 kWh/year. An average reduction in air-conditioning electricity consumption of 535 kWh/year ($38/year and 28% of pre-weatherization consumption) was obtained from replacement of one low-efficiency window air conditioner (EER less than 7.0) per house with a high-efficiency unit (EER greater than 9.0). For approximately the same cost, savings tripled to 1503 kWh/year ($107/year and 41% of pre-weatherization consumption) in those houses with initial air-conditioning electricity consumption greater than 2750 kWh/year. For these houses, replacement of a low-efficiency air conditioner with a high-efficiency unit was cost effective using the incremental cost of installing a new unit now rather than later; the average installation cost for these houses under a weatherization program was estimated to be $786. The

  8. Sprache als Barriere (Language as a Barrier)

    ERIC Educational Resources Information Center

    Mattheier, Klaus

    1974-01-01

    The concept of language barrier has its derivations in the fields of dialectology, sociology and psychology. In contemporary usage however, the concept has two meanings i.e. regional-cultural barrier and socio-cultural barrier. (Text is in German.) (DS)

  9. Exhaustively sampling peptide adsorption with metadynamics.

    PubMed

    Deighan, Michael; Pfaendtner, Jim

    2013-06-25

    Simulating the adsorption of a peptide or protein and obtaining quantitative estimates of thermodynamic observables remains challenging for many reasons. One reason is the dearth of molecular scale experimental data available for validating such computational models. We also lack simulation methodologies that effectively address the dual challenges of simulating protein adsorption: overcoming strong surface binding and sampling conformational changes. Unbiased classical simulations do not address either of these challenges. Previous attempts that apply enhanced sampling generally focus on only one of the two issues, leaving the other to chance or brute force computing. To improve our ability to accurately resolve adsorbed protein orientation and conformational states, we have applied the Parallel Tempering Metadynamics in the Well-Tempered Ensemble (PTMetaD-WTE) method to several explicitly solvated protein/surface systems. We simulated the adsorption behavior of two peptides, LKα14 and LKβ15, onto two self-assembled monolayer (SAM) surfaces with carboxyl and methyl terminal functionalities. PTMetaD-WTE proved effective at achieving rapid convergence of the simulations, whose results elucidated different aspects of peptide adsorption including: binding free energies, side chain orientations, and preferred conformations. We investigated how specific molecular features of the surface/protein interface change the shape of the multidimensional peptide binding free energy landscape. Additionally, we compared our enhanced sampling technique with umbrella sampling and also evaluated three commonly used molecular dynamics force fields. PMID:23706011

  10. INFORMATION BARRIERS - A HISTORICAL PERSPECTIVE

    SciTech Connect

    D. CLOSE; D. MACARTHUR; N. NICHOLAS

    2001-05-01

    The concept ''transparency'' was introduced into the safeguards lexicon in the early 1990s, and the term ''information barrier'' was introduced into the safeguards lexicon in the late 1990s. Although the terms might have been new, the concepts were not. Both concepts have been used by the International Atomic Energy Agency (IAEA) and its inspectors since the early 1980s, but the terms ''transparency'' and ''information barrier'' were not used for those concepts then. The definitions of these concepts have evolved in recent years, and these concepts have been applied to a broader category of special nuclear material measurement problems. The origin and features of the information barrier concept will be traced from an early implementation by the IAEA to the current state-of-the-art information barrier technology used in nonproliferation, arms control, and dismantlement.

  11. Hydrogen adsorption on sulphur-doped SiC nanotubes

    NASA Astrophysics Data System (ADS)

    Sevak Singh, Ram

    2016-07-01

    Hydrogen (H2) is an energy carrier and clean fuel that can be used for a broad range of applications that include fuel cell vehicles. Therefore, development of materials for hydrogen storage is demanded. Nanotubes, in this context, are appropriate materials. Recently, silicon carbide nanotube (SiCNTs) have been predicted as potential nanomaterials for hydrogen storage, and atomic doping into the nanotubes improves the H2 adsorption. Here, we report H2 adsorption properties of sulphur-doped (S-doped) SiCNTs using first-principles calculations based on density functional theory. The H2 adsorption properties are investigated by calculations of energy band structures, density of states (DOS), adsorption energy and Mulliken charge population analysis. Our findings show that, compared to the intrinsic SiCNT, S-doped SiCNT is more sensitive to H2 adsorption. H2 gas adsorption on S-doped C-sites of SiCNT brings about significant modulation of the electronic structure of the nanotube, which results in charge transfer from the nanotube to the gas, and dipole–dipole interactions cause chemisorptions of hydrogen. However, in the case of H2 gas adsorption on S-doped Si-sites of the nanotube, lesser charge transfer from the nanotube to the gas results in physisorptions of the gas. The efficient hydrogen sensing properties of S-doped SiCNTs, studied here, may have potential for its practical realization for hydrogen storage application.

  12. Ab initio studies on the adsorption and implantation of Al and Fe to nitride materials

    SciTech Connect

    Riedl, H.; Zálešák, J.; Arndt, M.; Polcik, P.; Holec, D.; Mayrhofer, P. H.

    2015-09-28

    The formation of transfer material products on coated cutting and forming tools is a major failure mechanism leading to various sorts of wear. To describe the atomistic processes behind the formation of transfer materials, we use ab initio to study the adsorption energy as well as the implantation barrier of Al and Fe atoms for (001)-oriented surfaces of TiN, Ti{sub 0.50}Al{sub 0.50}N, Ti{sub 0.90}Si{sub 0.10}N, CrN, and Cr{sub 0.90}Si{sub 0.10}N. The interactions between additional atoms and nitride-surfaces are described for pure adhesion, considering no additional stresses, and for the implantation barrier. The latter, we simplified to the stress required to implant Al and Fe into sub-surface regions of the nitride material. The adsorption energies exhibit pronounced extrema at high-symmetry positions and are generally highest at nitrogen sites. Here, the binary nitrides are comparable to their ternary counterparts and the average adhesive energy is higher (more negative) on CrN than TiN based systems. Contrary, the implantation barrier for Al and Fe atoms is higher for the ternary systems Ti{sub 0.50}Al{sub 0.50}N, Ti{sub 0.90}Si{sub 0.10}N, and Cr{sub 0.90}Si{sub 0.10}N than for their binary counterparts TiN and CrN. Based on our results, we can conclude that TiN based systems outperform CrN based systems with respect to pure adhesion, while the Si-containing ternaries exhibit higher implantation barriers for Al and Fe atoms. The data obtained are important to understand the atomistic interaction of metal atoms with nitride-based materials, which is valid not just for machining operations but also for any combination such as interfaces between coatings and substrates or multilayer and phase arrangements themselves.

  13. The barrier to the methyl rotation in Cis-2-butene and its isomerization energy to Trans-2-butene, revisited.

    PubMed

    Matta, Chérif F; Sadjadi, SeyedAbdolreza; Braden, Dale A; Frenking, Gernot

    2016-01-01

    We respond to the two questions posed by Weinhold, Schleyer, and McKee (WSM) in their study of cis-2-butene (Weinhold et al., J Comput Chem 2014, 35, 1499), in which they solicit explanations for the relative conformational energies of this molecule in terms of the Quantum Theory of Atoms in Molecules (QTAIM). WSM requested answers to the questions: (1) why is cis-2-butene less stable than trans-2-butene despite the presence of a hydrogen-hydrogen (H⋯H) bond path in the former but not in the latter if the H⋯H bond path is stabilizing? (2) Why is the potential well of the conformational global minimum of cis-2-butene only 0.8 kcal/mol deep when the H⋯H bonding is stabilizing by 5 kcal/mol? Both questions raised by WSM are answered by considering the changes in the energies of all atoms as a function of the rotation of one of the two methyl groups from the minimum-energy structure, which exhibits the H⋯H bond path, to the transition state, which is devoid of this bond path. It is found that the stability gained by the H⋯H bonding interaction is cancelled by the destabilization of one of the ethylenic carbon atoms which, alone, destabilizes the system by as much as 5 kcal/mol in the global minimum conformation. Further, it is found that the 1.1 kcal/mol stability of trans-2-butene with respect to the cis-isomer is driven by the considerable destabilization of the ethylenic carbons by 11 kcal/mol, while the changes in the atomic energies of the other corresponding atoms in the two isomers account for the observed different stabilities. The error introduced into QTAIM atomic energies by neglecting the virials of the forces on the nuclei for partially optimized structures is discussed. PMID:26581645

  14. Ab initio study of the torsional potential energy surfaces of N2O3 and N2O4: Origin of the torsional barriers

    NASA Astrophysics Data System (ADS)

    Halpern, Arthur M.; Glendening, Eric D.

    2007-04-01

    Intrinsic reaction coordinate (IRC) torsional potentials were calculated for N2O4 and N2O3 based on optimized B3LYP/aug-cc-pVDZ geometries of the respective 90°-twisted saddle points. These potentials were refined by obtaining CCSD(T )/aug-cc-pVXZ energies [in the complete basis set (CBS) limit] of points along the IRC. A comparison is made between these ab initio potentials and an analytical form based on a two-term cosine expansion in terms of the N-N dihedral angle. The shapes of these two potential curves are in close agreement. The torsional barriers in N2O4 and N2O3 obtained from the CCSD(T)/CBS//B3LYP/aug-cc-pVDZ calculations are 2333 and 1704cm-1, respectively. For N2O4 the torsion fundamental frequency from the IRC potential is 87.06cm-1, which is in good agreement with the experimentally reported value of 81.73cm-1. However, in the case of N2O3 the torsional frequency found from the IRC potential, 144cm-1, is considerably larger than the reported experimental values 63-76cm-1. Consistent with this discrepancy, the torsional barrier obtained from several different calculations, 1417-1718cm-1, is higher than the value of 350cm-1 deduced from experimental studies. It is suggested that the assignment of the torsional mode in N2O3 should be reexamined. N2O4 and N2O3 exhibit strong hyperconjugative interactions of in-plane O lone pairs with the central N-N σ* antibond. Hyperconjugative stabilization is somewhat stronger at the planar geometries because 1,4 interactions of lone pairs on cis O atoms promote delocalization of electrons into the N-N antibond. Calculations therefore suggest that the torsional barriers in these molecules arise principally from a combination of 1,4 interactions and hyperconjugation.

  15. Fundamentals of high pressure adsorption

    SciTech Connect

    Zhou, Y.P.; Zhou, L.

    2009-12-15

    High-pressure adsorption attracts research interests following the world's attention to alternative fuels, and it exerts essential effect on the study of hydrogen/methane storage and the development of novel materials addressing to the storage. However, theoretical puzzles in high-pressure adsorption hindered the progress of application studies. Therefore, the present paper addresses the major theoretical problems that challenged researchers: i.e., how to model the isotherms with maximum observed in high-pressure adsorption; what is the adsorption mechanism at high pressures; how do we determine the quantity of absolute adsorption based on experimental data. Ideology and methods to tackle these problems are elucidated, which lead to new insights into the nature of high-pressure adsorption and progress in application studies, for example, in modeling multicomponent adsorption, hydrogen storage, natural gas storage, and coalbed methane enrichment, was achieved.

  16. Adsorption and dissociation of O2 on Ni-doped (5, 5) SWCNT: A DFT study

    NASA Astrophysics Data System (ADS)

    Li, Xiaodong; Liu, Liangliang; Wang, Mingguang; Wang, Zhu

    2016-05-01

    The effect of nickel doping on the adsorption and dissociation of the O2 molecule on a (5, 5) single-walled carbon nanotube (SWCNT) is investigated using first-principles density functional theory calculations in company with the nudged elastic band (NEB). Our calculated results show that nickel doping can make it much easier for oxygen adsorbed on the SWCNT, and the chemisorption energy is high enough to alter the O-O bond. What's more, the activation barrier for oxygen dissociation is lowered to 0.399 eV through nickel doping, which is much lower than Pt doped CNT. Our work have done here would be of help to develop platinum-free oxygen reduction reaction catalysts based on SWCNTs.

  17. Ion energy and angular distributions onto polymer surfaces delivered by dielectric barrier discharge filaments in air: II. Particles

    NASA Astrophysics Data System (ADS)

    Babaeva, Natalia Yu; Kushner, Mark J.

    2011-06-01

    Atmospheric pressure streamers intersecting particles are of interest in the context of plasma aided combustion, where the particle may be a fuel aerosol droplet, or in sterilization of air, where the particle may be a bacterium. The ion energy and angular distributions (IEADs) incident on the particles, small curved dielectric surfaces, then in part determine the propensity for activating chemical reactions or, in the case of bacteria, the plasma's sterilization capability. In this paper, we discuss results from a computational investigation of IEADs on small particles (45 µm radius) produced by atmospheric pressure discharge. Streamers intersecting a particle momentarily generate a large sheath potential as the streamer passes by as the particle charges towards the plasma floating potential. During that time, ions of energies up to 3-10 eV can strike the particle. The permittivity of the particle and the streamer polarity in part determine the character of the IEAD.

  18. Imaging dynamics on the F + H2O -> HF + OH potential energy surfaces from wells to barriers.

    PubMed

    Otto, Rico; Ma, Jianyi; Ray, Amelia W; Daluz, Jennifer S; Li, Jun; Guo, Hua; Continetti, Robert E

    2014-01-24

    The study of gas-phase reaction dynamics has advanced to a point where four-atom reactions are the proving ground for detailed comparisons between experiment and theory. Here, a combined experimental and theoretical study of the dissociation dynamics of the tetra-atomic FH2O system is presented, providing snapshots of the F + H2O → HF + OH reaction. Photoelectron-photofragment coincidence measurements of the dissociative photodetachment (DPD) of the F(-)(H2O) anion revealed various dissociation pathways along different electronic states. A distinct photoelectron spectrum of stable FH-OH complexes was also measured and attributed to long-lived Feshbach resonances. Comparison to full-dimensional quantum calculations confirms the sensitivity of the DPD measurements to the subtle dynamics on the low-lying FH2O potential energy surfaces over a wide range of nuclear configurations and energies. PMID:24407479

  19. Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon.

    PubMed

    Wang, Gang; Dou, Baojuan; Zhang, Zhongshen; Wang, Junhui; Liu, Haier; Hao, Zhengping

    2015-04-01

    Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal. PMID:25872710

  20. Observations of Surface Energy Fluxes and Boundary-Layer Structure Over Heron Reef, Great Barrier Reef, Australia

    NASA Astrophysics Data System (ADS)

    MacKellar, Mellissa C.; McGowan, Hamish A.; Phinn, Stuart R.; Soderholm, Joshua S.

    2013-02-01

    Over warm, shallow coral reefs the surface radiation and energy fluxes differ from those of the open ocean and result in modification to the marine atmospheric boundary layer via the development of convective internal boundary layers. The complex interrelationships between the surface energy balance and boundary-layer characteristics influence local weather (wind, temperature, humidity) and hydrodynamics (water temperature and currents), as well as larger scale processes, including cloud field properties and precipitation. The nature of these inter-relationships has not been accurately described for coral reef environments. This study presents the first measurements of the surface energy balance, radiation budget and boundary layer thermodynamics made over a coral reef using an eddy-covariance system and radiosonde aerological profiling of the lower atmosphere. Results show that changes in surface properties and the associated energetics across the ocean-reef boundary resulted in modification to the marine atmospheric boundary layer during the Austral winter and summer. Internal convective boundary layers developed within the marine atmospheric boundary layer over the reef and were found to be deeper in the summer, yet more unstable during the winter when cold and drier flow from the mainland enhances heat and moisture fluxes to the atmosphere. A mixed layer was identified in the marine atmospheric boundary layer varying from 375 to 1,200 m above the surface, and was deeper during the summer, particularly under stable anticyclonic conditions. Significant cloud cover and at times rain resulted in the development of a stable stratified atmosphere over the reef. Our findings show that, for Heron Reef, a lagoonal platform reef, there was a horizontal discontinuity in surface energy fluxes across the ocean-reef boundary, which modified the marine atmospheric boundary layer.