WorldWideScience

Sample records for surfaces transition-state energies

  1. Surface hopping, transition state theory and decoherence. I. Scattering theory and time-reversibility.

    Science.gov (United States)

    Jain, Amber; Herman, Michael F; Ouyang, Wenjun; Subotnik, Joseph E

    2015-10-07

    We provide an in-depth investigation of transmission coefficients as computed using the augmented-fewest switches surface hopping algorithm in the low energy regime. Empirically, microscopic reversibility is shown to hold approximately. Furthermore, we show that, in some circumstances, including decoherence on top of surface hopping calculations can help recover (as opposed to destroy) oscillations in the transmission coefficient as a function of energy; these oscillations can be studied analytically with semiclassical scattering theory. Finally, in the spirit of transition state theory, we also show that transmission coefficients can be calculated rather accurately starting from the curve crossing point and running trajectories forwards and backwards.

  2. A critical assessment of theoretical methods for finding reaction pathways and transition states of surface processes

    International Nuclear Information System (INIS)

    Klimes, JirI; Michaelides, Angelos; Bowler, David R

    2010-01-01

    The performance of a variety of techniques for locating transition states on potential energy surfaces is evaluated within the density functional theory framework. Diffusion of a water molecule across NaCl(001) and HCl bond breaking on the same surface are treated as general test cases; the former is an example of a low barrier diffusion process and the latter an example of a relatively high barrier covalent bond rupture event. The methods considered include the nudged elastic band (NEB), Dewar, Healy and Stewart (DHS), dimer, constrained optimization (CO), activation-relaxation technique (ART) and one-side growing string (OGS) as well as novel combinations of the DHS with growing string (DHS + GS) and DHS plus climbing image (CI-DHS). A key conclusion to come from this study is that the NEB method is relatively fast, especially when just a single (climbing) image is used. Indeed, using more images represents an unnecessary computational burden for our set of processes. The dimer method exhibits variable performance; being poor for the water diffusion processes, which have small activation energies, but much more efficient for the HCl bond breaking process which has a higher barrier. When only a poor initial guess of the transition state geometry is available, the CI-DHS scheme is one of the most efficient techniques considered. And as a means to quickly establish an approximate minimum energy pathway the DHS + GS scheme offers some potential.

  3. Discovering Unique, Low-Energy Transition States Using Evolutionary Molecular Memetic Computing

    DEFF Research Database (Denmark)

    Ellabaan, Mostafa M Hashim; Ong, Y.S.; Handoko, S.D.

    2013-01-01

    In the last few decades, identification of transition states has experienced significant growth in research interests from various scientific communities. As per the transition states theory, reaction paths and landscape analysis as well as many thermodynamic properties of biochemical systems can...... be accurately identified through the transition states. Transition states describe the paths of molecular systems in transiting across stable states. In this article, we present the discovery of unique, low-energy transition states and showcase the efficacy of their identification using the memetic computing...... paradigm under a Molecular Memetic Computing (MMC) framework. In essence, the MMC is equipped with the tree-based representation of non-cyclic molecules and the covalent-bond-driven evolutionary operators, in addition to the typical backbone of memetic algorithms. Herein, we employ genetic algorithm...

  4. Surface hopping, transition state theory, and decoherence. II. Thermal rate constants and detailed balance

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Amber; Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104 (United States)

    2015-10-07

    We investigate a simple approach to compute a non-adiabatic thermal rate constant using the fewest switches surface hopping (FSSH) dynamics. We study the effects of both decoherence (using our augmented-FSSH (A-FSSH) algorithm) and forbidden hops over a large range of parameters, including high and low friction regimes, and weak and strong electronic coupling regimes. Furthermore, when possible, we benchmark our results against exact hierarchy equations of motion results, where we usually find a maximum error of roughly a factor of two (at reasonably large temperatures). In agreement with Hammes-Schiffer and Tully, we find that a merger of transition state theory and surface hopping can be both accurate and efficient when performed correctly. We further show that detailed balance is followed approximately by A-FSSH dynamics.

  5. State-to-State Mode Specificity: Energy Sequestration and Flow Gated by Transition State.

    Science.gov (United States)

    Zhao, Bin; Sun, Zhigang; Guo, Hua

    2015-12-23

    Energy flow and sequestration at the state-to-state level are investigated for a prototypical four-atom reaction, H2 + OH → H + H2O, using a transition-state wave packet (TSWP) method. The product state distribution is found to depend strongly on the reactant vibrational excitation, indicating mode specificity at the state-to-state level. From a local-mode perspective, it is shown that the vibrational excitation of the H2O product derives from two different sources, one attributable to the energy flow along the reaction coordinate into the newly formed OH bond and the other due to the sequestration of the vibrational energy in the OH spectator moiety during the reaction. The analysis provided a unified interpretation of some seemingly contradicting experimental observations. It is further shown that the transfer of vibrational energy from the OH reactant to H2O product is gated by the transition state, accomplished coherently by multiple TSWPs with the corresponding OH vibrational excitation.

  6. Bifurcations of transition states: Morse bifurcations

    International Nuclear Information System (INIS)

    MacKay, R S; Strub, D C

    2014-01-01

    A transition state for a Hamiltonian system is a closed, invariant, oriented, codimension-2 submanifold of an energy level that can be spanned by two compact codimension-1 surfaces of unidirectional flux whose union, called a dividing surface, locally separates the energy level into two components and has no local recrossings. For this to happen robustly to all smooth perturbations, the transition state must be normally hyperbolic. The dividing surface then has locally minimal geometric flux through it, giving an upper bound on the rate of transport in either direction. Transition states diffeomorphic to S 2m−3 are known to exist for energies just above any index-1 critical point of a Hamiltonian of m degrees of freedom, with dividing surfaces S 2m−2 . The question addressed here is what qualitative changes in the transition state, and consequently the dividing surface, may occur as the energy or other parameters are varied? We find that there is a class of systems for which the transition state becomes singular and then regains normal hyperbolicity with a change in diffeomorphism class. These are Morse bifurcations. Various examples are considered. Firstly, some simple examples in which transition states connect or disconnect, and the dividing surface may become a torus or other. Then, we show how sequences of Morse bifurcations producing various interesting forms of transition state and dividing surface are present in reacting systems, by considering a hypothetical class of bimolecular reactions in gas phase. (paper)

  7. Variational transition state theory

    International Nuclear Information System (INIS)

    Truhlar, D.G.

    1986-01-01

    This project is concerned with the development and applications of generalized transition state theory and multidimensional tunneling approximations to chemical reaction rates. They have developed and implemented several practical versions of variational transition state theory (VTST), namely canonical variational theory (CVT), improved canonical variational theory (ICVT), and microcanonical variational theory (μVT). They have also developed and implemented several accurate multidimensional semiclassical tunneling approximations, the most accurate of which are the small-curvature semiclassical adiabatic (SCSA), large-curvature version-3 (LC3), and least-action (LA) approximations. They have applied the methods to thermal rate constants, using transmission coefficients based on ground-state tunneling, and they have also presented and applied adiabatic and diabatic extensions to calculated rate constants for vibrationally excited reactants. Their general goal is to develop accurate methods for calculating chemical reaction rate constants that remain practical even for reasonably complicated molecules. The approximations mentioned above yield rate constants for systems whose potential energy surface is known or assumed. Thus a second, equally important aspect of their work is the determination or modeling, semi-empirically and/or from electronic structure calculations, of potential energy surfaces

  8. Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment

    Science.gov (United States)

    Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J. A.; Setser, Donald W.; Hase, William L.

    2017-10-01

    Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH3CN → HF + CH2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH2CN and then trapping in the CH2CN⋯HF post-reaction potential energy well of ˜10 kcal/mol with respect to the HF + CH2CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH2CN rotation, and CH2CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH3CN → HF + CH2CN

  9. Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment.

    Science.gov (United States)

    Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J A; Setser, Donald W; Hase, William L

    2017-10-14

    Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN⋯HF post-reaction potential energy well of ∼10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH 2 CN rotation, and CH 2 CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN

  10. Post-transition state dynamics and product energy partitioning following thermal excitation of the F∙∙∙HCH2 CN transition state: Disagreement with experiment

    Energy Technology Data Exchange (ETDEWEB)

    Pratihar, Subha [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ma, Xinyou [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Xie, Jing [Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA; Scott, Rebecca [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Gao, Eric [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ruscic, Branko [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA and Computation Institute, University of Chicago, Chicago, Illinois 60637, USA; Aquino, Adelia J. A. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People’s Republic of China; Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Setser, Donald W. [Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Hase, William L. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA

    2017-10-14

    Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH3CN → HF + CH2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. In accord with experiment and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F-HCH2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST for the simulation. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH2CN and then trapping in the CH2CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH2CN products. In contrast to this IRC, five different trajectory types were observed, with the majority involving direct dissociation and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. From the simulations and with an anharmonic zero-point energy constraint, the percentage partitioning of the product energy to relative translation, HF rotation, HF vibration, CH2CN rotation and CH2CN vibration is 5, 11, 60, 7, and 16%, respectively. In contrast the experimental energy partitioning percentages to HF rotation and vibration are 6 and 41%. Comparisons are made between the current simulation and those for other F + H

  11. Variational transition-state theory

    International Nuclear Information System (INIS)

    Truhlar, D.G.; Garrett, B.C.

    1980-01-01

    A general introduction to and some results from studies of a procedure called variational transition-state theory are presented. A fundamental assumption of this theory is that the net rate of forward reaction at equilibrium equals the equilibrium flux in the product direction through the transition state where the transition state is a surface in phase space dividing reactants from products. Classical generalized-transition-state-theory calculations for nine collinear systems are compared to classical trajectory calculations. This new technique should provide useful insight into the successes and failures of the conventional theory and useful quantitative estimates of possible errors on the predictions of conventional transition-state theory. This should also contribute to a more accurate theory now available for the practical calculations of chemical reaction rates and thermochemical and structural interpretations of rate processes

  12. Non-uniqueness of quantum transition state theory and general dividing surfaces in the path integral space.

    Science.gov (United States)

    Jang, Seogjoo; Voth, Gregory A

    2017-05-07

    Despite the fact that quantum mechanical principles do not allow the establishment of an exact quantum analogue of the classical transition state theory (TST), the development of a quantum TST (QTST) with a proper dynamical justification, while recovering the TST in the classical limit, has been a long standing theoretical challenge in chemical physics. One of the most recent efforts of this kind was put forth by Hele and Althorpe (HA) [J. Chem. Phys. 138, 084108 (2013)], which can be specified for any cyclically invariant dividing surface defined in the space of the imaginary time path integral. The present work revisits the issue of the non-uniqueness of QTST and provides a detailed theoretical analysis of HA-QTST for a general class of such path integral dividing surfaces. While we confirm that HA-QTST reproduces the result based on the ring polymer molecular dynamics (RPMD) rate theory for dividing surfaces containing only a quadratic form of low frequency Fourier modes, we find that it produces different results for those containing higher frequency imaginary time paths which accommodate greater quantum fluctuations. This result confirms the assessment made in our previous work [Jang and Voth, J. Chem. Phys. 144, 084110 (2016)] that HA-QTST does not provide a derivation of RPMD-TST in general and points to a new ambiguity of HA-QTST with respect to its justification for general cyclically invariant dividing surfaces defined in the space of imaginary time path integrals. Our analysis also offers new insights into similar path integral based QTST approaches.

  13. Communication: Photodissociation of CH3CHO at 308 nm: Observation of H-roaming, CH3-roaming, and transition state pathways together along the ground state surface

    Science.gov (United States)

    Li, Hou-Kuan; Tsai, Po-Yu; Hung, Kai-Chan; Kasai, Toshio; Lin, King-Chuen

    2015-01-01

    Following photodissociation of acetaldehyde (CH3CHO) at 308 nm, the CO(v = 1-4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH3CO core and CH3-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem. Sci. 5, 4633 (2014)). The H-roaming pathway disappears at the CO(v ≥ 2) states, because of insufficient available energy following bond-breaking of H + CH3CO. By analyzing the CH4 emission spectrum, we obtained a bimodal vibrational distribution; the low-energy component is ascribed to the transition state (TS) pathway, consistent with prediction by quasiclassical trajectory calculations, while the high-energy component results from H- and CH3-roamings. A branching fraction of H-roaming/CH3-roaming/TS contribution is evaluated to be (8% ± 3%)/(68% ± 10%)/(25% ± 5%), in which the TS pathway was observed for the first time. The three pathways proceed concomitantly along the electronic ground state surface.

  14. New ab initio potential surfaces and three-dimensional quantum dynamics for transition state spectroscopy in ozone photodissociation

    Science.gov (United States)

    Yamashita, Koichi; Morokuma, Keiji; Le Quéré, Frederic; Leforestier, Claude

    1992-04-01

    New ab initio potential energy surfaces (PESs) of the ground and B ( 1B 2) states of ozone have been calculated with the CASSCF-SECI/DZP method to describe the three-dimensional photodissociation process. The dissociation energy of the ground state and the vertical barrier height of the B PES are obtained to be 0.88 and 1.34 eV, respectively, in better agreement with the experimental values than the previous calculation. The photodissociation autocorrelation function, calculated on the new B PES, based on exact three-dimensional quantum dynamics, reproduces well the main recurrence feature extracted from the experimental spectra.

  15. Variational Transition State Theory

    Energy Technology Data Exchange (ETDEWEB)

    Truhlar, Donald G. [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-09-29

    This is the final report on a project involving the development and applications of variational transition state theory. This project involved the development of variational transition state theory for gas-phase reactions, including optimized multidimensional tunneling contributions and the application of this theory to gas-phase reactions with a special emphasis on developing reaction rate theory in directions that are important for applications to combustion. The development of variational transition state theory with optimized multidimensional tunneling as a useful computational tool for combustion kinetics involved eight objectives.

  16. Communication: State-to-state dynamics of the Cl + H2O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal

    International Nuclear Information System (INIS)

    Zhao, Bin; Guo, Hua; Sun, Zhigang

    2015-01-01

    Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H 2 O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H 2 O → H 2 + OH reaction. The strong enhancement of reactivity by the H 2 O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal

  17. Communication: State-to-state dynamics of the Cl + H2O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal.

    Science.gov (United States)

    Zhao, Bin; Sun, Zhigang; Guo, Hua

    2015-06-28

    Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H2O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H2O → H2 + OH reaction. The strong enhancement of reactivity by the H2O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.

  18. Transition state theory for enzyme kinetics

    Science.gov (United States)

    Truhlar, Donald G.

    2015-01-01

    This article is an essay that discusses the concepts underlying the application of modern transition state theory to reactions in enzymes. Issues covered include the potential of mean force, the quantization of vibrations, the free energy of activation, and transmission coefficients to account for nonequilibrium effect, recrossing, and tunneling. PMID:26008760

  19. 3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

    Science.gov (United States)

    Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

    2015-01-01

    Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

  20. Quantitative assessment of force fields on both low-energy conformational basins and transition-state regions of the (phi-psi) space

    NARCIS (Netherlands)

    Liu, Z.; Ensing, B.; Moore, P.B.

    2011-01-01

    The free energy surfaces (FESs) of alanine dipeptide are studied to illustrate a new strategy to assess the performance of classical molecular mechanics force field on the full range of the (phi-psi) conformational space. The FES is obtained from metadynamics simulations with five commonly used

  1. Quantum catalysis : the modelling of catalytic transition states

    NARCIS (Netherlands)

    Hall, M.B.; Margl, P.; Naray-Szabo, G.; Schramm, Vern; Truhlar, D.G.; Santen, van R.A.; Warshel, A.; Whitten, J.L.; Truhlar, D.G.; Morokuma, K.

    1999-01-01

    A review with 101 refs.; we present an introduction to the computational modeling of transition states for catalytic reactions. We consider both homogeneous catalysis and heterogeneous catalysis, including organometallic catalysts, enzymes, zeolites and metal oxides, and metal surfaces. We summarize

  2. Quantifying the limits of transition state theory in enzymatic catalysis.

    Science.gov (United States)

    Zinovjev, Kirill; Tuñón, Iñaki

    2017-11-21

    While being one of the most popular reaction rate theories, the applicability of transition state theory to the study of enzymatic reactions has been often challenged. The complex dynamic nature of the protein environment raised the question about the validity of the nonrecrossing hypothesis, a cornerstone in this theory. We present a computational strategy to quantify the error associated to transition state theory from the number of recrossings observed at the equicommittor, which is the best possible dividing surface. Application of a direct multidimensional transition state optimization to the hydride transfer step in human dihydrofolate reductase shows that both the participation of the protein degrees of freedom in the reaction coordinate and the error associated to the nonrecrossing hypothesis are small. Thus, the use of transition state theory, even with simplified reaction coordinates, provides a good theoretical framework for the study of enzymatic catalysis. Copyright © 2017 the Author(s). Published by PNAS.

  3. Transition state structures in solution

    International Nuclear Information System (INIS)

    Bertran, J.; Lluch, J. M.; Gonzalez-Lafont, A.; Dillet, V.; Perez, V.

    1995-01-01

    In the present paper the location of transition state structures for reactions in solution has been studied. Continuum model calculations have been carried out on the Friedel-Crafts alkylation reaction and a proton transfer through a water molecule between two oxygen atoms in formic acid. In this model the separation between the chemical system and the solvent has been introduced. On the other hand, the discrete Monte Carlo methodology has also been used to simulate the solvent effect on dissociative electron transfer processes. In this model, the hypothesis of separability is not assumed. Finally, the validity of both approaches is discussed

  4. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  5. Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules

    International Nuclear Information System (INIS)

    Garrett, B.C.; Truhlar, D.G.

    1979-01-01

    Canonical variational transition state theory, microcanonical variational transition state theory, and Miller's unified statistical theory were used in an attempt to correct two major deficiencies of the conventional transition state theory. These are: (1) the necessity of extra assumptions to include quantum mechanical tunneling effects and (2) the fundamental assumption that trajectories crossing a dividing surface in phase space proceed directly to products. The accuracy of these approximate methods were tested by performing calculations for several collinear reactions of hydrogen, deuterium, chlorine, or iodine, with five isotopes of hydrogen molecules and comparison of these results with those from accurate quantitative calculations of the reaction probabilities as functions of energy and of the thermal rate constants as functions of temperature. 49 references, 28 figures, 17 tables

  6. Concavity Theorems for Energy Surfaces

    OpenAIRE

    Giraud, B. G.; Karataglidis, S.

    2011-01-01

    Concavity properties prevent the existence of significant landscapes in energy surfaces obtained by strict constrained energy minimizations. The inherent contradiction is due to fluctuations of collective coordinates. A solution to those fluctuations is given.

  7. Surface Meteorology and Solar Energy

    Data.gov (United States)

    National Aeronautics and Space Administration — Surface Meteorology and Solar Energy data - over 200 satellite-derived meteorology and solar energy parameters, monthly averaged from 22 years of data, global solar...

  8. The surface energy of metals

    DEFF Research Database (Denmark)

    Vitos, Levente; Ruban, Andrei; Skriver, Hans Lomholt

    1998-01-01

    We have used density functional theory to establish a database of surface energies for low index surfaces of 60 metals in the periodic table. The data may be used as a consistent starting point for models of surface science phenomena. The accuracy of the database is established in a comparison...

  9. Variational transition state theory for multidimensional activated rate processes in the presence of anisotropic friction

    Science.gov (United States)

    Berezhkovskii, Alexander M.; Frishman, Anatoli M.; Pollak, Eli

    1994-09-01

    Variational transition state theory (VTST) is applied to the study of the activated escape of a particle trapped in a multidimensional potential well and coupled to a heat bath. Special attention is given to the dependence of the rate constant on the friction coefficients in the case of anisotropic friction. It is demonstrated explicitly that both the traditional as well as the nontraditional scenarios for the particle escape are recovered uniformly within the framework of VTST. Effects such as saddle point avoidance and friction dependence of the activation energy are derived from VTST using optimized planar dividing surfaces.

  10. Symmetry energy in nuclear surface

    International Nuclear Information System (INIS)

    Danielewicz, P.; Lee, Jenny

    2009-01-01

    Interplay between the dependence of symmetry energy on density and the variation of nucleonic densities across nuclear surface is discussed. That interplay gives rise to the mass dependence of the symmetry coefficient in an energy formula. Charge symmetry of the nuclear interactions allows to introduce isoscalar and isovector densities that are approximately independent of the magnitude of neutron-proton asymmetry. (author)

  11. Surface energy anisotropy of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, R; Grenga, H E [Georgia Inst. of Tech., Atlanta (USA). School of Chemical Engineering

    1976-10-01

    Field-ion microscopy was used to study the faceting behavior and/or surface energy anisotropy of tungsten in vacuum and in hydrogen. In vacuum below 1700 K the activation energy for (110) facet growth agreed with values previously reported for surface diffusion on tungsten. The observed anisotropy values at 0.5 Tsub(m), where Tsub(m) is the absolute melting temperature of tungsten (approximately 3680 K), were different from those previously reported at higher temperatures and more nearly agreed with broken bond calculations based on Mie potential using m=5, n=8, and a 1.5% lattice expansion. Hydrogen appeared to have a negligible effect on surface energy anisotropy, but did preferentially increase surface diffusion rates on (310) regions.

  12. Surface energy of explosive nanoparticles

    Science.gov (United States)

    Pineau, Nicolas; Bidault, Xavier; Soulard, Laurent

    2017-06-01

    Recent experimental studies show that nanostructuration has a substantial impact on the detonation of high explosives: a nanostructured one leads to smaller nanodiamonds than a microstructured one. Whether it comes from a higher surface energy or from porosity, the origin of these different behaviors must be investigated. The surface energy of TATB nanoparticles with a radius from 2 nm upto 60 nm has been determined by means of ReaxFF-based simulations. Then, using the Rankine-Hugoniot relations and the equation of states of the bulk material, the contribution of this excess energy to the heating of a shock-compressed nanostructured (and porous) material is evaluated and compared to the thermal effect due to its porosity collapse. A maximum temperature increase of 50 K is found for 4-nm nanoparticles, which remains negligible when compared to the few hundred degrees induced by the compaction work.

  13. Theoretical studies of potential energy surfaces and computational methods

    Energy Technology Data Exchange (ETDEWEB)

    Shepard, R. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This project involves the development, implementation, and application of theoretical methods for the calculation and characterization of potential energy surfaces involving molecular species that occur in hydrocarbon combustion. These potential energy surfaces require an accurate and balanced treatment of reactants, intermediates, and products. This difficult challenge is met with general multiconfiguration self-consistent-field (MCSCF) and multireference single- and double-excitation configuration interaction (MRSDCI) methods. In contrast to the more common single-reference electronic structure methods, this approach is capable of describing accurately molecular systems that are highly distorted away from their equilibrium geometries, including reactant, fragment, and transition-state geometries, and of describing regions of the potential surface that are associated with electronic wave functions of widely varying nature. The MCSCF reference wave functions are designed to be sufficiently flexible to describe qualitatively the changes in the electronic structure over the broad range of geometries of interest. The necessary mixing of ionic, covalent, and Rydberg contributions, along with the appropriate treatment of the different electron-spin components (e.g. closed shell, high-spin open-shell, low-spin open shell, radical, diradical, etc.) of the wave functions, are treated correctly at this level. Further treatment of electron correlation effects is included using large scale multireference CI wave functions, particularly including the single and double excitations relative to the MCSCF reference space. This leads to the most flexible and accurate large-scale MRSDCI wave functions that have been used to date in global PES studies.

  14. Surface meteorology and Solar Energy

    Science.gov (United States)

    Stackhouse, Paul W. (Principal Investigator)

    The Release 5.1 Surface meteorology and Solar Energy (SSE) data contains parameters formulated for assessing and designing renewable energy systems. Parameters fall under 11 categories including: Solar cooking, solar thermal applications, solar geometry, tilted solar panels, energy storage systems, surplus product storage systems, cloud information, temperature, wind, other meteorological factors, and supporting information. This latest release contains new parameters based on recommendations by the renewable energy industry and it is more accurate than previous releases. On-line plotting capabilities allow quick evaluation of potential renewable energy projects for any region of the world. The SSE data set is formulated from NASA satellite- and reanalysis-derived insolation and meteorological data for the 10-year period July 1983 through June 1993. Results are provided for 1 degree latitude by 1 degree longitude grid cells over the globe. Average daily and monthly measurements for 1195 World Radiation Data Centre ground sites are also available. [Mission Objectives] The SSE project contains insolation and meteorology data intended to aid in the development of renewable energy systems. Collaboration between SSE and technology industries such as the Hybrid Optimization Model for Electric Renewables ( HOMER ) may aid in designing electric power systems that employ some combination of wind turbines, photovoltaic panels, or diesel generators to produce electricity. [Temporal_Coverage: Start_Date=1983-07-01; Stop_Date=1993-06-30] [Spatial_Coverage: Southernmost_Latitude=-90; Northernmost_Latitude=90; Westernmost_Longitude=-180; Easternmost_Longitude=180].

  15. Variational transition-state theory. Progress report, February 1981-January 1983

    International Nuclear Information System (INIS)

    Truhlar, D.G.

    1983-01-01

    During the past two years we have extended the variational transition-state theory in several ways. Especially notable is that we have developed several new methods for calculating tunneling probabilities, including two general techniques applicable to systems with small and large reaction-path curvature. We have tested these methods successfully against accurate quantal calculations, and we have applied them to real systems in three dimensions. We have also developed general algorithms for variational transition state theory calculations on polyatomic systems and we have applied these to the combustion reaction OH + H 2 → H 2 O + H. We have developed and successfully applied a statistical-diabatic theory for state-selected rates. We made a totally ab initio prediction of an absolute chemical reaction rate, for the reaction Mu + H 2 → MuH + H, using an accurate potential energy surface and ethods that we had demonstrated to be reliable by tests against accurate quantal collinear results. This prediction has now been confirmed by unpublished experiments; I believe that this is the first reliable ab initio prediction of a chemical rection rate prior to its measurement. In the rest of this technical progress report we give further details of these and other studies we have carried out in the last two years under this contract

  16. Probing the transition state for nucleic acid hybridization using phi-value analysis.

    Science.gov (United States)

    Kim, Jandi; Shin, Jong-Shik

    2010-04-27

    Genetic regulation by noncoding RNA elements such as microRNA and small interfering RNA (siRNA) involves hybridization of a short single-stranded RNA with a complementary segment in a target mRNA. The physical basis of the hybridization process between the structured nucleic acids is not well understood primarily because of the lack of information about the transition-state structure. Here we use transition-state theory, inspired by phi-value analysis in protein folding studies, to provide quantitative analysis of the relationship between changes in the secondary structure stability and the activation free energy. Time course monitoring of the hybridization reaction was performed under pseudo-steady-state conditions using a single fluorophore. The phi-value analysis indicates that the native secondary structure remains intact in the transition state. The nativelike transition state was confirmed via examination of the salt dependence of the hybridization kinetics, indicating that the number of sodium ions associated with the transition state was not substantially affected by changes in the native secondary structure. These results propose that hybridization between structured nucleic acids undergoes a transition state leading to formation of a nucleation complex and then is followed by sequential displacement of preexisting base pairings involving successive small energy barriers. The proposed mechanism might provide new insight into physical processes during small RNA-mediated gene silencing, which is essential to selection of a target mRNA segment for siRNA design.

  17. Energy conservation potential of surface modification technologies

    Energy Technology Data Exchange (ETDEWEB)

    Le, H.K.; Horne, D.M.; Silberglitt, R.S.

    1985-09-01

    This report assesses the energy conservation impact of surface modification technologies on the metalworking industries. The energy conservation impact of surface modification technologies on the metalworking industries is assessed by estimating their friction and wear tribological sinks and the subsequent reduction in these sinks when surface modified tools are used. Ion implantation, coatings, and laser and electron beam surface modifications are considered.

  18. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  19. Modification of Surface Energy via Direct Laser Ablative Surface Patterning

    Science.gov (United States)

    Wohl, Christopher J., Jr. (Inventor); Belcher, Marcus A. (Inventor); Connell, John W. (Inventor); Hopkins, John W. (Inventor)

    2015-01-01

    Surface energy of a substrate is changed without the need for any template, mask, or additional coating medium applied to the substrate. At least one beam of energy directly ablates a substrate surface to form a predefined topographical pattern at the surface. Each beam of energy has a width of approximately 25 micrometers and an energy of approximately 1-500 microJoules. Features in the topographical pattern have a width of approximately 1-500 micrometers and a height of approximately 1.4-100 micrometers.

  20. Vibrational nonadiabaticity and tunneling effects in transition state theory

    International Nuclear Information System (INIS)

    Marcus, R.A.

    1979-01-01

    The usual quantum mechanical derivation of transition state theory is a statistical one (a quasi-equilibrium is assumed) or dynamical. The typical dynamical one defines a set of internal states and assumes vibrational adiabaticity. Effects of nonadiabaticity before and after the transition state are included in the present derivation, assuming a classical treatment of the reaction coordinate. The relation to a dynamical derivation of classical mechanical transition state theory is described, and tunneling effects are considered

  1. Surface Energy and Setting Process of Contacting Surfaces

    Directory of Open Access Journals (Sweden)

    M. V. Musokhranov

    2014-01-01

    Full Text Available The paper deals with a challenge in terms of ensuring an accuracy of the relative position of the conjugated surfaces that is to determine a coefficient of friction. To solve it, there is a proposal to use the surface energy, as a tool that influences the contacting parts nature. Presently, energy of the surface layers at best is only stated, but not used in practice.Analysis of the conditions of interaction between two contacting surfaces, such as seizing and setting cannot be explained only from the position of the roughness parameters. It is found that these phenomena are explained by the appearing gripe (setting bridges, which result from the energy of interaction between two or more adjacent surfaces. The emerging phenomenon such as micro welding, i.e. occurring bonds, is caused by the overflow of energy, according to the theory of physics, from the surface with a high level of energy to the surface with the smaller one to balance the system as a whole.The paper shows that through the use of process, controlling the depth of the surface layer and creating a certain structure, the energy level of the material as a whole can be specified. And this will allow us to provide the necessary performance and mechanical properties. It means to create as many gripe bridges as possible to ensure continuous positioning i.e. a fixed connection of the contacting surfaces.It was determined that to increase a value of the friction coefficient, the physical and mechanical properties of the surface layer of the parts material must be taken into account, namely, in the part body accumulate the energy to be consumed for forming the surface.The paper gives recommendations for including the parts of the surface energy in the qualitative indicators of characteristics. This will make a technologist, when routing a process, to choose such operations and modes to provide the designer-specified parameters not only of the accuracy and surface finish, but also of the

  2. Classical generalized transition-state theory. Application to a collinear reaction with two saddle points

    International Nuclear Information System (INIS)

    Garrett, B.C.; Truhlar, D.G.; Grev, R.S.

    1981-01-01

    Accurate classical dynamical fixed-energy reaction probabilities and fixed-temperature rate constants are calculated for the collinear reaction H + FH on a low-barrier model potential energy surface. The calculations cover energies from 0.1 to 100 kcal/mol above threshold and temperatures of 100 to 10,000 K. The accurate results are used to test five approximate theories: conventional transition-state theory (TST), canonical variational theory (CVT), improved canonical variational theory (ICVT), microcanonical variational theory (μVT), and the unified statistical model (US). The first four of these theories involve a single dividing surface in phase space, and the US theory involves three dividing surfaces. The tests are particularly interesting because the potential energy surface has two identical saddle points. At temperatures from 100 to 2000 K, the μVt is the most accurate theory, with errors in the range 11 to 14%; for temperatures from 2000 to 10,000 K, the US theory is the most successful, with errors in the range 3 to 14%. Over the whole range, a factor of 100 in temperature, both theories have errors of 35% or less. Even TST has errors of 47% or less over the whole factor-of-100 temperature range. Although the US model should become exact at threshold for this system, it already underestimates the reaction probability by a factor of 0.64 at 0.1 kcal/mol above threshold. TST and μVT agree with each other within 12% up to an energy 13 kcal/mol above the saddle point energy. 3 figures, 2 tables

  3. Multilayer Relaxation and Surface Energies of Metallic Surfaces

    Science.gov (United States)

    Bozzolo, Guillermo; Rodriguez, Agustin M.; Ferrante, John

    1994-01-01

    The perpendicular and parallel multilayer relaxations of fcc (210) surfaces are studied using equivalent crystal theory (ECT). A comparison with experimental and theoretical results is made for AI(210). The effect of uncertainties in the input parameters on the magnitudes and ordering of surface relaxations for this semiempirical method is estimated. A new measure of surface roughness is proposed. Predictions for the multilayer relaxations and surface energies of the (210) face of Cu and Ni are also included.

  4. NATO Advanced Research Workshop on Geometrical Derivatives of Energy Surfaces and Molecular Properties

    CERN Document Server

    Simons, Jack

    1986-01-01

    The development and computational implementation of analytical expres­ sions for the low-order derivatives of electronic energy surfaces and other molecular properties has undergone rapid growth in recent years. It is now fairly routine for chemists to make use of energy gradient information in locating and identifying stable geometries and transition states. The use of second analytical derivative (Hessian or curvature) expressions is not yet routine, and third and higher energy derivatives as well as property (e.g., dipole moment, polarizability) derivatives are just beginning to be applied to chemical problems. This NATO Advanced Research Workshop focused on analyzing the re­ lative merits of various strategies for deriving the requisite analyti­ cal expressions, for computing necessary integral derivatives and wave­ function parameter derivatives, and for efficiently coding these expres­ sions on conventional scalar machines and vector-oriented computers. The participant list contained many scientist...

  5. Ab initio calculation of transition state normal mode properties and rate constants for the H(T)+CH4(CD4) abstraction and exchange reactions

    International Nuclear Information System (INIS)

    Schatz, G.C.; Walch, S.P.; Wagner, A.F.

    1980-01-01

    We present ab initio (GVB--POL--CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH 4 (CD 4 ) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF--SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL--CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL--CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL--CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL--CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH 3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange

  6. A Quantum Version of Wigner's Transition State Theory

    NARCIS (Netherlands)

    Schubert, R.; Waalkens, H.; Wiggins, S.

    A quantum version of a recent realization of Wigner's transition state theory in phase space is presented. The theory developed builds on a quantum normal form which locally decouples the quantum dynamics near the transition state to any desired order in (h) over bar. This leads to an explicit

  7. A Quantum Version of Wigner’s Transition State Theory

    NARCIS (Netherlands)

    Schubert, R.; Waalkens, H.; Wiggins, S.

    2009-01-01

    A quantum version of a recent realization of Wigner’s transition state theory in phase space is presented. The theory developed builds on a quantum normal form which locally decouples the quantum dynamics near the transition state to any desired order in ħ. This leads to an explicit algorithm to

  8. Periodic-orbit formula for quantum reactions through transition states

    NARCIS (Netherlands)

    Schubert, Roman; Waalkens, Holger; Goussev, Arseni; Wiggins, Stephen

    2010-01-01

    Transition state theory forms the basis of computing reaction rates in chemical and other systems. Recently, it has been shown how transition state theory can rigorously be realized in phase space by using an explicit algorithm. The quantization has been demonstrated to lead to an efficient

  9. The Variable Transition State in Polar Additions to Pi Bonds

    Science.gov (United States)

    Weiss, Hilton M.

    2010-01-01

    A vast majority of polar additions of Bronsted acids to alkynes involve a termolecular transition state. With strong acids, considerable positive charge is developed on carbon and Markovnikov addition predominates. In less acidic solutions, however, the reaction is much slower and the transition state more closely resembles the olefinic product.…

  10. Waves energy comes to surface

    International Nuclear Information System (INIS)

    Guezel, J.Ch.

    2006-01-01

    The wave- or thalasso-energy, potentially as promising as wind energy, have started to develop in Europe. Great Britain has already a good experience in this domain but France shows also ambitions in this beginning industry with several projects in progress. This article makes an overview of the existing tide-, current- and wave-powered generators: tide mills, underwater hydro-turbines, immersed linear generators, air-compression systems, buoy systems, etc. (J.S.)

  11. Atomistic modeling determination of placeholder binding energy of Ti, C, and N atoms on a-Fe (100) surfaces

    International Nuclear Information System (INIS)

    Wei, X J; Liu, Y P; Han, S P

    2015-01-01

    A Fe(100) surface containing Ti, C, and N was constructed and optimized to study the placeholder binding energy of the Ti, C, and N surface atoms; this was achieved by searching the transition state with the LST (linear synchronous transit) method of the CASTEP (Cambridge Serial Total Energy Package) module. Also, the authors analyzed electron structures to determine how Ti, C, and N atoms strengthen the Fe(100) surface. The results show that when Ti, C, or N atoms take placeholder alone, or simultaneously at the Fe(100) surface, the structure stability is at its best. When including Ti, C, and N as solid solutions on the Fe(100) surface, orbital electrons of Fe3d, Ti3d, C2p, and N2p hybridize near the Fermi level; the number of electronic bonding peaks increase and bonding capacity enhances. Also, a large amount of covalent bonds formed. Covalent bonds and metallic bond coexisted. (paper)

  12. Solar energy converter using surface plasma waves

    Science.gov (United States)

    Anderson, L. M. (Inventor)

    1984-01-01

    Sunlight is dispersed over a diffraction grating formed on the surface of a conducting film on a substrate. The angular dispersion controls the effective grating period so that a matching spectrum of surface plasmons is excited for parallel processing on the conducting film. The resulting surface plasmons carry energy to an array of inelastic tunnel diodes. This solar energy converter does not require different materials for each frequency band, and sunlight is directly converted to electricity in an efficient manner by extracting more energy from the more energetic photons.

  13. Evaluation of fitting functions for the representation of an O(3P)+H2 potential energy surface. I

    International Nuclear Information System (INIS)

    Wagner, A.F.; Schatz, G.C.; Bowman, J.M.

    1981-01-01

    The DIM surface of Whitlock, Muckerman, and Fisher for the O( 3 P)+H 2 system is used as a test case to evaluate the usefulness of a variety of fitting functions for the representation of potential energy surfaces. Fitting functions based on LEPS, BEBO, and rotated Morse oscillator (RMO) forms are examined. Fitting procedures are developed for combining information about a small portion of the surface and the fitting function to predict where on the surface more information must be obtained to improve the accuracy of the fit. Both unbiased procedures and procedures heavily biased toward the saddle point region of the surface are investigated. Collinear quasiclassical trajectory calculations of the reaction rate constant and one and three dimensional transition state theory rate constant calculations are performed and compared for selected fits and the exact DIM test surface. Fitting functions based on BEBO and RMO forms are found to give quite accurate results

  14. Surface energy of metal alloy nanoparticles

    Science.gov (United States)

    Takrori, Fahed M.; Ayyad, Ahmed

    2017-04-01

    The measurement of surface energy of alloy nanoparticles experimentally is still a challenge therefore theoretical work is necessary to estimate its value. In continuation of our previous work on the calculation of the surface energy of pure metallic nanoparticles we have extended our work to calculate the surface energy of different alloy systems, namely, Co-Ni, Au-Cu, Cu-Al, Cu-Mg and Mo-Cs binary alloys. It is shown that the surface energy of metallic binary alloy decreases with decreasing particle size approaching relatively small values at small sizes. When both metals in the alloy obey the Hume-Rothery rules, the difference in the surface energy is small at the macroscopic as well as in the nano-scale. However when the alloy deviated from these rules the difference in surface energy is large in the macroscopic and in the nano scales. Interestingly when solid solution formation is not possible at the macroscopic scale according to the Hume-Rothery rules, it is shown it may form at the nano-scale. To our knowledge these findings here are presented for the first time and is challenging from fundamental as well as technological point of views.

  15. Sorption Energy Maps of Clay Mineral Surfaces

    International Nuclear Information System (INIS)

    Cygan, Randall T.; Kirkpatrick, R. James

    1999-01-01

    A molecular-level understanding of mineral-water interactions is critical for the evaluation and prediction of the sorption properties of clay minerals that may be used in various chemical and radioactive waste disposal methods. Molecular models of metal sorption incorporate empirical energy force fields, based on molecular orbital calculations and spectroscopic data, that account for Coulombic, van der Waals attractive, and short-range repulsive energies. The summation of the non-bonded energy terms at equally-spaced grid points surrounding a mineral substrate provides a three dimensional potential energy grid. The energy map can be used to determine the optimal sorption sites of metal ions on the exposed surfaces of the mineral. By using this approach, we have evaluated the crystallographic and compositional control of metal sorption on the surfaces of kaolinite and illite. Estimates of the relative sorption energy and most stable sorption sites are derived based on a rigid ion approximation

  16. Effect of surface energy on powder compactibility.

    Science.gov (United States)

    Fichtner, Frauke; Mahlin, Denny; Welch, Ken; Gaisford, Simon; Alderborn, Göran

    2008-12-01

    The influence of surface energy on the compactibility of lactose particles has been investigated. Three powders were prepared by spray drying lactose solutions without or with low proportions of the surfactant polysorbate 80. Various powder and tablet characterisation procedures were applied. The surface energy of the powders was characterized by Inverse Gas Chromatography and the compressibility of the powders was described by the relationship between tablet porosity and compression pressure. The compactibility of the powders was analyzed by studying the evolution of tablet tensile strength with increasing compaction pressure and porosity. All powders were amorphous and similar in particle size, shape, and surface area. The compressibility of the powders and the microstructure of the formed tablets were equal. However, the compactibility and dispersive surface energy was dependent of the composition of the powders. The decrease in tablet strength correlated to the decrease in powder surface energy at constant tablet porosities. This supports the idea that tablet strength is controlled by formation of intermolecular forces over the areas of contact between the particles and that the strength of these bonding forces is controlled by surface energy which, in turn, can be altered by the presence of surfactants.

  17. Are boat transition states likely to occur in Cope rearrangements? A DFT study of the biogenesis of germacranes

    Directory of Open Access Journals (Sweden)

    José Enrique Barquera-Lozada

    2017-09-01

    Full Text Available It has been proposed that elemanes are biogenetically formed from germacranes by Cope sigmatropic rearrangements. Normally, this reaction proceeds through a transition state with a chair conformation. However, the transformation of schkuhriolide (germacrane into elemanschkuhriolide (elemane may occur through a boat transition state due to the final configuration of the elemanschkuhriolide, but this transition state is questionable due to its high energy. The possible mechanisms of this transformation were studied in the density functional theory frame. The mechanistic differences between the transformation of (Z,E-germacranes and (E,E-germacranes were also studied. We found that (Z,E-germacranolides are significantly more stable than (E,E-germacranolides and elemanolides. In the specific case of schkuhriolide, even when the boat transition state is not energetically favored, a previous hemiacetalization lowers enough the energetic barrier to allow the formation of a very stable elemanolide that is even more stable than its (Z,E-germacrane.

  18. Transition States from Empirical Force Fields

    DEFF Research Database (Denmark)

    Jensen, Frank; Norrby, Per-Ola

    2003-01-01

    This is an overview of the use of empirical force fields in the study of reaction mechanisms. EVB-type methods (including RFF and MCMM) produce full reaction surfaces by mixing, in the simplest case, known force fields describing reactants and products. The SEAM method instead locates approximate...

  19. SURFACE ENERGY BALANCE OVER ORANGE ORCHARD USING SURFACE RENEWAL ANALYSIS

    Directory of Open Access Journals (Sweden)

    Salvatore Barbagallo

    2009-12-01

    Full Text Available Reliable estimation of surface sensible and latent heat flux is the most important process to appraise energy and mass exchange among atmosphere and biosphere. In this study the surface energy fluxes were measured over an irrigated orange orchard during 2005-2008 monitoring periods using a Surface Renewal- Energy Balance approach. The experimental area is located in a representative orchard growing area of eastern Sicily (Italy. The performance of Surface Renewal (SR analysis for estimating sensible heat flux (H was analysed and evaluated in terms of correlation with H fluxes from the eddy covariance (EC method. Study revealed that the mean available energy (RN- G and latent heat flux (LE were of about 300 W m-2 and 237 W m-2, respectively, during dry periods and unstable-case atmospheric conditions. The estimated crop coefficient Kc values for the orchard crop averaged close to 0.80, which is considerably higher than previous FAO studies that found the value to be 0.65 for citrus with 70% of ground cover. The intercepted photosynthetically active radiation (LI PAR by the crop was measured and relationships between LAI and crop coefficient (Kc were established.

  20. Energy loss spectroscopy applied to surface studies

    International Nuclear Information System (INIS)

    Lecante, J.

    1975-01-01

    The analysis of energy losses suffered by slow electrons (5eV to 300eV) back-scattered by single crystal surfaces appears to be a powerful method for surfaces studies. The inelastic scattering of these slow electrons limits their escape depth to the surface region. After a review of the basic excitation processes due to the interaction between electrons and surfaces (phonons, plasmons and electronic transitions) a brief discussion is given about the instruments needed for this electrons spectroscopy. Finally some experimental results are listed and it is shown that the comparison of the results given by ELS with other surface sensitive methods such as UPS is very fruitful and new information can be obtained. The improvement of theoretical studies on surface excitations due to slow electrons will provide in the next future the possibility of analysing in a more quantitative way the results given by ELS [fr

  1. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  2. Surface Plasmon-Assisted Solar Energy Conversion.

    Science.gov (United States)

    Dodekatos, Georgios; Schünemann, Stefan; Tüysüz, Harun

    2016-01-01

    The utilization of localized surface plasmon resonance (LSPR) from plasmonic noble metals in combination with semiconductors promises great improvements for visible light-driven photocatalysis, in particular for energy conversion. This review summarizes the basic principles of plasmonic photocatalysis, giving a comprehensive overview about the proposed mechanisms for enhancing the performance of photocatalytically active semiconductors with plasmonic devices and their applications for surface plasmon-assisted solar energy conversion. The main focus is on gold and, to a lesser extent, silver nanoparticles in combination with titania as semiconductor and their usage as active plasmonic photocatalysts. Recent advances in water splitting, hydrogen generation with sacrificial organic compounds, and CO2 reduction to hydrocarbons for solar fuel production are highlighted. Finally, further improvements for plasmonic photocatalysts, regarding performance, stability, and economic feasibility, are discussed for surface plasmon-assisted solar energy conversion.

  3. Thermal rate coefficients in collinear versus bent transition state reactions: the N+N{sub 2} case study

    Energy Technology Data Exchange (ETDEWEB)

    Lagana, Antonio; Faginas Lago, Noelia; Rampino, Sergio [Dipartimento di Chimica, Universita di Perugia, 06123 Perugia (Italy); Huarte-Larranaga, FermIn [Computer Simulation and Modeling Lab (CoSMoLab), Parc CientIfic de Barcelona, 08028 Barcelona (Spain); GarcIa, Ernesto [Departamento de Quimica Fisica, Universidad del PaIs Vasco, 01006 Vitoria (Spain)], E-mail: lagana05@gmail.com, E-mail: fhuarte@pcb.ub.es, E-mail: e.garcia@ehu.es

    2008-10-15

    Zero total angular momentum exact quantum calculations of the probabilities of the N+N{sub 2} reaction have been performed on the L3 potential energy surface having a bent transition state. This has allowed us to work out J-shifting estimates of the thermal rate coefficient based on the calculation of either detailed (state-to-state) or cumulative (multiconfiguration) probabilities. The results obtained are used to compare the numerical outcomes and the concurrent computational machineries of both quantum and semiclassical approaches as well as to exploit the potentialities of the J-shifting model. The implications of moving the barrier to reaction from the previously proposed collinear geometry of the LEPS to the bent one of L3 are also investigated by comparing the related detailed reactive probabilities.

  4. Energy loss spectroscopy applied to surface studies

    International Nuclear Information System (INIS)

    Lecante, J.

    1975-01-01

    The analysis of energy losses suffered by slow electrons (5 eV to 300 eV) back-scattered by single crystal surfaces appears to be a powerful method for surfaces studies. The inelastic scattering of these slow electrons limits their escape depth to the surface region which is defined here. After a review of the basic excitation processes due to the interaction between electrons and surfaces (phonons, plasmons and electronic transitions) a brief discussion is given about the instruments needed for this electron spectroscopy. Finally some experimental results are listed and it is shown that the comparison of the results given by ELS with other surface sensitive methods such as UPS is very fruitful and new information can be obtained [fr

  5. Surface energy of very neutron rich nuclei

    CERN Document Server

    Von Groote, H

    1976-01-01

    For a microscopic model calculation of the nuclear surface-energy coefficient sigma the surface energy is defined as the energy loss of an uncharged, semiinfinite (inhomogeneous) two-component system compared to an infinite (homogeneous) system with the same particle asymmetry delta . Using the Thomas-Fermi model the calculations are performed for a series of systems with increasing delta , starting from symmetric matter ( delta =0) and extending beyond the drip line of the neutrons, until the system undergoes a phase transition to a homogeneous system. The results for the surface energy as well as for the neutron skin and for the surface diffuseness are compared to the macroscopic approach of the Droplet Model (DM), which turns out to be a good approximation for small asymmetries typical for the region of the valley of beta -stability. For larger asymmetries, close to the drip lines, terms of higher order than contained in the DM approach are no longer negligible. Beyond the drip lines the pressure of the ou...

  6. Potential energy surface of alanine polypeptide chains

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Yakubovich, Alexander V.; Solov'yov, Andrey V.

    2006-01-01

    The multidimensional potential energy surfaces of the peptide chains consisting of three and six alanine (Ala) residues have been studied with respect to the degrees of freedom related to the twist of these molecules relative to the peptide backbone (these degrees of freedom are responsible...

  7. SURFACE SYMMETRY ENERGY OF NUCLEAR ENERGY DENSITY FUNCTIONALS

    Energy Technology Data Exchange (ETDEWEB)

    Nikolov, N; Schunck, N; Nazarewicz, W; Bender, M; Pei, J

    2010-12-20

    We study the bulk deformation properties of the Skyrme nuclear energy density functionals. Following simple arguments based on the leptodermous expansion and liquid drop model, we apply the nuclear density functional theory to assess the role of the surface symmetry energy in nuclei. To this end, we validate the commonly used functional parametrizations against the data on excitation energies of superdeformed band-heads in Hg and Pb isotopes, and fission isomers in actinide nuclei. After subtracting shell effects, the results of our self-consistent calculations are consistent with macroscopic arguments and indicate that experimental data on strongly deformed configurations in neutron-rich nuclei are essential for optimizing future nuclear energy density functionals. The resulting survey provides a useful benchmark for further theoretical improvements. Unlike in nuclei close to the stability valley, whose macroscopic deformability hangs on the balance of surface and Coulomb terms, the deformability of neutron-rich nuclei strongly depends on the surface-symmetry energy; hence, its proper determination is crucial for the stability of deformed phases of the neutron-rich matter and description of fission rates for r-process nucleosynthesis.

  8. Fast Shepard interpolation on graphics processing units: potential energy surfaces and dynamics for H + CH4 → H2 + CH3.

    Science.gov (United States)

    Welsch, Ralph; Manthe, Uwe

    2013-04-28

    A strategy for the fast evaluation of Shepard interpolated potential energy surfaces (PESs) utilizing graphics processing units (GPUs) is presented. Speed ups of several orders of magnitude are gained for the title reaction on the ZFWCZ PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)]. Thermal rate constants are calculated employing the quantum transition state concept and the multi-layer multi-configurational time-dependent Hartree approach. Results for the ZFWCZ PES are compared to rate constants obtained for other ab initio PESs and problems are discussed. A revised PES is presented. Thermal rate constants obtained for the revised PES indicate that an accurate description of the anharmonicity around the transition state is crucial.

  9. Applications of Molecular Modeling to Transition State Energies and Conformations

    Science.gov (United States)

    1992-05-08

    reactivity trends for similar systems are known. Illuminati and Mandolini have done research on the lactone formation from w-bromoalkane-carboxylate...strikingly similar to that determined for Illuminati and Mandolini’s similar lactonization system (see Figure 20). The AE, for the 4- 69 membered ring...Brown, F.K.; Spellmeyer, D.C.; Metz, J.T.; Li, Y.; Loncharich, R.L. Science. 1986, 231, 1108-17. Illuminati , G.; Mandolini, L. Accts. of Chem. Res. 1981

  10. Energy redistribution in diatomic molecules on surfaces

    International Nuclear Information System (INIS)

    Asscher, M.; Somorjai, G.A.

    1984-04-01

    Translational and internal degrees of freedom of a scattered beam of NO molecules from a Pt(111) single crystal surface were measured as a function of scattering angle and crystal temperature in the range 450 to 1250K. None of the three degrees of freedom were found to fully accommodate to the crystal temperature, the translational degree being the most accommodated and the rotational degree of freedom the least. A precursor state model is suggested to account for the incomplete accommodation of translational and vibrational degrees of freedom as a function of crystal temperature and incident beam energy. The vibrational accommodation is further discussed in terms of a competition between desorption and vibrational excitation processes, thus providing valuable information on the interaction between vibrationally excited molecules and surfaces. Energy transfer into rotational degrees of freedom is qualitatively discussed

  11. Transition state theory approach to polymer escape from a one dimensional potential well.

    Science.gov (United States)

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

    2015-06-14

    The rate of escape of an ideal bead-spring polymer in a symmetric double-well potential is calculated using transition state theory (TST) and the results compared with direct dynamical simulations. The minimum energy path of the transitions becomes flat and the dynamics diffusive for long polymers making the Kramers-Langer estimate poor. However, TST with dynamical corrections based on short time trajectories started at the transition state gives rate constant estimates that agree within a factor of two with the molecular dynamics simulations over a wide range of bead coupling constants and polymer lengths. The computational effort required by the TST approach does not depend on the escape rate and is much smaller than that required by molecular dynamics simulations.

  12. Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone

    Energy Technology Data Exchange (ETDEWEB)

    Mauguière, Frédéric A. L., E-mail: frederic.mauguiere@bristol.ac.uk; Collins, Peter, E-mail: peter.collins@bristol.ac.uk; Wiggins, Stephen, E-mail: stephen.wiggins@mac.com [School of Mathematics, University of Bristol, Bristol BS8 1TW (United Kingdom); Kramer, Zeb C., E-mail: zebcolterkramer@gmail.com; Ezra, Gregory S., E-mail: gse1@cornell.edu [Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853 (United States); Carpenter, Barry K., E-mail: carpenterb1@cardiff.ac.uk [School of Chemistry, Cardiff University, Cardiff CF10 3AT (United Kingdom); Farantos, Stavros C., E-mail: farantos@iesl.forth.gr [Institute of Electronic Structure and Laser, Foundation for Research and Technology - Hellas, and Department of Chemistry, University of Crete, Iraklion 711 10, Crete (Greece)

    2016-02-07

    We examine the phase space structures that govern reaction dynamics in the absence of critical points on the potential energy surface. We show that in the vicinity of hyperbolic invariant tori, it is possible to define phase space dividing surfaces that are analogous to the dividing surfaces governing transition from reactants to products near a critical point of the potential energy surface. We investigate the problem of capture of an atom by a diatomic molecule and show that a normally hyperbolic invariant manifold exists at large atom-diatom distances, away from any critical points on the potential. This normally hyperbolic invariant manifold is the anchor for the construction of a dividing surface in phase space, which defines the outer or loose transition state governing capture dynamics. We present an algorithm for sampling an approximate capture dividing surface, and apply our methods to the recombination of the ozone molecule. We treat both 2 and 3 degrees of freedom models with zero total angular momentum. We have located the normally hyperbolic invariant manifold from which the orbiting (outer) transition state is constructed. This forms the basis for our analysis of trajectories for ozone in general, but with particular emphasis on the roaming trajectories.

  13. Low Energy Nuclear Reaction Products at Surfaces

    Science.gov (United States)

    Nagel, David J.

    2008-03-01

    This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

  14. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    Science.gov (United States)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

  15. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    International Nuclear Information System (INIS)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-01-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S 0 ) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm −1 . The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm −1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction

  16. Theoretical studies of potential energy surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Harding, L.B. [Argonne National Laboratory, IL (United States)

    1993-12-01

    The goal of this program is to calculate accurate potential energy surfaces (PES) for both reactive and nonreactive systems. To do this the electronic Schrodinger equation must be solved. Our approach to this problem starts with multiconfiguration self-consistent field (MCSCF) reference wavefunctions. These reference wavefunctions are designed to be sufficiently flexible to accurately describe changes in electronic structure over a broad range of geometries. Electron correlation effects are included via multireference, singles and doubles configuration interaction (MRSDCI) calculations. With this approach, the authors are able to provide useful predictions of the energetics for a broad range of systems.

  17. Communication: Electronic flux induced by crossing the transition state

    Science.gov (United States)

    Jia, Dongming; Manz, Jörn; Yang, Yonggang

    2018-01-01

    We present a new effect of chemical reactions, e.g., isomerizations, that occurs when the reactants pass along the transition state, on the way to products. It is based on the well-known fact that at the transition state, the electronic structure of one isomer changes to the other. We discover that this switch of electronic structure causes a strong electronic flux that is well distinguishable from the usual flux of electrons that travel with the nuclei. As a simple but clear example, the effect is demonstrated here for bond length isomerization of Na2 (21Σu+), with adiabatic crossing the barrier between the inner and outer wells of the double minimum potential that support different "Rydberg" and "ionic" type electronic structures, respectively.

  18. Wigner's dynamical transition state theory in phase space: classical and quantum

    International Nuclear Information System (INIS)

    Waalkens, Holger; Schubert, Roman; Wiggins, Stephen

    2008-01-01

    We develop Wigner's approach to a dynamical transition state theory in phase space in both the classical and quantum mechanical settings. The key to our development is the construction of a normal form for describing the dynamics in the neighbourhood of a specific type of saddle point that governs the evolution from reactants to products in high dimensional systems. In the classical case this is the standard Poincaré–Birkhoff normal form. In the quantum case we develop a normal form based on the Weyl calculus and an explicit algorithm for computing this quantum normal form. The classical normal form allows us to discover and compute the phase space structures that govern classical reaction dynamics. From this knowledge we are able to provide a direct construction of an energy dependent dividing surface in phase space having the properties that trajectories do not locally 're-cross' the surface and the directional flux across the surface is minimal. Using this, we are able to give a formula for the directional flux through the dividing surface that goes beyond the harmonic approximation. We relate this construction to the flux–flux autocorrelation function which is a standard ingredient in the expression for the reaction rate in the chemistry community. We also give a classical mechanical interpretation of the activated complex as a normally hyperbolic invariant manifold (NHIM), and further describe the structure of the NHIM. The quantum normal form provides us with an efficient algorithm to compute quantum reaction rates and we relate this algorithm to the quantum version of the flux–flux autocorrelation function formalism. The significance of the classical phase space structures for the quantum mechanics of reactions is elucidated by studying the phase space distribution of scattering states. The quantum normal form also provides an efficient way of computing Gamov–Siegert resonances. We relate these resonances to the lifetimes of the quantum activated

  19. RELATIONSHIP BETWEEN FOAMING BEHAVIOR AND SURFACE ENERGY OF ASPHALT BINDER

    Directory of Open Access Journals (Sweden)

    Jian-ping Xu

    2017-12-01

    Full Text Available To solve the problem of insufficiency in microscopic performance of foamed asphalt binder, surface energy theory was utilized to analyze the foaming behavior and wettability of asphalt binder. Based on the surface energy theory, the Wilhelmy plate method and universal sorption device method were employed to measure the surface energy components of asphalt binders and aggregates, respectively. Combined with the traditional evaluation indictor for foamed asphalt, the relationship between the foaming property and surface energy of asphalt binder was analyzed. According to the surface energy components, the wettability of asphalt binder to aggregate was calculated to verify the performance of foamed asphalt mixture. Results indicate that the foaming behavior of asphalt will be influenced by surface energy, which will increase with the decline of surface energy. In addition, the surface energy of asphalt binder significantly influences the wettability of asphalt binder to aggregates. Meanwhile, there is an inversely proportional relationship between surface energy of asphalt binder and wettability. Therefore, it can be demonstrated that surface energy is a good indictor which can be used to evaluate the foaming behavior of the asphalt binder. And it is suggested to choose the asphalt binder with lower surface energy in the process of design of foamed asphalt mixture.

  20. Four Generations of Transition State Analogues for Human Purine Nucleoside Phosphorylase

    Energy Technology Data Exchange (ETDEWEB)

    Ho, M.; Shi, W; Rinaldo-Mathis, A; Tyler, P; Evans, G; Almo, S; Schramm, V

    2010-01-01

    Inhibition of human purine nucleoside phosphorylase (PNP) stops growth of activated T-cells and the formation of 6-oxypurine bases, making it a target for leukemia, autoimmune disorders, and gout. Four generations of ribocation transition-state mimics bound to PNP are structurally characterized. Immucillin-H (K*{sub i} = 58 pM, first-generation) contains an iminoribitol cation with four asymmetric carbons. DADMe-Immucillin-H (K*{sub i} = 9 pM, second-generation), uses a methylene-bridged dihydroxypyrrolidine cation with two asymmetric centers. DATMe-Immucillin-H (K*{sub i} = 9 pM, third-generation) contains an open-chain amino alcohol cation with two asymmetric carbons. SerMe-ImmH (K*{sub i} = 5 pM, fourth-generation) uses achiral dihydroxyaminoalcohol seramide as the ribocation mimic. Crystal structures of PNPs establish features of tight binding to be; (1) ion-pair formation between bound phosphate (or its mimic) and inhibitor cation, (2) leaving-group interactions to N1, O6, and N7 of 9-deazahypoxanthine, (3) interaction between phosphate and inhibitor hydroxyl groups, and (4) His257 interacting with the 5{prime}-hydroxyl group. The first generation analogue is an imperfect fit to the catalytic site with a long ion pair distance between the iminoribitol and bound phosphate and weaker interactions to the leaving group. Increasing the ribocation to leaving-group distance in the second- to fourth-generation analogues provides powerful binding interactions and a facile synthetic route to powerful inhibitors. Despite chemical diversity in the four generations of transition-state analogues, the catalytic site geometry is almost the same for all analogues. Multiple solutions in transition-state analogue design are available to convert the energy of catalytic rate enhancement to binding energy in human PNP.

  1. Transitional states of central serotonin receptors in Parkinson's disease

    International Nuclear Information System (INIS)

    Kienzl, E.; Riederer, P.; Jellinger, K.; Wesemann, W.; Marburg Univ.

    1981-01-01

    Crude membrane preparations from the frontal cortex of controls and pakinsonian patients were used to demonstrate affinity changes of the specific 3 H-5-hydroxytryptamine (5-HT) binding sites. Two such sites were noteable in controls, a finding consistent with earlier observations. In Parkinson's disease, both high- and low-affinity sites are significantly decreased. Additional experiments either with prolonged incubation times or pre-incubation with N-ethylmaleimide change the two affinities to a single high-affinity or low-affinity constant. The concept of transitional states of 5-HT receptors is discussed and seems to have important implications in the treatment of parkinsonism. (author)

  2. Transitional states of central serotonin receptors in Parkinson's disease

    Energy Technology Data Exchange (ETDEWEB)

    Kienzl, E; Riederer, P; Jellinger, K; Wesemann, W [Krankenhaus der Stadt Wien-Lainz (Austria). Ludwig Boltzmann Inst. fuer Neurobiologie; Marburg Univ. (Germany, F.R.). Inst. fuer Physiologie II, Abt. fuer Neurochemie)

    1981-01-01

    Crude membrane preparations from the frontal cortex of controls and pakinsonian patients were used to demonstrate affinity changes of the specific /sup 3/H-5-hydroxytryptamine (5-HT) binding sites. Two such sites were noteable in controls, a finding consistent with earlier observations. In Parkinson's disease, both high- and low-affinity sites are significantly decreased. Additional experiments either with prolonged incubation times or pre-incubation with N-ethylmaleimide change the two affinities to a single high-affinity or low-affinity constant. The concept of transitional states of 5-HT receptors is discussed and seems to have important implications in the treatment of parkinsonism.

  3. Explicit correlation treatment of the potential energy surface of CO{sub 2} dimer

    Energy Technology Data Exchange (ETDEWEB)

    Kalugina, Yulia N., E-mail: kalugina@phys.tsu.ru [Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Buryak, Ilya A. [Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, Moscow (Russian Federation); Chemistry Department, Lomonosov Moscow State University, Moscow (Russian Federation); Ajili, Yosra [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 Bd Descartes, 77454 Marne-La-Vallée (France); Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA Université de Tunis El Manar (Tunisia); Vigasin, Andrei A. [Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, Moscow (Russian Federation); Jaidane, Nejm Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA Université de Tunis El Manar (Tunisia); Hochlaf, Majdi [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 Bd Descartes, 77454 Marne-La-Vallée (France)

    2014-06-21

    We present an extensive study of the four-dimensional potential energy surface (4D-PES) of the carbon dioxide dimer, (CO{sub 2}){sub 2}. This PES is developed over the set of intermolecular coordinates. The electronic computations are carried out at the explicitly correlated coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)-F12] level of theory in connection with the augmented correlation-consistent aug-cc-pVTZ basis set. An analytic representation of the 4D-PES is derived. Our extensive calculations confirm that “Slipped Parallel” is the most stable form and that the T-shaped structure corresponds to a transition state. Later on, this PES is employed for the calculations of the vibrational energy levels of the dimer. Moreover, the temperature dependence of the dimer second virial coefficient and of the first spectral moment of rototranslational collision-induced absorption spectrum is derived. For both quantities, a good agreement is found between our values and the experimental data for a wide range of temperatures. This attests to the high quality of our PES. Generally, our PES and results can be used for modeling CO{sub 2} supercritical fluidity and examination of its role in planetary atmospheres. It can be also incorporated into dynamical computations of CO{sub 2} capture and sequestration. This allows deep understanding, at the microscopic level, of these processes.

  4. Comment on 'Modelling of surface energies of elemental crystals'

    International Nuclear Information System (INIS)

    Li Jinping; Luo Xiaoguang; Hu Ping; Dong Shanliang

    2009-01-01

    Jiang et al (2004 J. Phys.: Condens. Matter 16 521) present a model based on the traditional broken-bond model for predicting surface energies of elemental crystals. It is found that bias errors can be produced in calculating the coordination numbers of surface atoms, especially in the prediction of high-Miller-index surface energies. (comment)

  5. Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory

    Science.gov (United States)

    Rietze, Clemens; Titov, Evgenii; Lindner, Steven; Saalfrank, Peter

    2017-08-01

    The thermal Z\\to E (back-)isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model—Z\\to E isomerization in azobenzene—a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z\\to E (back-)isomerization of azobenzenes under solvent-free conditions.

  6. The energy balance of the earth's surface : a practical approach

    NARCIS (Netherlands)

    Bruin, de H.A.R.

    1982-01-01

    This study is devoted to the energy balance of the earth's surface with a special emphasis on practical applications. A simple picture of the energy exchange processes that take place at the ground is the following. Per unit time and area an amount of radiant energy is supplied to the surface. This

  7. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Don Wesley [Univ. of California, Berkeley, CA (United States)

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O3-. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO2, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C2- - C11-), and van der Waals clusters (X-(CO2)n, X = I, Br, Cl; n {le} 13 and I- (N2O)n=1--11). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X-(CO2)n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

  8. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Arnold, D.W.

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O 3 - . A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO 2 , has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO 2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO 2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C 2 - - C 11 - ), and van der Waals clusters (X - (CO 2 ) n , X = I, Br, Cl; n ≤ 13 and I - (N 2 O) n=1--11 ). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X - (CO 2 )n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products

  9. Energy Accommodation from Surface Catalyzed Reactions in Air Plasmas

    Data.gov (United States)

    National Aeronautics and Space Administration — Understanding energy transport at the gas-surface interface between catalytic/reacting surfaces exposed to highly dissociated plasmas remains a significant research...

  10. Surface free energy of alkali and transition metal nanoparticles

    International Nuclear Information System (INIS)

    Aqra, Fathi; Ayyad, Ahmed

    2014-01-01

    Graphical abstract: Size dependent surface free energy of spherical, cubic and disk Au nanoparticles. - Highlights: • A model to account for the surface free energy of metallic nanoparticles is described. • The model requires only the cohesive energy of the nanoparticle. • The surface free energy of a number of metallic nanoparticles has been calculated, and the obtained values agree well with existing data. • Surface energy falls down very fast when the number of atoms is less than hundred. • The model is applicable to any metallic nanoparticle. - Abstract: This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data

  11. Analysis of energy flow during playground surface impacts.

    Science.gov (United States)

    Davidson, Peter L; Wilson, Suzanne J; Chalmers, David J; Wilson, Barry D; Eager, David; McIntosh, Andrew S

    2013-10-01

    The amount of energy dissipated away from or returned to a child falling onto a surface will influence fracture risk but is not considered in current standards for playground impact-attenuating surfaces. A two-mass rheological computer simulation was used to model energy flow within the wrist and surface during hand impact with playground surfaces, and the potential of this approach to provide insights into such impacts and predict injury risk examined. Acceleration data collected on-site from typical playground surfaces and previously obtained data from children performing an exercise involving freefalling with a fully extended arm provided input. The model identified differences in energy flow properties between playground surfaces and two potentially harmful surface characteristics: more energy was absorbed by (work done on) the wrist during both impact and rebound on rubber surfaces than on bark, and rubber surfaces started to rebound (return energy to the wrist) while the upper limb was still moving downward. Energy flow analysis thus provides information on playground surface characteristics and the impact process, and has the potential to identify fracture risks, inform the development of safer impact-attenuating surfaces, and contribute to development of new energy-based arm fracture injury criteria and tests for use in conjunction with current methods.

  12. Modeling Enzymatic Transition States by Force Field Methods

    DEFF Research Database (Denmark)

    Hansen, Mikkel Bo; Jensen, Hans Jørgen Aagaard; Jensen, Frank

    2009-01-01

    The SEAM method, which models a transition structure as a minimum on the seam of two diabatic surfaces represented by force field functions, has been used to generate 20 transition structures for the decarboxylation of orotidine by the orotidine-5'-monophosphate decarboxylase enzyme. The dependence...... of the TS geometry on the flexibility of the system has been probed by fixing layers of atoms around the active site and using increasingly larger nonbonded cutoffs. The variability over the 20 structures is found to decrease as the system is made more flexible. Relative energies have been calculated...... by various electronic structure methods, where part of the enzyme is represented by a force field description and the effects of the solvent are represented by a continuum model. The relative energies vary by several hundreds of kJ/mol between the transition structures, and tests showed that a large part...

  13. Energy quantization for approximate H-surfaces and applications

    Directory of Open Access Journals (Sweden)

    Shenzhou Zheng

    2013-07-01

    Full Text Available We consider weakly convergent sequences of approximate H-surface maps defined in the plane with their tension fields bounded in $L^p$ for p> 4/3, and establish an energy quantization that accounts for the loss of their energies by the sum of energies over finitely many nontrivial bubbles maps on $mathbb{R}^2$. As a direct consequence, we establish the energy identity at finite singular time to their H-surface flows.

  14. Hydrogen-bonded intermediates and transition states during spontaneous and acid-catalyzed hydrolysis of the carcinogen (+)-anti-BPDE.

    Science.gov (United States)

    Palenik, Mark C; Rodriguez, Jorge H

    2014-07-07

    Understanding mechanisms of (+)-anti-BPDE detoxification is crucial for combating its mutagenic and potent carcinogenic action. However, energetic-structural correlations of reaction intermediates and transition states during detoxification via hydrolysis are poorly understood. To gain mechanistic insight we have computationally characterized intermediate and transition species associated with spontaneous and general-acid catalyzed hydrolysis of (+)-anti-BPDE. We studied the role of cacodylic acid as a proton donor in the rate limiting step. The computed activation energy (ΔG‡) is in agreement with the experimental value for hydrolysis in a sodium cacodylate buffer. Both types of, spontaneous and acid catalyzed, BPDE hydrolysis can proceed through low-entropy hydrogen bonded intermediates prior to formation of transition states whose energies determine reaction activation barriers and rates.

  15. Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

    Science.gov (United States)

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2015-12-17

    Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems.

  16. Analysis of surface with low energy ions

    International Nuclear Information System (INIS)

    Oliver, A.; Miranda, J.

    1989-01-01

    Nuclear techniques applied to element analysis presents different characteristics depending on projectile energy. It can seen observed than an energy (E ≅ 1 MeV) exists which separate two regions for which sensitivity, information analysis and resolution in detection are different. For this work, we describe for the energy region E ≤ 1 MeV, the advantage of the three most used techniques which are PIXE, RBS y RNR. (Author)

  17. Reflections on the surface energy imbalance problem

    Science.gov (United States)

    Ray Leuning; Eva van Gorsela; William J. Massman; Peter R. Isaac

    2012-01-01

    The 'energy imbalance problem' in micrometeorology arises because at most flux measurement sites the sum of eddy fluxes of sensible and latent heat (H + λE) is less than the available energy (A). Either eddy fluxes are underestimated or A is overestimated. Reasons for the imbalance are: (1) a failure to satisfy the fundamental assumption of one-...

  18. Surface energy for electroluminescent polymers and indium-tin-oxide

    International Nuclear Information System (INIS)

    Zhong Zhiyou; Yin Sheng; Liu Chen; Zhong Youxin; Zhang Wuxing; Shi Dufang; Wang Chang'an

    2003-01-01

    The contact angles on the thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and indium-tin-oxide (ITO) were measured by the sessile-drop technique. The surface energies of the films were calculated using the Owens-Wendt (OW) and van Oss-Chaudhury-Good (vOCG) approaches. The overall total surface energies of MEH-PPV and the as-received ITO were 30.75 and 30.07 mJ/m 2 , respectively. Both approaches yielded almost the same surface energies. The surface energies were mainly contributed from the dispersion interactions or Lifshitz-van der Waals (LW) interactions for both MEH-PPV and ITO. The changes in the contact angles and surface energies of the ITO films, due to different solvent cleaning processes and oxygen plasma treatments, were analyzed. Experimental results revealed that the total surface energy of the ITO films increased after various cleaning processes. In comparison with different solvents used in this study, we found that methanol is an effective solvent for ITO cleaning, as a higher surface energy was observed. ITO films treated with oxygen plasma showed the highest surface energy. This work demonstrated that contact angle measurement is a useful method to diagnose the cleaning effect on ITO films

  19. A systematic first-principles study of surface energies, surface relaxation and Friedel oscillation of magnesium surfaces

    International Nuclear Information System (INIS)

    Tang, Jia-Jun; Yang, Xiao-Bao; Zhao, Yu-Jun; OuYang, LiuZhang; Zhu, Min

    2014-01-01

    We systematically study the surface energies and surface relaxations of various low-index and high-index Mg surfaces. It is found that low-index surfaces are not necessarily stable as Mg(1 0  1-bar  0) is the most unstable surface in the series of Mg(1 0  1-bar  n) (n = 0–9). A surface-energy predicting model based on the bond cutting is proposed to explain the relative surface stabilities. The local relaxations of the low-index surfaces could be explained by the Friedel oscillation. For the high-index surfaces, the combination of charge smoothing effect and dramatic charge depletion influences the relaxations, which show a big difference from the low-index ones. Our findings provide theoretical data for considerable insights into the surface energies of hexagonal close-packed metals. (paper)

  20. Kramers-Kronig transform for the surface energy loss function

    International Nuclear Information System (INIS)

    Tan, G.L.; DeNoyer, L.K.; French, R.H.; Guittet, M.J.; Gautier-Soyer, M.

    2005-01-01

    A new pair of Kramers-Kronig (KK) dispersion relationships for the transformation of surface energy loss function Im[-1/(ε + 1)] has been proposed. The validity of the new surface KK transform is confirmed, using both a Lorentz oscillator model and the surface energy loss functions determined from the experimental complex dielectric function of SrTiO 3 and tungsten metal. The interband transition strength spectra (J cv ) have been derived either directly from the original complex dielectric function or from the derived dielectric function obtained from the KK transform of the surface energy loss function. The original J cv trace and post-J cv trace overlapped together for the three modes, indicating that the new surface Kramers-Kronig dispersion relationship is valid for the surface energy loss function

  1. Model calculation for energy loss in ion-surface collisions

    International Nuclear Information System (INIS)

    Miraglia, J.E.; Gravielle, M.S.

    2003-01-01

    The so-called local plasma approximation is generalized to deal with projectiles colliding with surfaces of amorphous solids and with a specific crystalline structure (plannar channeling). Energy loss of protons grazingly colliding with aluminum, SnTe alloy, and LiF surfaces is investigated. The calculations agree quite well with previous theoretical results and explain the experimental findings of energy loss for aluminum and SnTe alloy, but they fall short to explain the data for LiF surfaces

  2. Critical assessment of Pt surface energy - An atomistic study

    Science.gov (United States)

    Kim, Jin-Soo; Seol, Donghyuk; Lee, Byeong-Joo

    2018-04-01

    Despite the fact that surface energy is a fundamental quantity in understanding surface structure of nanoparticle, the results of experimental measurements and theoretical calculations for the surface energy of pure Pt show a wide range of scattering. It is necessary to further ensure the surface energy of Pt to find the equilibrium shape and atomic configuration in Pt bimetallic nanoparticles accurately. In this article, we critically assess and optimize the Pt surface energy using a semi-empirical atomistic approach based on the second nearest-neighbor modified embedded-atom method interatomic potential. That is, the interatomic potential of pure Pt was adjusted in a way that the surface segregation tendency in a wide range of Pt binary alloys is reproduced in accordance with experimental information. The final optimized Pt surface energy (mJ/m2) is 2036 for (100) surface, 2106 for (110) surface, and 1502 for (111) surface. The potential can be utilized to find the equilibrium shape and atomic configuration of Pt bimetallic nanoparticles more accurately.

  3. Improving Energy Efficiency In Thermal Oil Recovery Surface Facilities

    Energy Technology Data Exchange (ETDEWEB)

    Murthy Nadella, Narayana

    2010-09-15

    Thermal oil recovery methods such as Cyclic Steam Stimulation (CSS), Steam Assisted Gravity Drainage (SAGD) and In-situ Combustion are being used for recovering heavy oil and bitumen. These processes expend energy to recover oil. The process design of the surface facilities requires optimization to improve the efficiency of oil recovery by minimizing the energy consumption per barrel of oil produced. Optimization involves minimizing external energy use by heat integration. This paper discusses the unit processes and design methodology considering thermodynamic energy requirements and heat integration methods to improve energy efficiency in the surface facilities. A design case study is presented.

  4. Valence bond model potential energy surface for H4

    International Nuclear Information System (INIS)

    Silver, D.M.; Brown, N.J.

    1980-01-01

    Potential energy surfaces for the H 4 system are derived using the valence bond procedure. An ab initio evaluation of the valence bond energy expression is described and some of its numerical properties are given. Next, four semiempirical evaluations of the valence bond energy are defined and parametrized to yield reasonable agreement with various ab initio calculations of H 4 energies. Characteristics of these four H 4 surfaces are described by means of tabulated energy minima and equipotential contour maps for selected geometrical arrangements of the four nuclei

  5. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  6. Surface sterilization by low energy electron beams

    International Nuclear Information System (INIS)

    Sekiguchi, Masayuki; Tabei, Masae

    1989-01-01

    The germicidal effectiveness of low energy electron beams (175 KV) against bacterial cells was investigated. The dry spores of Bacillus pumilus ATCC 27142 and Bacillus globigii ATCC 9372 inoculated on carrier materials and irradiated by gamma rays showed the exponential type of survival curves whereas they showed sigmoidal ones when exposed to low energy electron beams. When similarly irradiated, the wet spores inoculated on membrane filter showed the same survival curves as the dry spores inoculated on carrier materials. The wet vegetative cells of Escherichia coli ATCC 25922 showed exponential curves when exposed to gamma and electron beam irradiation. Low energy electron beams in air showed little differences from nitrogen stream in their germicidal effectiveness against dry spores of B. pumilus. The D values of B. pumilus spores inoculated on metal plates decreased as the amounts of backscattering electrons from the plates increased. There was adequate correlation between the D value (linear region of survival curve), average D value (6D/6) and 1% survival dose and backscattering factor. Depth dose profile and backscatterig dose of low energy electron beams were measured by radiochromic dye film dosimeter (RCD). These figures were not always in accord with the observed germicidal effectiveness against B. pumilus spores because of varying thickness of RCD and spores inoculated on carrier material. The dry spores were very thin and this thinness was useful in evaluating the behavior of low energy electrons. (author)

  7. Transition-state theory predicts clogging at the microscale

    Science.gov (United States)

    Laar, T. Van De; Klooster, S. Ten; Schroën, K.; Sprakel, J.

    2016-06-01

    Clogging is one of the main failure mechanisms encountered in industrial processes such as membrane filtration. Our understanding of the factors that govern the build-up of fouling layers and the emergence of clogs is largely incomplete, so that prevention of clogging remains an immense and costly challenge. In this paper we use a microfluidic model combined with quantitative real-time imaging to explore the influence of pore geometry and particle interactions on suspension clogging in constrictions, two crucial factors which remain relatively unexplored. We find a distinct dependence of the clogging rate on the entrance angle to a membrane pore which we explain quantitatively by deriving a model, based on transition-state theory, which describes the effect of viscous forces on the rate with which particles accumulate at the channel walls. With the same model we can also predict the effect of the particle interaction potential on the clogging rate. In both cases we find excellent agreement between our experimental data and theory. A better understanding of these clogging mechanisms and the influence of design parameters could form a stepping stone to delay or prevent clogging by rational membrane design.

  8. Surface free energy for systems with integrable boundary conditions

    International Nuclear Information System (INIS)

    Goehmann, Frank; Bortz, Michael; Frahm, Holger

    2005-01-01

    The surface free energy is the difference between the free energies for a system with open boundary conditions and the same system with periodic boundary conditions. We use the quantum transfer matrix formalism to express the surface free energy in the thermodynamic limit of systems with integrable boundary conditions as a matrix element of certain projection operators. Specializing to the XXZ spin-1/2 chain we introduce a novel 'finite temperature boundary operator' which characterizes the thermodynamical properties of surfaces related to integrable boundary conditions

  9. Probing Free-Energy Surfaces with Differential Scanning Calorimetry

    Science.gov (United States)

    Sanchez-Ruiz, Jose M.

    2011-05-01

    Many aspects of protein folding can be understood in terms of projections of the highly dimensional energy landscape onto a few (or even only one) particularly relevant coordinates. These free-energy surfaces can be probed conveniently from experimental differential scanning calorimetry (DSC) thermograms, as DSC provides a direct relation with the protein partition function. Free-energy surfaces thus obtained are consistent with two fundamental scenarios predicted by the energy-landscape perspective: (a) well-defined macrostates separated by significant free-energy barriers, in some cases, and, in many other cases, (b) marginal or even vanishingly small barriers, which furthermore show a good correlation with kinetics for fast- and ultrafast-folding proteins. Overall, the potential of DSC to assess free-energy surfaces for a wide variety of proteins makes it possible to address fundamental issues, such as the molecular basis of the barrier modulations produced by natural selection in response to functional requirements or to ensure kinetic stability.

  10. PyCPR - a python-based implementation of the Conjugate Peak Refinement (CPR) algorithm for finding transition state structures.

    Science.gov (United States)

    Gisdon, Florian J; Culka, Martin; Ullmann, G Matthias

    2016-10-01

    Conjugate peak refinement (CPR) is a powerful and robust method to search transition states on a molecular potential energy surface. Nevertheless, the method was to the best of our knowledge so far only implemented in CHARMM. In this paper, we present PyCPR, a new Python-based implementation of the CPR algorithm within the pDynamo framework. We provide a detailed description of the theory underlying our implementation and discuss the different parts of the implementation. The method is applied to two different problems. First, we illustrate the method by analyzing the gauche to anti-periplanar transition of butane using a semiempirical QM method. Second, we reanalyze the mechanism of a glycyl-radical enzyme, namely of 4-hydroxyphenylacetate decarboxylase (HPD) using QM/MM calculations. In the end, we suggest a strategy how to use our implementation of the CPR algorithm. The integration of PyCPR into the framework pDynamo allows the combination of CPR with the large variety of methods implemented in pDynamo. PyCPR can be used in combination with quantum mechanical and molecular mechanical methods (and hybrid methods) implemented directly in pDynamo, but also in combination with external programs such as ORCA using pDynamo as interface. PyCPR is distributed as free, open source software and can be downloaded from http://www.bisb.uni-bayreuth.de/index.php?page=downloads . Graphical Abstract PyCPR is a search tool for finding saddle points on the potential energy landscape of a molecular system.

  11. Cohesion and coordination effects on transition metal surface energies

    Science.gov (United States)

    Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

    2017-10-01

    Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

  12. Direct Measurement of the Surface Energy of Graphene.

    Science.gov (United States)

    van Engers, Christian D; Cousens, Nico E A; Babenko, Vitaliy; Britton, Jude; Zappone, Bruno; Grobert, Nicole; Perkin, Susan

    2017-06-14

    Graphene produced by chemical vapor deposition (CVD) is a promising candidate for implementing graphene in a range of technologies. In most device configurations, one side of the graphene is supported by a solid substrate, wheras the other side is in contact with a medium of interest, such as a liquid or other two-dimensional material within a van der Waals stack. In such devices, graphene interacts on both faces via noncovalent interactions and therefore surface energies are key parameters for device fabrication and operation. In this work, we directly measured adhesive forces and surface energies of CVD-grown graphene in dry nitrogen, water, and sodium cholate using a modified surface force balance. For this, we fabricated large (∼1 cm 2 ) and clean graphene-coated surfaces with smooth topography at both macro- and nanoscales. By bringing two such surfaces into contact and measuring the force required to separate them, we measured the surface energy of single-layer graphene in dry nitrogen to be 115 ± 4 mJ/m 2 , which was similar to that of few-layer graphene (119 ± 3 mJ/m 2 ). In water and sodium cholate, we measured interfacial energies of 83 ± 7 and 29 ± 6 mJ/m 2 , respectively. Our work provides the first direct measurement of graphene surface energy and is expected to have an impact both on the development of graphene-based devices and contribute to the fundamental understanding of surface interactions.

  13. A Surface Temperature Initiated Closure (STIC) for surface energy balance fluxes

    DEFF Research Database (Denmark)

    Mallick, Kaniska; Jarvis, Andrew J.; Boegh, Eva

    2014-01-01

    The use of Penman–Monteith (PM) equation in thermal remote sensing based surface energy balance modeling is not prevalent due to the unavailability of any direct method to integrate thermal data into the PM equation and due to the lack of physical models expressing the surface (or stomatal......) and boundary layer conductances (gS and gB) as a function of surface temperature. Here we demonstrate a new method that physically integrates the radiometric surface temperature (TS) into the PM equation for estimating the terrestrial surface energy balance fluxes (sensible heat, H and latent heat, λ......E). The method combines satellite TS data with standard energy balance closure models in order to derive a hybrid closure that does not require the specification of surface to atmosphere conductance terms. We call this the Surface Temperature Initiated Closure (STIC), which is formed by the simultaneous solution...

  14. Surface energy and work function of elemental metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt; Rosengaard, N. M.

    1992-01-01

    and noble metals, as derived from the surface tension of liquid metals. In addition, they give work functions which agree with the limited experimental data obtained from single crystals to within 15%, and explain the smooth behavior of the experimental work functions of polycrystalline samples......We have performed an ab initio study of the surface energy and the work function for six close-packed surfaces of 40 elemental metals by means of a Green’s-function technique, based on the linear-muffin-tin-orbitals method within the tight-binding and atomic-sphere approximations. The results...... are in excellent agreement with a recent full-potential, all-electron, slab-supercell calculation of surface energies and work functions for the 4d metals. The present calculations explain the trend exhibited by the surface energies of the alkali, alkaline earth, divalent rare-earth, 3d, 4d, and 5d transition...

  15. Calculation of the surface free energy of fcc copper nanoparticles

    International Nuclear Information System (INIS)

    Jia Ming; Lai Yanqing; Tian Zhongliang; Liu Yexiang

    2009-01-01

    Using molecular dynamics simulations with the modified analytic embedded-atom method we calculate the Gibbs free energy and surface free energy for fcc Cu bulk, and further obtain the Gibbs free energy of nanoparticles. Based on the Gibbs free energy of nanoparticles, we have investigated the heat capacity of copper nanoparticles. Calculation results indicate that the Gibbs free energy and the heat capacity of nanoparticles can be divided into two parts: bulk quantity and surface quantity. The molar heat capacity of the bulk sample is lower compared with the molar heat capacity of nanoparticles, and this difference increases with the decrease in the particle size. It is also observed that the size effect on the thermodynamic properties of Cu nanoparticles is not really significant until the particle is less than about 20 nm. It is the surface atoms that decide the size effect on the thermodynamic properties of nanoparticles

  16. Energy exchange in thermal energy atom-surface scattering: impulsive models

    International Nuclear Information System (INIS)

    Barker, J.A.; Auerbach, D.J.

    1979-01-01

    Energy exchange in thermal energy atom surface collisions is studied using impulsive ('hard cube' and 'hard sphere') models. Both models reproduce the observed nearly linear relation between outgoing and incoming energies. In addition, the hard-sphere model accounts for the widths of the outcoming energy distributions. (Auth.)

  17. Surface energy and crystallization phenomena of ammonium dinitramide

    Energy Technology Data Exchange (ETDEWEB)

    Teipel, Ulrich; Heintz, Thomas [Fraunhofer-Institut fuer Chemische Technologie (ICT), PO Box 1240, D-76318 Pfinztal (Germany)

    2005-12-01

    Ammonium dinitramide (ADN) was characterized during recrystallization from the melt. The surface tension of molten ADN at 97 C was measured to be 89 mN/m. The wetting angles between molten ADN and different solid surfaces (polytetrafluoroethylene, glass, steel, and aluminum) were determined. The wettability depends on the surface tension of molten ADN, the free surface energy of the solid surfaces and the interfacial tension between the solid and liquid. Observations of the recrystallization behavior of molten ADN showed that nucleation does not occur, even at super cooling rates of 70 K. Crystallization can be initiated by the application of seed crystals. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

  18. Wettability and surface free energy of polarised ceramic biomaterials

    International Nuclear Information System (INIS)

    Nakamura, Miho; Hori, Naoko; Namba, Saki; Yamashita, Kimihiro; Toyama, Takeshi; Nishimiya, Nobuyuki

    2015-01-01

    The surface modification of ceramic biomaterials used for medical devices is expected to improve osteoconductivity through control of the interfaces between the materials and living tissues. Polarisation treatment induced surface charges on hydroxyapatite, β-tricalcium phosphate, carbonate-substituted hydroxyapatite and yttria-stabilized zirconia regardless of the differences in the carrier ions participating in the polarisation. Characterization of the surfaces revealed that the wettability of the polarised ceramic biomaterials was improved through the increase in the surface free energies compared with conventional ceramic surfaces. (note)

  19. Crystal Nucleation Using Surface-Energy-Modified Glass Substrates.

    Science.gov (United States)

    Nordquist, Kyle A; Schaab, Kevin M; Sha, Jierui; Bond, Andrew H

    2017-08-02

    Systematic surface energy modifications to glass substrates can induce nucleation and improve crystallization outcomes for small molecule active pharmaceutical ingredients (APIs) and proteins. A comparatively broad probe for function is presented in which various APIs, proteins, organic solvents, aqueous media, surface energy motifs, crystallization methods, form factors, and flat and convex surface energy modifications were examined. Replicate studies ( n ≥ 6) have demonstrated an average reduction in crystallization onset times of 52(4)% (alternatively 52 ± 4%) for acetylsalicylic acid from 91% isopropyl alcohol using two very different techniques: bulk cooling to 0 °C using flat surface energy modifications or microdomain cooling to 4 °C from the interior of a glass capillary having convex surface energy modifications that were immersed in the solution. For thaumatin and bovine pancreatic trypsin, a 32(2)% reduction in crystallization onset times was demonstrated in vapor diffusion experiments ( n ≥ 15). Nucleation site arrays have been engineered onto form factors frequently used in crystallization screening, including microscope slides, vials, and 96- and 384-well high-throughput screening plates. Nucleation using surface energy modifications on the vessels that contain the solutes to be crystallized adds a layer of useful variables to crystallization studies without requiring significant changes to workflows or instrumentation.

  20. Surface studies with high-energy ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Stensgaard, Ivan [Aarhus Univ. (Denmark). Inst. of Physics

    1992-07-01

    High-energy ion scattering is an extremely useful technique for surface studies. Three methods for surface composition analysis (Rutherford backscattering, nuclear-reaction analysis and elastic recoil detection) are discussed. Directional effects in ion-beam surface interactions (shadowing and blocking) form the basis for surface structure analysis with high-energy ion beams and these phenomena are addressed in some detail. It is shown how surface relaxation and reconstruction, as well as positions of adsorbed atoms, can be determined by comparison with computer simulations. A special technique called transmission channelling is introduced and shown to be particularly well suited for studies of adsorption positions, even of hydrogen. Recent developments in the field are demonstrated by discussing a large number of important (experimental) applications which also include surface dynamics and melting, as well as epitaxy and interface structure. (author).

  1. Ultralow energy ion beam surface modification of low density polyethylene.

    Science.gov (United States)

    Shenton, Martyn J; Bradley, James W; van den Berg, Jaap A; Armour, David G; Stevens, Gary C

    2005-12-01

    Ultralow energy Ar+ and O+ ion beam irradiation of low density polyethylene has been carried out under controlled dose and monoenergetic conditions. XPS of Ar+-treated surfaces exposed to ambient atmosphere show that the bombardment of 50 eV Ar+ ions at a total dose of 10(16) cm(-2) gives rise to very reactive surfaces with oxygen incorporation at about 50% of the species present in the upper surface layer. Using pure O+ beam irradiation, comparatively low O incorporation is achieved without exposure to atmosphere (approximately 13% O in the upper surface). However, if the surface is activated by Ar+ pretreatment, then large oxygen contents can be achieved under subsequent O+ irradiation (up to 48% O). The results show that for very low energy (20 eV) oxygen ions there is a dose threshold of about 5 x 10(15) cm(-2) before surface oxygen incorporation is observed. It appears that, for both Ar+ and O+ ions in this regime, the degree of surface modification is only very weakly dependent on the ion energy. The results suggest that in the nonequilibrium plasma treatment of polymers, where the ion flux is typically 10(18) m(-2) s(-1), low energy ions (<50 eV) may be responsible for surface chemical modification.

  2. Low energy quasi free scattering on nuclear surface

    Energy Technology Data Exchange (ETDEWEB)

    Shiyuan, S.

    1983-05-01

    The result of RGM calculation of low energy /sup 3/He(n, n)/sup 3/ He total elastic cross section does not agree well with experimental data for E/sub n/<1 MeV. This discrepancy can be improved by assuming lwo energy quasi-free scattering of particles beyond the nuclear surface.

  3. Soil heat flux and day time surface energy balance closure

    Indian Academy of Sciences (India)

    Soil heat flux; surface energy balance; Bowen's ratio; sensible and latent ... The energy storage term for the soil layer 0–0.05 m is calculated and the ground heat ... When a new method that accounts for both soil thermal conduction and soil ...

  4. Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

    Science.gov (United States)

    Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

    2017-11-30

    The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

  5. Atom-surface interaction: Zero-point energy formalism

    International Nuclear Information System (INIS)

    Paranjape, V.V.

    1985-01-01

    The interaction energy between an atom and a surface formed by a polar medium is derived with use of a new approach based on the zero-point energy formalism. It is shown that the energy depends on the separation Z between the atom and the surface. With increasing Z, the energy decreases according to 1/Z 3 , while with decreasing Z the energy saturates to a finite value. It is also shown that the energy is affected by the velocity of the atom, but this correction is small. Our result for large Z is consistent with the work of Manson and Ritchie [Phys. Rev. B 29, 1084 (1984)], who follow a more traditional approach to the problem

  6. Energy loss in grazing proton-surface collisions

    Energy Technology Data Exchange (ETDEWEB)

    Juaristi, J I [Dept. Fisica de Materiales, Facultad de Quimicas, UPV/EHU, San Sebastian (Spain); Garcia de Abajo, F J [Dept. Ciencias de la Computacion e Inteligencia Artificial, Facultad de Informatica, UPV/EHU, San Sebastian (Spain)

    1994-05-01

    The energy loss of fast protons, with energy E > 100 keV, specularly reflected on a solid surface with glancing angle of incidence of the order of a mrad is analysed on theoretical grounds. Two different contributions can be distinguished: (i) energy losses originating from the interaction with the valence band, accounted for through an induced force, and (ii) the excitation of electron bound states of the target atoms. The results are compared with available experimental data. (orig.)

  7. Energy loss in grazing proton-surface collisions

    International Nuclear Information System (INIS)

    Juaristi, J.I.; Garcia de Abajo, F.J.

    1994-01-01

    The energy loss of fast protons, with energy E > 100 keV, specularly reflected on a solid surface with glancing angle of incidence of the order of a mrad is analysed on theoretical grounds. Two different contributions can be distinguished: i) energy losses originating from the interaction with the valence band, accounted for through an induced force, and ii) the excitation of electron bound states of the target atoms. The results are compared with available experimental data. (orig.)

  8. Potential energy surfaces for nucleon exchanging in dinuclear systems

    International Nuclear Information System (INIS)

    Li Jianfeng; Xu Hushan; Li Wenfei; Zuo Wei; Li Junqing; Wang Nan; Zhao Enguang

    2003-01-01

    The experimental measurements have provided the evidence that the suppression of fusion cross-section caused by quasi-fission is very important for the synthesis of super-heavy nuclei by heavy ion collisions. The potential energy surface due to the nucleon transfer in the collision process is the driven potential, which governs the nucleon transfer, so that governs the competition between the fusion and quasi-fission. The dinuclear system potential energy surface also gives the information about the optimum projectile-target combination, as well as the optimum excitation energy for the synthesis of super-heavy nuclei by heavy ion collisions

  9. Adsorption energy of iron-phthalocyanine on crystal surfaces

    International Nuclear Information System (INIS)

    Struzzi, C.; Scardamaglia, M.; Angelucci, M; Massimi, L.; Mariani, C.; Betti, G.

    2013-01-01

    The adsorption energy of iron-phthalocyanine (FePc) deposited on different crystal surfaces is studied by thermal desorption spectroscopy. A thin film of molecules has been absorbed on highly oriented pyrolytic graphite (HOPG), on graphene epitaxially grown on Ir(111), and on Au(110). Activation energies for the desorption of a molecular thin film and for the FePc single layer are determined at the three surfaces. The desorption temperature measured for the thin films is only slightly dependent on the substrate, since it is mostly dominated by molecule-molecule interactions. A definitely different desorption temperature is found at the single-layer coverage: we find an increasing desorption temperature going from HOPG, to graphene/Ir, to the Au(110) surface. The different adsorption energies of the first FePc layer in contact with the substrate surface are discussed taking into account the interaction and the growth morphology.

  10. A simulation of laser energy absorption by nanowired surface

    Energy Technology Data Exchange (ETDEWEB)

    Vasconcelos, Miguel F.S.; Ramos, Alexandre F., E-mail: miguel.vasconcelos@usp.br, E-mail: alex.ramos@usp.br [Universidade de São Paulo (USP), SP (Brazil). Escola de Artes, Ciências e Humanidades

    2017-07-01

    Despite recent advances on research about laser inertial fusion energy, to increase the portion of energy absorbed by the target's surface from lasers remains as an important challenge. The plasma formed during the initial instants of laser arrival shields the target and prevents the absorption of laser energy by the deeper layers of the material. One strategy to circumvent that effect is the construction of targets whose surfaces are populated with nanowires. The nanowired surfaces have increased absorption of laser energy and constitutes a promising pathway for enhancing laser-matter coupling. In our work we present the results of simulations aiming to investigate how target's geometrical properties might contribute for maximizing laser energy absorption by material. Simulations have been carried out using the software FLASH, a multi-physics platform developed by researchers from the University of Chicago, written in FORTRAN 90 and Python. Different tools for generating target's geometry and analysis of results were developed using Python. Our results show that a nanowired surfaces has an increased energy absorption when compared with non wired surface. The software for visualization developed in this work also allowed an analysis of the spatial dynamics of the target's temperature, electron density, ionization levels and temperature of the radiation emitted by it. (author)

  11. A simulation of laser energy absorption by nanowired surface

    International Nuclear Information System (INIS)

    Vasconcelos, Miguel F.S.; Ramos, Alexandre F.

    2017-01-01

    Despite recent advances on research about laser inertial fusion energy, to increase the portion of energy absorbed by the target's surface from lasers remains as an important challenge. The plasma formed during the initial instants of laser arrival shields the target and prevents the absorption of laser energy by the deeper layers of the material. One strategy to circumvent that effect is the construction of targets whose surfaces are populated with nanowires. The nanowired surfaces have increased absorption of laser energy and constitutes a promising pathway for enhancing laser-matter coupling. In our work we present the results of simulations aiming to investigate how target's geometrical properties might contribute for maximizing laser energy absorption by material. Simulations have been carried out using the software FLASH, a multi-physics platform developed by researchers from the University of Chicago, written in FORTRAN 90 and Python. Different tools for generating target's geometry and analysis of results were developed using Python. Our results show that a nanowired surfaces has an increased energy absorption when compared with non wired surface. The software for visualization developed in this work also allowed an analysis of the spatial dynamics of the target's temperature, electron density, ionization levels and temperature of the radiation emitted by it. (author)

  12. Elastic layer under axisymmetric indentation and surface energy effects

    Science.gov (United States)

    Intarit, Pong-in; Senjuntichai, Teerapong; Rungamornrat, Jaroon

    2018-04-01

    In this paper, a continuum-based approach is adopted to investigate the contact problem of an elastic layer with finite thickness and rigid base subjected to axisymmetric indentation with the consideration of surface energy effects. A complete Gurtin-Murdoch surface elasticity is employed to consider the influence of surface stresses. The indentation problem of a rigid frictionless punch with arbitrary axisymmetric profiles is formulated by employing the displacement Green's functions, derived with the aid of Hankel integral transform technique. The problem is solved by assuming the contact pressure distribution in terms of a linear combination of admissible functions and undetermined coefficients. Those coefficients are then obtained by employing a collocation technique and an efficient numerical quadrature scheme. The accuracy of proposed solution technique is verified by comparing with existing solutions for rigid indentation on an elastic half-space. Selected numerical results for the indenters with flat-ended cylindrical and paraboloidal punch profiles are presented to portray the influence of surface energy effects on elastic fields of the finite layer. It is found that the presence of surface stresses renders the layer stiffer, and the size-dependent behavior of elastic fields is observed in the present solutions. In addition, the surface energy effects become more pronounced with smaller contact area; thus, the influence of surface energy cannot be ignored in the analysis of indentation problem especially when the indenter size is very small such as in the case of nanoindentation.

  13. Fracture surface energy of the Punchbowl fault, San Andreas system.

    Science.gov (United States)

    Chester, Judith S; Chester, Frederick M; Kronenberg, Andreas K

    2005-09-01

    Fracture energy is a form of latent heat required to create an earthquake rupture surface and is related to parameters governing rupture propagation and processes of slip weakening. Fracture energy has been estimated from seismological and experimental rock deformation data, yet its magnitude, mechanisms of rupture surface formation and processes leading to slip weakening are not well defined. Here we quantify structural observations of the Punchbowl fault, a large-displacement exhumed fault in the San Andreas fault system, and show that the energy required to create the fracture surface area in the fault is about 300 times greater than seismological estimates would predict for a single large earthquake. If fracture energy is attributed entirely to the production of fracture surfaces, then all of the fracture surface area in the Punchbowl fault could have been produced by earthquake displacements totalling <1 km. But this would only account for a small fraction of the total energy budget, and therefore additional processes probably contributed to slip weakening during earthquake rupture.

  14. Surface properties of Ti-6Al-4V alloy part I: Surface roughness and apparent surface free energy.

    Science.gov (United States)

    Yan, Yingdi; Chibowski, Emil; Szcześ, Aleksandra

    2017-01-01

    Titanium (Ti) and its alloys are the most often used implants material in dental treatment and orthopedics. Topography and wettability of its surface play important role in film formation, protein adhesion, following osseointegration and even duration of inserted implant. In this paper, we prepared Ti-6Al-4V alloy samples using different smoothing and polishing materials as well the air plasma treatment, on which contact angles of water, formamide and diiodomethane were measured. Then the apparent surface free energy was calculated using four different approaches (CAH, LWAB, O-W and Neumann's Equation of State). From LWAB approach the components of surface free energy were obtained, which shed more light on the wetting properties of samples surface. The surface roughness of the prepared samples was investigated with the help of optical profilometer and AFM. It was interesting whether the surface roughness affects the apparent surface free energy. It was found that both polar interactions the electron donor parameter of the energy and the work of water adhesion increased with decreasing roughness of the surfaces. Moreover, short time plasma treatment (1min) caused decrease in the surface hydrophilic character, while longer time (10min) treatment caused significant increase in the polar interactions and the work of water adhesion. Although Ti-6Al-4V alloy has been investigated many times, to our knowledge, so far no paper has been published in which surface roughness and changes in the surface free energy of the alloy were compared in the quantitative way in such large extent. This novel approach deliver better knowledge about the surface properties of differently smoothed and polished samples which may be helpful to facilitate cell adhesion, proliferation and mineralization. Therefore the results obtained present also potentially practical meaning. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Surface properties of Ti-6Al-4V alloy part I: Surface roughness and apparent surface free energy

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yingdi; Chibowski, Emil; Szcześ, Aleksandra, E-mail: aszczes@poczta.umcs.lublin.pl

    2017-01-01

    Titanium (Ti) and its alloys are the most often used implants material in dental treatment and orthopedics. Topography and wettability of its surface play important role in film formation, protein adhesion, following osseointegration and even duration of inserted implant. In this paper, we prepared Ti-6Al-4V alloy samples using different smoothing and polishing materials as well the air plasma treatment, on which contact angles of water, formamide and diiodomethane were measured. Then the apparent surface free energy was calculated using four different approaches (CAH, LWAB, O-W and Neumann's Equation of State). From LWAB approach the components of surface free energy were obtained, which shed more light on the wetting properties of samples surface. The surface roughness of the prepared samples was investigated with the help of optical profilometer and AFM. It was interesting whether the surface roughness affects the apparent surface free energy. It was found that both polar interactions the electron donor parameter of the energy and the work of water adhesion increased with decreasing roughness of the surfaces. Moreover, short time plasma treatment (1 min) caused decrease in the surface hydrophilic character, while longer time (10 min) treatment caused significant increase in the polar interactions and the work of water adhesion. Although Ti-6Al-4V alloy has been investigated many times, to our knowledge, so far no paper has been published in which surface roughness and changes in the surface free energy of the alloy were compared in the quantitative way in such large extent. This novel approach deliver better knowledge about the surface properties of differently smoothed and polished samples which may be helpful to facilitate cell adhesion, proliferation and mineralization. Therefore the results obtained present also potentially practical meaning. - Highlights: • Surface of five Ti-6Al-4V alloy samples were smoothed and polished successively. • The

  16. Influence of the target surface contamination on UHV screening energies

    Energy Technology Data Exchange (ETDEWEB)

    Targosz-Sleczka, N; Czerski, K; Kilic, A I [Institute of Physics, University of Szczecin, Szczecin (Poland); Huke, A; Martin, L; Heide, P [Institut fuer Atomare Physik und Optik, Technische Universitaet Berlin, Berlin (Germany); Blauth, D; Winter, H, E-mail: natalia.targosz@wmf.univ.szczecin.p [Institut fuer Physik, Humboldt-Universitaet zu Berlin, Berlin (Germany)

    2010-01-01

    The d + d fusion reactions have been investigated in the Zirconium environment under ultra high vacuum (UHV) conditions for projectile energies below 30 keV. The experimentally determined screening energy value of 497 {+-} 7 eV is larger than the previous results by a factor of almost two. Despite the UHV conditions a small deviation between experimental data and the theoretical curve arising from the target surface contamination could be still observed at the lowest projectile energies. Calculations made under the assumption of formation of a Zirconium oxide contamination, show that every atomic monolayer reduces the estimated screening energy significantly.

  17. Influence of the target surface contamination on UHV screening energies

    International Nuclear Information System (INIS)

    Targosz-Sleczka, N; Czerski, K; Kilic, A I; Huke, A; Martin, L; Heide, P; Blauth, D; Winter, H

    2010-01-01

    The d + d fusion reactions have been investigated in the Zirconium environment under ultra high vacuum (UHV) conditions for projectile energies below 30 keV. The experimentally determined screening energy value of 497 ± 7 eV is larger than the previous results by a factor of almost two. Despite the UHV conditions a small deviation between experimental data and the theoretical curve arising from the target surface contamination could be still observed at the lowest projectile energies. Calculations made under the assumption of formation of a Zirconium oxide contamination, show that every atomic monolayer reduces the estimated screening energy significantly.

  18. Surface energy budget and turbulent fluxes at Arctic terrestrial sites

    Science.gov (United States)

    Grachev, Andrey; Persson, Ola; Uttal, Taneil; Konopleva-Akish, Elena; Crepinsek, Sara; Cox, Christopher; Fairall, Christopher; Makshtas, Alexander; Repina, Irina

    2017-04-01

    Determination of the surface energy budget (SEB) and all SEB components at the air-surface interface are required in a wide variety of applications including atmosphere-land/snow simulations and validation of the surface fluxes predicted by numerical models over different spatial and temporal scales. Here, comparisons of net surface energy budgets at two Arctic sites are made using long-term near-continuous measurements of hourly averaged surface fluxes (turbulent, radiation, and soil conduction). One site, Eureka (80.0 N; Nunavut, Canada), is located in complex topography near a fjord about 200 km from the Arctic Ocean. The other site, Tiksi (71.6 N; Russian East Siberia), is located on a relatively flat coastal plain less than 1 km from the shore of Tiksi Bay, a branch of the Arctic Ocean. We first analyzed diurnal and annual cycles of basic meteorological parameters and key SEB components at these locations. Although Eureka and Tiksi are located on different continents and at different latitudes, the annual course of the surface meteorology and SEB components are qualitatively similar. Surface energy balance closure is a formulation of the conservation of energy principle. Our direct measurements of energy balance for both Arctic sites show that the sum of the turbulent sensible and latent heat fluxes and the ground (conductive) heat flux systematically underestimate the net radiation by about 25-30%. This lack of energy balance closure is a fundamental and pervasive problem in micrometeorology. We discuss a variety of factors which may be responsible for the lack of SEB closure. In particular, various storage terms (e.g., air column energy storage due to radiative and/or sensible heat flux divergence, ground heat storage above the soil flux plate, energy used in photosynthesis, canopy biomass heat storage). For example, our observations show that the photosynthesis storage term is relatively small (about 1-2% of the net radiation), but about 8-12% of the

  19. Surface relaxation and surface energy of face –centered Cubic ...

    African Journals Online (AJOL)

    DR. MIKE HORSFALL

    Surface relaxation and surface energy of face –centered Cubic metals. 1AGHEMENLO H E; *2IYAYI, S E; 3AVWIRI ,G O. 1, 3 Department of Physics, Ambrose Alli University, Ekpoma, Nigeria. 2 Department of Physics, University of Benin, Benin City, Nigeria. 3 Department of Physics, University of Port Harcourt, PH, Nigeria.

  20. Zero-point Energy is Needed in Molecular Dynamics Calculations to Access the Saddle Point for H+HCN→H2CN* and cis/trans-HCNH* on a New Potential Energy Surface.

    Science.gov (United States)

    Wang, Xiaohong; Bowman, Joel M

    2013-02-12

    We calculate the probabilities for the association reactions H+HCN→H2CN* and cis/trans-HCNH*, using quasiclassical trajectory (QCT) and classical trajectory (CT) calculations, on a new global ab initio potential energy surface (PES) for H2CN including the reaction channels. The surface is a linear least-squares fit of roughly 60 000 CCSD(T)-F12b/aug-cc-pVDZ electronic energies, using a permutationally invariant basis with Morse-type variables. The reaction probabilities are obtained at a variety of collision energies and impact parameters. Large differences in the threshold energies in the two types of dynamics calculations are traced to the absence of zero-point energy in the CT calculations. We argue that the QCT threshold energy is the realistic one. In addition, trajectories find a direct pathway to trans-HCNH, even though there is no obvious transition state (TS) for this pathway. Instead the saddle point (SP) for the addition to cis-HCNH is evidently also the TS for direct formation of trans-HCNH.

  1. Surface energies of metals in both liquid and solid states

    International Nuclear Information System (INIS)

    Aqra, Fathi; Ayyad, Ahmed

    2011-01-01

    Although during the last years one has seen a number of systematic studies of the surface energies of metals, the aim and the scientific meaning of this research is to establish a simple and a straightforward theoretical model to calculate accurately the mechanical and the thermodynamic properties of metal surfaces due to their important application in materials processes and in the understanding of a wide range of surface phenomena. Through extensive theoretical calculations of the surface tension of most of the liquid metals, we found that the fraction of broken bonds in liquid metals (f) is constant which is equal to 0.287. Using our estimated f value, the surface tension (γ m ), surface energy (γ SV ), surface excess entropy (-dγ/dT), surface excess enthalpy (H s ), coefficient of thermal expansion (α m and α b ), sound velocity (c m ) and its temperature coefficient (-dc/dT) have been calculated for more than sixty metals. The results of the calculated quantities agree well with available experimental data.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    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.

  3. Calculated surface-energy anomaly in the 3d metals

    DEFF Research Database (Denmark)

    Aldén, M.; Skriver, Hans Lomholt; Mirbt, S.

    1992-01-01

    Local-spin-density theory and a Green’s-function technique based on the linear muffin-tin orbitals method have been used to calculate the surface energy of the 3d metals. The theory explains the variation of the values derived from measurements of the surface tension of liquid metals including...... the pronounced anomaly occurring between vanadium and nickel in terms of a decrease in the d contribution caused by spin polarization....

  4. An adaptive interpolation scheme for molecular potential energy surfaces

    Science.gov (United States)

    Kowalewski, Markus; Larsson, Elisabeth; Heryudono, Alfa

    2016-08-01

    The calculation of potential energy surfaces for quantum dynamics can be a time consuming task—especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within a given accuracy compared to the non-adaptive version.

  5. Exchange energy of inhomogenous electron gas near a metal surface

    International Nuclear Information System (INIS)

    Miglio, L.; Tosi, M.P.; March, N.H.

    1980-12-01

    Using the first-order density matrix of an infinite-barrier model of a metal surface, the exchange energy density can be evaluated exactly as a function of distance z from the barrier. This result is compared with the local approximation -3/4e 2 (3/π)sup(1/3) rhosup(4/3)(z) where rho is the electron density in the model. The local approximation is demonstrated to be quantitatively accurate at all z. The integrated surface exchange energy is given to within 3% by the local theory. (author)

  6. Surface segregation energies in transition-metal alloys

    DEFF Research Database (Denmark)

    Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

    1999-01-01

    We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...... to the electrostatic potential and energy. We use the database to establish the major factors which govern surface segregation in transition metal alloys. We find that the calculated trends are well described by Friedel's rectangular state density model and that the few but significant deviations from the simple...

  7. Kinetic-energy functionals studied by surface calculations

    DEFF Research Database (Denmark)

    Vitos, Levente; Skriver, Hans Lomholt; Kollár, J.

    1998-01-01

    The self-consistent jellium model of metal surfaces is used to study the accuracy of a number of semilocal kinetic-energy functionals for independent particles. It is shown that the poor accuracy exhibited by the gradient expansion approximation and most of the semiempirical functionals in the lo...... density, high gradient limit may be subtantially improved by including locally a von Weizsacker term. Based on this, we propose a simple one-parameter Pade's approximation, which reproduces the exact Kohn-Sham surface kinetic energy over the entire range of metallic densities....

  8. A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH4 system

    International Nuclear Information System (INIS)

    Li, Jun; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H.; Xie, Daiqian; Guo, Hua

    2015-01-01

    We report a permutationally invariant global potential energy surface (PES) for the H + CH 4 system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J tot = 0) including the abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)

  9. Self-diffusion on (100), (110), and (111) surfaces of Ni and Cu: A detailed study of prefactors and activation energies

    International Nuclear Information System (INIS)

    Ku'rpick, Ulrike

    2001-01-01

    We calculate activation barriers and prefactors for diffusion via hopping on (100), (110), and (111) surfaces of Ni and Cu. The calculations reveal that, when activation barriers decrease there is also a decrease in the prefactors such that the changes in both quantities partly compensate for each other with respect to the diffusivities. Thermodynamic functions which contribute to the prefactors are calculated from local vibrational density of states, showing that mainly entropy contributions control the prefactors. Our method allows one to trace the obtained values back to vibrational properties of the adatoms in both the minimum-energy and transition-state configurations, and enables a physical understanding of why prefactors have certain values

  10. Urban Surface Radiative Energy Budgets Determined Using Aircraft Scanner Data

    Science.gov (United States)

    Luvall, Jeffrey C.; Quattrochi, Dale A.; Rickman, Doug L.; Estes, Maury G.; Arnold, James E. (Technical Monitor)

    2002-01-01

    It is estimated that by the year 2025, 80% of the world's population will live in cities. The extent of these urban areas across the world can be seen in an image of city lights from the Defense Meteorological Satellite Program. In many areas of North America and Europe, it is difficult to separate individual cities because of the dramatic growth and sprawl of urbanized areas. This conversion of the natural landscape vegetation into man-made urban structures such as roads and buildings drastically alter the regional surface energy budgets, hydrology, precipitation patterns, and meteorology. One of the earliest recognized and measured phenomena of urbanization is the urban heat island (UHI) which was reported as early as 1833 for London and 1862 for Paris. The urban heat island results from the energy that is absorbed by man-made materials during the day and is released at night resulting in the heating of the air within the urban area. The magnitude of the air temperature difference between the urban and surrounding countryside is highly dependent on the structure of the urban area, amount of solar immolation received during the day, and atmospheric conditions during the night. These night time air temperature differences can be in the range of 2 to 5 C. or greater. Although day time air temperature differences between urban areas and the countryside exists during the day, atmospheric mixing and stability reduce the magnitude. This phenomena is not limited to large urban areas, but also occurs in smaller metropolitan areas. The UHI has significant impacts on the urban air quality, meteorology, energy use, and human health. The UPI can be mitigated through increasing the amount of vegetation and modification of urban surfaces using high albedo materials for roofs and paved surfaces. To understand why the urban heat island phenomenon exists it is useful to define the surface in terms of the surface energy budget. Surface temperature and albedo is a major component of

  11. Self-energies and the interactions of particles with surfaces

    International Nuclear Information System (INIS)

    Manson, J.R.; Ritchie, R.H.; Echenique, P.M.; Gras-Marti, A.

    1987-01-01

    We have in this paper reviewed the method of treating many-body problems by means of an effective interaction self-energy. We have developed an alternatvie approach to the self-energy which is simpler and more straight-forward than standard methods, and we have illustrated its use with two examples of a charge interacting with a metal surface. In each case the self-energy produces the classical image potential together with corrections due to quantum mechanical effects. This method has also been successfully applied to the problem of an atom interacting with a surface. Corrections to the Van der Waals dispersion force are obtained, and via the non-conservative imaginary parts to /summation//sub i/(z) we discuss transition rates and energy exchange. 14 refs., 1 fig

  12. Surface Passivation and Junction Formation Using Low Energy Hydrogen Implants

    Science.gov (United States)

    Fonash, S. J.

    1985-01-01

    New applications for high current, low energy hydrogen ion implants on single crystal and polycrystal silicon grain boundaries are discussed. The effects of low energy hydrogen ion beams on crystalline Si surfaces are considered. The effect of these beams on bulk defects in crystalline Si is addressed. Specific applications of H+ implants to crystalline Si processing are discussed. In all of the situations reported on, the hydrogen beams were produced using a high current Kaufman ion source.

  13. Free energy surfaces in the superconducting mixed state

    Science.gov (United States)

    Finnemore, D. K.; Fang, M. M.; Bansal, N. P.; Farrell, D. E.

    1989-01-01

    The free energy surface for Tl2Ba2Ca2Cu3O1O has been measured as a function of temperature and magnetic field to determine the fundamental thermodynamic properties of the mixed state. The change in free energy, G(H)-G(O), is found to be linear in temperature over a wide range indicating that the specific heat is independent of field.

  14. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Bo, Maolin [Yangtze Normal University, College of Mechanical and Electrical Engineering, Chongqing 408100 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Liu, Yonghui [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q. [NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China)

    2017-02-28

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O{sup 2−} lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta{sup +} electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta{sup +}; the sp{sup 3}-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent

  15. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    International Nuclear Information System (INIS)

    Guo, Yongling; Bo, Maolin; Wang, Yan; Liu, Yonghui; Sun, Chang Q.; Huang, Yongli

    2017-01-01

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O"2"− lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta"+ electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta"+; the sp"3-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent insight into the

  16. He-, Ne-, and Ar-phosgene intermolecular potential energy surfaces

    DEFF Research Database (Denmark)

    Munteanu, Cristian R.; Henriksen, Christian; Felker, Peter M.

    2013-01-01

    Using the CCSD(T) model, we evaluated the intermolecular potential energy surfaces of the He-, Ne-, and Ar-phosgene complexes. We considered a representative number of intermolecular geometries for which we calculated the corresponding interaction energies with the augmented (He complex) and doub...... of the complexes, providing valuable results for future experimental investigations. Comparing our results to those previously available for other phosgene complexes, we suggest that the results for Cl2-phosgene should be revised....

  17. Finding possible transition states of defects in silicon-carbide and alpha-iron using the dimer method

    CERN Document Server

    Gao Fei; Weber, W J; Corrales, L R; Jonsson, H

    2003-01-01

    Energetic primary recoil atoms from ion implantation or fast neutron irradiation produce isolated point defects and clusters of both vacancies and interstitials. The migration energies and mechanisms for these defects are crucial to successful multiscale modeling of microstructural evolution during ion-implantation, thermal annealing, or under irradiation over long periods of time. The dimer method is employed to search for possible transition states of interstitials and small interstitial clusters in SiC and alpha-Fe. The method uses only the first derivatives of the potential energy to find saddle points without knowledge of the final state of the transition. In SiC, the possible migration pathway for the C interstitial is found to consist of the first neighbor jump via a Si site or second neighbor jump, but the relative probability for the second neighbor jump is very low. In alpha-Fe, the possible transition states are studied as a function of interstitial cluster size, and the lowest energy barriers corr...

  18. Re-examination of the threshold energy surface in copper

    International Nuclear Information System (INIS)

    King, W.E.; Benedek, R.; Merkle, K.L.; Meshii, M.

    1981-01-01

    Radiation-induced defect production in copper has been studied using in-situ electrical resistivity damage-rate measurements in the HVEM and molecular dynamics simulations. Analysis of the results yields a threshold energy surface characterized by two isolated pockets of low threshold energy centered at and surrounded by regions of much higher threshold energy; the corresponding damage function exhibits a plateau at 0.65 Frenkel pairs. A Frenkel pair resistivity of (2.75/sub -0.2/ + 0 6 ) x 10 - 4 Ω-cm is proposed. A model damage function is constructed and compared to results from ion irradiation damage-rate measurements. 7 figures

  19. Energy utilization in surface mining project : with case study illustration

    International Nuclear Information System (INIS)

    Sinha, D.K.; De, Amitosh

    1992-01-01

    The importance of reducing energy consumption per tonne of output in the mining projects needs an innovative approach and style to change the behaviour and postures of the technical characteristics. The need for suitable energy policy can not be overlooked with the addition of new large size surface mining projects having a lot of technological development. But the immediate prescription to the problem is to pinpoint specific high energy consuming areas prefixed by thorough diagnosis and followed by deep scientific thought into it. To that extent this paper makes a primary attempt to characterise the various problems. (author). 7 tabs

  20. Experimental and Theoretical Studies of the F + H–F Transition-State Region by Photodetachment of [F–H–F] -

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei [Physical; Wang, Xue-Bin [Physical; McCoy, Anne B. [Department; Borden, Weston Thatcher [Department

    2017-10-05

    The transition-state (TS) region of the simplest heavy-light-heavy type of reaction, F• + H-F F-H + F•, is investigated in this work by a joint experimental and theoretical approach. Photodetaching the bifluride anion, [F…H…F]–, generates a negative ion photoelectron (NIPE) spectrum with three partially resolved bands in the electron binding energy (eBE) range of 5.4 – 7.0 eV. These bands correspond to the transition from the ground state of the anion to the electronic ground state of [F-H-F]• neutral, with associated vibrational excitations. The significant increase of eBE of the bifluride anion, relative to that of F-, reflects a hydrogen bond energy between F- and HF of 46 kcal/mol. Theoretical modeling reveals that the antisymmetric motion of H between the two F atoms, near the TS on the neutral [F-H-F]• surface, dominates the observed three bands, while the F-H-F bending, F—F symmetric stretching modes, and the couplings between them is calculated to account for the breadth of the observed spectrum. From the NIPE spectrum, a lower limit on the activation enthalpy for F• + H-F F-H + F can be estimated to be H‡ = 12 ± 2 kcal/mol, a value below that of H‡ = 14.9 kcal/mol, given by our G4 calculations.

  1. Inelastic surface vibrations versus energy-dependent nucleus ...

    Indian Academy of Sciences (India)

    Limitations of the static Woods–Saxon potential and the applicability of the energy dependent Woods–Saxon potential (EDWSP) model within the framework of one-dimensional Wong formula to explore the sub-barrier fusion data are highlighted. The inelastic surface excitations of the fusing nuclei are found to be ...

  2. Inelastic surface vibrations versus energy-dependent nucleus ...

    Indian Academy of Sciences (India)

    Abstract. Limitations of the static Woods–Saxon potential and the applicability of the energy- dependent Woods–Saxon potential (EDWSP) model within the framework of one-dimensional. Wong formula to explore the sub-barrier fusion data are highlighted. The inelastic surface exci- tations of the fusing nuclei are found to ...

  3. The evaporative fraction as a measure of surface energy partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, W.E. [Pacific Northwest Lab., Richland, WA (United States); Cuenca, R.H. [Oregon State Univ., Corvallis, OR (United States)

    1990-12-31

    The evaporative fraction is a ratio that expresses the proportion of turbulent flux energy over land surfaces devoted to evaporation and transpiration (evapotranspiration). It has been used to characterize the energy partition over land surfaces and has potential for inferring daily energy balance information based on mid-day remote sensing measurements. The HAPEX-MOBILHY program`s SAMER system provided surface energy balance data over a range of agricultural crops and soil types. The databases from this large-scale field experiment was analyzed for the purpose of studying the behavior and daylight stability of the evaporative fraction in both ideal and general meteorological conditions. Strong linear relations were found to exist between the mid-day evaporative fraction and the daylight mean evaporative fraction. Statistical tests however rejected the hypothesis that the two quantities were equal. The relations between the evaporative fraction and the surface soil moisture as well as soil moisture in the complete vegetation root zone were also explored.

  4. The evaporative fraction as a measure of surface energy partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, W.E. (Pacific Northwest Lab., Richland, WA (United States)); Cuenca, R.H. (Oregon State Univ., Corvallis, OR (United States))

    1990-01-01

    The evaporative fraction is a ratio that expresses the proportion of turbulent flux energy over land surfaces devoted to evaporation and transpiration (evapotranspiration). It has been used to characterize the energy partition over land surfaces and has potential for inferring daily energy balance information based on mid-day remote sensing measurements. The HAPEX-MOBILHY program's SAMER system provided surface energy balance data over a range of agricultural crops and soil types. The databases from this large-scale field experiment was analyzed for the purpose of studying the behavior and daylight stability of the evaporative fraction in both ideal and general meteorological conditions. Strong linear relations were found to exist between the mid-day evaporative fraction and the daylight mean evaporative fraction. Statistical tests however rejected the hypothesis that the two quantities were equal. The relations between the evaporative fraction and the surface soil moisture as well as soil moisture in the complete vegetation root zone were also explored.

  5. Universal binding energy relation for cleaved and structurally relaxed surfaces

    International Nuclear Information System (INIS)

    Srirangarajan, Aarti; Datta, Aditi; Gandi, Appala Naidu; Ramamurty, U; Waghmare, U V

    2014-01-01

    The universal binding energy relation (UBER), derived earlier to describe the cohesion between two rigid atomic planes, does not accurately capture the cohesive properties when the cleaved surfaces are allowed to relax. We suggest a modified functional form of UBER that is analytical and at the same time accurately models the properties of surfaces relaxed during cleavage. We demonstrate the generality as well as the validity of this modified UBER through first-principles density functional theory calculations of cleavage in a number of crystal systems. Our results show that the total energies of all the relaxed surfaces lie on a single (universal) energy surface, that is given by the proposed functional form which contains an additional length-scale associated with structural relaxation. This functional form could be used in modelling the cohesive zones in crack growth simulation studies. We find that the cohesive law (stress–displacement relation) differs significantly in the case where cracked surfaces are allowed to relax, with lower peak stresses occurring at higher displacements. (paper)

  6. Universal binding energy relation for cleaved and structurally relaxed surfaces.

    Science.gov (United States)

    Srirangarajan, Aarti; Datta, Aditi; Gandi, Appala Naidu; Ramamurty, U; Waghmare, U V

    2014-02-05

    The universal binding energy relation (UBER), derived earlier to describe the cohesion between two rigid atomic planes, does not accurately capture the cohesive properties when the cleaved surfaces are allowed to relax. We suggest a modified functional form of UBER that is analytical and at the same time accurately models the properties of surfaces relaxed during cleavage. We demonstrate the generality as well as the validity of this modified UBER through first-principles density functional theory calculations of cleavage in a number of crystal systems. Our results show that the total energies of all the relaxed surfaces lie on a single (universal) energy surface, that is given by the proposed functional form which contains an additional length-scale associated with structural relaxation. This functional form could be used in modelling the cohesive zones in crack growth simulation studies. We find that the cohesive law (stress-displacement relation) differs significantly in the case where cracked surfaces are allowed to relax, with lower peak stresses occurring at higher displacements.

  7. Can quantum transition state theory be defined as an exact t = 0+ limit?

    Science.gov (United States)

    Jang, Seogjoo; Voth, Gregory A.

    2016-02-01

    The definition of the classical transition state theory (TST) as a t → 0+ limit of the flux-side time correlation function relies on the assumption that simultaneous measurement of population and flux is a well defined physical process. However, the noncommutativity of the two measurements in quantum mechanics makes the extension of such a concept to the quantum regime impossible. For this reason, quantum TST (QTST) has been generally accepted as any kind of quantum rate theory reproducing the TST in the classical limit, and there has been a broad consensus that no unique QTST retaining all the properties of TST can be defined. Contrary to this widely held view, Hele and Althorpe (HA) [J. Chem. Phys. 138, 084108 (2013)] recently suggested that a true QTST can be defined as the exact t → 0+ limit of a certain kind of quantum flux-side time correlation function and that it is equivalent to the ring polymer molecular dynamics (RPMD) TST. This work seeks to question and clarify certain assumptions underlying these suggestions and their implications. First, the time correlation function used by HA as a starting expression is not related to the kinetic rate constant by virtue of linear response theory, which is the first important step in relating a t = 0+ limit to a physically measurable rate. Second, a theoretical analysis calls into question a key step in HA's proof which appears not to rely on an exact quantum mechanical identity. The correction of this makes the true t = 0+ limit of HA's QTST different from the RPMD-TST rate expression, but rather equal to the well-known path integral quantum transition state theory rate expression for the case of centroid dividing surface. An alternative quantum rate expression is then formulated starting from the linear response theory and by applying a recently developed formalism of real time dynamics of imaginary time path integrals [S. Jang, A. V. Sinitskiy, and G. A. Voth, J. Chem. Phys. 140, 154103 (2014)]. It is shown

  8. Modelling of low energy ion sputtering from oxide surfaces

    International Nuclear Information System (INIS)

    Kubart, T; Nyberg, T; Berg, S

    2010-01-01

    The main aim of this work is to present a way to estimate the values of surface binding energy for oxides. This is done by fitting results from the binary collisions approximation code Tridyn with data from the reactive sputtering processing curves, as well as the elemental composition obtained from x-ray photoelectron spectroscopy (XPS). Oxide targets of Al, Ti, V, Nb and Ta are studied. The obtained surface binding energies are then used to predict the partial sputtering yields. Anomalously high sputtering yield is observed for the TiO 2 target. This is attributed to the high sputtering yield of Ti lower oxides. Such an effect is not observed for the other studied metals. XPS measurement of the oxide targets confirms the formation of suboxides during ion bombardment as well as an oxygen deficient surface in the steady state. These effects are confirmed from the processing curves from the oxide targets showing an elevated sputtering rate in pure argon.

  9. Surface energy and radiation balance systems - General description and improvements

    Science.gov (United States)

    Fritschen, Leo J.; Simpson, James R.

    1989-01-01

    Surface evaluation of sensible and latent heat flux densities and the components of the radiation balance were desired for various vegetative surfaces during the ASCOT84 experiment to compare with modeled results and to relate these values to drainage winds. Five battery operated data systems equipped with sensors to determine the above values were operated for 105 station days during the ASCOT84 experiment. The Bowen ratio energy balance technique was used to partition the available energy into the sensible and latent heat flux densities. A description of the sensors and battery operated equipment used to collect and process the data is presented. In addition, improvements and modifications made since the 1984 experiment are given. Details of calculations of soil heat flow at the surface and an alternate method to calculate sensible and latent heat flux densities are provided.

  10. Urbanization Process and Variation of Energy Budget of Land Surfaces

    Directory of Open Access Journals (Sweden)

    Ciro Gardi

    2007-06-01

    Full Text Available Urban areas are increasing at a rate much higher than human population growth in many part of the world; actually more than 73 towns in the world are larger than 1000 km2. The European Environmental Agency indicates an urban area average growth rate, over the last 20 years, of 20%. The urbanization process, and the consequent soil sealing, determines not only the losses of the ecological functions of the soil, but also a variation of the energy budget of land surfaces, that affect the microclimatic conditions (heat islands. The alteration of the energy budget are determined by the variations of albedo and roughness of surfaces, but especially by the net losses of evapotranspirating areas. In the present research we have assessed the variation of Parma territory energy budget, induced by the change in land use over the last 122 years. The urban area increase between 1881 and 2003 was 535%.

  11. Exploring the free energy surfaces of clusters using reconnaissance metadynamics

    Science.gov (United States)

    Tribello, Gareth A.; Cuny, Jérôme; Eshet, Hagai; Parrinello, Michele

    2011-09-01

    A new approach is proposed for exploring the low-energy structures of small to medium-sized aggregates of atoms and molecules. This approach uses the recently proposed reconnaissance metadynamics method [G. A. Tribello, M. Ceriotti, and M. Parrinello. Proc. Natl. Acad. Sci. U.S.A. 107(41), 17509 (2010), 10.1073/pnas.1011511107] in tandem with collective variables that describe the average structure of the coordination sphere around the atoms/molecules. We demonstrate this method on both Lennard-Jones and water clusters and show how it is able to quickly find the global minimum in the potential energy surface, while exploring the finite temperature free energy surface.

  12. Communication: Fitting potential energy surfaces with fundamental invariant neural network

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Kejie; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People’s Republic of China and University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China. (China)

    2016-08-21

    A more flexible neural network (NN) method using the fundamental invariants (FIs) as the input vector is proposed in the construction of potential energy surfaces for molecular systems involving identical atoms. Mathematically, FIs finitely generate the permutation invariant polynomial (PIP) ring. In combination with NN, fundamental invariant neural network (FI-NN) can approximate any function to arbitrary accuracy. Because FI-NN minimizes the size of input permutation invariant polynomials, it can efficiently reduce the evaluation time of potential energy, in particular for polyatomic systems. In this work, we provide the FIs for all possible molecular systems up to five atoms. Potential energy surfaces for OH{sub 3} and CH{sub 4} were constructed with FI-NN, with the accuracy confirmed by full-dimensional quantum dynamic scattering and bound state calculations.

  13. A harmonic transition state theory model for defect initiation in crystals

    International Nuclear Information System (INIS)

    Delph, T J; Cao, P; Park, H S; Zimmerman, J A

    2013-01-01

    We outline here a model for the initiation of defects in crystals based upon harmonic transition state theory (hTST). This model combines a previously developed model for zero-temperature defect initiation with a multi-dimensional hTST model that is capable of accurately predicting the effects of temperature and loading rate upon defect initiation. The model has several features that set it apart from previous efforts along these lines, most notably a straightforward method of determining the energy barrier between adjacent equilibrium states that does not depend upon a priori information concerning the nature of the defect. We apply the model to two examples, triaxial stretching of a perfect fcc crystal and nanoindentation of a gold substrate. Very good agreement is found between the predictions of the model and independent molecular dynamics (MD) simulations. Among other things, the model predicts a strong dependence of the defect initiation behavior upon the loading parameter. A very attractive feature of this model is that it is valid for arbitrarily slow loading rates, in particular loading rates achievable in the laboratory, and suffers from none of the limitations in this regard inherent in MD simulations. (paper)

  14. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension

    Energy Technology Data Exchange (ETDEWEB)

    Greene, Samuel M., E-mail: samuel.greene@chem.ox.ac.uk; Shan, Xiao, E-mail: xiao.shan@chem.ox.ac.uk; Clary, David C., E-mail: david.clary@chem.ox.ac.u [Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2016-06-28

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

  15. Ensemble of Transition State Structures for the Cis-Trans Isomerization of N-Methylacetamide

    Energy Technology Data Exchange (ETDEWEB)

    Mantz, Yves A. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Branduardi, Davide [Italian Inst. of Technology, Genoa (Italy); Bussi, Giovanni [Univ. of Modena and Reggio Emilia and INFM-CNR (Italy); Parrinello, Michele [ETH Zurich, Lugano (Switzerland). Dept. of Chemistry and Applied Biosciences

    2009-09-17

    The cis-trans isomerization of N-methylacetamide (NMA), a model peptidic fragment, is studied theoretically in vacuo and in explicit water solvent at 300 K using the metadynamics technique. The computed cis-trans free energy difference is very similar for NMA(g) and NMA(aq), in agreement with experimental measurements of population ratios and theoretical studies at 0 K. By exploiting the flexibility in the definition of a pair of recently introduced collective variables (Branduardi, D.; Gervasio, F. L.; Parrinello, M. J. Chem. Phys. 2007, 126, 054103), an ensemble of transition state structures is generated at finite temperature for both NMA(g) and NMA(aq), as verified by computing committor distribution functions. Ensemble members of NMA(g) are shown to have correlated values of the backbone dihedral angle and a second dihedral angle involving the amide hydrogen atom. The dynamical character of these structures is preserved in the presence of solvent, whose influence on the committor functions can be modeled using effective friction/noise terms.

  16. An automated method to find transition states using chemical dynamics simulations.

    Science.gov (United States)

    Martínez-Núñez, Emilio

    2015-02-05

    A procedure to automatically find the transition states (TSs) of a molecular system (MS) is proposed. It has two components: high-energy chemical dynamics simulations (CDS), and an algorithm that analyzes the geometries along the trajectories to find reactive pathways. Two levels of electronic structure calculations are involved: a low level (LL) is used to integrate the trajectories and also to optimize the TSs, and a higher level (HL) is used to reoptimize the structures. The method has been tested in three MSs: formaldehyde, formic acid (FA), and vinyl cyanide (VC), using MOPAC2012 and Gaussian09 to run the LL and HL calculations, respectively. Both the efficacy and efficiency of the method are very good, with around 15 TS structures optimized every 10 trajectories, which gives a total of 7, 12, and 83 TSs for formaldehyde, FA, and VC, respectively. The use of CDS makes it a powerful tool to unveil possible nonstatistical behavior of the system under study. © 2014 Wiley Periodicals, Inc.

  17. Summertime influences of tidal energy advection on the surface energy balance in a mangrove forest

    Directory of Open Access Journals (Sweden)

    J. G. Barr

    2013-01-01

    Full Text Available Mangrove forests are ecosystems susceptible to changing water levels and temperatures due to climate change as well as perturbations resulting from tropical storms. Numerical models can be used to project mangrove forest responses to regional and global environmental changes, and the reliability of these models depends on surface energy balance closure. However, for tidal ecosystems, the surface energy balance is complex because the energy transport associated with tidal activity remains poorly understood. This study aimed to quantify impacts of tidal flows on energy dynamics within a mangrove ecosystem. To address the research objective, an intensive 10-day study was conducted in a mangrove forest located along the Shark River in the Everglades National Park, FL, USA. Forest–atmosphere turbulent exchanges of energy were quantified with an eddy covariance system installed on a 30-m-tall flux tower. Energy transport associated with tidal activity was calculated based on a coupled mass and energy balance approach. The mass balance included tidal flows and accumulation of water on the forest floor. The energy balance included temporal changes in enthalpy, resulting from tidal flows and temperature changes in the water column. By serving as a net sink or a source of available energy, flood waters reduced the impact of high radiational loads on the mangrove forest. Also, the regression slope of available energy versus sink terms increased from 0.730 to 0.754 and from 0.798 to 0.857, including total enthalpy change in the water column in the surface energy balance for 30-min periods and daily daytime sums, respectively. Results indicated that tidal inundation provides an important mechanism for heat removal and that tidal exchange should be considered in surface energy budgets of coastal ecosystems. Results also demonstrated the importance of including tidal energy advection in mangrove biophysical models that are used for predicting ecosystem

  18. Seasonal contrast in the surface energy balance of the Sahel

    Science.gov (United States)

    Miller, R. L.; Slingo, A.; Barnard, J. C.; Kassianov, E.

    2009-07-01

    Over much of the world, heating of the surface by sunlight is balanced predominately by evaporative cooling. However, at the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) in Niamey, Niger, evaporation makes a significant contribution to the surface energy balance only at the height of the rainy season, when precipitation has replenished the reservoir of soil moisture. The AMF was placed at Niamey from late 2005 to early 2007 to provide measurements of surface fluxes in coordination with geostationary satellite retrievals of radiative fluxes at the top of the atmosphere, as part of the RADAGAST experiment to calculate atmospheric radiative divergence. We use observations at the mobile facility to investigate how the surface adjusts to radiative forcing throughout the year. The surface response to solar heating varies with changes in atmospheric water vapor associated with the seasonal reversal of the West African monsoon, which modulates the greenhouse effect and the ability of the surface to radiate thermal energy directly to space. During the dry season, sunlight is balanced mainly by longwave radiation and the turbulent flux of sensible heat. The ability of longwave radiation to cool the surface drops after the onset of southwesterly surface winds at Niamey, when moist, oceanic air flows onshore, increasing local column moisture and atmospheric opacity. Following the onset of southwesterly flow, evaporation remains limited by the supply of moisture from precipitation. By the height of the rainy season, however, sufficient precipitation has accumulated that evaporation is controlled by incident sunlight, and radiative forcing of the surface is balanced comparably by the latent, sensible, and longwave fluxes. Evaporation increases with the leaf area index, suggesting that plants are a significant source of atmospheric moisture and may tap moisture stored beneath the surface that accumulated during a previous rainy season. Surface radiative forcing

  19. An algorithm to locate optimal bond breaking points on a potential energy surface for applications in mechanochemistry and catalysis.

    Science.gov (United States)

    Bofill, Josep Maria; Ribas-Ariño, Jordi; García, Sergio Pablo; Quapp, Wolfgang

    2017-10-21

    The reaction path of a mechanically induced chemical transformation changes under stress. It is well established that the force-induced structural changes of minima and saddle points, i.e., the movement of the stationary points on the original or stress-free potential energy surface, can be described by a Newton Trajectory (NT). Given a reactive molecular system, a well-fitted pulling direction, and a sufficiently large value of the force, the minimum configuration of the reactant and the saddle point configuration of a transition state collapse at a point on the corresponding NT trajectory. This point is called barrier breakdown point or bond breaking point (BBP). The Hessian matrix at the BBP has a zero eigenvector which coincides with the gradient. It indicates which force (both in magnitude and direction) should be applied to the system to induce the reaction in a barrierless process. Within the manifold of BBPs, there exist optimal BBPs which indicate what is the optimal pulling direction and what is the minimal magnitude of the force to be applied for a given mechanochemical transformation. Since these special points are very important in the context of mechanochemistry and catalysis, it is crucial to develop efficient algorithms for their location. Here, we propose a Gauss-Newton algorithm that is based on the minimization of a positively defined function (the so-called σ-function). The behavior and efficiency of the new algorithm are shown for 2D test functions and for a real chemical example.

  20. Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex

    Energy Technology Data Exchange (ETDEWEB)

    Nasri, Sameh; Ajili, Yosra [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Jaidane, Nejm-Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Kalugina, Yulia N. [Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Halvick, Philippe; Stoecklin, Thierry [Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex (France); Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2015-05-07

    Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

  1. Nano Sensing and Energy Conversion Using Surface Plasmon Resonance (SPR

    Directory of Open Access Journals (Sweden)

    Iltai (Isaac Kim

    2015-07-01

    Full Text Available Nanophotonic technique has been attracting much attention in applications of nano-bio-chemical sensing and energy conversion of solar energy harvesting and enhanced energy transfer. One approach for nano-bio-chemical sensing is surface plasmon resonance (SPR imaging, which can detect the material properties, such as density, ion concentration, temperature, and effective refractive index in high sensitivity, label-free, and real-time under ambient conditions. Recent study shows that SPR can successfully detect the concentration variation of nanofluids during evaporation-induced self-assembly process. Spoof surface plasmon resonance based on multilayer metallo-dielectric hyperbolic metamaterials demonstrate SPR dispersion control, which can be combined with SPR imaging, to characterize high refractive index materials because of its exotic optical properties. Furthermore, nano-biophotonics could enable innovative energy conversion such as the increase of absorption and emission efficiency and the perfect absorption. Localized SPR using metal nanoparticles show highly enhanced absorption in solar energy harvesting. Three-dimensional hyperbolic metamaterial cavity nanostructure shows enhanced spontaneous emission. Recently ultrathin film perfect absorber is demonstrated with the film thickness is as low as ~1/50th of the operating wavelength using epsilon-near-zero (ENZ phenomena at the wavelength close to SPR. It is expected to provide a breakthrough in sensing and energy conversion applications using the exotic optical properties based on the nanophotonic technique.

  2. Functional Representation for the Born-Oppenheimer Diagonal Correction and Born-Huang Adiabatic Potential Energy Surfaces for Isotopomers of H3

    International Nuclear Information System (INIS)

    Mielke, Steven L.; Schwenke, David; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.

    2009-01-01

    Multireference configuration interaction (MRCI) calculations of the Born-Oppenheimer diagonal correction (BODC) for H3 were performed at 1397 symmetry-unique configurations using the Born-Huang approach; isotopic substitution leads to 4041 symmetry-unique configurations for the DH2 mass combination. These results were then fit to a functional form that permits calculation of the BODC for any combination of isotopes. Mean unsigned fitting errors on a test grid of configurations not included in the fitting process were 0.14, 0.12, and 0.65 cm-1 for the H3, DH2, and MuH2 isotopomers, respectively. This representation can be combined with any Born-Oppenheimer potential energy surface (PES) to yield Born-Huang (BH) PESs; herein we choose the CCI potential energy surface, the uncertainties of which (∼0.01 kcal/mol) are much smaller than the magnitude of the BODC. FORTRAN routines to evaluate these BH surfaces are provided. Variational transition state theory calculations are presented comparing thermal rate constants for reactions on the BO and BH surfaces to provide an initial estimate of the significance of the diagonal correction for the dynamics.

  3. Surface energy of amorphous carbon films containing iron

    International Nuclear Information System (INIS)

    Chen, J. S.; Lau, S. P.; Tay, B. K.; Chen, G. Y.; Sun, Z.; Tan, Y. Y.; Tan, G.; Chai, J. W.

    2001-01-01

    Iron containing diamond-like amorphous carbon (a-C:Fe) films were deposited by filtered cathodic vacuum arc technique. The influences of Fe content and substrate bias on the surface energy of the films were investigated. The surface energy of a-C:Fe films was determined by the contact angle measurement. Atomic force microscopy, Raman spectroscopy, and x-ray induced photoelectron spectroscopy were employed to analyze the origin of the variation of surface energy with various Fe content and substrate bias. It is found that the contact angle for water increases significantly after incorporating Fe into the films and the films become hydrophobic. The roughness of these films has no effect on the contact angle. The surface energy is reduced from 42.8 to 25 dyne/cm after incorporating Fe into the a-C film (10% Fe in the target), which is due to the reduction of both dispersive and polar component. The reduction in dispersive component is ascribed to the decrease of atomic density of the a-C:Fe films due to the increase in sp 2 bonded carbon. When sp 2 content increases to some extent, the atomic density remains constant and hence dispersive component does not change. The absorption of oxygen on the surface plays an important role in the reduction of the polar component for the a-C:Fe films. It is proposed that such network as (C n - O - Fe) - O - (Fe - O - C n ) may be formed and responsible for the reduction of polar component. [copyright] 2001 American Institute of Physics

  4. Low energy pion detection by a silicon surface barrier telescope

    International Nuclear Information System (INIS)

    Sealock, R.M.; Caplan, H.S.; Leung, M.K.

    1978-01-01

    Four telescopes of three (2-ΔE, 1-E) silicon surface barrier detectors each, mounted in the focal plane of a magnetic spectrometer, have been used to detect positive pions in the energy range from 4.7-17.9 MeV and negative pions from 14.1-17.9 MeV. Positive pions from 4.7-12.7 MeV were stopped in the third detector while positive and negative pions from 14.1-17.9 MeV were detected in transmission. For energies greater than 7.4 MeV aluminum moderators were placed in front of the first detector to degrade the pion energy. Energy spectra show well resolved pion peaks with extremely low background. Double differential cross sections for the 12 C(e,π + ) 12 B,e' reaction have been measured. (Auth.)

  5. Harvesting electrostatic energy using super-hydrophobic surfaces

    Science.gov (United States)

    Pociecha, Dominik; Zylka, Pawel

    2016-11-01

    Almost all environments are now being extensively populated by miniaturized, nano-powered electronic sensor devices communicated together through wireless sensor networks building Internet of Things (IoT). Various energy harvesting techniques are being more and more frequently proposed for battery-less powering of such remote, unattended, implantable or wearable sensors or other low-power electronic gadgets. Energy harvesting relays on extracting energy from the ambient sources readily accessible at the sensor location and converting it into electrical power. The paper exploits possibility of generating electric energy safely accessible for nano-power electronics using tribo-electric and electrostatic induction phenomena displayed at super-hydrophobic surfaces impinged by water droplets. Mechanism of such interaction is discussed and illustrated by experimental results.

  6. Comparison of surface energy fluxes with satellite-derived surface energy flux estimates from a shrub-steppe

    International Nuclear Information System (INIS)

    Kirkham, R.R.

    1993-12-01

    This thesis relates the components of the surface energy balance (i.e., net radiation, sensible and latent heat flux densities, soil heat flow) to remotely sensed data for native vegetation in a semi-arid environment. Thematic mapper data from Landsat 4 and 5 were used to estimate net radiation, sensible heat flux (H), and vegetation amount. Several sources of ground truth were employed. They included soil water balance using the neutron thermalization method and weighing lysimeters, and the measurement of energy fluxes with the Bowen ratio energy balance (BREB) technique. Sensible and latent heat flux were measured at four sites on the U.S. Department of Energy's Hanford Site using a weighing lysimeter and/or BREB stations. The objective was to calibrate an aerodynamic transport equation that related H to radiant surface temperature. The transport equation was then used with Landsat thermal data to generate estimates of H and compare these estimates against H values obtained with BREB/lysimeters at the time of overflight. Landsat and surface meteorologic data were used to estimate the radiation budget terms at the surface. Landsat estimates of short-wave radiation reflected from the surface correlate well with reflected radiation measured using inverted Eppley pyranometers. Correlation of net radiation estimates determined from satellite data, pyranometer, air temperature, and vapor pressure compared to net radiometer values obtained at time of overflight were excellent for a single image, but decrease for multiple images. Soil heat flux, G T , is a major component of the energy balance in arid systems and G T generally decreases as vegetation cover increases. Normalized difference vegetation index (NDVI) values generated from Landsat thermatic mapper data were representative of field observations of the presence of green vegetation, but it was not possible to determine a single relationship between NDVI and G T for all sites

  7. Surface wind energy trends near Taiwan in winter since 1871

    Directory of Open Access Journals (Sweden)

    Lei Zhang

    2017-01-01

    Full Text Available The tropical surface wind speed in boreal winter reaches a maximum near Taiwan. This stable wind resource may be used for future clean energy development. How this surface wind energy source has changed in past 141 years is investigated using the 20th century reanalysis dataset and CMIP5 models. Our observational analysis shows that the surface wind speed experienced a weakening trend in the past 141 years (1871 - 2010. The average decreasing rate is around -1.4 m s-1 per century. The decrease is primarily attributed to the relative sea surface temperature (SST cooling in the subtropical North Pacific, which forces a large-scale low-level anti-cyclonic circulation anomaly in situ and is thus responsible for the southerly trend near Taiwan. The relative SST trend pattern is attributed mainly to the greenhouse gas effect associated with anthropogenic activities. The southerly trend near Taiwan is more pronounced in the boreal winter than in summer. Such seasonal difference is attributed to the reversed seasonal mean wind, which promotes more efficient positive feedback in the boreal winter. The CMIP5 historical run analysis reveals that climate models capture less SST warming and large-scale anti-cyclonic circulation in the subtropical North Pacific, but the simulated weakening trend of the surface wind speed near Taiwan is too small.

  8. Scaling of surface energy fluxes using remotely sensed data

    Science.gov (United States)

    French, Andrew Nichols

    Accurate estimates of evapotranspiration (ET) across multiple terrains would greatly ease challenges faced by hydrologists, climate modelers, and agronomists as they attempt to apply theoretical models to real-world situations. One ET estimation approach uses an energy balance model to interpret a combination of meteorological observations taken at the surface and data captured by remote sensors. However, results of this approach have not been accurate because of poor understanding of the relationship between surface energy flux and land cover heterogeneity, combined with limits in available resolution of remote sensors. The purpose of this study was to determine how land cover and image resolution affect ET estimates. Using remotely sensed data collected over El Reno, Oklahoma, during four days in June and July 1997, scale effects on the estimation of spatially distributed ET were investigated. Instantaneous estimates of latent and sensible heat flux were calculated using a two-source surface energy balance model driven by thermal infrared, visible-near infrared, and meteorological data. The heat flux estimates were verified by comparison to independent eddy-covariance observations. Outcomes of observations taken at coarser resolutions were simulated by aggregating remote sensor data and estimated surface energy balance components from the finest sensor resolution (12 meter) to hypothetical resolutions as coarse as one kilometer. Estimated surface energy flux components were found to be significantly dependent on observation scale. For example, average evaporative fraction varied from 0.79, using 12-m resolution data, to 0.93, using 1-km resolution data. Resolution effects upon flux estimates were related to a measure of landscape heterogeneity known as operational scale, reflecting the size of dominant landscape features. Energy flux estimates based on data at resolutions less than 100 m and much greater than 400 m showed a scale-dependent bias. But estimates

  9. Surface modifications of polypropylene by high energy carbon ions

    International Nuclear Information System (INIS)

    Saha, A.; Chakraborty, V.; Dutta, R.K.; Chintalapudi, S.N.

    2000-01-01

    Polypropylene was irradiated with 12 C ions of 3.6 and 5.4 MeV energies using 3 MV tandem accelerator. The surface modification was investigated by Scanning Electron Microscopy (SEM). Optical changes were monitored by UV-VIS and FTIR spectroscopy. At the lowest ion fluence, only blister formation of various sizes (1-6 μm) was observed. Polymer when irradiated at a fluence of 1x10 14 ions/cm 2 exhibited a network structure. A comparative study on dose dependence of surface and bulk modification has been described. (author)

  10. Electrostatic energy and screened charge interaction near the surface of metals with different Fermi surface shape

    Science.gov (United States)

    Gabovich, A. M.; Il'chenko, L. G.; Pashitskii, E. A.; Romanov, Yu. A.

    1980-04-01

    Using the Poisson equation Green function for a self-consistent field in a spatially inhomogeneous system, expressions for the electrostatic energy and screened charge interaction near the surface of a semi-infinite metal and a thin quantizing film are derived. It is shown that the decrease law and Friedel oscillation amplitude of adsorbed atom indirect interaction are determined by the electron spectrum character and the Fermi surface shape. The results obtained enable us to explain, in particular, the submonolayer adsorbed film structure on the W and Mo surfaces.

  11. Surface free energy of polypropylene and polycarbonate solidifying at different solid surfaces

    International Nuclear Information System (INIS)

    Chibowski, Emil; Terpilowski, Konrad

    2009-01-01

    Advancing and receding contact angles of water, formamide, glycerol and diiodomethane were measured on polypropylene (PP) and polycarbonate (PC) sample surfaces which solidified at Teflon, glass or stainless steel as matrix surfaces. Then from the contact angle hystereses (CAH) the apparent free energies γ s tot of the surfaces were evaluated. The original PP surface is practically nonpolar, possessing small electron donor interaction (γ s - =1.91mJ/m 2 ), as determined from the advancing contact angles of these liquids. It may result from impurities of the polymerization process. However, it increases up to 8-10 mJ/m 2 for PP surfaces contacted with the solids. The PC surfaces both original and modified show practically the same γ s - =6.56.7mJ/m 2 . No electron acceptor interaction is found on the surfaces. The γ s tot of modified PP and PC surfaces depend on the kind of probe liquid and contacted solid surface. The modified PP γ s tot values determined from CAH of polar liquids are greater than that of original surface and they increase in the sequence: Teflon, glass, stainless steel surface, at which they solidified. No clear dependence is observed between γ s tot and dielectric constant or dipole moment of the polar probe liquids. The changes in γ s tot of the polymer surfaces are due to the polymer nature and changes in its surface structure caused by the structure and force field of the contacting solid. It has been confirmed by AFM images.

  12. The interaction of low energy ion beams with surfaces

    International Nuclear Information System (INIS)

    Carter, G.; Armour, D.G.

    1981-01-01

    Four of the most important physical processes which occur during ion plating and allied techniques (1) ion-induced (and energetic-atom-induced) desorption of adsorbed impurities from the substrate surface, (2) ion penetration and entrapment in the substrate and coating, (3) ion-induced sputtering of substrate and coating atoms and (4) recoil displacement of substrate and coating atoms leading to their intermixing. The ion and energetic atom energy range of importance is from thermal energies to the order of 1keV. Current understanding of these processes, supported by discussion of available experimental data, is reviewed. (Auth.)

  13. Ab initio surface core-level shifts and surface segregation energies

    DEFF Research Database (Denmark)

    Aldén, Magnus; Skriver, Hans Lomholt; Johansson, Börje

    1993-01-01

    We have calculated the surface core-level energy shifts of the 4d and 5d transition metals by means of local-density theory and a Green’s-function technique based on the linear muffin-tin orbitals method. Final-state effects are included by treating the core-ionized atom as an impurity located in...

  14. Electronic structure, molecular bonding and potential energy surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ruedenberg, K. [Ames Laboratory, IA (United States)

    1993-12-01

    By virtue of the universal validity of the generalized Born-Oppenheimer separation, potential energy surfaces (PES`) represent the central conceptual as well as quantitative entities of chemical physics and provide the basis for the understanding of most physicochemical phenomena in many diverse fields. The research in this group deals with the elucidation of general properties of PES` as well as with the quantitative determination of PES` for concrete systems, in particular pertaining to reactions involving carbon, oxygen, nitrogen and hydrogen molecules.

  15. The Global Energy Balance Archive (GEBA): A database for the worldwide measured surface energy fluxes

    Science.gov (United States)

    Wild, Martin; Ohmura, Atsumu; Schär, Christoph; Müller, Guido; Hakuba, Maria Z.; Mystakidis, Stefanos; Arsenovic, Pavle; Sanchez-Lorenzo, Arturo

    2017-02-01

    The Global Energy Balance Archive (GEBA) is a database for the worldwide measured energy fluxes at the Earth's surface. GEBA is maintained at ETH Zurich (Switzerland) and has been founded in the 1980s by Prof. Atsumu Ohmura. It has continuously been updated and currently contains around 2500 stations with 500`000 monthly mean entries of various surface energy balance components. Many of the records extend over several decades. The most widely measured quantity available in GEBA is the solar radiation incident at the Earth's surface ("global radiation"). The data sources include, in addition to the World Radiation Data Centre (WRDC) in St. Petersburg, data reports from National Weather Services, data from different research networks (BSRN, ARM, SURFRAD), data published in peer-reviewed publications and data obtained through personal communications. Different quality checks are applied to check for gross errors in the dataset. GEBA is used in various research applications, such as for the quantification of the global energy balance and its spatiotemporal variation, or for the estimation of long-term trends in the surface fluxes, which enabled the detection of multi-decadal variations in surface solar radiation, known as "global dimming" and "brightening". GEBA is further extensively used for the evaluation of climate models and satellite-derived surface flux products. On a more applied level, GEBA provides the basis for engineering applications in the context of solar power generation, water management, agricultural production and tourism. GEBA is publicly accessible over the internet via www.geba.ethz.ch.

  16. Constraining the Surface Energy Balance of Snow in Complex Terrain

    Science.gov (United States)

    Lapo, Karl E.

    Physically-based snow models form the basis of our understanding of current and future water and energy cycles, especially in mountainous terrain. These models are poorly constrained and widely diverge from each other, demonstrating a poor understanding of the surface energy balance. This research aims to improve our understanding of the surface energy balance in regions of complex terrain by improving our confidence in existing observations and improving our knowledge of remotely sensed irradiances (Chapter 1), critically analyzing the representation of boundary layer physics within land models (Chapter 2), and utilizing relatively novel observations to in the diagnoses of model performance (Chapter 3). This research has improved the understanding of the literal and metaphorical boundary between the atmosphere and land surface. Solar irradiances are difficult to observe in regions of complex terrain, as observations are subject to harsh conditions not found in other environments. Quality control methods were developed to handle these unique conditions. These quality control methods facilitated an analysis of estimated solar irradiances over mountainous environments. Errors in the estimated solar irradiance are caused by misrepresenting the effect of clouds over regions of topography and regularly exceed the range of observational uncertainty (up to 80Wm -2) in all regions examined. Uncertainty in the solar irradiance estimates were especially pronounced when averaging over high-elevation basins, with monthly differences between estimates up to 80Wm-2. These findings can inform the selection of a method for estimating the solar irradiance and suggest several avenues of future research for improving existing methods. Further research probed the relationship between the land surface and atmosphere as it pertains to the stable boundary layers that commonly form over snow-covered surfaces. Stable conditions are difficult to represent, especially for low wind speed

  17. The importance of surface finish to energy performance

    Directory of Open Access Journals (Sweden)

    Smith Geoff B.

    2017-01-01

    Full Text Available Power generation in solar energy systems, thermal control in buildings and mitigation of the Urban Heat Island problem, are all sensitive to directional response to incoming radiation. The radiation absorption and emission profile also plays a crucial role in each system's response and depends strongly on surface finish. This important sensitivity needs wider recognition in materials data sheets, system modeling, plus in materials and environmental engineering. The impact of surface roughness on thermal response of natural and man-made external environments is examined. Important examples will be given of the role of surface finish within each class. Total emittance links to the way surface finish influences directional emittance E(θ. Smooth surface thermal emittance on PV module covers, many solar absorbers, some roof paints, polished concrete, and glass windows can be up to 15% different from insulator results based on fully diffuse models of the same material. Widespread evidence indicates smooth metals and low-E solar absorber surfaces cool faster, and smooth insulators slower than previously thought. Matt paint is cooler than low sheen paint under the same solar heating impacts and normal concrete cooler than polished. Emittance for water is the prime environmental example of oblique impacts as it reflects strongly at oblique incidence, which leads to a significant drop in E(θ. Ripples or waves however raise water's average emittance. A surprise in this work was the high sensitivity of total E and its angular components to roughness in the depth range of 0.1–0.8 μm, which are well under ambient thermal IR wavelengths of 3–30 μm but common in metal finishing. Parallel energy flows such as evaporation and convective cooling vary if emittance varies. Thermal image analysis can provide insights into angular radiative effects.

  18. Fowler's approximation for the surface tension and surface energy of Lennard-Jones fluids revisited

    International Nuclear Information System (INIS)

    Mulero, A; Galan, C; Cuadros, F

    2003-01-01

    We present a detailed study of the validity of Fowler's approximation for calculating the surface tension and the surface energy of Lennard-Jones fluids. To do so, we consider three different explicit analytical expressions for the radial distribution function (RDF), including one proposed by our research group, together with very accurate expressions for the liquid and vapour densities, also proposed by our group. The calculation of the surface tension from the direct correlation function using both the Percus-Yevick and the hypernetted-chain approximations is also considered. Finally, our results are compared with those obtained by other authors by computer simulations or through relevant theoretical approximations. In particular, we consider the analytical expression proposed by Kalikmanov and Hofmans (1994 J. Phys.: Condens. Matter 6 2207-14) for the surface tension. Our results indicate that the values for the surface energy in Fowler's approximation obtained by other authors are adequate, and can be calculated from the RDF models. For the surface tension, however, the values considered as valid in previous works seem to be incorrect. The correct values can be obtained from our model for the RDF or from the Kalikmanov and Hofmans expression with suitable inputs

  19. Study on the energy performance of glazing surfaces

    Directory of Open Access Journals (Sweden)

    Ligia MOGA

    2014-12-01

    Full Text Available A proper thermal design of the building envelope represents an important factor for the energy economics. Glazing surfaces represent one of the important elements in the hygrothermal design activity of a building envelope. The window’s thermal performance has also a strong influence on the thermal performance of the opaque area of the wall. This fact imposed the research of the real interaction, of cooperation and of mutual influences of the characteristics between the two components of the wall of the building envelope, respectively the opaque and the glazing area. Optimal constructive details for the opaque and glazing area of the wall need to be properly designed in order to achieve the required thermal and energy performances imposed for new types of buildings, e.g. passive houses, zero energy buildings.

  20. How important is getting the land surface energy exchange correct in WRF for wind energy forecasting?

    Science.gov (United States)

    Wharton, S.; Simpson, M.; Osuna, J. L.; Newman, J. F.; Biraud, S.

    2013-12-01

    Wind power forecasting is plagued with difficulties in accurately predicting the occurrence and intensity of atmospheric conditions at the heights spanned by industrial-scale turbines (~ 40 to 200 m above ground level). Better simulation of the relevant physics would enable operational practices such as integration of large fractions of wind power into power grids, scheduling maintenance on wind energy facilities, and deciding design criteria based on complex loads for next-generation turbines and siting. Accurately simulating the surface energy processes in numerical models may be critically important for wind energy forecasting as energy exchange at the surface strongly drives atmospheric mixing (i.e., stability) in the lower layers of the planetary boundary layer (PBL), which in turn largely determines wind shear and turbulence at heights found in the turbine rotor-disk. We hypothesize that simulating accurate a surface-atmosphere energy coupling should lead to more accurate predictions of wind speed and turbulence at heights within the turbine rotor-disk. Here, we tested 10 different land surface model configurations in the Weather Research and Forecasting (WRF) model including Noah, Noah-MP, SSiB, Pleim-Xiu, RUC, and others to evaluate (1) the accuracy of simulated surface energy fluxes to flux tower measurements, (2) the accuracy of forecasted wind speeds to observations at rotor-disk heights, and (3) the sensitivity of forecasting hub-height rotor disk wind speed to the choice of land surface model. WRF was run for four, two-week periods covering both summer and winter periods over the Southern Great Plains ARM site in Oklahoma. Continuous measurements of surface energy fluxes and lidar-based wind speed, direction and turbulence were also available. The SGP ARM site provided an ideal location for this evaluation as it centrally located in the wind-rich Great Plains and multi-MW wind farms are rapidly expanding in the area. We found significant differences in

  1. Visualization of the Differential Transition State Stabilization within the Active Site Environment

    Directory of Open Access Journals (Sweden)

    Jerzy Leszczynski

    2004-05-01

    Full Text Available Abstract: Increasing interest in the enzymatic reaction mechanisms and in the nature of catalytic effects in enzymes causes the need of appropriate visualization methods. A new interactive method to investigate catalytic effects using differential transition state stabilization approach (DTSS [1, 2] is presented. The catalytic properties of the active site of cytidine deaminase (E.C. 3.5.4.5 is visualized in the form of differential electrostatic properties. The visualization was implemented using scripting interface of VMD [3]. Cumulative Atomic Multipole Moments (CAMM [4,5,6] were utilized for efficient yet accurate evaluation of the electrostatic properties. The implementation is efficient enough for interactive presentation of catalytic effects in the active site of the enzyme due to transition state or substrate movement. This system of visualization of DTTS approach can be potentially used to validate hypotheses regarding the catalytic mechanism or to study binding properties of transition state analogues.

  2. A dielectric matrix calculation of the surface-plasmon energy for the silicon (100) surface

    International Nuclear Information System (INIS)

    Forsyth, A.J.; Smith, A.E.; Josefsson, T.W.

    1996-01-01

    Full text: As an extension of previous work, we present preliminary calculations for the dielectric properties of the silicon (100) surface. In particular, the |q|→0 and |q|=2π/a(1,0,0) surface loss function, and corresponding surface plasmon energies have been calculated within a simple model for the silicon surface. The results have been obtained from the Adler and Wiser dielectric matrix (DM). The bandstructure used for the calculation was based on the highly successful empirical pseudopotential method of Cohen and Chelikovsky. We have used a 59 plane wave basis for the bandstructure, and have chosen a DM size of 59 x 59. Results are compared and contrasted with volume plasmon calculations, free electron calculations and experiment

  3. Measuring surface energy and evapotranspiration across Caribbean mangrove forests

    Science.gov (United States)

    Lagomasino, D.; Fatoyinbo, T. E.; Price, R.

    2014-12-01

    Coastal mangroves lose large amounts of water through evapotranspiration (ET) that can be equivalent to the amount of annual rainfall in certain years. Satellite remote sensing has been used to estimate surface energy and ET variability in many forested ecosystems, yet has been widely overlooked in mangrove forests. Using a combination of long-term datasets (30-year) acquired from the NASA Landsat 5 and 7 satellite databases, the present study investigated ET and surface energy balance variability between two mangrove forest sites in the Caribbean: 1) Everglades National Park (ENP; Florida, USA) and 2) Sian Ka'an Biosphere Reserve (SKBR; Quintana Roo, Mexico). A satellite-derived surface energy balance model was used to estimate ET in tall and scrub mangroves environments at ENP and SKBR. Results identified significant differences in soil heat flux measurements and ET between the tall and scrub mangrove environments. Scrub mangroves exhibited the highest soil heat flux coincident with the lowest biophysical indices (i.e., Fractional Vegetation Cover, Normalized Difference Vegetation Index, and Soil-Adjusted Vegetation Index) and ET rates. Mangrove damage and mortality was observed on the satellite images following strong tropical storms and associated with anthropogenic modifications and resulted in low values in spectral vegetation indices, higher soil heat flux, and higher ET. Recovery of the spectral characteristics, soil heat flux and ET was within 1-2 years following hurricane disturbance while, degradation caused by human disturbance persisted for many years. Remotely sensed ET of mangrove forests can provide estimates over a few decades and provide us with some understanding of how these environments respond to disturbances to the landscape in periods where no ground data exists or in locations that are difficult to access. Moreover, relationships between energy and water balance components developed for the coastal mangroves of Florida and Mexico could be

  4. Tuning surface porosity on vanadium surface by low energy He{sup +} ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tripathi, J.K., E-mail: jtripat@purdue.edu; Novakowski, T.J.; Hassanein, A.

    2016-08-15

    Highlights: • Surface nanostructuring on vanadium surface using novel He{sup +} ion irradiation process. • Tuning surface-porosity using high-flux, low-energy He{sup +} ion irradiation at constant elevated sample temperature (823–173 K). • Presented top-down approach guarantees good contact between different crystallites. • Sequential significant enhancement in surface-pore edge size (and corresponding reduction in surface-pore density) with increasing sample temperature. - Abstract: In the present study, we report on tuning the surface porosity on vanadium surfaces using high-flux, low-energy He{sup +} ion irradiation as function of sample temperature. Polished, mirror-finished vanadium samples were irradiated with 100 eV He{sup +} ions at a constant ion-flux of 7.2 × 10{sup 20} ions m{sup −2} s{sup −1} for 1 h duration at constant sample temperatures in the wide range of 823–1173 K. Our results show that the surface porosity of V{sub 2}O{sub 5} (naturally oxidized vanadium porous structure, after taking out from UHV) is strongly correlated to the sample temperature and is highly tunable. In fact, the surface porosity significantly increases with reducing sample temperature and reaches up to ∼87%. Optical reflectivity on these highly porous V{sub 2}O{sub 5} surfaces show ∼0% optical reflectivity at 670 nm wavelength, which is very similar to that of “black metal”. Combined with the naturally high melting point of V{sub 2}O{sub 5}, this very low optical reflectivity suggests potential application in solar power concentration technology. Additionally, this top-down approach guarantees relatively good contact between the different crystallites and avoids electrical conductivity limitations (if required). Since V{sub 2}O{sub 5} is naturally a potential photocatalytic material, the resulting sub-micron-sized cube-shaped porous structures could be used in solar water splitting for hydrogen production in energy applications.

  5. The surface-forming energy release rate versus the local energy release rate

    OpenAIRE

    Xiao, Si; Wang, He-ling; Landis, Chad M; Hwang, Keh-Chih; Liu, Bin

    2016-01-01

    This paper identifies two ways to extract the energy (or power) flowing into a crack tip during propagation based on the power balance of areas enclosed by a stationary contour and a comoving contour. It is very interesting to find a contradiction that two corresponding energy release rates (ERRs), a surface-forming ERR and a local ERR, are different when stress singularity exists at a crack tip. Besides a rigorous mathematical interpretation, we deduce that the stress singularity leads to an...

  6. Kinetic Analysis for Macrocyclizations Involving Anionic Template at the Transition State

    Directory of Open Access Journals (Sweden)

    Vicente Martí-Centelles

    2012-01-01

    competitive oligomerization/polymerization processes yielding undesired oligomeric/polymeric byproducts. The effect of anions has also been included in the kinetic models, as they can act as catalytic templates in the transition state reducing and stabilizing the transition state. The corresponding differential equation systems for each kinetic model can be solved numerically. Through a comprehensive analysis of these results, it is possible to obtain a better understanding of the different parameters that are involved in the macrocyclization reaction mechanism and to develop strategies for the optimization of the desired processes.

  7. Surface energy and surface stress on vicinals by revisiting the Shuttleworth relation

    Science.gov (United States)

    Hecquet, Pascal

    2018-04-01

    In 1998 [Surf. Sci. 412/413, 639 (1998)], we showed that the step stress on vicinals varies as 1/L, L being the distance between steps, while the inter-step interaction energy primarily follows the law as 1/L2 from the well-known Marchenko-Parshin model. In this paper, we give a better understanding of the interaction term of the step stress. The step stress is calculated with respect to the nominal surface stress. Consequently, we calculate the diagonal surface stresses in both the vicinal system (x, y, z) where z is normal to the vicinal and the projected system (x, b, c) where b is normal to the nominal terrace. Moreover, we calculate the surface stresses by using two methods: the first called the 'Zero' method, from the surface pressure forces and the second called the 'One' method, by homogeneously deforming the vicinal in the parallel direction, x or y, and by calculating the surface energy excess proportional to the deformation. By using the 'One' method on the vicinal Cu(0 1 M), we find that the step deformations, due to the applied deformation, vary as 1/L by the same factor for the tensor directions bb and cb, and by twice the same factor for the parallel direction yy. Due to the vanishing of the surface stress normal to the vicinal, the variation of the step stress in the direction yy is better described by using only the step deformation in the same direction. We revisit the Shuttleworth formula, for while the variation of the step stress in the direction xx is the same between the two methods, the variation in the direction yy is higher by 76% for the 'Zero' method with respect to the 'One' method. In addition to the step energy, we confirm that the variation of the step stress must be taken into account for the understanding of the equilibrium of vicinals when they are not deformed.

  8. Treatment of surfaces with low-energy electrons

    Science.gov (United States)

    Frank, L.; Mikmeková, E.; Lejeune, M.

    2017-06-01

    Electron-beam-induced deposition of various materials from suitable precursors has represented an established branch of nanotechnology for more than a decade. A specific alternative is carbon deposition on the basis of hydrocarbons as precursors that has been applied to grow various nanostructures including masks for subsequent technological steps. Our area of study was unintentional electron-beam-induced carbon deposition from spontaneously adsorbed hydrocarbon molecules. This process traditionally constitutes a challenge for scanning electron microscopy practice preventing one from performing any true surface studies outside an ultrahigh vacuum and without in-situ cleaning of samples, and also jeopardising other electron-optical devices such as electron beam lithographs. Here we show that when reducing the energy of irradiating electrons sufficiently, the e-beam-induced deposition can be converted to e-beam-induced release causing desorption of hydrocarbons and ultimate cleaning of surfaces in both an ultrahigh and a standard high vacuum. Using series of experiments with graphene samples, we demonstrate fundamental features of e-beam-induced desorption and present results of checks for possible radiation damage using Raman spectroscopy that led to optimisation of the electron energy for damage-free cleaning. The method of preventing carbon contamination described here paves the way for greatly enhanced surface sensitivity of imaging and substantially reduced demands on vacuum systems for nanotechnological applications.

  9. Structured pathway across the transition state for peptide folding revealed by molecular dynamics simulations.

    Directory of Open Access Journals (Sweden)

    Lipi Thukral

    2011-09-01

    Full Text Available Small globular proteins and peptides commonly exhibit two-state folding kinetics in which the rate limiting step of folding is the surmounting of a single free energy barrier at the transition state (TS separating the folded and the unfolded states. An intriguing question is whether the polypeptide chain reaches, and leaves, the TS by completely random fluctuations, or whether there is a directed, stepwise process. Here, the folding TS of a 15-residue β-hairpin peptide, Peptide 1, is characterized using independent 2.5 μs-long unbiased atomistic molecular dynamics (MD simulations (a total of 15 μs. The trajectories were started from fully unfolded structures. Multiple (spontaneous folding events to the NMR-derived conformation are observed, allowing both structural and dynamical characterization of the folding TS. A common loop-like topology is observed in all the TS structures with native end-to-end and turn contacts, while the central segments of the strands are not in contact. Non-native sidechain contacts are present in the TS between the only tryptophan (W11 and the turn region (P7-G9. Prior to the TS the turn is found to be already locked by the W11 sidechain, while the ends are apart. Once the ends have also come into contact, the TS is reached. Finally, along the reactive folding paths the cooperative loss of the W11 non-native contacts and the formation of the central inter-strand native contacts lead to the peptide rapidly proceeding from the TS to the native state. The present results indicate a directed stepwise process to folding the peptide.

  10. Modeling evolution of hydrogen bonding and stabilization of transition states in the process of cocaine hydrolysis catalyzed by human butyrylcholinesterase.

    Science.gov (United States)

    Gao, Daquan; Zhan, Chang-Guo

    2006-01-01

    Molecular dynamics (MD) simulations and quantum mechanical/molecular mechanical (QM/MM) calculations were performed on the prereactive enzyme-substrate complex, transition states, intermediates, and product involved in the process of human butyrylcholinesterase (BChE)-catalyzed hydrolysis of (-)-cocaine. The computational results consistently reveal a unique role of the oxyanion hole (consisting of G116, G117, and A199) in BChE-catalyzed hydrolysis of cocaine, compared to acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylcholine. During BChE-catalyzed hydrolysis of cocaine, only G117 has a hydrogen bond with the carbonyl oxygen (O31) of the cocaine benzoyl ester in the prereactive BChE-cocaine complex, and the NH groups of G117 and A199 are hydrogen-bonded with O31 of cocaine in all of the transition states and intermediates. Surprisingly, the NH hydrogen of G116 forms an unexpected hydrogen bond with the carboxyl group of E197 side chain and, therefore, is not available to form a hydrogen bond with O31 of cocaine in the acylation. The NH hydrogen of G116 is only partially available to form a weak hydrogen bond with O31 of cocaine in some structures involved in the deacylation. The change of the estimated hydrogen-bonding energy between the oxyanion hole and O31 of cocaine during the reaction process demonstrates how the protein environment can affect the energy barrier for each step of the BChE-catalyzed hydrolysis of cocaine. These insights concerning the effects of the oxyanion hole on the energy barriers provide valuable clues on how to rationally design BChE mutants with a higher catalytic activity for the hydrolysis of (-)-cocaine. 2005 Wiley-Liss, Inc.

  11. Improvement of a land surface model for accurate prediction of surface energy and water balances

    International Nuclear Information System (INIS)

    Katata, Genki

    2009-02-01

    In order to predict energy and water balances between the biosphere and atmosphere accurately, sophisticated schemes to calculate evaporation and adsorption processes in the soil and cloud (fog) water deposition on vegetation were implemented in the one-dimensional atmosphere-soil-vegetation model including CO 2 exchange process (SOLVEG2). Performance tests in arid areas showed that the above schemes have a significant effect on surface energy and water balances. The framework of the above schemes incorporated in the SOLVEG2 and instruction for running the model are documented. With further modifications of the model to implement the carbon exchanges between the vegetation and soil, deposition processes of materials on the land surface, vegetation stress-growth-dynamics etc., the model is suited to evaluate an effect of environmental loads to ecosystems by atmospheric pollutants and radioactive substances under climate changes such as global warming and drought. (author)

  12. Treatment of surfaces with low-energy electrons

    Energy Technology Data Exchange (ETDEWEB)

    Frank, L., E-mail: ludek@isibrno.cz [Institute of Scientific Instruments of the CAS, v.v.i., Královopolská 147, 61264 Brno (Czech Republic); Mikmeková, E. [Institute of Scientific Instruments of the CAS, v.v.i., Královopolská 147, 61264 Brno (Czech Republic); FEI Company, Achtseweg Noord 5, 5651 GG Eindhoven (Netherlands); Lejeune, M. [LPMC – Faculte des Sciences d’Amiens, Universite de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens Cedex 2 (France)

    2017-06-15

    Highlights: • Using proper irradiation parameters, adsorbed hydrocarbons are released from surfaces. • Slow electrons remove hydrocarbons instead of depositing carbon. • Prolonged irradiation with very slow electrons does not create defects in graphene. - Abstract: Electron-beam-induced deposition of various materials from suitable precursors has represented an established branch of nanotechnology for more than a decade. A specific alternative is carbon deposition on the basis of hydrocarbons as precursors that has been applied to grow various nanostructures including masks for subsequent technological steps. Our area of study was unintentional electron-beam-induced carbon deposition from spontaneously adsorbed hydrocarbon molecules. This process traditionally constitutes a challenge for scanning electron microscopy practice preventing one from performing any true surface studies outside an ultrahigh vacuum and without in-situ cleaning of samples, and also jeopardising other electron-optical devices such as electron beam lithographs. Here we show that when reducing the energy of irradiating electrons sufficiently, the e-beam-induced deposition can be converted to e-beam-induced release causing desorption of hydrocarbons and ultimate cleaning of surfaces in both an ultrahigh and a standard high vacuum. Using series of experiments with graphene samples, we demonstrate fundamental features of e-beam-induced desorption and present results of checks for possible radiation damage using Raman spectroscopy that led to optimisation of the electron energy for damage-free cleaning. The method of preventing carbon contamination described here paves the way for greatly enhanced surface sensitivity of imaging and substantially reduced demands on vacuum systems for nanotechnological applications.

  13. Treatment of surfaces with low-energy electrons

    Czech Academy of Sciences Publication Activity Database

    Frank, Luděk; Mikmeková, Eliška; Lejeune, M.

    2017-01-01

    Roč. 407, JUN 15 (2017), s. 105-108 ISSN 0169-4332 R&D Projects: GA TA ČR(CZ) TE01020118; GA MŠk(CZ) LO1212; GA MŠk ED0017/01/01 Institutional support: RVO:68081731 Keywords : Low- energy electrons * Electron beam induced release * Graphene * Ultimate cleaning of surfaces Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering OBOR OECD: Nano-processes (applications on nano-scale) Impact factor: 3.387, year: 2016

  14. Low-energy electron scattering from molecules, biomolecules and surfaces

    CERN Document Server

    Carsky, Petr

    2011-01-01

    Since the turn of the 21st century, the field of electron molecule collisions has undergone a renaissance. The importance of such collisions in applications from radiation chemistry to astrochemistry has flowered, and their role in industrial processes such as plasma technology and lighting are vital to the advancement of next generation devices. Furthermore, the development of the scanning tunneling microscope highlights the role of such collisions in the condensed phase, in surface processing, and in the development of nanotechnology.Low-Energy Electron Scattering from Molecules, Biomolecule

  15. Stabilized quasi-Newton optimization of noisy potential energy surfaces

    International Nuclear Information System (INIS)

    Schaefer, Bastian; Goedecker, Stefan; Alireza Ghasemi, S.; Roy, Shantanu

    2015-01-01

    Optimizations of atomic positions belong to the most commonly performed tasks in electronic structure calculations. Many simulations like global minimum searches or characterizations of chemical reactions require performing hundreds or thousands of minimizations or saddle computations. To automatize these tasks, optimization algorithms must not only be efficient but also very reliable. Unfortunately, computational noise in forces and energies is inherent to electronic structure codes. This computational noise poses a severe problem to the stability of efficient optimization methods like the limited-memory Broyden–Fletcher–Goldfarb–Shanno algorithm. We here present a technique that allows obtaining significant curvature information of noisy potential energy surfaces. We use this technique to construct both, a stabilized quasi-Newton minimization method and a stabilized quasi-Newton saddle finding approach. We demonstrate with the help of benchmarks that both the minimizer and the saddle finding approach are superior to comparable existing methods

  16. Experimental survey of the potential energy surfaces associated with fission

    International Nuclear Information System (INIS)

    Britt, H.C.

    1980-01-01

    Progress in the experimental determination of the properties of the potential energy surface associated with fission is reviewed. The importance of nuclear symmetry effects on the calculation of fission widths is demonstrated. Evidence is presented for the fragmentation of the mass-asymmetric second barrier in the thorium region and the axial asymmetric first barrier in the californium region. Detailed analyses of experimental data suggest the presence of two parallel second barriers; the normal mass-asymmetric, axial-symmetric barrier and a slightly higher mass-symmetric, axial-asymmetric barrier. Experimental barrier parameters are determined systematically and compared with calculations from various theoretical models. Techniques for expanding fission probability measurements to higher energies are discussed. (author)

  17. Stabilized quasi-Newton optimization of noisy potential energy surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, Bastian; Goedecker, Stefan, E-mail: stefan.goedecker@unibas.ch [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Alireza Ghasemi, S. [Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, IR-Zanjan (Iran, Islamic Republic of); Roy, Shantanu [Computational and Systems Biology, Biozentrum, University of Basel, CH-4056 Basel (Switzerland)

    2015-01-21

    Optimizations of atomic positions belong to the most commonly performed tasks in electronic structure calculations. Many simulations like global minimum searches or characterizations of chemical reactions require performing hundreds or thousands of minimizations or saddle computations. To automatize these tasks, optimization algorithms must not only be efficient but also very reliable. Unfortunately, computational noise in forces and energies is inherent to electronic structure codes. This computational noise poses a severe problem to the stability of efficient optimization methods like the limited-memory Broyden–Fletcher–Goldfarb–Shanno algorithm. We here present a technique that allows obtaining significant curvature information of noisy potential energy surfaces. We use this technique to construct both, a stabilized quasi-Newton minimization method and a stabilized quasi-Newton saddle finding approach. We demonstrate with the help of benchmarks that both the minimizer and the saddle finding approach are superior to comparable existing methods.

  18. Polynomials, Riemann surfaces, and reconstructing missing-energy events

    CERN Document Server

    Gripaios, Ben; Webber, Bryan

    2011-01-01

    We consider the problem of reconstructing energies, momenta, and masses in collider events with missing energy, along with the complications introduced by combinatorial ambiguities and measurement errors. Typically, one reconstructs more than one value and we show how the wrong values may be correlated with the right ones. The problem has a natural formulation in terms of the theory of Riemann surfaces. We discuss examples including top quark decays in the Standard Model (relevant for top quark mass measurements and tests of spin correlation), cascade decays in models of new physics containing dark matter candidates, decays of third-generation leptoquarks in composite models of electroweak symmetry breaking, and Higgs boson decay into two tau leptons.

  19. Intermolecular potential energy surface and thermophysical properties of propane.

    Science.gov (United States)

    Hellmann, Robert

    2017-03-21

    A six-dimensional potential energy surface (PES) for the interaction of two rigid propane molecules was determined from supermolecular ab initio calculations up to the coupled cluster with single, double, and perturbative triple excitations level of theory for 9452 configurations. An analytical site-site potential function with 14 sites per molecule was fitted to the calculated interaction energies. To validate the analytical PES, the second virial coefficient and the dilute gas shear viscosity and thermal conductivity of propane were computed. The dispersion part of the potential function was slightly adjusted such that quantitative agreement with the most accurate experimental data for the second virial coefficient at room temperature was achieved. The adjusted PES yields values for the three properties that are in very good agreement with the best experimental data at all temperatures.

  20. New Material Development for Surface Layer and Surface Technology in Tribology Science to Improve Energy Efficiency

    International Nuclear Information System (INIS)

    Ismail, R.; Tauviqirrahman, M.; Jamari; Schipper, D. J.

    2009-01-01

    This paper reviews the development of new material and surface technology in tribology and its contribution to energy efficiency. Two examples of the economic benefits, resulted from the optimum tribology in the transportation sector and the manufacturing industry are discussed. The new materials are proposed to modify the surface property by laminating the bulk material with thin layer/coating. Under a suitable condition, the thin layer on a surface can provide a combination of good wear, a low friction and corrosion resistance for the mechanical components. The innovation in layer technology results molybdenum disulfide (MoS2), diamond like carbon (DLC), cubic boron nitride (CBN) and diamond which perform satisfactory outcome. The application of the metallic coatings to carbon fibre reinforced polymer matrix composites (CFRP) has the capacity to provide considerable weight and power savings for many engineering components. The green material for lubricant and additives such as the use of sunflower oil which possesses good oxidation resistance and the use of mallee leaves as bio‐degradable solvent are used to answer the demand of the environmentally friendly material with good performance. The tribology research implementation for energy efficiency also touches the simple things around us such as: erasing the laser‐print in a paper with different abrasion techniques. For the technology in the engineering surface, the consideration for generating the suitable surface of the components in running‐in period has been discussed in order to prolong the components life and reduce the machine downtime. The conclusion, tribology can result in reducing manufacturing time, reducing the maintenance requirements, prolonging the service interval, improving durability, reliability and mechanical components life, and reducing harmful exhaust emission and waste. All of these advantages will increase the energy efficiency and the economic benefits.

  1. New Material Development for Surface Layer and Surface Technology in Tribology Science to Improve Energy Efficiency

    Science.gov (United States)

    Ismail, R.; Tauviqirrahman, M.; Jamari, Jamari; Schipper, D. J.

    2009-09-01

    This paper reviews the development of new material and surface technology in tribology and its contribution to energy efficiency. Two examples of the economic benefits, resulted from the optimum tribology in the transportation sector and the manufacturing industry are discussed. The new materials are proposed to modify the surface property by laminating the bulk material with thin layer/coating. Under a suitable condition, the thin layer on a surface can provide a combination of good wear, a low friction and corrosion resistance for the mechanical components. The innovation in layer technology results molybdenum disulfide (MoS2), diamond like carbon (DLC), cubic boron nitride (CBN) and diamond which perform satisfactory outcome. The application of the metallic coatings to carbon fibre reinforced polymer matrix composites (CFRP) has the capacity to provide considerable weight and power savings for many engineering components. The green material for lubricant and additives such as the use of sunflower oil which possesses good oxidation resistance and the use of mallee leaves as bio-degradable solvent are used to answer the demand of the environmentally friendly material with good performance. The tribology research implementation for energy efficiency also touches the simple things around us such as: erasing the laser-print in a paper with different abrasion techniques. For the technology in the engineering surface, the consideration for generating the suitable surface of the components in running-in period has been discussed in order to prolong the components life and reduce the machine downtime. The conclusion, tribology can result in reducing manufacturing time, reducing the maintenance requirements, prolonging the service interval, improving durability, reliability and mechanical components life, and reducing harmful exhaust emission and waste. All of these advantages will increase the energy efficiency and the economic benefits.

  2. A quantum chemical calculation of the potential energy surface in the formation of HOSO 2 from OH + SO 2

    Science.gov (United States)

    Sitha, Sanyasi; Jewell, Linda L.; Piketh, Stuart J.; Fourie, Gerhard

    2011-01-01

    The formation of HOSO 2 from OH and SO 2 has been thoroughly investigated using several different methods (MP2=Full, MP2=FC, B3LYP, HF and composite G∗ methods) and basis sets (6-31G(d,p), 6-31++G(d,p), 6-31++G(2d,2p), 6-31++G(2df,2p) and aug-cc-pVnZ). We have found two different possible transition state structures, one of which is a true transition state since it has a higher energy than the reactants and products (MP2=Full, MP2=FC and HF), while the other is not a true transition state since it has an energy which lies between that of the reactants and products (B3LYP and B3LYP based methods). The transition state structure (from MP2) has a twist angle of the OH fragment relative to the SO bond of the SO 2 fragment of -50.0°, whereas this angle is 26.7° in the product molecule. Examination of the displacement vectors confirms that this is a true transition state structure. The MP2=Full method with a larger basis set (MP2=Full/6-31++G(2df,2p)) predicts the enthalpy of reaction to be -112.8 kJ mol -1 which is close to the experimental value of -113.3 ± 6 kJ mol -1, and predicts a rather high barrier of 20.0 kJ mol -1. When the TS structure obtained by the MP2 method is used as the input for calculating the energetics using the QCISD/6-31++G(2df,2p) method, a barrier of 4.1 kJ mol -1 is obtained (ZPE corrected). The rate constant calculated from this barrier is 1.3 × 10 -13 cm 3 molecule -1 s -1. We conclude that while the MP2 methods correctly predict the TS from a structural point of view, higher level energy corrections are needed for estimation of exact barrier height.

  3. A topological screening heuristic for low-energy, high-index surfaces

    Science.gov (United States)

    Sun, Wenhao; Ceder, Gerbrand

    2018-03-01

    Robust ab initio investigations of nanoparticle surface properties require a method to identify candidate low-energy surface facets a priori. By assuming that low-energy surfaces are planes with high atomic density, we devise an efficient algorithm to screen for low-energy surface orientations, even if they have high (hkl) miller indices. We successfully predict the observed low-energy, high-index { 10 12 bar } and { 10 1 bar 4 } surfaces of hematite α-Fe2O3, the {311} surfaces of cuprite Cu2O, and the {112} surfaces of anatase TiO2. We further tabulate candidate low-energy surface orientations for nine of the most common binary oxide structures. Screened surfaces are found to be generally applicable across isostructural compounds with varying chemistries, although relative surface energies between facets may vary based on the preferred coordination of the surface atoms.

  4. The Global Energy Balance Archive (GEBA) version 2017: a database for worldwide measured surface energy fluxes

    Science.gov (United States)

    Wild, Martin; Ohmura, Atsumu; Schär, Christoph; Müller, Guido; Folini, Doris; Schwarz, Matthias; Zyta Hakuba, Maria; Sanchez-Lorenzo, Arturo

    2017-08-01

    The Global Energy Balance Archive (GEBA) is a database for the central storage of the worldwide measured energy fluxes at the Earth's surface, maintained at ETH Zurich (Switzerland). This paper documents the status of the GEBA version 2017 dataset, presents the new web interface and user access, and reviews the scientific impact that GEBA data had in various applications. GEBA has continuously been expanded and updated and contains in its 2017 version around 500 000 monthly mean entries of various surface energy balance components measured at 2500 locations. The database contains observations from 15 surface energy flux components, with the most widely measured quantity available in GEBA being the shortwave radiation incident at the Earth's surface (global radiation). Many of the historic records extend over several decades. GEBA contains monthly data from a variety of sources, namely from the World Radiation Data Centre (WRDC) in St. Petersburg, from national weather services, from different research networks (BSRN, ARM, SURFRAD), from peer-reviewed publications, project and data reports, and from personal communications. Quality checks are applied to test for gross errors in the dataset. GEBA has played a key role in various research applications, such as in the quantification of the global energy balance, in the discussion of the anomalous atmospheric shortwave absorption, and in the detection of multi-decadal variations in global radiation, known as global dimming and brightening. GEBA is further extensively used for the evaluation of climate models and satellite-derived surface flux products. On a more applied level, GEBA provides the basis for engineering applications in the context of solar power generation, water management, agricultural production and tourism. GEBA is publicly accessible through the internet via http://www.geba.ethz.ch. Supplementary data are available at https://doi.org/10.1594/PANGAEA.873078.

  5. Comparison of 3D Classical Trajectory and Transition-State Theory Reaction Cross Sections

    Science.gov (United States)

    Koeppl, G. W.; Karplus, Martin

    1970-10-01

    Although there is excellent agreement for a system such as H+H{sub 2} --> H{sub 2}+H, in which both the potential and the particle masses are symmetric, significant deviations occur for more asymmetric reactions. A detailed analysis show that the calculated differences are from the violation of two assumptions of transition-state theory.

  6. Transition State Gauche Effects Control the Torquoselectivities of the Electrocyclizations of Chiral 1-Azatrienes.

    Science.gov (United States)

    Patel, Ashay; Vella, Joseph R; Ma, Zhi-Xiong; Hsung, R P; Houk, K N

    2015-12-04

    Hsung et al. have reported a series of torquoselective electrocyclizations of chiral 1-azahexa-1E,3Z,5E-trienes that yield functionalized dihydropyridines. To understand the origins of the torquoselectivities of these azaelectrocyclizations, we modeled these electrocyclic ring closures using the M06-2X density functional. A new stereochemical model that rationalizes the observed 1,2 stereoinduction emerges from these computations. This model is an improvement and generalization of the "inside-alkoxy" model used to rationalize stereoselectivities of the 1,3-dipolar cycloaddition of chiral allyl ethers and emphasizes a stabilizing hyperconjugative effect, which we have termed a transition state gauche effect. This stereoelectronic effect controls the conformational preferences at the electrocyclization transition states, and only in one of the allowed disrotatory electrocyclization transition states is the ideal stereoelectronic arrangement achieved without the introduction of a steric clash. Computational experiments confirm the role of this effect as a stereodeterminant since substrates with electropositive groups and electronegative groups have different conformational preferences at the transition state and undergo ring closure with divergent stereochemical outcomes. This predicted reversal of stereoselectivity for the ring closures of several silyl substituted azatrienes have been demonstrated experimentally.

  7. Efficient Computation of Transition State Resonances and Reaction Rates from a Quantum Normal Form

    NARCIS (Netherlands)

    Schubert, Roman; Waalkens, Holger; Wiggins, Stephen

    2006-01-01

    A quantum version of a recent formulation of transition state theory in phase space is presented. The theory developed provides an algorithm to compute quantum reaction rates and the associated Gamov-Siegert resonances with very high accuracy. The algorithm is especially efficient for

  8. Wigner's dynamical transition state theory in phase space : classical and quantum

    NARCIS (Netherlands)

    Waalkens, Holger; Schubert, Roman; Wiggins, Stephen

    We develop Wigner's approach to a dynamical transition state theory in phase space in both the classical and quantum mechanical settings. The key to our development is the construction of a normal form for describing the dynamics in the neighbourhood of a specific type of saddle point that governs

  9. Molecular dynamics simulations from putative transition states of alpha-spectrin SH3 domain

    NARCIS (Netherlands)

    Periole, Xavier; Vendruscolo, Michele; Mark, Alan E.

    2007-01-01

    A series of molecular dynamics simulations in explicit solvent were started from nine structural models of the transition state of the SH3 domain of alpha-spectrin, which were generated by Lindorff Larsen et al. (Nat Struct Mol Biol 2004;11:443-449) using molecular dynamics simulations in which

  10. Tunneling in green tea: understanding the antioxidant activity of catechol-containing compounds. A variational transition-state theory study.

    Science.gov (United States)

    Tejero, Ismael; Gonzalez-García, Núria; Gonzalez-Lafont, Angels; Lluch, José M

    2007-05-09

    The catechol functionality present in the catechins is responsible for the protective effects exerted by green tea against a wide range of human diseases. High-level electronic structure calculations and canonical variational transition-state theory including multidimensional tunneling corrections have allowed us to understand the key factors of the antioxidant effectiveness of the catechol group. This catechol group forms two hydrogen bonds with the two oxygen atoms of the lipid peroxyl radical, leading to a very compact reactant complex. This fact produces an extremely narrow adiabatic potential-energy profile corresponding to the hydrogen abstraction by the peroxyl radical, which makes it possible for a huge tunneling contribution to take place. So, quantum-mechanical tunneling highly increases the corresponding rate constant value, in such a way that catechins become able to trap the lipid peroxyl radicals in a dominant competition with the very damaging free-radical chain-lipid peroxidation reaction.

  11. Reassessment of fission fragment angular distributions from continuum states in the context of transition-state theory

    International Nuclear Information System (INIS)

    Vaz, L.C.; Alexander, J.M.

    1983-01-01

    Fission angular distributions have been studied for years and have been treated as classic examples of transition-state theory. Early work involving composite nuclei of relatively low excitation energy Esup(*) ( 2 0 (K 2 0 = Psub(eff)T/(h/2π) 2 ) are presented along with comparissons of Psub(eff) to moments of inertia for saddle-point nuclei from the rotating liquid drop model. This model gives an excellent guide for the intermediate spin zone (30 < or approx. I < or approx. 65), while strong shell and/or pairing effects are evident for excitations less than < or approx. 35 MeV. Observations of strong anisotropies for very high-spin systems signal the demise of certain approximations commonly made in the theory, and suggestions are made toward this end. (orig.)

  12. Forces on nuclei moving on autoionizing molecular potential energy surfaces.

    Science.gov (United States)

    Moiseyev, Nimrod

    2017-01-14

    Autoionization of molecular systems occurs in diatomic molecules and in small biochemical systems. Quantum chemistry packages enable calculation of complex potential energy surfaces (CPESs). The imaginary part of the CPES is associated with the autoionization decay rate, which is a function of the molecular structure. Molecular dynamics simulations, within the framework of the Born-Oppenheimer approximation, require the definition of a force field. The ability to calculate the forces on the nuclei in bio-systems when autoionization takes place seems to rely on an understanding of radiative damages in RNA and DNA arising from the release of slow moving electrons which have long de Broglie wavelengths. This work addresses calculation of the real forces on the nuclei moving on the CPES. By using the transformation of the time-dependent Schrödinger equation, previously used by Madelung, we proved that the classical forces on nuclei moving on the CPES correlated with the gradient of the real part of the CPES. It was proved that the force on the nuclei of the metastable molecules is time independent although the probability to detect metastable molecules exponentially decays. The classical force is obtained from the transformed Schrödinger equation when ℏ=0 and the Schrödinger equation is reduced to the classical (Newtonian) equations of motion. The forces on the nuclei regardless on what potential energy surface they move (parent CPES or product real PESs) vary in time due to the autoionization process.

  13. An Energy Conservation Approach to Adsorbate-Induced Surface Stress and the Extraction of Binding Energy Using Nanomechanics

    Energy Technology Data Exchange (ETDEWEB)

    Pinnaduwage, Lal A [ORNL; Boiadjiev, Vassil I [ORNL; Fernando, G. W. [University of Connecticut, Storrs; Hawk, J. E. [Oak Ridge National Laboratory (ORNL); Wijewardhana, L.C. R. [University of Cincinnati; Gehl, Anthony C [ORNL

    2008-01-01

    Microcantilevers are ideally-suited for the study of surface phenomena due to their large surface-to-volume ratios, which amplify surface effects. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. When the excess energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such experiments were conducted for three binding processes in vapor phase experiments: physisorption, hydrogen bonding, and chemisorption. To our knowledge, such an energy conservation approach has not been taken into account in adsorbate-induced surface effect investigations. Furthermore, these experiments illustrate that detailed molecular-level information on binding energies can be extracted from this simple micromechanical sensor.

  14. Low-energy particle treatment of GaAs surface

    International Nuclear Information System (INIS)

    Pincik, E.; Ivanco, J.; Brunner, R.; Jergel, M.; Falcony, C.; Ortega, L.; Kucera, J. M.

    2002-01-01

    The paper presents results of a complex study of surface properties of high-doped (2x10 18 cm -3 ) and semi-insulating GaAs after an interaction with the particles coming from low-energy ion sources such as RF plasma and ion beams. The virgin samples were mechano-chemically polished liquid-encapsulated Czochralski-grown GaAs (100) oriented wafers. The crystals were mounted on the grounded electrode (holder). The mixture Ar+H 2 as well as O 2 and CF 4 were used as working gases: In addition, a combination of two different in-situ exposures was applied, such as e.g. hydrogen and oxygen. Structural, electrical and optical properties of the exposed surfaces were investigated using X-ray diffraction at grazing incidence, quasi-static and high-frequency C-V curve measurements, deep-level transient spectroscopy, photo-reflectance, and photoluminescence. Plasma and ion beam exposures were performed in a commercial RF capacitively coupled plasma equipment SECON XPL-200P and a commercial LPAI device, respectively. The evolution of surface properties as a function of the pressure of working gas and the duration of exposure was observed. (Authors)

  15. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  16. Surface energy loss processes in XPS studied by absolute reflection electron energy loss spectroscopy

    International Nuclear Information System (INIS)

    Nagatomi, T.; Goto, K.

    2010-01-01

    The results of the investigation of the inelastic interaction of 300-3000 eV electrons with the Ni and Au surfaces by the analysis of absolute reflection electron energy loss spectroscopy (REELS) spectra were described. The present analysis enables the inelastic mean free path (IMFP), surface excitation parameter (SEP) and differential SEP (DSEP) to be obtained simultaneously from an absolute REELS spectrum. The obtained IMFPs for Ni and Au showed a good agreement with those calculated using the TPP-2M predictive equation. The present SEPs determined for Ni and Au were fitted to the Chen's formula describing the dependence of the SEP on the electron energy, and material parameters for Ni and Au in Chen's formula were proposed. The present DESPs were compared with the theoretical results, and a reasonable agreement between the experimentally determined DSEPs and theoretical results was confirmed. The MC modeling of calculating the REELS spectrum, in which energy loss processes due to surface excitations are taken into account, was also described. The IMFP, SEP and DSEP determined by the present absolute REELS analysis were employed to describe energy loss processes by inelastic scattering in the proposed MC simulation. The simulated REELS spectra were found to be in a good agreement with the experimental spectra for both Ni and Au.

  17. Nanoscale control of energy and matter in plasma-surface interactions: towards energy-efficient nanotech

    Science.gov (United States)

    Ostrikov, Kostya

    2010-11-01

    This presentation focuses on the plasma issues related to the solution of the grand challenge of directing energy and matter at nanoscales. This ability is critical for the renewable energy and energy-efficient technologies for sustainable future development. It will be discussed how to use environmentally and human health benign non-equilibrium plasma-solid systems and control the elementary processes of plasma-surface interactions to direct the fluxes of energy and matter at multiple temporal and spatial scales. In turn, this makes it possible to achieve the deterministic synthesis of self- organised arrays of metastable nanostructures in the size range beyond the reach of the present-day nanofabrication. Such structures have tantalising prospects to enhance performance of nanomaterials in virtually any area of human activity yet remain almost inaccessible because the Nature's energy minimisation rules allow only a small number of stable equilibrium states. By using precisely controlled and kinetically fast nanoscale transfer of energy and matter under non-equilibrium conditions and harnessing numerous plasma- specific controls of species creation, delivery to the surface, nucleation and large-scale self-organisation of nuclei and nanostructures, the arrays of metastable nanostructures can be created, arranged, stabilised, and further processed to meet the specific requirements of the envisaged applications. These approaches will eventually lead to faster, unprecedentedly- clean, human-health-friendly, and energy-efficient nanoscale synthesis and processing technologies for the next-generation renewable energy and light sources, biomedical devices, information and communication systems, as well as advanced functional materials for applications ranging from basic food, water, health and clean environment needs to national security and space missions.

  18. Surface layer scintillometry for estimating the sensible heat flux component of the surface energy balance

    Directory of Open Access Journals (Sweden)

    M. J. Savage

    2010-01-01

    Full Text Available The relatively recently developed scintillometry method, with a focus on the dual-beam surface layer scintillometer (SLS, allows boundary layer atmospheric turbulence, surface sensible heat and momentum flux to be estimated in real-time. Much of the previous research using the scintillometer method has involved the large aperture scintillometer method, with only a few studies using the SLS method. The SLS method has been mainly used by agrometeorologists, hydrologists and micrometeorologists for atmospheric stability and surface energy balance studies to obtain estimates of sensible heat from which evaporation estimates representing areas of one hectare or larger are possible. Other applications include the use of the SLS method in obtaining crucial input parameters for atmospheric dispersion and turbulence models. The SLS method relies upon optical scintillation of a horizontal laser beam between transmitter and receiver for a separation distance typically between 50 and 250 m caused by refractive index inhomogeneities in the atmosphere that arise from turbulence fluctuations in air temperature and to a much lesser extent the fluctuations in water vapour pressure. Measurements of SLS beam transmission allow turbulence of the atmosphere to be determined, from which sub-hourly, real-time and in situ path-weighted fluxes of sensible heat and momentum may be calculated by application of the Monin-Obukhov similarity theory. Unlike the eddy covariance (EC method for which corrections for flow distortion and coordinate rotation are applied, no corrections to the SLS measurements, apart from a correction for water vapour pressure, are applied. Also, path-weighted SLS estimates over the propagation path are obtained. The SLS method also offers high temporal measurement resolution and usually greater spatial coverage compared to EC, Bowen ratio energy balance, surface renewal and other sensible heat measurement methods. Applying the shortened surface

  19. Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacherjee, Aditi, E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu; Attar, Andrew R., E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Leone, Stephen R., E-mail: srl@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States)

    2016-03-28

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH{sub 2} =CHCH{sub 2}I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground ({sup 2}P{sub 3/2}, I) and spin-orbit excited ({sup 2}P{sub 1/2}, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N{sub 4/5} edge (45–60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive n{sub I}σ{sup ∗}{sub C—I} excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ{sup ∗} states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ{sup ∗}(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs–65 fs and decay completely by 145 fs–185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic

  20. The calculation of surface free energy based on embedded atom method for solid nickel

    International Nuclear Information System (INIS)

    Luo Wenhua; Hu Wangyu; Su Kalin; Liu Fusheng

    2013-01-01

    Highlights: ► A new solution for accurate prediction of surface free energy based on embedded atom method was proposed. ► The temperature dependent anisotropic surface energy of solid nickel was obtained. ► In isotropic environment, the approach does not change most predictions of bulk material properties. - Abstract: Accurate prediction of surface free energy of crystalline metals is a challenging task. The theory calculations based on embedded atom method potentials often underestimate surface free energy of metals. With an analytical charge density correction to the argument of the embedding energy of embedded atom method, an approach to improve the prediction for surface free energy is presented. This approach is applied to calculate the temperature dependent anisotropic surface energy of bulk nickel and surface energies of nickel nanoparticles, and the obtained results are in good agreement with available experimental data.

  1. Vibrational Surface Electron-Energy-Loss Spectroscopy Probes Confined Surface-Phonon Modes

    Directory of Open Access Journals (Sweden)

    Hugo Lourenço-Martins

    2017-12-01

    Full Text Available Recently, two reports [Krivanek et al. Nature (London 514, 209 (2014NATUAS0028-083610.1038/nature13870, Lagos et al. Nature (London 543, 529 (2017NATUAS0028-083610.1038/nature21699] have demonstrated the amazing possibility to probe vibrational excitations from nanoparticles with a spatial resolution much smaller than the corresponding free-space phonon wavelength using electron-energy-loss spectroscopy (EELS. While Lagos et al. evidenced a strong spatial and spectral modulation of the EELS signal over a nanoparticle, Krivanek et al. did not. Here, we show that discrepancies among different EELS experiments as well as their relation to optical near- and far-field optical experiments [Dai et al. Science 343, 1125 (2014SCIEAS0036-807510.1126/science.1246833] can be understood by introducing the concept of confined bright and dark surface phonon modes, whose density of states is probed by EELS. Such a concise formalism is the vibrational counterpart of the broadly used formalism for localized surface plasmons [Ouyang and Isaacson Philos. Mag. B 60, 481 (1989PMABDJ1364-281210.1080/13642818908205921, García de Abajo and Aizpurua Phys. Rev. B 56, 15873 (1997PRBMDO0163-182910.1103/PhysRevB.56.15873, García de Abajo and Kociak Phys. Rev. Lett. 100, 106804 (2008PRLTAO0031-900710.1103/PhysRevLett.100.106804, Boudarham and Kociak Phys. Rev. B 85, 245447 (2012PRBMDO1098-012110.1103/PhysRevB.85.245447]; it makes it straightforward to predict or interpret phenomena already known for localized surface plasmons such as environment-related energy shifts or the possibility of 3D mapping of the related surface charge densities [Collins et al. ACS Photonics 2, 1628 (2015APCHD52330-402210.1021/acsphotonics.5b00421].

  2. Delta self-consistent field method to obtain potential energy surfaces of excited molecules on surfaces

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Olsen, Thomas; Engelund, Mads

    2008-01-01

    is a density-functional method closely resembling standard density-functional theory (DFT), the only difference being that in Delta SCF one or more electrons are placed in higher lying Kohn-Sham orbitals instead of placing all electrons in the lowest possible orbitals as one does when calculating the ground......-state energy within standard DFT. We extend the Delta SCF method by allowing excited electrons to occupy orbitals which are linear combinations of Kohn-Sham orbitals. With this extra freedom it is possible to place charge locally on adsorbed molecules in the calculations, such that resonance energies can...... be estimated, which is not possible in traditional Delta SCF because of very delocalized Kohn-Sham orbitals. The method is applied to N2, CO, and NO adsorbed on different metallic surfaces and compared to ordinary Delta SCF without our modification, spatially constrained DFT, and inverse...

  3. Nuclear momentum distribution and potential energy surface in hexagonal ice

    Science.gov (United States)

    Lin, Lin; Morrone, Joseph; Car, Roberto; Parrinello, Michele

    2011-03-01

    The proton momentum distribution in ice Ih has been recently measured by deep inelastic neutron scattering and calculated from open path integral Car-Parrinello simulation. Here we report a detailed investigation of the relation between momentum distribution and potential energy surface based on both experiment and simulation results. The potential experienced by the proton is largely harmonic and characterized by 3 principal frequencies, which can be associated to weighted averages of phonon frequencies via lattice dynamics calculations. This approach also allows us to examine the importance of quantum effects on the dynamics of the oxygen nuclei close to the melting temperature. Finally we quantify the anharmonicity that is present in the potential acting on the protons. This work is supported by NSF and by DOE.

  4. Transition-state analysis of a Vmax mutant of AMP nucleosidase by the application of heavy-atom kinetic isotope effects

    International Nuclear Information System (INIS)

    Parkin, D.W.; Mentch, F.; Banks, G.A.; Horenstein, B.A.; Schramm, V.L.

    1991-01-01

    The transition state of the V max mutant of AMP nucleosidase from Azotobacter vinelandii has been characterized by heavy-atom kinetic isotope effects in the presence and absence of MgATP, the allosteric activator. The enzyme catalyzes hydrolysis of the N-glycosidic bond of AMP at approximately 2% of the rate of the normal enzyme with only minor changes in the K m for substrate, the activation constant for MgATP, and the K i for formycin 5'-phosphate, a tight-binding competitive inhibitor. Isotope effects were measured as a function of the allosteric activator concentration that increases the turnover number of the enzyme from 0.006 s -1 . The kinetic isotope effects were measured with the substrates [1'- 3 H]AMP, [2'- 2 H]AMP, [9- 15 N]AMP, and [1',9- 14 C, 15 N]AMP. All substrates gave significant kinetic isotope effects in a pattern that establishes that the reaction expresses intrinsic kinetic isotope effects in the presence or absence of MgATP. Transition-state analysis using bond-energy and bond-order vibrational analysis indicated that the transition state for the mutant enzyme has a similar position in the reaction coordinate compared to that for the normal enzyme. The mutant enzyme is less effective in stabilizing the carbocation-like intermediate and in the ability to protonate N7 of adenine to create a better leaving group. This altered transition-state structure was confirmed by an altered substrate specificity for the mutant protein

  5. High Accuracy Potential Energy Surface, Dipole Moment Surface, Rovibrational Energies and Line List Calculations for ^{14}NH_3

    Science.gov (United States)

    Coles, Phillip; Yurchenko, Sergei N.; Polyansky, Oleg; Kyuberis, Aleksandra; Ovsyannikov, Roman I.; Zobov, Nikolay Fedorovich; Tennyson, Jonathan

    2017-06-01

    We present a new spectroscopic potential energy surface (PES) for ^{14}NH_3, produced by refining a high accuracy ab initio PES to experimental energy levels taken predominantly from MARVEL. The PES reproduces 1722 matched J=0-8 experimental energies with a root-mean-square error of 0.035 cm-1 under 6000 cm^{-1} and 0.059 under 7200 cm^{-1}. In conjunction with a new DMS calculated using multi reference configuration interaction (MRCI) and H=aug-cc-pVQZ, N=aug-cc-pWCVQZ basis sets, an infrared (IR) line list has been computed which is suitable for use up to 2000 K. The line list is used to assign experimental lines in the 7500 - 10,500 cm^{-1} region and previously unassigned lines in HITRAN in the 6000-7000 cm^{-1} region. Oleg L. Polyansky, Roman I. Ovsyannikov, Aleksandra A. Kyuberis, Lorenzo Lodi, Jonathan Tennyson, Andrey Yachmenev, Sergei N. Yurchenko, Nikolai F. Zobov, J. Mol. Spec., 327 (2016) 21-30 Afaf R. Al Derzia, Tibor Furtenbacher, Jonathan Tennyson, Sergei N. Yurchenko, Attila G. Császár, J. Quant. Spectrosc. Rad. Trans., 161 (2015) 117-130

  6. The puckering free-energy surface of proline

    Directory of Open Access Journals (Sweden)

    Di Wu

    2013-03-01

    Full Text Available Proline has two preferred puckering states, which are often characterized by the pseudorotation phase angle and amplitude. Although proline's five endocyclic torsion angles can be utilized to calculate the phase angle and amplitude, it is not clear if there is any direct correlation between each torsion angle and the proline-puckering pathway. Here we have designed five proline puckering pathways utilizing each torsion angle χj (j = 1∼5 as the reaction coordinate. By examining the free-energy surfaces of the five puckering pathways, we find they can be categorized into two groups. The χ2 pathway (χ2 is about the Cβ—Cγ bond is especially meaningful in describing proline puckering: it changes linearly with the puckering amplitude and symmetrically with the phase angle. Our results show that this conclusion applies to both trans and cis proline conformations. We have also analyzed the correlations of proline puckering and its backbone torsion angles ϕ and ψ. We show proline has preferred puckering states at the specific regions of ϕ, ψ angles. Interestingly, the shapes of ψ-χ2 free-energy surfaces are similar among the trans proline in water, cis proline in water and cis proline in the gas phase, but they differ substantially from that of the trans proline in the gas phase. Our calculations are conducted using molecular simulations; we also verify our results using the proline conformations selected from the Protein Data Bank. In addition, we have compared our results with those calculated by the quantum mechanical methods.

  7. Origin of the Hawaiian rainforest and its transition states in long-term primary succession

    Science.gov (United States)

    Mueller-Dombois, D.; Boehmer, H. J.

    2013-07-01

    This paper addresses the question of transition states in the Hawaiian rainforest ecosystem with emphasis on their initial developments. Born among volcanoes in the north central Pacific about 4 million years ago, the Hawaiian rainforest became assembled from spores of algae, fungi, lichens, bryophytes, ferns and from seeds of about 275 flowering plants that over the millennia evolved into ca. 1000 endemic species. Outstanding among the forest builders were the tree ferns (Cibotium spp.) and the 'ōhi'a lehua trees (Metrosideros spp.), which still dominate the Hawaiian rainforest ecosystem today. The structure of this forest is simple. The canopy in closed mature rainforests is dominated by cohorts of Metrosideros polymorpha and the undergrowth by tree fern species of Cibotium. When a new lava flow cuts through this forest, kipuka are formed, i.e., islands of remnant vegetation. On the new volcanic substrate, the assemblage of plant life forms is similar to the assemblage during the evolution of this system. In open juvenile forests, a mat-forming fern, the uluhe fern (Dicranopteris linearis), becomes established. It inhibits further regeneration of the dominant 'ōhi'a tree, thereby reinforcing the cohort structure of the canopy guild. In the later part of its life cycle, the canopy guild breaks down often in synchrony. The trigger is hypothesized to be a climatic perturbation. After the disturbance, the forest becomes reestablished in about 30-40 yr. As the volcanic surfaces age, they go from a mesotrophic to a eutrophic phase, reaching a biophilic nutrient climax by about 1-25 K yr. Thereafter, a regressive oligotrophic phase follows; the soils become exhausted of nutrients. The shield volcanoes break down. Marginally, forest habitats change into bogs and stream ecosystems. The broader 'ōhi'a rainforest redeveloping in the more dissected landscapes of the older islands loses stature, often forming large gaps that are invaded by the aluminum tolerant uluhe fern

  8. Origin of the Hawaiian rainforest and its transition states in long-term primary succession

    Directory of Open Access Journals (Sweden)

    D. Mueller-Dombois

    2013-07-01

    Full Text Available This paper addresses the question of transition states in the Hawaiian rainforest ecosystem with emphasis on their initial developments. Born among volcanoes in the north central Pacific about 4 million years ago, the Hawaiian rainforest became assembled from spores of algae, fungi, lichens, bryophytes, ferns and from seeds of about 275 flowering plants that over the millennia evolved into ca. 1000 endemic species. Outstanding among the forest builders were the tree ferns (Cibotium spp. and the 'ōhi'a lehua trees (Metrosideros spp., which still dominate the Hawaiian rainforest ecosystem today. The structure of this forest is simple. The canopy in closed mature rainforests is dominated by cohorts of Metrosideros polymorpha and the undergrowth by tree fern species of Cibotium. When a new lava flow cuts through this forest, kipuka are formed, i.e., islands of remnant vegetation. On the new volcanic substrate, the assemblage of plant life forms is similar to the assemblage during the evolution of this system. In open juvenile forests, a mat-forming fern, the uluhe fern (Dicranopteris linearis, becomes established. It inhibits further regeneration of the dominant 'ōhi'a tree, thereby reinforcing the cohort structure of the canopy guild. In the later part of its life cycle, the canopy guild breaks down often in synchrony. The trigger is hypothesized to be a climatic perturbation. After the disturbance, the forest becomes reestablished in about 30–40 yr. As the volcanic surfaces age, they go from a mesotrophic to a eutrophic phase, reaching a biophilic nutrient climax by about 1–25 K yr. Thereafter, a regressive oligotrophic phase follows; the soils become exhausted of nutrients. The shield volcanoes break down. Marginally, forest habitats change into bogs and stream ecosystems. The broader 'ōhi'a rainforest redeveloping in the more dissected landscapes of the older islands loses stature, often forming large gaps that are invaded by the aluminum

  9. A metamaterial electromagnetic energy rectifying surface with high harvesting efficiency

    Directory of Open Access Journals (Sweden)

    Xin Duan

    2016-12-01

    Full Text Available A novel metamaterial rectifying surface (MRS for electromagnetic energy capture and rectification with high harvesting efficiency is presented. It is fabricated on a three-layer printed circuit board, which comprises an array of periodic metamaterial particles in the shape of mirrored split rings, a metal ground, and integrated rectifiers employing Schottky diodes. Perfect impedance matching is engineered at two interfaces, i.e. one between free space and the surface, and the other between the metamaterial particles and the rectifiers, which are connected through optimally positioned vias. Therefore, the incident electromagnetic power is captured with almost no reflection by the metamaterial particles, then channeled maximally to the rectifiers, and finally converted to direct current efficiently. Moreover, the rectifiers are behind the metal ground, avoiding the disturbance of high power incident electromagnetic waves. Such a MRS working at 2.45 GHz is designed, manufactured and measured, achieving a harvesting efficiency up to 66.9% under an incident power density of 5 mW/cm2, compared with a simulated efficiency of 72.9%. This high harvesting efficiency makes the proposed MRS an effective receiving device in practical microwave power transmission applications.

  10. A metamaterial electromagnetic energy rectifying surface with high harvesting efficiency

    Science.gov (United States)

    Duan, Xin; Chen, Xing; Zhou, Lin

    2016-12-01

    A novel metamaterial rectifying surface (MRS) for electromagnetic energy capture and rectification with high harvesting efficiency is presented. It is fabricated on a three-layer printed circuit board, which comprises an array of periodic metamaterial particles in the shape of mirrored split rings, a metal ground, and integrated rectifiers employing Schottky diodes. Perfect impedance matching is engineered at two interfaces, i.e. one between free space and the surface, and the other between the metamaterial particles and the rectifiers, which are connected through optimally positioned vias. Therefore, the incident electromagnetic power is captured with almost no reflection by the metamaterial particles, then channeled maximally to the rectifiers, and finally converted to direct current efficiently. Moreover, the rectifiers are behind the metal ground, avoiding the disturbance of high power incident electromagnetic waves. Such a MRS working at 2.45 GHz is designed, manufactured and measured, achieving a harvesting efficiency up to 66.9% under an incident power density of 5 mW/cm2, compared with a simulated efficiency of 72.9%. This high harvesting efficiency makes the proposed MRS an effective receiving device in practical microwave power transmission applications.

  11. Quasilocal energy and surface geometry of Kerr spacetime

    Science.gov (United States)

    Yu, Chengjie; Liu, Jian-Liang

    2017-04-01

    We study the quasilocal energy (QLE) and the surface geometry for Kerr spacetime in the Boyer-Lindquist coordinates without taking the slow rotation approximation. We also consider in the region r ≤2 m , which is inside the ergosphere. For a certain region, r >rk(a ) , the Gaussian curvature of the surface with constant t , r is positive, and for r >√{3 }a the critical value of the QLE is positive. We found that the three curves: the outer horizon r =r+(a ), r =rk(a ) and r =√{3 }a intersect at the point a =√{3 }m /2 , which is the limit for the horizon to be isometrically embedded into R3. The numerical result indicates that the Kerr QLE is monotonically decreasing to the ADM m from the region inside the ergosphere to large r . Based on the second law of black hole dynamics, the QLE is increasing with respect to the irreducible mass Mir. From the results of Chen-Wang-Yau, we conclude that in a certain region, r >rh(a ), the critical value of the Kerr QLE is a global minimum.

  12. On analogy between surface fracture energy and activaiton energy of bonding in solid phase

    International Nuclear Information System (INIS)

    Shatinsky, V.F.; Kopylov, V.I.

    1976-01-01

    This article makes an attempt on the basis of experimental data to compare the processes of failure and formation of a bond by comparing the energy consumptions going in one case or another into initial plastic deformation of a certain volume and the further interatomic interaction at the boundary (separation, formation of the bond). Two values characterizing the different processes - the unit failure energy γ and the activation energy for the formation of a bond Q - are compared. It has been established that the energy consumed for plastic deformation and adhesion interaction of atoms on the surface of microprojections and providing the formation of a bond in the solid-phase condition is close to the specific failure energy. The equality of energies consumed for the formation of a bond and failure allows to make use of any of those characteristics to calculate parameters of processes of the formation of a bond and failure. It seems to be convenient in the analysis of the failure process at a temperature when the ductility is high and methodically, the crack propagation is hard to investigate, in particular to estimate the volume of the preliminary failure zone. Having determined γ from the contact interaction data, the strength characteristics can be evaluated. (author)

  13. Crystallization of glass-forming liquids: Specific surface energy

    International Nuclear Information System (INIS)

    Schmelzer, Jürn W. P.; Abyzov, Alexander S.

    2016-01-01

    A generalization of the Stefan-Skapski-Turnbull relation for the melt-crystal specific interfacial energy is developed in terms of the generalized Gibbs approach extending its standard formulation to thermodynamic non-equilibrium states. With respect to crystal nucleation, this relation is required in order to determine the parameters of the critical crystal clusters being a prerequisite for the computation of the work of critical cluster formation. As one of its consequences, a relation for the dependence of the specific surface energy of critical clusters on temperature and pressure is derived applicable for small and moderate deviations from liquid-crystal macroscopic equilibrium states. Employing the Stefan-Skapski-Turnbull relation, general expressions for the size and the work of formation of critical crystal clusters are formulated. The resulting expressions are much more complex as compared to the respective relations obtained via the classical Gibbs theory. Latter relations are retained as limiting cases of these more general expressions for moderate undercoolings. By this reason, the formulated, here, general relations for the specification of the critical cluster size and the work of critical cluster formation give a key for an appropriate interpretation of a variety of crystallization phenomena occurring at large undercoolings which cannot be understood in terms of the Gibbs’ classical treatment.

  14. Transition state theory thermal rate constants and RRKM-based branching ratios for the N((2)D) + CH(4) reaction based on multi-state and multi-reference ab initio calculations of interest for the Titan's chemistry.

    Science.gov (United States)

    Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice

    2012-10-30

    Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH. Copyright © 2012 Wiley Periodicals, Inc.

  15. An accurate global potential energy surface, dipole moment surface, and rovibrational frequencies for NH3

    Science.gov (United States)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2008-12-01

    A global potential energy surface (PES) that includes short and long range terms has been determined for the NH3 molecule. The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations and the internally contracted averaged coupled-pair functional electronic structure methods have been used in conjunction with very large correlation-consistent basis sets, including diffuse functions. Extrapolation to the one-particle basis set limit was performed and core correlation and scalar relativistic contributions were included directly, while the diagonal Born-Oppenheimer correction was added. Our best purely ab initio PES, denoted "mixed," is constructed from two PESs which differ in whether the ic-ACPF higher-order correlation correction was added or not. Rovibrational transition energies computed from the mixed PES agree well with experiment and the best previous theoretical studies, but most importantly the quality does not deteriorate even up to 10300cm-1 above the zero-point energy (ZPE). The mixed PES was improved further by empirical refinement using the most reliable J =0-2 rovibrational transitions in the HITRAN 2004 database. Agreement between high-resolution experiment and rovibrational transition energies computed from our refined PES for J =0-6 is excellent. Indeed, the root mean square (rms) error for 13 HITRAN 2004 bands for J =0-2 is 0.023cm-1 and that for each band is always ⩽0.06cm-1. For J =3-5 the rms error is always ⩽0.15cm-1. This agreement means that transition energies computed with our refined PES should be useful in the assignment of new high-resolution NH3 spectra and in correcting mistakes in previous assignments. Ideas for further improvements to our refined PES and for extension to other isotopolog are discussed.

  16. Potential Energy Surface of NO on Pt(997: Adsorbed States and Surface Diffusion

    Directory of Open Access Journals (Sweden)

    N. Tsukahara

    2012-01-01

    Full Text Available The potential energy surface (PES of NO on Pt(997 has been elucidated: the adsorption states and diffusion processes of NO on Pt(997 at low coverage were investigated by using infrared reflection absorption spectroscopy (IRAS and scanning tunneling microscopy (STM. When NO molecules adsorb on a surface at a low temperature (11 K, each molecule transiently migrates on the surface from the first impact point to a possible adsorption site. We found that there are four stable adsorption sites for NO on Pt(997: a bridge site of the upper step, an fcc- (or hcp- hollow site of the terrace, an on-top site of the terrace, and an fcc-hollow site of the lower step. At higher temperatures above 45 K, NO molecules start to migrate thermally to more stable adsorption sites on a terrace, and they are finally trapped at the bridge sites of the step, which are the most stable among the four sites.

  17. Roughness, surface energy, and superficial damages of CAD/CAM materials after surface treatment.

    Science.gov (United States)

    Strasser, Thomas; Preis, Verena; Behr, Michael; Rosentritt, Martin

    2018-02-05

    The aim of this study was to examine the effects of surface pre-treatment on CAD/CAM materials including ceramics, zirconia, resin-infiltrated ceramic, and resin-based composite. Specimens were made of ten CAD/CAM materials (Celtra Duo, Degudent, D; Vita Suprinity, Vita, D; E.max CAD, Ivoclar-Vivadent, FL; E.max ZirCAD, Ivoclar-Vivadent, FL; Vita Enamic, Vita, D; Cerasmart, GC, B; LAVA Ultimate, 3M, D; SHOFU Block HC, SHOFU, US; Grandio Blocs, VOCO, D; BRILLIANT Crios, Coltene, CH) and pretreated to represent clinical procedures (Hf 20 s/5%; phosphoric acid 20 s/37%; Monobond etch and prime (Ivoclar-Vivadent, FL); water-cooled diamond bur (80 μm; 4 μm); Al 2 O 3 -blasting (50 μm/1 bar, 50 μm/2 bar, 120 μm/1 bar, 120 μm/2 bar); untreated; manufacturer's instructions). SEM-analysis (Phenom, FEI, NL) of the surfaces was performed (magnifications ≤ 10,000×). Roughness values R a , R z (KJ 3D, Keyence, J), and surface energy SE (OCA15 plus, SCA20, DataPhysics, D) were determined (statistics: non-parametric Mann-Whitney U test/Kruskal-Wallis test for independent specimen, α = 0.05). Kruskal-Wallis revealed significant (p CAD/CAM materials require individual pre-treatment for optimized and protective surface activation. Cementation is a key factor for clinical success. Given the variety of available CAD/CAM materials, specific procedures are needed.

  18. An energy conservation approach to adsorbate-induced surface stress and the extraction of binding energy using nanomechanics

    Science.gov (United States)

    Pinnaduwage, Lal A.; Boiadjiev, Vassil I.; Hawk, John E.; Gehl, Anthony C.; Fernando, Gayanath W.; Rohana Wijewardhana, L. C.

    2008-03-01

    Surface stress induced by molecular adsorption in three different binding processes has been studied experimentally using a microcantilever sensor. A comprehensive free-energy analysis based on an energy conservation approach is proposed to explain the experimental observations. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. The released binding energy appears to be almost exclusively channeled to the surface energy, and energy distribution to other channels, including heat, appears to be inactive for this micromechanical system. When this excess surface energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such vapor phase experiments were conducted for three binding processes: physisorption, hydrogen bonding, and chemisorption. Binding energies for these three processes were also estimated.

  19. An energy conservation approach to adsorbate-induced surface stress and the extraction of binding energy using nanomechanics

    Energy Technology Data Exchange (ETDEWEB)

    Pinnaduwage, Lal A; Boiadjiev, Vassil I; Hawk, John E; Gehl, Anthony C [Oak Ridge National Laboratory, PO Box 2008, Oak Ridge, TN 37831-6122 (United States); Fernando, Gayanath W [Physics Department, University of Connecticut, Storrs, CT 06269 (United States); Wijewardhana, L C Rohana [Physics Department, University of Cincinnati, Cincinnati, OH 45221 (United States)

    2008-03-12

    Surface stress induced by molecular adsorption in three different binding processes has been studied experimentally using a microcantilever sensor. A comprehensive free-energy analysis based on an energy conservation approach is proposed to explain the experimental observations. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. The released binding energy appears to be almost exclusively channeled to the surface energy, and energy distribution to other channels, including heat, appears to be inactive for this micromechanical system. When this excess surface energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such vapor phase experiments were conducted for three binding processes: physisorption, hydrogen bonding, and chemisorption. Binding energies for these three processes were also estimated.

  20. Quantifying the mechanism of phosphate monoester hydrolysis in aqueous solution by evaluating the relevant ab initio QM/MM free-energy surfaces.

    Science.gov (United States)

    Plotnikov, Nikolay V; Prasad, B Ram; Chakrabarty, Suman; Chu, Zhen T; Warshel, Arieh

    2013-10-24

    Understanding the nature of the free-energy surfaces for phosphate hydrolysis is a prerequisite for understanding the corresponding key chemical reactions in biology. Here, the challenge has been to move to careful ab initio QM/MM (QM(ai)/MM) free-energy calculations, where obtaining converging results is very demanding and computationally expensive. This work describes such calculations, focusing on the free-energy surface for the hydrolysis of phosphate monoesters, paying special attention to the comparison between the one water (1W) and two water (2W) paths for the proton-transfer (PT) step. This issue has been explored before by energy minimization with implicit solvent models and by nonsystematic QM/MM energy minimization, as well as by nonsystematic free-energy mapping. However, no study has provided the needed reliable 2D (3D) surfaces that are necessary for reaching concrete conclusions. Here we report a systematic evaluation of the 2D (3D) free-energy maps for several relevant systems, comparing the results of QM(ai)/MM and QM(ai)/implicit solvent surfaces, and provide an advanced description of the relevant energetics. It is found that the 1W path for the hydrolysis of the methyl diphosphate (MDP) trianion is 6-9 kcal/mol higher than that the 2W path. This difference becomes slightly larger in the presence of the Mg(2+) ion because this ion reduces the pKa of the conjugated acid form of the phosphate oxygen that accepts the proton. Interestingly, the BLYP approach (which has been used extensively in some studies) gives a much smaller difference between the 1W and 2W activation barriers. At any rate, it is worth pointing out that the 2W transition state for the PT is not much higher that the common plateau that serves as the starting point of both the 1W and 2W PT paths. Thus, the calculated catalytic effects of proteins based on the 2W PT mechanistic model are not expected to be different from the catalytic effects predicted using the 1W PT mechanistic

  1. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  2. On the measurement of the surface energy budget over a land ...

    Indian Academy of Sciences (India)

    The measurement of surface energy balance over a land surface in an open area in Bangalore is reported. Measurements of all variables needed to calculate the surface energy balance on time scales longer than a week are made. Components of radiative fluxes are measured while sensible and latent heat fluxes are ...

  3. Quantifying Surface Energy Flux Estimation Uncertainty Using Land Surface Temperature Observations

    Science.gov (United States)

    French, A. N.; Hunsaker, D.; Thorp, K.; Bronson, K. F.

    2015-12-01

    Remote sensing with thermal infrared is widely recognized as good way to estimate surface heat fluxes, map crop water use, and detect water-stressed vegetation. When combined with net radiation and soil heat flux data, observations of sensible heat fluxes derived from surface temperatures (LST) are indicative of instantaneous evapotranspiration (ET). There are, however, substantial reasons LST data may not provide the best way to estimate of ET. For example, it is well known that observations and models of LST, air temperature, or estimates of transport resistances may be so inaccurate that physically based model nevertheless yield non-meaningful results. Furthermore, using visible and near infrared remote sensing observations collected at the same time as LST often yield physically plausible results because they are constrained by less dynamic surface conditions such as green fractional cover. Although sensitivity studies exist that help identify likely sources of error and uncertainty, ET studies typically do not provide a way to assess the relative importance of modeling ET with and without LST inputs. To better quantify model benefits and degradations due to LST observational inaccuracies, a Bayesian uncertainty study was undertaken using data collected in remote sensing experiments at Maricopa, Arizona. Visible, near infrared and thermal infrared data were obtained from an airborne platform. The prior probability distribution of ET estimates were modeled using fractional cover, local weather data and a Penman-Monteith mode, while the likelihood of LST data was modeled from a two-source energy balance model. Thus the posterior probabilities of ET represented the value added by using LST data. Results from an ET study over cotton grown in 2014 and 2015 showed significantly reduced ET confidence intervals when LST data were incorporated.

  4. In vitro effect of energy drinks on human enamel surface

    Directory of Open Access Journals (Sweden)

    Marise Sano Suga MATUMOTO

    Full Text Available Abstract Introduction Energy drinks (ED possess low pH and citric acid in their composition, making them potentially erosive beverages that can contribute to the high dental erosion rates found currently in the general population and also in young people. Objective To evaluate the mean pH and titratable acidity of commercial ED and the influence of a brand of ED on the superficial microhardness of human enamel. Material and method Ten commercial ED were selected and the pH of two lots of each ED with and without gas was obtained. Acid titration was conducted with the addition of NaOH aliquots until the pH 7 was reached. Eighteen human enamel specimens were allocated in three groups (N=6, Red Bull (RB, Red Bull Light (RBL and distilled water (C, submitted to an acid challenge with the ED, six consecutive times, with 12 hours intervals, during three days. Knoop microhardness was measured before and after the acid challenge. Result All ED brands tested presented low pH levels ranging from 2.1 to 3.2. Regarding titratable acidity, it was found that the amount of base required promoting the neutralization of the solutions ranged from 1200μL to 3750μL. Samples of human enamel in the RB and RBL groups submitted to the acid challenge presented significantly decreased Knoop microhardness when compared with the group C. Conclusion All ED examined have potential to promote mineral loss due to the low pH and high titratable acidity. The ED analyzed promoted significant mineral losses on the dental enamel surface.

  5. Using radiometric surface temperature for surface energy flux estimation in Mediterranean drylands from a two-source perspective

    DEFF Research Database (Denmark)

    Morillas, L.; Garcia Garcia, Monica; Nieto Solana, Hector

    2013-01-01

    A two-source model (TSM) for surface energy balance, considering explicitly soil and vegetation components, was tested under water stress conditions. The TSM evaluated estimates the sensible heat flux (H) using the surface-air thermal gradient and the latent heat flux (LE) as a residual from the ...

  6. SCANNING ELECTRON-MICROSCOPIC EVALUATION OF THE FRACTURED SURFACES OF CANINE CALCULI FROM SUBSTRATA WITH DIFFERENT SURFACE FREE-ENERGY

    NARCIS (Netherlands)

    UYEN, HMW; JONGEBLOED, WL; BUSSCHER, HJ

    1991-01-01

    The strength of adhesion between dental calculus and enamel or dentin surfaces determines the ease with which the calculus can be removed by brushing or professional dental treatment. In this study, we examined the adhesion of canine calculi formed on substrata with different surface free energies

  7. Structural dependence of the 5d-metal surface energies as deduced from surface core-level shift measurements

    International Nuclear Information System (INIS)

    Mrartensson, N.; Saalfeld, H.B.; Kuhlenbeck, H.; Neumann, M.

    1989-01-01

    Surface core-level shift measurements performed at the BESSY storage ring yield -0.41(2) eV for Os(0001) and 0.00(10) eV for Re(0001). An analysis of the surface shifts in the 5d transition series shows that the surface energy as a function of Z has a maximum at lower Z for the bcc phase than for the fcc-hcp phases, at W and between Re and Os, respectively

  8. Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory.

    Science.gov (United States)

    Bao, Junwei Lucas; Zheng, Jingjing; Truhlar, Donald G

    2016-03-02

    Pressure-dependent reactions are ubiquitous in combustion and atmospheric chemistry. We employ a new calibration procedure for quantum Rice-Ramsperger-Kassel (QRRK) unimolecular rate theory within a chemical activation mechanism to calculate the pressure-falloff effect of a radical association with an aromatic ring. The new theoretical framework is applied to the reaction of H with toluene, which is a prototypical reaction in the combustion chemistry of aromatic hydrocarbons present in most fuels. Both the hydrogen abstraction reactions and the hydrogen addition reactions are calculated. Our system-specific (SS) QRRK approach is adjusted with SS parameters to agree with multistructural canonical variational transition state theory with multidimensional tunneling (MS-CVT/SCT) at the high-pressure limit. The new method avoids the need for the usual empirical estimations of the QRRK parameters, and it eliminates the need for variational transition state theory calculations as a function of energy, although in this first application we do validate the falloff curves by comparing SS-QRRK results without tunneling to multistructural microcanonical variational transition state theory (MS-μVT) rate constants without tunneling. At low temperatures, the two approaches agree well with each other, but at high temperatures, SS-QRRK tends to overestimate falloff slightly. We also show that the variational effect is important in computing the energy-resolved rate constants. Multiple-structure anharmonicity, torsional-potential anharmonicity, and high-frequency-mode vibrational anharmonicity are all included in the rate computations, and torsional anharmonicity effects on the density of states are investigated. Branching fractions, which are both temperature- and pressure-dependent (and for which only limited data is available from experiment), are predicted as a function of pressure.

  9. Experimental and theoretical examples of the value and limitations of transition state theory

    International Nuclear Information System (INIS)

    Golden, D.M.

    1979-01-01

    Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the ''direct'' reactions CH 3 + CH 3 CHO → CH 4 + CH 3 CO (1) and O + CH 4 → OH + CH 3 (2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of ''complex'' vs ''direct'' mechanisms. The reaction OH + CO → CO 2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted. 2 figures, 5 tables

  10. Experimental and theoretical examples of the value and limitations of transition state theory

    Science.gov (United States)

    Golden, D. M.

    1979-01-01

    Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the 'direct' reactions CH3 + CH3CHO yields CH4 + CH3CO(1) and O + CH4 yields OH + CH3(2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of 'complex' vs. 'direct' mechanisms. The reaction OH + CO yields CO2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted.

  11. Electrode surface engineering by atomic layer deposition: A promising pathway toward better energy storage

    KAUST Repository

    Ahmed, Bilal; Xia, Chuan; Alshareef, Husam N.

    2016-01-01

    high capacities and energy and power densities. These developments can extend battery life in portable devices, and open new markets such as electric vehicles and large-scale grid energy storage. It is well known that surface reactions largely determine

  12. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

    Science.gov (United States)

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  13. Efficient Computational Research Protocol to Survey Free Energy Surface for Solution Chemical Reaction in the QM/MM Framework: The FEG-ER Methodology and Its Application to Isomerization Reaction of Glycine in Aqueous Solution.

    Science.gov (United States)

    Takenaka, Norio; Kitamura, Yukichi; Nagaoka, Masataka

    2016-03-03

    In solution chemical reaction, we often need to consider a multidimensional free energy (FE) surface (FES) which is analogous to a Born-Oppenheimer potential energy surface. To survey the FES, an efficient computational research protocol is proposed within the QM/MM framework; (i) we first obtain some stable states (or transition states) involved by optimizing their structures on the FES, in a stepwise fashion, finally using the free energy gradient (FEG) method, and then (ii) we directly obtain the FE differences among any arbitrary states on the FES, efficiently by employing the QM/MM method with energy representation (ER), i.e., the QM/MM-ER method. To validate the calculation accuracy and efficiency, we applied the above FEG-ER methodology to a typical isomerization reaction of glycine in aqueous solution, and reproduced quite satisfactorily the experimental value of the reaction FE. Further, it was found that the structural relaxation of the solute in the QM/MM force field is not negligible to estimate correctly the FES. We believe that the present research protocol should become prevailing as one computational strategy and will play promising and important roles in solution chemistry toward solution reaction ergodography.

  14. Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

    Science.gov (United States)

    Wang, Hui-Fang; Liu, Zhi-Pan

    2008-08-20

    Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

  15. Surface energy effect on free vibration of nano-sized piezoelectric double-shell structures

    Science.gov (United States)

    Fang, Xue-Qian; Zhu, Chang-Song; Liu, Jin-Xi; Liu, Xiang-Lin

    2018-01-01

    Combining Goldenveizer-Novozhilov shell theory, thin plate theory and electro-elastic surface theory, the size-dependent vibration of nano-sized piezoelectric double-shell structures under simply supported boundary condition is presented, and the surface energy effect on the natural frequencies is discussed. The displacement components of the cylindrical nano-shells and annular nano-plates are expanded as the superposition of standard Fourier series based on Hamilton's principle. The total stresses with consideration of surface energy effect are derived, and the total energy function is obtained by using Rayleigh-Ritz energy method. The free vibration equation is solved, and the natural frequency is analyzed. In numerical examples, it is found that the surface elastic constant, piezoelectric constant and surface residual stress show different effects on the natural frequencies. The effect of surface piezoelectric constant is the maximum. The effect of dimensions of the double-shell under different surface material properties is also examined.

  16. The peptide-receptive transition state of MHC-1 molecules: Insight from structure and molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Robinson H.; Mage, M.; Dolan, M.; Wang, R.; Boyd, L.; Revilleza, M.; Natarajan, K.; Myers, N.; Hansen, T.; Margulies, D.

    2012-05-01

    MHC class I (MHC-I) proteins of the adaptive immune system require antigenic peptides for maintenance of mature conformation and immune function via specific recognition by MHC-I-restricted CD8(+) T lymphocytes. New MHC-I molecules in the endoplasmic reticulum are held by chaperones in a peptide-receptive (PR) transition state pending release by tightly binding peptides. In this study, we show, by crystallographic, docking, and molecular dynamics methods, dramatic movement of a hinged unit containing a conserved 3(10) helix that flips from an exposed 'open' position in the PR transition state to a 'closed' position with buried hydrophobic side chains in the peptide-loaded mature molecule. Crystallography of hinged unit residues 46-53 of murine H-2L(d) MHC-I H chain, complexed with mAb 64-3-7, demonstrates solvent exposure of these residues in the PR conformation. Docking and molecular dynamics predict how this segment moves to help form the A and B pockets crucial for the tight peptide binding needed for stability of the mature peptide-loaded conformation, chaperone dissociation, and Ag presentation.

  17. Secondary deuterium isotope effects and transition state structure in the aromatic claisen rearrangement

    International Nuclear Information System (INIS)

    McMichael, K.D.; Korver, G.L.

    1979-01-01

    Kinetic experiments were carried out simultaneously on separate methyl salicylate solutions of allyl phenyl ether and its deuterated phenyl analogues at 170 to 195 0 C. Gas chromatographic analysis for allyl phenyl ether using an internal standard (anisole) and mechanical integration produced concentration/time data which were fitted to the exponential form of the first-order rate equation by a standard and nonlinear least-square program. At least 15 points were obtained for each run, covering 10 to 85% reaction. The derived isotope effects show no temperature dependence. Averages for 6 runs with each compound are k/sub H//k/sub α-D 2 / = 1.18 and K/sub H//k/sub γ-D 2 / = 0.95. An equilibrium α effect of 1.30 and a γ effect of 0.87 may be calculated for both deuterium atoms at 185 0 C. These results show that the C--H vibration frequencies are approximately (1.18 - 1)/(1.27 - 1) or 57 to 77% of the way from those of allyl phenyl ether to those of the cyclohexadiene intermediate. The C--H frequencies of the γ carbon in the transition state are about (0.95 - 1)/(0.88 - 1) or 22 to 62% of the way to those of the intermediate. The structure of the transition state, as far as these bonding frequencies are concerned, is consistent with the Claisen rearrangement

  18. Surface influence on convoy electron emission at low energies

    International Nuclear Information System (INIS)

    Sanchez, E.A.

    1988-01-01

    It is studied the dependence of the production of convoy electrons induced by H + - 60 KeV with surface conditions of Al targets by in situ deposition of Na and O. The conclusion is that convoy electron production increases with the work function of the surface. (A.C.A.S.) [pt

  19. Low energy He+ irradiation effect on graphite surface

    International Nuclear Information System (INIS)

    Asari, E.; Nakamura, K.G.; Kitajima, M.; Kawabe, T.

    1992-01-01

    Study on the lattice disordering and the secondary electron emission under low energy (1-5keV) He + irradiation is reported. Real-time Raman measurements show that difference in the observed Raman spectra for different ion energies is due to the difference of the damage depth. The relation between the observed Raman spectrum and the depth profile of lattice damage is discussed. Energy dependence of the secondary electron emission coefficient are also described. (author)

  20. Surface structure determinations of crystalline ionic thin films grown on transition metal single crystal surfaces by low energy electron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Joel Glenn [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    The surface structures of NaCl(100), LiF(100) and alpha-MgCl2(0001) adsorbed on various metal single crystals have been determined by low energy electron diffraction (LEED). Thin films of these salts were grown on metal substrates by exposing the heated metal surface to a molecular flux of salt emitted from a Knudsen cell. This method of investigating thin films of insulators (ionic salts) on a conducting substrate (metal) circumvents surface charging problems that plagued bulk studies, thereby allowing the use of electron-based techniques to characterize the surface.

  1. Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

    International Nuclear Information System (INIS)

    Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

    2002-01-01

    Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

  2. Native Hydrophobic Binding Interactions at the Transition State for Association between the TAZ1 Domain of CBP and the Disordered TAD-STAT2 Are Not a Requirement.

    Science.gov (United States)

    Lindström, Ida; Dogan, Jakob

    2017-08-15

    A significant fraction of the eukaryotic proteome consists of proteins that are either partially or completely disordered under native-like conditions. Intrinsically disordered proteins (IDPs) are common in protein-protein interactions and are involved in numerous cellular processes. Although many proteins have been identified as disordered, much less is known about the binding mechanisms of the coupled binding and folding reactions involving IDPs. Here we have analyzed the rate-limiting transition state for binding between the TAZ1 domain of CREB binding protein and the intrinsically disordered transactivation domain of STAT2 (TAD-STAT2) by site-directed mutagenesis and kinetic experiments (Φ-value analysis) and found that the native protein-protein binding interface is not formed at the transition state for binding. Instead, native hydrophobic binding interactions form late, after the rate-limiting barrier has been crossed. The association rate constant in the absence of electrostatic enhancement was determined to be rather high. This is consistent with the Φ-value analysis, which showed that there are few or no obligatory native contacts. Also, linear free energy relationships clearly demonstrate that native interactions are cooperatively formed, a scenario that has usually been observed for proteins that fold according to the so-called nucleation-condensation mechanism. Thus, native hydrophobic binding interactions at the rate-limiting transition state for association between TAD-STAT2 and TAZ1 are not a requirement, which is generally in agreement with previous findings on other IDP systems and might be a common mechanism for IDPs.

  3. Ab Initio and DFT Potential Energy Surfaces for Cyanuric Chloride Reactions

    National Research Council Canada - National Science Library

    Pai, Sharmila

    1998-01-01

    ... on the potential energy surface were calculated using the 6-31G and 6-311 +Gbasis sets. DFT(B3LYP) geometry optimizations and zero-point corrections for critical points on the potential energy surface were calculated with the 6-31G, 6-311...

  4. Hot-electron-mediated desorption rates calculated from excited-state potential energy surfaces

    DEFF Research Database (Denmark)

    Olsen, Thomas; Gavnholt, Jeppe; Schiøtz, Jakob

    2009-01-01

    We present a model for desorption induced by (multiple) electronic transitions [DIET (DIMET)] based on potential energy surfaces calculated with the delta self-consistent field extension of density-functional theory. We calculate potential energy surfaces of CO and NO molecules adsorbed on variou...

  5. Cluster ion-surface interactions: from meV to MeV energies

    Energy Technology Data Exchange (ETDEWEB)

    Nordlund, Kai; Meinander, Kristoffer; Jaervi, Tommi T.; Peltola, Jarkko; Samela, Juha [Accelerator Laboratory, University of Helsinki (Finland)

    2008-07-01

    The nature of cluster ion-surface interactions changes dramatically with the kinetic energy of the incoming cluster species. In this talk I review some of our recent work on the nature of cluster-surface interactions spanning an energy range from a few MeV/cluster to about 1 MeV/cluster and cluster sizes in the range of 10 - 1000 atoms/cluster. In the energy range of a few MeV/cluster ion, the kinetic energy of the incoming ion is insignificant compared to the energy gained when the surface potential energy at the cluster-surface interface is released and partly translated into kinetic energy. Even in this energy regime I show that surprisingly drastic effects can occur. When the energy of the incoming cluster is raised to a few eV/atom, the kinetic energy of the incoming cluster starts to affect the deposition. It will cause the cluster to entirely reform on impact. When the energy is raised to the range of keV's/cluster, the clusters start to penetrate the sample, fairly similar to conventional ion implantation. However, in dense targets the cluster ions may stick close to each other long enough to cause a significant enhancement of the heat spike in the material. Finally, I show that at kinetic energies around 1 MeV/cluster the cluster enhancement of the heat spike may lead to dramatic surface effects.

  6. Dispersion and energy conservation relations of surface waves in semi-infinite plasma

    International Nuclear Information System (INIS)

    Atanassov, V.

    1981-01-01

    The hydrodynamic theory of surface wave propagation in semi-infinite homogeneous isotropic plasma is considered. Explicit linear surface wave solutions are given for the electric and magnetic fields, charge and current densities. These solutions are used to obtain the well-known dispersion relations and, together with the general energy conservation equation, to find appropriate definitions for the energy and the energy flow densities of surface waves. These densities are associated with the dispersion relation and the group velocity by formulae similar to those for bulk waves in infinite plasmas. Both cases of high-frequency (HF) and low-frequency (LF) surface waves are considered. (author)

  7. Converting chemical energy into electricity through a functionally cooperating device with diving-surfacing cycles.

    Science.gov (United States)

    Song, Mengmeng; Cheng, Mengjiao; Ju, Guannan; Zhang, Yajun; Shi, Feng

    2014-11-05

    A smart device that can dive or surface in aqueous medium has been developed by combining a pH-responsive surface with acid-responsive magnesium. The diving-surfacing cycles can be used to convert chemical energy into electricity. During the diving-surfacing motion, the smart device cuts magnetic flux lines and produces a current, demonstrating that motional energy can be realized by consuming chemical energy of magnesium, thus producing electricity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Vibrational effects on surface energies and band gaps in hexagonal and cubic ice

    International Nuclear Information System (INIS)

    Engel, Edgar A.; Needs, Richard J.; Monserrat, Bartomeu

    2016-01-01

    Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range from −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.

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

    DEFF Research Database (Denmark)

    Calle-Vallejo, F.; Martínez, J. I.; García Lastra, Juan Maria

    2012-01-01

    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....

  10. Molecular dynamics simulation of temperature effects on low energy near-surface cascades and surface damage in Cu

    Science.gov (United States)

    Zhu, Guo; Sun, Jiangping; Guo, Xiongxiong; Zou, Xixi; Zhang, Libin; Gan, Zhiyin

    2017-06-01

    The temperature effects on near-surface cascades and surface damage in Cu(0 0 1) surface under 500 eV argon ion bombardment were studied using molecular dynamics (MD) method. In present MD model, substrate system was fully relaxed for 1 ns and a read-restart scheme was introduced to save total computation time. The temperature dependence of damage production was calculated. The evolution of near-surface cascades and spatial distribution of adatoms at varying temperature were analyzed and compared. It was found that near-surface vacancies increased with temperature, which was mainly due to the fact that more atoms initially located in top two layers became adatoms with the decrease of surface binding energy. Moreover, with the increase of temperature, displacement cascades altered from channeling-like structure to branching structure, and the length of collision sequence decreased gradually, because a larger portion of energy of primary knock-on atom (PKA) was scattered out of focused chain. Furthermore, increasing temperature reduced the anisotropy of distribution of adatoms, which can be ascribed to that regular registry of surface lattice atoms was changed with the increase of thermal vibration amplitude of surface atoms.

  11. Molecular dynamics simulation of temperature effects on low energy near-surface cascades and surface damage in Cu

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Guo; Sun, Jiangping; Guo, Xiongxiong; Zou, Xixi; Zhang, Libin; Gan, Zhiyin, E-mail: ganzhiyin@126.com

    2017-06-15

    The temperature effects on near-surface cascades and surface damage in Cu(0 0 1) surface under 500 eV argon ion bombardment were studied using molecular dynamics (MD) method. In present MD model, substrate system was fully relaxed for 1 ns and a read-restart scheme was introduced to save total computation time. The temperature dependence of damage production was calculated. The evolution of near-surface cascades and spatial distribution of adatoms at varying temperature were analyzed and compared. It was found that near-surface vacancies increased with temperature, which was mainly due to the fact that more atoms initially located in top two layers became adatoms with the decrease of surface binding energy. Moreover, with the increase of temperature, displacement cascades altered from channeling-like structure to branching structure, and the length of collision sequence decreased gradually, because a larger portion of energy of primary knock-on atom (PKA) was scattered out of focused chain. Furthermore, increasing temperature reduced the anisotropy of distribution of adatoms, which can be ascribed to that regular registry of surface lattice atoms was changed with the increase of thermal vibration amplitude of surface atoms.

  12. Climate-induced hotspots in surface energy fluxes from 1948 to 2000

    International Nuclear Information System (INIS)

    Sheng Li; Liu Shuhua; Liu Heping

    2010-01-01

    Understanding how land surfaces respond to climate change requires knowledge of land-surface processes, which control the degree to which interannual variability and mean trends in climatic variables affect the surface energy budget. We use the latest version of the Community Land Model version 3.5 (CLM3.5), which is driven by the latest updated hybrid reanalysis-observation atmospheric forcing dataset constructed by Princeton University, to obtain global distributions of the surface energy budget from 1948 to 2000. We identify climate change hotspots and surface energy flux hotspots from 1948 to 2000. Surface energy flux hotspots, which reflect regions with strong changes in surface energy fluxes, reveal seasonal variations with strong signals in winter, spring, and autumn and weak ones in summer. Locations for surface energy flux hotspots are not, however, fully linked with those for climate change hotspots, suggesting that only in some regions are land surfaces more responsive to climate change in terms of interannual variability and mean trends.

  13. A transitioning Arctic surface energy budget: the impacts of solar zenith angle, surface albedo and cloud radiative forcing

    Energy Technology Data Exchange (ETDEWEB)

    Sedlar, Joseph; Tjernstroem, Michael; Leck, Caroline [Stockholm University, Department of Meteorology, Stockholm (Sweden); Mauritsen, Thorsten [Max-Planck-Institute for Meteorology, Hamburg (Germany); Shupe, Matthew D.; Persson, P.O.G. [University of Colorado, NOAA-ESRL-PSD, Boulder, CO (United States); Brooks, Ian M.; Birch, Cathryn E. [University of Leeds, School of Earth and Environment, Leeds (United Kingdom); Sirevaag, Anders [University of Bergen, Bjerknes Center for Climate Research, Bergen (Norway); Nicolaus, Marcel [Norwegian Polar Institute, Tromsoe (Norway); Alfred Wegener Institute for Polar and Marine Research, Bremerhaven (Germany)

    2011-10-15

    Snow surface and sea-ice energy budgets were measured near 87.5 N during the Arctic Summer Cloud Ocean Study (ASCOS), from August to early September 2008. Surface temperature indicated four distinct temperature regimes, characterized by varying cloud, thermodynamic and solar properties. An initial warm, melt-season regime was interrupted by a 3-day cold regime where temperatures dropped from near zero to -7 C. Subsequently mean energy budget residuals remained small and near zero for 1 week until once again temperatures dropped rapidly and the energy budget residuals became negative. Energy budget transitions were dominated by the net radiative fluxes, largely controlled by the cloudiness. Variable heat, moisture and cloud distributions were associated with changing air-masses. Surface cloud radiative forcing, the net radiative effect of clouds on the surface relative to clear skies, is estimated. Shortwave cloud forcing ranged between -50 W m{sup -2} and zero and varied significantly with surface albedo, solar zenith angle and cloud liquid water. Longwave cloud forcing was larger and generally ranged between 65 and 85 W m{sup -2}, except when the cloud fraction was tenuous or contained little liquid water; thus the net effect of the clouds was to warm the surface. Both cold periods occurred under tenuous, or altogether absent, low-level clouds containing little liquid water, effectively reducing the cloud greenhouse effect. Freeze-up progression was enhanced by a combination of increasing solar zenith angles and surface albedo, while inhibited by a large, positive surface cloud forcing until a new air-mass with considerably less cloudiness advected over the experiment area. (orig.)

  14. 4H-SiC surface energy tuning by nitrogen up-take

    Energy Technology Data Exchange (ETDEWEB)

    Pitthan, E., E-mail: eduardo.pitthan@ufrgs.br [Institute for Advanced Materials, Devices and Nanotechnology, Rutgers University, Piscataway, NJ 08854 (United States); PGMICRO, UFRGS, 91509-900, Porto Alegre, RS (Brazil); Amarasinghe, V.P. [Institute for Advanced Materials, Devices and Nanotechnology, Rutgers University, Piscataway, NJ 08854 (United States); Xu, C.; Gustafsson, T. [Institute for Advanced Materials, Devices and Nanotechnology, Rutgers University, Piscataway, NJ 08854 (United States); Department of Physics and Astronomy, Rutgers University, Piscataway, NJ 08854 (United States); Stedile, F.C. [PGMICRO, UFRGS, 91509-900, Porto Alegre, RS (Brazil); Instituto de Química, UFRGS, 91509-900, Porto Alegre, RS (Brazil); Feldman, L.C. [Institute for Advanced Materials, Devices and Nanotechnology, Rutgers University, Piscataway, NJ 08854 (United States); Department of Physics and Astronomy, Rutgers University, Piscataway, NJ 08854 (United States)

    2017-04-30

    Highlights: • Wettability modification of 4H-SiC as a function of nitrogen adsorption is reported. • SiC surface energy was significantly reduced as nitrogen was incorporated. • Modifications obtained were proved to be inert to etching and stable against time. • Variable control of SiC surface provides new opportunities for biomedical applications. - Abstract: Surface energy modification and surface wettability of 4H silicon carbide (0001) as a function of nitrogen adsorption is reported. The surface wettability is shown to go from primarily hydrophilic to hydrophobic and the surface energy was significantly reduced with increasing nitrogen incorporation. These changes are investigated by x-ray photoelectron spectroscopy and contact angle measurements. The surface energy was quantitatively determined by the Fowkes model and interpreted primarily in terms of the variation of the surface chemistry with nitrogen coverage. Variable control of SiC surface energies with a simple and controllable atomic additive such as nitrogen that is inert to etching, stable against time, and also effective in electrical passivation, can provide new opportunities for SiC biomedical applications, where surface wetting plays an important role in the interaction with the biological interfaces.

  15. Effect of crystal habits on the surface energy and cohesion of crystalline powders.

    Science.gov (United States)

    Shah, Umang V; Olusanmi, Dolapo; Narang, Ajit S; Hussain, Munir A; Gamble, John F; Tobyn, Michael J; Heng, Jerry Y Y

    2014-09-10

    The role of surface properties, influenced by particle processing, in particle-particle interactions (powder cohesion) is investigated in this study. Wetting behaviour of mefenamic acid was found to be anisotropic by sessile drop contact angle measurements on macroscopic (>1cm) single crystals, with variations in contact angle of water from 56.3° to 92.0°. This is attributed to variations in surface chemical functionality at specific facets, and confirmed using X-ray photoelectron spectroscopy (XPS). Using a finite dilution inverse gas chromatography (FD-IGC) approach, the surface energy heterogeneity of powders was determined. The surface energy profile of different mefenamic acid crystal habits was directly related to the relative exposure of different crystal facets. Cohesion, determined by a uniaxial compression test, was also found to relate to surface energy of the powders. By employing a surface modification (silanisation) approach, the contribution from crystal shape from surface area and surface energy was decoupled. By "normalising" contribution from surface energy and surface area, needle shaped crystals were found to be ∼2.5× more cohesive compared to elongated plates or hexagonal cuboid shapes crystals. Copyright © 2014. Published by Elsevier B.V.

  16. Molecular beam studies of energy transfer in scattering from crystal surfaces

    International Nuclear Information System (INIS)

    Guthrie, W.L.

    1983-01-01

    The translational energy distributions and angular distributions of D 2 O produced from the reaction of incident D 2 and O 2 on a (111) platinum single crystal surface have been measured through the use of a molecular beam-surface scattering apparatus equipped with a time-of-flight spectrometer. The translation energies were measured over the surface temperature range T/sub s/ = 664 K - 913 K and at scattering angles of 7 0 and 40 0 from the surface normal. The D 2 O translational energy, , was found to be approximately half the equilibrium value over the temperature range examined, with /2k varying from 280 K to 480 K. These results are discussed in terms of a non-equilibrium desorption model. The two-photon ionization spectrometer was built to investigate the internal rotational and vibrational energy distributions of NO scattered from Pt(111) surfaces. The rotational energy distributions were measured over the crystal temperature range of T/sub s/ = 400 K - 1200 K. The translational energy distributions and angular distributions were measured using the time-of-flight spectrometer over the crystal temperature range of 400 K - 110 K and for beam translational energies of 0.046 eV, 0.11 eV and 0.24 eV, so that complete energy exchange information for translation, rotation and vibration is available for this gas-surface system. Significant energy transfer was observed in all three modes

  17. Exploration, Sampling, And Reconstruction of Free Energy Surfaces with Gaussian Process Regression.

    Science.gov (United States)

    Mones, Letif; Bernstein, Noam; Csányi, Gábor

    2016-10-11

    Practical free energy reconstruction algorithms involve three separate tasks: biasing, measuring some observable, and finally reconstructing the free energy surface from those measurements. In more than one dimension, adaptive schemes make it possible to explore only relatively low lying regions of the landscape by progressively building up the bias toward the negative of the free energy surface so that free energy barriers are eliminated. Most schemes use the final bias as their best estimate of the free energy surface. We show that large gains in computational efficiency, as measured by the reduction of time to solution, can be obtained by separating the bias used for dynamics from the final free energy reconstruction itself. We find that biasing with metadynamics, measuring a free energy gradient estimator, and reconstructing using Gaussian process regression can give an order of magnitude reduction in computational cost.

  18. Effects of Surface Nonuniformities on the Mean Transverse Energy from Photocathodes

    Science.gov (United States)

    Karkare, Siddharth; Bazarov, Ivan

    2015-08-01

    The performance of photoinjectors is limited by the lowest value of the mean transverse energy of the electrons obtained from photocathodes. The factors that influence the mean transverse energy are poorly understood. In this paper, we develop models to calculate the effect of spatial work-function variations and subnanometer-scale roughness and surface defects on the mean transverse energy. We show that these can limit the lowest value of mean transverse energy achieved and that atomically perfect surfaces will be required to further reduce the mean transverse energy obtained from photocathodes.

  19. Surface characterization by energy distribution measurements of secondary electrons and of ion-induced electrons

    International Nuclear Information System (INIS)

    Bauer, H.E.; Seiler, H.

    1988-01-01

    Instruments for surface microanalysis (e.g. scanning electron or ion microprobes, emission electron or ion microscopes) use the current of emitted secondary electrons or of emitted ion-induced electrons for imaging of the analysed surface. These currents, integrating over all energies of the emitted low energy electrons, are however, not well suited to surface analytical purposes. On the contrary, the energy distribution of these electrons is extremely surface-sensitive with respect to shape, size, width, most probable energy, and cut-off energy. The energy distribution measurements were performed with a cylindrical mirror analyser and converted into N(E), if necessary. Presented are energy spectra of electrons released by electrons and argon ions of some contaminated and sputter cleaned metals, the change of the secondary electron energy distribution from oxidized aluminium to clean aluminium, and the change of the cut-off energy due to work function change of oxidized aluminium, and of a silver layer on a platinum sample. The energy distribution of the secondary electrons often shows detailed structures, probably due to low-energy Auger electrons, and is broader than the energy distribution of ion-induced electrons of the same object point. (author)

  20. Insights from the structure of a smallpox virus topoisomerase-DNA transition state mimic

    Science.gov (United States)

    Perry, Kay; Hwang, Young; Bushman, Frederic D.; Van Duyne, Gregory D.

    2010-01-01

    Summary Poxviruses encode their own type IB topoisomerases (TopIBs) which release superhelical tension generated by replication and transcription of their genomes. To investigate the reaction catalyzed viral TopIBs, we have determined the structure of a variola virus topoisomerase-DNA complex trapped as a vanadate transition state mimic. The structure reveals how the viral TopIB enzymes are likely to position the DNA duplex for ligation following relaxation of supercoils and identifies the sources of friction observed in single molecule experiments that argue against free rotation. The structure also identifies a conformational change in the leaving group sugar that must occur prior to cleavage and reveals a mechanism for promoting ligation following relaxation of supercoils that involves a novel Asp-minor groove interaction. Overall, the new structural data support a common catalytic mechanism for the TopIB superfamily but indicate distinct methods for controlling duplex rotation in the small vs. large enzyme subfamilies. PMID:20152159

  1. Dynamics of SARS-coronavirus HR2 domain in the prefusion and transition states

    Science.gov (United States)

    McReynolds, Susanna; Jiang, Shaokai; Rong, Lijun; Caffrey, Michael

    2009-12-01

    The envelope glycoproteins S1 and S2 of severe acute respiratory syndrome coronavirus (SARS-CoV) mediate viral entry by conformational change from a prefusion state to a postfusion state that enables fusion of the viral and target membranes. In this work we present the characterization of the dynamic properties of the SARS-CoV S2-HR2 domain (residues 1141-1193 of S) in the prefusion and newly discovered transition states by NMR 15N relaxation studies. The dynamic properties of the different states, which are stabilized under different experimental conditions, extend the current model of viral membrane fusion and give insight into the design of structure-based antagonists of SARS-CoV in particular, as well as other enveloped viruses such as HIV.

  2. Inhibition and Structure of Trichomonas vaginalis Purine Nucleoside Phosphorylase with Picomolar Transition State Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Rinaldo-Matthis,A.; Wing, C.; Ghanem, M.; Deng, H.; Wu, P.; Gupta, A.; Tyler, P.; Evans, G.; Furneaux, R.; et al.

    2007-01-01

    Trichomonas vaginalis is a parasitic protozoan purine auxotroph possessing a unique purine salvage pathway consisting of a bacterial type purine nucleoside phosphorylase (PNP) and a purine nucleoside kinase. Thus, T. vaginalis PNP (TvPNP) functions in the reverse direction relative to the PNPs in other organisms. Immucillin-A (ImmA) and DADMe-Immucillin-A (DADMe-ImmA) are transition stte mimics of adenosine with geometric and electrostatic features that resemble early and late transition states of adenosine at the transition state stabilized by TvPNP. ImmA demonstrates slow-onset tight-binding inhibition with TvPNP, to give an equilibrium dissociation constant of 87 pM, an inhibitor release half-time of 17.2 min, and a K{sub m}/K{sub d} ratio of 70,100. DADMe-ImmA resembles a late ribooxacarbenium ion transition state for TvPNP to give a dissociation constant of 30 pM, an inhibitor release half-time of 64 min, and a K{sub m}/K{sub d} ratio of 203,300. The tight binding of DADMe-ImmA supports a late S{sub N}1 transition state. Despite their tight binding to TvPNP, ImmA and DADMe-ImmA are weak inhibitors of human and P. falciparum PNPs. The crystal structures of the TvPNP-ImmA{center_dot}PO{sub 4} and TvPNP{center_dot}DADMe-ImmA{center_dot}PO{sub 4} ternary complexes differ from previous structures with substrate anologues. The tight binding with DADMe-ImmA is in part due to a 2.7 {angstrom} ionic interaction between a PO{sub 4} oxygen and the N1 cation of the hydroxypyrrolidine and is weaker in the TvPNP{center_dot}ImmA{center_dot}PO{sub 4} structure at 3.5 {angstrom}. However, the TvPNP{center_dot}ImmA{center_dot}PO{sub 4} structure includes hydrogen bonds between the 2'-hydroxyl and the protein that are not present in TvPNP{center_dot}DADMe-ImmA{center_dot}PO{sub 4}. These structures explain why DADMe-ImmA binds tighter than ImmA. Immucillin-H is a 12 nM inhibitor of TvPNP but a 56 pM inhibitor of human PNP. And this difference is explained by isotope

  3. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  4. Microclimatic models. Estimation of components of the energy balance over land surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Heikinheimo, M.; Venaelaeinen, A.; Tourula, T. [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

    1996-12-31

    Climates at regional scale are strongly dependent on the interaction between atmosphere and its lower boundary, the oceans and the land surface mosaic. Land surfaces influence climate through their albedo, and the aerodynamic roughness, the processes of the biosphere and many soil hydrological properties; all these factors vary considerably geographically. Land surfaces receive a certain portion of the solar irradiance depending on the cloudiness, atmospheric transparency and surface albedo. Short-wave solar irradiance is the source of the heat energy exchange at the earth`s surface and also regulates many biological processes, e.g. photosynthesis. Methods for estimating solar irradiance, atmospheric transparency and surface albedo were reviewed during the course of this project. The solar energy at earth`s surface is consumed for heating the soil and the lower atmosphere. Where moisture is available, evaporation is one of the key components of the surface energy balance, because the conversion of liquid water into water vapour consumes heat. The evaporation process was studied by carrying out field experiments and testing parameterisation for a cultivated agricultural surface and for lakes. The micrometeorological study over lakes was carried out as part of the international `Northern Hemisphere Climatic Processes Experiment` (NOPEX/BAHC) in Sweden. These studies have been aimed at a better understanding of the energy exchange processes of the earth`s surface-atmosphere boundary for a more accurate and realistic parameterisation of the land surface in atmospheric models

  5. Microclimatic models. Estimation of components of the energy balance over land surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Heikinheimo, M; Venaelaeinen, A; Tourula, T [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

    1997-12-31

    Climates at regional scale are strongly dependent on the interaction between atmosphere and its lower boundary, the oceans and the land surface mosaic. Land surfaces influence climate through their albedo, and the aerodynamic roughness, the processes of the biosphere and many soil hydrological properties; all these factors vary considerably geographically. Land surfaces receive a certain portion of the solar irradiance depending on the cloudiness, atmospheric transparency and surface albedo. Short-wave solar irradiance is the source of the heat energy exchange at the earth`s surface and also regulates many biological processes, e.g. photosynthesis. Methods for estimating solar irradiance, atmospheric transparency and surface albedo were reviewed during the course of this project. The solar energy at earth`s surface is consumed for heating the soil and the lower atmosphere. Where moisture is available, evaporation is one of the key components of the surface energy balance, because the conversion of liquid water into water vapour consumes heat. The evaporation process was studied by carrying out field experiments and testing parameterisation for a cultivated agricultural surface and for lakes. The micrometeorological study over lakes was carried out as part of the international `Northern Hemisphere Climatic Processes Experiment` (NOPEX/BAHC) in Sweden. These studies have been aimed at a better understanding of the energy exchange processes of the earth`s surface-atmosphere boundary for a more accurate and realistic parameterisation of the land surface in atmospheric models

  6. Radiation exchange between persons and surfaces for building energy simulations

    DEFF Research Database (Denmark)

    Vorre, Mette Havgaard; Jensen, Rasmus Lund; Dreau, Jerome Le

    2015-01-01

    Thermal radiation within buildings is a significant component of thermal comfort. Typically the methods applied for calculating view factors between a person and its building surfaces requires great computational time. This research developed a view factor calculation method suitable for building...

  7. BEP-relations for N2 dissociation over stepped transition metal and alloy surfaces

    DEFF Research Database (Denmark)

    Fronczek-Munter, Ture Rønved; Bligaard, Thomas; Christensen, Claus H.

    2008-01-01

    , a perfectly linear Bronsted-Evans-Polanyi (BEP) relation between the transition-state potential energy and the dissociative chemisorption energy is obtained. The perfect BEP relation, which extends over 12 eV in chemisorption energy, suggests that the manifestation of BEP relations for surface reactions...... is a general electronic structure effect, and that geometric effects are responsible for the scatter which is normally observed around the BEP line. The BEP relation is also shown to be valid for both surface and bulk alloys. The scatter is, however, larger than for the pure elements. This can be understood...

  8. Free energy surfaces from nonequilibrium processes without work measurement

    Science.gov (United States)

    Adib, Artur B.

    2006-04-01

    Recent developments in statistical mechanics have allowed the estimation of equilibrium free energies from the statistics of work measurements during processes that drive the system out of equilibrium. Here a different class of processes is considered, wherein the system is prepared and released from a nonequilibrium state, and no external work is involved during its observation. For such "clamp-and-release" processes, a simple strategy for the estimation of equilibrium free energies is offered. The method is illustrated with numerical simulations and analyzed in the context of tethered single-molecule experiments.

  9. Earthquake Energy Distribution along the Earth Surface and Radius

    International Nuclear Information System (INIS)

    Varga, P.; Krumm, F.; Riguzzi, F.; Doglioni, C.; Suele, B.; Wang, K.; Panza, G.F.

    2010-07-01

    The global earthquake catalog of seismic events with M W ≥ 7.0, for the time interval from 1950 to 2007, shows that the depth distribution of earthquake energy release is not uniform. The 90% of the total earthquake energy budget is dissipated in the first ∼30km, whereas most of the residual budget is radiated at the lower boundary of the transition zone (410 km - 660 km), above the upper-lower mantle boundary. The upper border of the transition zone at around 410 km of depth is not marked by significant seismic energy release. This points for a non-dominant role of the slabs in the energy budged of plate tectonics. Earthquake number and energy release, although not well correlated, when analysed with respect to the latitude, show a decrease toward the polar areas. Moreover, the radiated energy has the highest peak close to (±5 o ) the so-called tectonic equator defined by Crespi et al. (2007), which is inclined about 30 o with respect to the geographic equator. At the same time the presence of a clear axial co- ordination of the radiated seismic energy is demonstrated with maxima at latitudes close to critical (±45 o ). This speaks about the presence of external forces that influence seismicity and it is consistent with the fact that Gutenberg-Richter law is linear, for events with M>5, only when the whole Earth's seismicity is considered. These data are consistent with an astronomical control on plate tectonics, i.e., the despinning (slowing of the Earth's angular rotation) of the Earth's rotation caused primarily by the tidal friction due to the Moon. The mutual position of the shallow and ∼660 km deep earthquake energy sources along subduction zones allows us to conclude that they are connected with the same slab along the W-directed subduction zones, but they may rather be disconnected along the opposed E-NE-directed slabs, being the deep seismicity controlled by other mechanisms. (author)

  10. Theoretical aspects of studies of oxide and semiconductor surfaces using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2011-01-01

    This paper presents the results of a theoretical study of positron surface and bulk states and annihilation characteristics of surface trapped positrons at the oxidized Cu(100) single crystal and at both As- and Ga-rich reconstructed GaAs(100) surfaces. The variations in atomic structure and chemical composition of the topmost layers of the surfaces associated with oxidation and reconstructions and the charge redistribution at the surfaces are found to affect localization and spatial extent of the positron surface-state wave functions. The computed positron binding energy, work function, and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the surfaces. Theoretical positron annihilation probabilities with relevant core electrons computed for the oxidized Cu(100) surface and the As- and Ga-rich reconstructed GaAs(100) surfaces are compared with experimental ones estimated from the positron annihilation induced Auger peak intensities measured from these surfaces.

  11. Improvement of Polytetrafluoroethylene Surface Energy by Repetitive Pulse Non-Thermal Plasma Treatment in Atmospheric Air

    International Nuclear Information System (INIS)

    Yang Guoqing; Zhang Guanjun; Zhang Wenyuan

    2011-01-01

    Improvement of polytetrafluoroethylene surface energy by non-thermal plasma treatment is presented, using a nanosecond-positive-edge repetitive pulsed dielectric barrier discharge generator in atmospheric air. The electrical parameters including discharging power, peak and density of micro-discharge current were calculated, and the electron energy was estimated. Surface treatment experiments of polytetrafluoroethylene films were conducted for both different applied voltages and different treating durations. Results show that the surface energy of polytetrafluoroethylene film could be improved to 40 mJ/m 2 or more by plasma treatment. Surface roughness measurement and surface X-ray photoelectron spectroscopy analysis indicate that there are chemical etching and implantation of polar oxygen groups in the sample surface treating process, resulting in the improvement of the sample surface energy. Compared with an AC source of 50 Hz, the dielectric barrier discharges generated by a repetitive pulsed source could provide higher peak power, lower mean power, larger micro-discharge current density and higher electron energy. Therefore, with the same applied peak voltage and treating duration, the improvement of polytetrafluoroethylene surface energy using repetitive pulsed plasma is more effective, and the plasma treatment process based on repetitive pulsed dielectric barrier discharges in air is thus feasible and applicable.

  12. Nanoscale control of energy and matter in plasma-surface interactions: Toward energy- and matter-efficient nanotech

    International Nuclear Information System (INIS)

    Ostrikov, K.

    2011-01-01

    The approach to control the elementary processes of plasma-surface interactions to direct the fluxes of energy and matter at nano- and subnanometer scales is introduced. This ability is related to the solution of the grand challenge of directing energy and matter at nanoscales and is critical for the renewable energy and energy-efficient technologies for a sustainable future development. The examples of deterministic synthesis of self-organized arrays of metastable nanostructures in the size range beyond the reach of the present-day nanofabrication are considered to illustrate this possibility. By using precisely controlled and kinetically fast nanoscale transfer of energy and matter under nonequilibrium conditions and harnessing numerous plasma-specific controls of species creation, delivery to the surface, nucleation, and large-scale self-organization of nuclei and nanostructures, the arrays of metastable nanostructures can be created, arranged, stabilized, and further processed to meet the specific requirements of the envisaged applications.

  13. Reconnoitering the effect of shallow groundwater on land surface temperature and surface energy balance using MODIS and SEBS

    Directory of Open Access Journals (Sweden)

    F. Alkhaier

    2012-07-01

    Full Text Available The possibility of observing shallow groundwater depth and areal extent using satellite measurements can support groundwater models and vast irrigation systems management. Moreover, these measurements can help to include the effect of shallow groundwater on surface energy balance within land surface models and climate studies, which broadens the methods that yield more reliable and informative results. To examine the capacity of MODIS in detecting the effect of shallow groundwater on land surface temperature and the surface energy balance in an area within Al-Balikh River basin in northern Syria, we studied the interrelationship between in-situ measured water table depths and land surface temperatures measured by MODIS. We, also, used the Surface Energy Balance System (SEBS to calculate surface energy fluxes, evaporative fraction and daily evaporation, and inspected their relationships with water table depths. We found out that the daytime temperature increased while the nighttime temperature decreased when the depth of the water table increased. And, when the water table depth increased, net radiation, latent and ground heat fluxes, evaporative fraction and daily evaporation decreased, while sensible heat flux increased. This concords with the findings of a companion paper (Alkhaier et al., 2012. The observed clear relationships were the result of meeting both conditions that were concluded in the companion paper, i.e. high potential evaporation and big contrast in day-night temperature. Moreover, the prevailing conditions in this study area helped SEBS to yield accurate estimates. Under bare soil conditions and under the prevailing weather conditions, we conclude that MODIS is suitable for detecting the effect of shallow groundwater because it has proper imaging times and adequate sensor accuracy; nevertheless, its coarse spatial resolution is disadvantageous.

  14. A quasiclassical trajectory study for the N(4S)+O2(X3Σg-)->NO(X2Π)+O(3P) atmospheric reaction based on a new ground potential energy surface

    International Nuclear Information System (INIS)

    He Jianfeng; Liu Shixing; Liu Xueshen; Ding Peizhu

    2005-01-01

    A quasiclassical trajectory study with the fourth-order explicit symplectic algorithm for the N( 4 S)+O 2 (X 3 Σ g - )->NO(X 2 Π)+O( 3 P) atmospheric reaction has been performed by employing a new analytical fit of ab initio electronic structure calculations for the ground potential energy surface reported by Sayos et al. The effect of the relative translational energy, the vibrational energy and rotational energy of O 2 molecule on the reaction probability and the reaction cross-section has been analyzed in details. The microscopic rate constant and the thermal rate constant have also been evaluated at the low translational temperature, and results have been compared with the experimental data and previous theoretical values. It is concluded that the thermal rate constants at the low temperature considered in this work agree well with the recommended experimental data and are very close to the variational transition state theory values carried out by Sayos et al

  15. Band energy control of molybdenum oxide by surface hydration

    Energy Technology Data Exchange (ETDEWEB)

    Butler, Keith T., E-mail: k.t.butler@bath.ac.uk; Walsh, Aron [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Crespo-Otero, Rachel [School of Biological and Chemical Sciences, Queen Mary University London, Mile End Road, London E1 4NS (United Kingdom); Buckeridge, John; Scanlon, David O. [University College London, Kathleen Lonsdale Materials Chemistry, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Bovill, Edward; Lidzey, David [Department of Physics and Astronomy, University of Sheffield, Hicks Building, Hounsfield Road, Sheffield S3 7RH (United Kingdom)

    2015-12-07

    The application of oxide buffer layers for improved carrier extraction is ubiquitous in organic electronics. However, the performance is highly susceptible to processing conditions. Notably, the interface stability and electronic structure is extremely sensitive to the uptake of ambient water. In this study we use density functional theory calculations to asses the effects of adsorbed water on the electronic structure of MoO{sub x}, in the context of polymer-fullerene solar cells based on PCDTBT. We obtain excellent agreement with experimental values of the ionization potential for pristine MoO{sub 3} (010). We find that IP and EA values can vary by as much as 2.5 eV depending on the oxidation state of the surface and that adsorbed water can either increase or decrease the IP and EA depending on the concentration of surface water.

  16. Optical emission from low-energy ion-surface collisions

    International Nuclear Information System (INIS)

    White, C.W.; Thomas, E.W.; Van der Weg, W.F.; Tolk, N.H.

    1977-01-01

    Impact of energetic heavy particles on surfaces gives rise to emission of optical radiation from reflected particles, sputtered particles and also from excited states of the solid. The present status of research in this area is reviewed with emphasis on understanding the basic mechanisms which give rise to formation of excited states. The spectral line shape from ejected atoms may be analyzed to provide information on the distribution of speeds and directions of the excited species; the line intensity provides a measure of the probability for creating the state. Formation of excited species is related both to the collision processes within the solid and also to the interaction of the recoiling ejected species with the target surface. Most ejected species are atomic but important examples of ejected molecules are also discussed. Luminescence induced in the solid itself is related to recombination of electron hole pairs and is related significantly to the presence of defects

  17. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin

    2016-01-01

    Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

  18. Bending energy penalty enhances the adhesive strength of functional amyloid curli to surfaces

    Science.gov (United States)

    Zhang, Yao; Wang, Ao; DeBenedictis, Elizabeth P.; Keten, Sinan

    2017-11-01

    The functional amyloid curli fiber, a major proteinaceous component of biofilm extracellular matrices, plays an important role in biofilm formation and enterobacteriaceae adhesion. Curli nanofibers exhibit exceptional underwater adhesion to various surfaces, have high rigidity and strong tensile mechanical properties, and thus hold great promise in biomaterials. The mechanisms of how curli fibers strongly attach to surfaces and detach under force remain elusive. To investigate curli fiber adhesion to surfaces, we developed a coarse-grained curli fiber model, in which the protein subunit CsgA (curli specific gene A) self-assembles into the fiber. The coarse-grained model yields physiologically relevant and tunable bending rigidity and persistence length. The force-induced desorption of a single curli fiber is examined using coarse-grained modeling and theoretical analysis. We find that the bending energy penalty arising from high persistence length enhances the resistance of the curli fiber against desorption and thus strengthens the adhesion of the curli fiber to surfaces. The CsgA-surface adhesion energy and the curli fiber bending rigidity both play crucial roles in the resistance of curli fiber against desorption from surfaces. To enable the desorption process, the applied peeling force must overcome both the interfacial adhesion energy and the energy barrier for bending the curli fiber at the peeling front. We show that the energy barrier to desorption increases with the interfacial adhesion energy, however, the bending induced failure of a single curli fiber limits the work of adhesion if the proportion of the CsgA-surface adhesion energy to the CsgA-CsgA cohesive energy becomes large. These results illustrate that the optimal adhesion performance of nanofibers is dictated by the interplay between bending, surface energy and cohesive energy. Our model provides timely insight into enterobacteriaceae adhesion mechanisms as well as future designs of engineered

  19. Radiotherapy high energy surface dose measurements: effects of chamber polarity

    International Nuclear Information System (INIS)

    Cheung, T.; Yu, P.K.N.; Butson, M.J.; Cancer Services, Wollongong, NSW

    2004-01-01

    Full text: The effects of chamber polarity have been investigated for the measurement of 6MV and 18MV x-ray surface dose using a parallel plate ionization chamber. Results have shown that a significant difference in measured ionization is recorded between to polarities at 6MV and 18MV at the phantom surface. A polarity ratio ranging from 1 062 to 1 005 is seen for 6MV x-rays at the phantom surface for field sizes 5cm x 5cm to 40cm x 40cm when comparing positive to negative polarity. These ratios range from 1.024 to 1.004 for 18MV x-rays with the same field sizes. When these charge reading are compared to the D max readings of the same polarity it is found that these polarity effects are minimal for the calculation of percentage dose results with variations being less than 1% of maximum. Copyright (2004) Australasian College of Physical Scientists and Engineers in Medicine

  20. Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

    International Nuclear Information System (INIS)

    Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; Abild-Pedersen, Frank; Nørskov, Jens K.; Chan, Karen

    2017-01-01

    Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. This shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.

  1. Apparent Surface Free Energy of Polymer/Paper Composite Material Treated by Air Plasma

    Directory of Open Access Journals (Sweden)

    Konrad Terpiłowski

    2017-01-01

    Full Text Available Surface plasma treatment consists in changes of surface properties without changing internal properties. In this paper composite polymer/paper material is used for production of packaging in cosmetic industry. There are problems with bonding this material at the time of packaging production due to its properties. Composite surface was treated by air plasma for 1, 10, 20, and 30 s. The advancing and receding contact angles of water, formamide, and diiodomethane were measured using both treated and untreated samples. Apparent surface free energy was estimated using the hysteresis (CAH and Van Oss, Good, Chaudhury approaches (LWAB. Surface roughness was investigated using optical profilometry and identification of after plasma treatment emerging chemical groups was made by means of the XPS (X-ray photoelectron spectroscopy technique. After plasma treatment the values of contact angles decreased which is particularly evident for polar liquids. Apparent surface free energy increased compared to that of untreated samples. Changes of energy value are due to the electron-donor parameter of energy. This parameter increases as a result of adding polar groups at the time of surface plasma activation. Changes of surface properties are combination of increase of polar chemical functional groups, increase on the surface, and surface roughness increase.

  2. Spatiotemporal variability in surface energy balance across tundra, snow and ice in Greenland

    DEFF Research Database (Denmark)

    Lund, Magnus; Stiegler, Christian; Abermann, Jakob

    2017-01-01

    The surface energy balance (SEB) is essential for understanding the coupled cryosphere–atmosphere system in the Arctic. In this study, we investigate the spatiotemporal variability in SEB across tundra, snow and ice. During the snow-free period, the main energy sink for ice sites is surface melt....... For tundra, energy is used for sensible and latent heat flux and soil heat flux leading to permafrost thaw. Longer snow-free period increases melting of the Greenland Ice Sheet and glaciers and may promote tundra permafrost thaw. During winter, clouds have a warming effect across surface types whereas during...

  3. Energy characteristics of finest coal particles surfaces versus their upgrading using flotation

    Energy Technology Data Exchange (ETDEWEB)

    Jerzy Sablik

    2007-07-01

    The paper presents selected results of investigations on energy properties of the fine coal particles, and methodological grounds for conducting such investigations. Using the discussed relationships, values of contact angle of coal particles with various degree of coalification in the range defined by the energy nonhomogeneity of the surfaces were computed. There have been determined the values of the contact angles of coal particles with hydrophobic and hydrophilic surfaces after coating with nonpolar and polar reagents. The energy state of the surfaces of coal particles in the feeds and products of industrial flotation were determined, which enabled to evaluate this process. 22 refs., 6 figs., 4 tabs.

  4. Observations of discrete energy loss effects in spectra of positrons reflected from solid surfaces

    International Nuclear Information System (INIS)

    Dale, J.M.; Hulett, L.D.; Pendyala, S.

    1980-01-01

    Surfaces of tungsten and silicon have been bombarded with monoenergetic beams of positrons and electrons. Spectra of reflected particles show energy loss tails with discrete peaks at kinetic energies about 15 eV lower than that of the elastic peaks. In the higher energy loss range for tungsten, positron spectra show fine structure that is not apparent in the electron spectra. This suggests that the positrons are losing energy through mechanisms different from that of the electrons

  5. Intermolecular potential energy surface and thermophysical properties of ethylene oxide.

    Science.gov (United States)

    Crusius, Johann-Philipp; Hellmann, Robert; Hassel, Egon; Bich, Eckard

    2014-10-28

    A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C2H4O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

  6. Surface energy balance measurements in the Mexico City: a review

    Energy Technology Data Exchange (ETDEWEB)

    Tejeda Martinez, A. [Universidad Veracruzana, Xalapa, Veracruz (Mexico); Jauregui Ostos, E. [Centro de Ciencias de la Atmosfera, Universidad Nacional Autonoma de Mexico, UNAM, Mexico, D.F. (Mexico)

    2005-01-01

    During the last decade of the 20th Century, diverse campaigns for measuring the atmospheric energy balance were performed in downtown Mexico City (School of Mines and Preparatory School No. 7), in the southern suburbs (University Reserve) and in the surrounding rural areas (Plan Texcoco), in addition to a campaign carried out in 1985 in the Tacubaya district, a suburban western peripheral site. The objective was to obtain data for a better understanding of the climatic alterations due to urbanization, particularly to describe the role that the modification of the natural ground cover has played as a result of paving and the construction of urban canyons. In this paper, a review of these campaigns is presented. Energy partitioning in some areas (Tacubaya and Preparatory School No.7) is similar to that observed in urban centers of middle latitudes, whereas the major contrast was observed between Texcoco, with maximum energy consumption through evaporation, and School of Mines, where the latent heat is as low as in a desert. From the values of the correlations among the different components of energy balance, it may be possible to attempt the modeling of the diverse components of energy balance by means of regression equations starting from the net radiation. Those same coefficients distinguish the type of environment: urban, suburban or rural. [Spanish] Las primeras mediciones de balance energetico en la Ciudad de Mexico se realizaron en 1985 en un suburbio al poniente de la ciudad (el observatorio de Tacubaya). Ya en la decada de los anos noventa del siglo XX, dichas observaciones se multiplicaron tanto en el centro historico (antigua Escuela de Minas y en el edificio de la Preparatoria No. 7), como en otros sitios al sur (en terrenos de Ciudad Universitaria) y en la periferia rural (Plan Texcoco). El proposito de estas mediciones ha sido tener un mejor entendimiento de las alteraciones climaticas debidas a la urbanizacion. En este trabajo se presenta una revision

  7. Extension of a He-H2 potential energy surface

    International Nuclear Information System (INIS)

    Raczkowski, A.W.; Lester, W.A. Jr.

    1977-01-01

    The CI surface of Tsapline and Kutzelnigg is extended to smaller H 2 -He separations. Defining R as the H 2 -He distance, r as the H 2 separation, and γ as the angle between them, the ab initio values are fit to a Legendre series in cosγ retaining the first three (even) terms with the coefficients given as analytic functions of R and r to facilitate semiclassical scattering computations. The fit is quantitative for 1.0 approximately r/2+1. (Auth.)

  8. Fowler's approximation for the surface tension and surface energy of Lennard-Jones fluids revisited

    Energy Technology Data Exchange (ETDEWEB)

    Mulero, A [Departamento de Fisica, Universidad de Extremadura, 06071-Badajoz (Spain); Galan, C [Departamento de Fisica, Universidad de Extremadura, 06071-Badajoz (Spain); Cuadros, F [Departamento de Fisica, Universidad de Extremadura, 06071-Badajoz (Spain)

    2003-04-16

    We present a detailed study of the validity of Fowler's approximation for calculating the surface tension and the surface energy of Lennard-Jones fluids. To do so, we consider three different explicit analytical expressions for the radial distribution function (RDF), including one proposed by our research group, together with very accurate expressions for the liquid and vapour densities, also proposed by our group. The calculation of the surface tension from the direct correlation function using both the Percus-Yevick and the hypernetted-chain approximations is also considered. Finally, our results are compared with those obtained by other authors by computer simulations or through relevant theoretical approximations. In particular, we consider the analytical expression proposed by Kalikmanov and Hofmans (1994 J. Phys.: Condens. Matter 6 2207-14) for the surface tension. Our results indicate that the values for the surface energy in Fowler's approximation obtained by other authors are adequate, and can be calculated from the RDF models. For the surface tension, however, the values considered as valid in previous works seem to be incorrect. The correct values can be obtained from our model for the RDF or from the Kalikmanov and Hofmans expression with suitable inputs.

  9. Constructing a multidimensional free energy surface like a spider weaving a web.

    Science.gov (United States)

    Chen, Changjun

    2017-10-15

    Complete free energy surface in the collective variable space provides important information of the reaction mechanisms of the molecules. But, sufficient sampling in the collective variable space is not easy. The space expands quickly with the number of the collective variables. To solve the problem, many methods utilize artificial biasing potentials to flatten out the original free energy surface of the molecule in the simulation. Their performances are sensitive to the definitions of the biasing potentials. Fast-growing biasing potential accelerates the sampling speed but decreases the accuracy of the free energy result. Slow-growing biasing potential gives an optimized result but needs more simulation time. In this article, we propose an alternative method. It adds the biasing potential to a representative point of the molecule in the collective variable space to improve the conformational sampling. And the free energy surface is calculated from the free energy gradient in the constrained simulation, not given by the negative of the biasing potential as previous methods. So the presented method does not require the biasing potential to remove all the barriers and basins on the free energy surface exactly. Practical applications show that the method in this work is able to produce the accurate free energy surfaces for different molecules in a short time period. The free energy errors are small in the cases of various biasing potentials. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  10. Oxathiiranes 8 On the OCS2 Singlet Potential Energy Surface

    DEFF Research Database (Denmark)

    Carlsen, Lars

    1982-01-01

    The reaction between atomic oxygen and carbon disulfide is predicted to lead to at least two primary products, which are the dithiiranone (1) and the oxathiirane-thione (2) and/or the carbon disulfide S-oxide (4). The possible intramolecular equilibria 1 ⇄ 2, 1 ⇄ 3, 2 ⇄ 4, and 2 ⇄ 5 as well...... as the fragmentations of the possible intermediates 1–5 have been studied theoretically within the semiempirical cndo/B framework as conceivable ground-state reactions. On the basis of mo correlations and potential energy changes along the reaction paths, supplementary with previously reported experimental data...

  11. Surface potential measurement of negative-ion-implanted insulators by analysing secondary electron energy distribution

    International Nuclear Information System (INIS)

    Toyota, Yoshitaka; Tsuji, Hiroshi; Nagumo, Syoji; Gotoh, Yasuhito; Ishikawa, Junzo; Sakai, Shigeki.

    1994-01-01

    The negative ion implantation method we have proposed is a noble technique which can reduce surface charging of isolated electrodes by a large margin. In this paper, the way to specify the surface potential of negative-ion-implanted insulators by the secondary electron energy analysis is described. The secondary electron energy distribution is obtained by a retarding field type energy analyzer. The result shows that the surface potential of fused quartz by negative-ion implantation (C - with the energy of 10 keV to 40 keV) is negatively charged by only several volts. This surface potential is extremely low compared with that by positive-ion implantation. Therefore, the negative-ion implantation is a very effective method for charge-up free implantation without charge compensation. (author)

  12. Discrete lattice plane broken bond interfacial energy calculations and the use of the dividing surface concept

    International Nuclear Information System (INIS)

    Ramanujan, R.V.

    2003-01-01

    The concept of the dividing surface has been extensively used to define the relationships between thermodynamic quantities at the interface between two phases; it is also useful in calculations of interfacial energy (γ). However, in the original formulation, the two phases are continuum phases, the atomistic nature of the interface was not considered. It is, therefore, useful to examine the use of the dividing surface in the context of atomistic interfacial energy calculations. The case of a planar fcc:hcp interface is considered and the dividing surface positions which are useful in atomistic interfacial energy calculations are stated, one position equates γ to the excess internal energy, the other position allows us to use the Gibbs adsorption equation. An example of a calculation using the convenient dividing surface positions is presented

  13. Relation between bulk compressibility and surface energy of electron-hole liquids

    International Nuclear Information System (INIS)

    Singwi, K.S.; Tosi, M.P.

    1979-08-01

    Attention is drawn to the existence of an empirical relation chiσ/asup(*)sub(B) approximately 1 between the compressibility, the surface energy and the excitonic radius in electron-hole liquids. (author)

  14. Energy storage considerations for a robotic Mars surface sampler

    International Nuclear Information System (INIS)

    O'Donnell, P.M.; Cataldo, R.L.; Gonzalez-Sanabria, O.D.

    1988-01-01

    Manned exploration of Mars is being proposed by the National Commission on Space for the next century. To accomplish this task with minimal resupply cost for extended stay times, use of Mars' resources is essential. Methods must be developed to manufacture or extract water and oxygen from elements indigenous to Mars before they send explorers to the planet. Therefore, they must send precursor surveying equipment to determine Mars' resources to a greater extent than is now known from Viking 1 and Viking 2 data. A 1992 launch is planned for the Mars Observer that will contribute greater mapping resolution and expand the scientific data base. The proposed rover will provide scientists with the necessary information about abundant resources that would guide the required technology development needed to support a manned Mars infrastructure. The actual rover operations plan for both the sample return and extended mission will have a large impact on rover capabilities and the power system supplying power for traversing and scientific instrumentation. POWER SOURCE AND CONVERSION. Several power source/conversion options for the rover have been identified. These include power generation on the lander, Entry Vehicle (EV), Mars Orbiter Vehicle (MOV) and on the rover itself. Power from the lander would require the rover to return to landing site to recharge the energy storage systems, which limits rover excursions to one-half the range of the storage capacity. For on-board rover power, a Radioisotope Thermoelectric Generator (RTG) has been considered with the appropriate energy storage to handle peak power demands

  15. Impact of Dust on Mars Surface Albedo and Energy Flux with LMD General Circulation Model

    Science.gov (United States)

    Singh, D.; Flanner, M.; Millour, E.; Martinez, G.

    2015-12-01

    Mars, just like Earth experience different seasons because of its axial tilt (about 25°). This causes growth and retreat of snow cover (primarily CO2) in Martian Polar regions. The perennial caps are the only place on the planet where condensed H2O is available at surface. On Mars, as much as 30% atmospheric CO2 deposits in each hemisphere depending upon the season. This leads to a significant variation on planet's surface albedo and hence effecting the amount of solar flux absorbed or reflected at the surface. General Circulation Model (GCM) of Laboratoire de Météorologie Dynamique (LMD) currently uses observationally derived surface albedo from Thermal Emission Spectrometer (TES) instrument for the polar caps. These TES albedo values do not have any inter-annual variability, and are independent of presence of any dust/impurity on surface. Presence of dust or other surface impurities can significantly reduce the surface albedo especially during and right after a dust storm. This change will also be evident in the surface energy flux interactions. Our work focuses on combining earth based Snow, Ice, and Aerosol Radiation (SNICAR) model with current state of GCM to incorporate the impact of dust on Martian surface albedo, and hence the energy flux. Inter-annual variability of surface albedo and planet's top of atmosphere (TOA) energy budget along with their correlation with currently available mission data will be presented.

  16. Kinetic energy distributions of ions after surface collisions

    International Nuclear Information System (INIS)

    Short, R.T.; Todd, P.J.; Grimm, C.C.

    1991-01-01

    As a part of the development of an organic ion microprobe, to be used for imaging of particular organic compounds in biological tissue, various methods of quadrupole-based tandem mass spectroscopy (MS/MS) have been investigated. High transmission efficiency is essential for the success of the organic ion microprobe, due to expected low analyte concentrations in biological tissue and the potential for sample damage from prolonged exposure to the primary ion beam. MS/MS is necessary for organic ion imaging because of the complex nature of the biological matrices. The goal of these studies of was to optimize the efficiency of daughter ion production and transmission by first determining daughter ion properties and then designing ion optics based on those properties. The properties of main interest are daughter ion kinetic energy and angular distribution. 1 fig

  17. Electronic energy transfer from molecules to metal and semiconductor surfaces, and chemisorption-induced changes in optical response of the nickel (111) surface

    International Nuclear Information System (INIS)

    Whitmore, P.M.

    1982-10-01

    The evolution of molecular excited states near solid surfaces is investigated. The mechanisms through which energy is transferred to the surface are described within a classical image dipole picture of the interaction. More sophisticated models for the dielectric response of the solid surface add important new decay channels for the energy dissipation. The predictions and applicability of three of these refined theories are discussed

  18. Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

    Science.gov (United States)

    Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

    2018-01-01

    Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

  19. Correlation of Effective Dispersive and Polar Surface Energies in Heterogeneous Self-Assembled Monolayer Coatings

    DEFF Research Database (Denmark)

    Zhuang, Yanxin; Hansen, Ole

    2009-01-01

    grown oil oxidized (100) silicon Surfaces in a vapor phase process using five different precursors. Experimentally, effective surface energy components of the fluorocarbon self-assembled monolayers were determined from measured contact angles using the Owens-Wendt-Rabel-Kaelble method. We show...

  20. Scattering of low energy noble gas ions from a metal surface

    International Nuclear Information System (INIS)

    Luitjens, S.B.

    1980-01-01

    Reflection of low energy (0.1-10 keV) noble gas ions can be used to analyse a solid surface. To study charge exchange processes, the ion fractions of neon and of argon, scattered from a Cu(100) surface, have been determined. (Auth.)

  1. Influence of compaction and surface roughness on low-energy ion scattering signals

    NARCIS (Netherlands)

    Jansen, W.P.A.; Knoester, A.; Maas, A.J.H.; Schmit, P.; Kytökivi, A.; Denier van der Gon, A.W.; Brongersma, H.H.

    2004-01-01

    Investigation of the surface composition of powders often requires compaction. To study the effect of compaction on surface analysis, samples have been compacted at various pressures ranging from 0 Pa (i.e. no compaction) up to 2000 MPa (2 × 104 kg cm-2) Low-energy ion scattering (LEIS) was used to

  2. Ab initio and work function and surface energy anisotropy of LaB6

    NARCIS (Netherlands)

    Uijttewaal, M. A.; de Wijs, G. A.; de Groot, R. A.

    2006-01-01

    Lanthanum hexaboride is one of the cathode materials most used in high-power electronics technology, but the many experimental results do not provide a consistent picture of the surface properties. Therefore, we report the first ab initio calculations of the work functions and surface energies of

  3. Calibration of a distributed hydrology and land surface model using energy flux measurements

    DEFF Research Database (Denmark)

    Larsen, Morten Andreas Dahl; Refsgaard, Jens Christian; Jensen, Karsten H.

    2016-01-01

    In this study we develop and test a calibration approach on a spatially distributed groundwater-surface water catchment model (MIKE SHE) coupled to a land surface model component with particular focus on the water and energy fluxes. The model is calibrated against time series of eddy flux measure...

  4. Polar surface energies of iono-covalent materials: implications of a charge-transfer model tested on Li2FeSiO4 surfaces.

    Science.gov (United States)

    Hörmann, Nicolas G; Groß, Axel

    2014-07-21

    The ionic compounds that are used as electrode materials in Li-based rechargeable batteries can exhibit polar surfaces that in general have high surface energies. We derive an analytical estimate for the surface energy of such polar surfaces assuming charge redistribution as a polarity compensating mechanism. The polar contribution to the converged surface energy is found to be proportional to the bandgap multiplied by the surface charge necessary to compensate for the depolarization field, and some higher order correction terms that depend on the specific surface. Other features, such as convergence behavior, coincide with published results. General conclusions are drawn on how to perform polar surface energy calculations in a slab configuration and upper boundaries of "purely" polar surface energies are estimated. Furthermore, we compare these findings with results obtained in a density functional theory study of Li(2)FeSiO(4) surfaces. We show that typical polar features are observed and provide a decomposition of surface energies into polar and local bond-cutting contributions for 29 different surfaces. We show that the model is able to explain subtle differences of GGA and GGA+U surface energy calculations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Investigation of inelastic scattering of ultracold neutrons with small energy transfer at solid state surfaces

    International Nuclear Information System (INIS)

    Lychagin, E.V.; Muzychka, A.Yu.; Nekhaev, G.V.; Strelkov, A.V.; Shvetsov, V.N.; Nesvizhevskij, V.V.; Tal'daev, R.R.

    2001-01-01

    Inelastic scattering of neutrons with small energy transfer of ∼10 -7 eV was investigated using gravitational UCN spectrometer. The probability of such a process at stainless steel and beryllium surfaces was measured. It was also estimated at copper surface. The measurement showed that the detected flux of neutrons scattered at beryllium and copper surfaces is ∼ 2 times higher at room temperature compared to that at the liquid nitrogen temperature. (author)

  6. Energy-switching potential energy surface for the water molecule revisited: A highly accurate singled-sheeted form.

    Science.gov (United States)

    Galvão, B R L; Rodrigues, S P J; Varandas, A J C

    2008-07-28

    A global ab initio potential energy surface is proposed for the water molecule by energy-switching/merging a highly accurate isotope-dependent local potential function reported by Polyansky et al. [Science 299, 539 (2003)] with a global form of the many-body expansion type suitably adapted to account explicitly for the dynamical correlation and parametrized from extensive accurate multireference configuration interaction energies extrapolated to the complete basis set limit. The new function mimics also the complicated Sigma/Pi crossing that arises at linear geometries of the water molecule.

  7. Surface plasmon modes of a single silver nanorod: An electron energy loss study

    DEFF Research Database (Denmark)

    Nicoletti, Olivia; Wubs, Martijn; Mortensen, N. Asger

    2011-01-01

    We present an electron energy loss study using energy filtered TEM of spatially resolved surface plasmon excitations on a silver nanorod of aspect ratio 14.2 resting on a 30 nm thick silicon nitride membrane. Our results show that the excitation is quantized as resonant modes whose intensity maxima...

  8. Soil heat flux and day time surface energy balance closure at ...

    Indian Academy of Sciences (India)

    Soil heat flux is an important input component of surface energy balance. Estimates of soil heat flux were ... mate source of energy for all physical and bio- logical processes ... May) account for major thunderstorm activity in the state and winter ...

  9. Transition-state characterization: a new approach combining inhibitor analogues and variation in enzyme structure.

    Science.gov (United States)

    Phillips, M A; Kaplan, A P; Rutter, W J; Bartlett, P A

    1992-02-04

    A new strategy of potentially broad application for probing transition-state (TS) analogy in enzymatic systems is described in this paper. The degree to which a series of phosphonate inhibitors act as TS analogues of rat carboxypeptidase A1 has been determined for the wild-type enzyme, for the R127K, R127M, and R127A mutants, and for the R127A mutant in the presence of 0.5 M guanidine hydrochloride. The impact that the mutations have on the inverse second-order rate constants (Km/kcat) for substrate hydrolysis is mirrored by the effect on the inhibition constants (Ki) for the corresponding phosphonate inhibitors. These results demonstrate that the phosphonate moiety mimics some of the electronic as well as the geometric characteristics of the TS. A similar but distinctly separate correlation is observed for tripeptide analogues in comparison to analogues of the dipeptide Cbz-Gly-Phe, reflecting an anomalous mode of binding for the latter system. The selective rate increases and corresponding enhancement in inhibitor binding observed on addition of 0.5 M guanidine hydrochloride to the R127A mutant indicate that the exogenous cation can assume the role played by Arg-127 in stabilizing the TS and in providing substrate selectivity at the P2 position.

  10. Characterisation of transition state structures for protein folding using 'high', 'medium' and 'low' {Phi}-values.

    Science.gov (United States)

    Geierhaas, Christian D; Salvatella, Xavier; Clarke, Jane; Vendruscolo, Michele

    2008-03-01

    It has been suggested that Phi-values, which allow structural information about transition states (TSs) for protein folding to be obtained, are most reliably interpreted when divided into three classes (high, medium and low). High Phi-values indicate almost completely folded regions in the TS, intermediate Phi-values regions with a detectable amount of structure and low Phi-values indicate mostly unstructured regions. To explore the extent to which this classification can be used to characterise in detail the structure of TSs for protein folding, we used Phi-values divided into these classes as restraints in molecular dynamics simulations. This type of procedure is related to that used in NMR spectroscopy to define the structure of native proteins from the measurement of inter-proton distances derived from nuclear Overhauser effects. We illustrate this approach by determining the TS ensembles of five proteins and by showing that the results are similar to those obtained by using as restraints the actual numerical Phi-values measured experimentally. Our results indicate that the simultaneous consideration of a set of low-resolution Phi-values can provide sufficient information for characterising the architecture of a TS for folding of a protein.

  11. Role of Chemical Reactivity and Transition State Modeling for Virtual Screening.

    Science.gov (United States)

    Karthikeyan, Muthukumarasamy; Vyas, Renu; Tambe, Sanjeev S; Radhamohan, Deepthi; Kulkarni, Bhaskar D

    2015-01-01

    Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product- like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

  12. Computational study of substrate isotope effect probes of transition state structure for acetylcholinesterase catalysis

    International Nuclear Information System (INIS)

    Sikorski, R.S.; Malany, S.; Seravalli, J.; Quinn, D.M.

    2002-01-01

    Secondary isotope effects for carbonyl addition reactions of methyl thioacetate, acetone and acetaldehyde have been calculated by ab initio quantum mechanical methods in an effect to interpret measured β-deuterium isotope effects on acetylcholinesterase-catalysed hydrolysis of acetylthiocholine. The calculated β-deuterium isotope effect for equilibrium addition of methanol to methyl thioacetate is D3 K eq = 0.965, and the corresponding effect for addition of methoxide ion to methyl thioacetate wherein three waters are hydrogen bonded to the carbonyl oxyanion is D3 K eq = 1.086. Neither of these calculated isotope effects is an inverse as the experimental β-deuterium isotope effect for acetylcholinesterase-catalysed hydrolysis of acetylthiocholine, D3 K eq = 0.90±0.03. Structural comparisons show that the water-solvated methoxide adduct of methyl thioacetate is more expanded than is the natural methanol addition adduct, and suggest that the degree of which the isotope effect is inverse (i.e. less than) is inversely correlated to the degree of expansion of the adduct. A similar correlation of α-deuterium and β-deuterium secondary isotope effects with the degree of expansion of the adducts is found for equilibrium additions of methanol and methoxide ion to acetylaldehyde. These computational results suggest that the markedly inverse β-deuterium isotope effect for the acetylcholinesterase reaction arises from enzymatic compression of the transition state. (author)

  13. Understanding the Catalytic Mechanism and the Nature of the Transition State of an Attractive Drug-Target Enzyme (Shikimate Kinase) by Quantum Mechanical/Molecular Mechanical (QM/MM) Studies.

    Science.gov (United States)

    Yao, Jianzhuang; Wang, Xia; Luo, Haixia; Gu, Pengfei

    2017-11-16

    Shikimate kinase (SK) is the fifth bacterial enzyme involved in the shikimate pathway for biosynthesis of life-indispensable components, such as aromatic amino acids. The absence of the shikimate pathway in humans makes SK an attractive target for the rational design of drugs aimed at pathogenesis bacteria, such as Mycobacterium tuberculosis and Helicobacter pylori. However, an effective inhibitor of SK (e.g., a transition-state analogue) is still not available on the market due, at least in part, to a lack of knowledge on the catalytic mechanism and the nature of the rate-limiting transition state. Herein, quantum mechanical/molecular mechanical (QM/MM) reaction coordinate, molecular dynamics (MD), and free-energy simulations have been performed to answer these questions. The results presented herein demonstrate that the phosphoryl-transfer process, which is the rate-limiting step of SK-catalyzed phosphorylation of shikimic acid (SKM), is a concerted one-step reaction proceeding through a loose transition state. The computational results agree well with those of experimental studies, specifically NMR results, X-ray crystal structure observation, and activation free-energy barrier. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Molecular dynamics simulation of bovine pancreatic ribonuclease A-CpA and transition state-like complexes.

    Science.gov (United States)

    Formoso, Elena; Matxain, Jon M; Lopez, Xabier; York, Darrin M

    2010-06-03

    The mechanisms of enzymes are intimately connected with their overall structure and dynamics in solution. Experimentally, it is considerably challenging to provide detailed atomic level information about the conformational events that occur at different stages along the chemical reaction path. Here, theoretical tools may offer new potential insights that complement those obtained from experiments that may not yield an unambiguous mechanistic interpretation. In this study, we apply molecular dynamics simulations of bovine pancreatic ribonuclease A, an archetype ribonuclease, to study the conformational dynamics, structural relaxation, and differential solvation that occur at discrete stages of the transesterification and cleavage reaction. Simulations were performed with explicit solvation with rigorous electrostatics and utilize recently developed molecular mechanical force field parameters for transphosphorylation and hydrolysis transition state analogues. Herein, we present results for the enzyme complexed with the dinucleotide substrate cytidilyl-3',5'-adenosine (CpA) in the reactant, and transphosphorylation and hydrolysis transition states. A detailed analysis of active site structures and hydrogen-bond patterns is presented and compared. The integrity of the overall backbone structure is preserved in the simulations and supports a mechanism whereby His12 stabilizes accumulating negative charge at the transition states through hydrogen-bond donation to the nonbridge oxygens. Lys41 is shown to be highly versatile along the reaction coordinate and can aid in the stabilization of the dianionic transition state, while being poised to act as a general acid catalyst in the hydrolysis step.

  15. Transition state kinetics of Hg(II) adsorption at gibbsite-water interface

    International Nuclear Information System (INIS)

    Weerasooriya, Rohan; Tobschall, Heinz J.; Seneviratne, Wasana; Bandara, Atula

    2007-01-01

    Kinetics of adsorption plays a pivotal factor in determining the bio-availability and mobility of Hg(II) in the environment. The kinetics of Hg(II) adsorption on gibbsite was examined as a function of pH, temperature and electrolyte type. Adsorption of Hg(II) was highly non-linear where the rate of Hg(II) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing contact time. The respective rate constants designated as k 1 (S-1: fast step) and k 2 (S-2: slow step). Always k 1 follows the order: k 1 ClO 4 >=k 1 (NO 3 ) 4 >>k 1 Cl . Such a relationship was not observed for the S-2 route. A two-step reaction model with pseudo-first order kinetics successfully described the adsorption rates of Hg(II) on gibbsite. Arrhenius and Erying models determined the thermodynamic parameters at activation states, which correspond to S-1 and S-2 routes. In a given system, always the activation energies showed a decrease with the pH. Gibbs free energy (ΔG numbersign ), enthalpy (ΔH numbersign ), and entropy (ΔS numbersign ) values of activation states were almost similar both in NaClO 4 and NaNO 3 which signal a similar Hg(II) adsorptive mechanism on gibbsite. The configurations of different Hg(II)-surface complexes were elucidated by transmission vibration spectroscopy

  16. Survival probability in small angle scattering of low energy alkali ions from alkali covered metal surfaces

    International Nuclear Information System (INIS)

    Neskovic, N.; Ciric, D.; Perovic, B.

    1982-01-01

    The survival probability in small angle scattering of low energy alkali ions from alkali covered metal surfaces is considered. The model is based on the momentum approximation. The projectiles are K + ions and the target is the (001)Ni+K surface. The incident energy is 100 eV and the incident angle 5 0 . The interaction potential of the projectile and the target consists of the Born-Mayer, the dipole and the image charge potentials. The transition probability function corresponds to the resonant electron transition to the 4s projectile energy level. (orig.)

  17. Potential energy surfaces for N = Z, 20Ne-112Ba nuclei

    International Nuclear Information System (INIS)

    Mehta, M.S.; Gupta, Raj K.; Jha, T.K.; Patra, S.K.

    2004-01-01

    We have calculated the potential energy surfaces for N = Z, 20 Ne- 112 Ba nuclei in an axially deformed relativistic mean field approach. A quadratic constraint scheme is applied to determine the complete energy surface for a wide range of the quadrupole deformation. The NL3, NL-RAl and TM1 parameter sets are used. The phenomenon of (multiple) shape coexistence is studied and the calculated ground and excited state binding energies, quadrupole deformation parameters and root mean square (rms) charge radii are compared with the available experimental data and other theoretical predictions. (author)

  18. Energy and angle resolved ion scattering spectroscopy: new possibilities for surface analysis

    International Nuclear Information System (INIS)

    Hellings, G.J.A.

    1986-01-01

    In this thesis the design and development of a novel, very sensitive and high-resolving spectrometer for surface analysis is described. This spectrometer is designed for Energy and Angle Resolved Ion Scattering Spectroscopy (EARISS). There are only a few techniques that are sensitive enough to study the outermost atomic layer of surfaces. One of these techniques, Low-Energy Ion Scattering (LEIS), is discussed in chapter 2. Since LEIS is destructive, it is important to make a very efficient use of the scattered ions. This makes it attractive to simultaneously carry out energy and angle dependent measurements (EARISS). (Auth.)

  19. Experimental parameters for quantitative surface analysis by medium energy ion scattering, ch. 1

    International Nuclear Information System (INIS)

    Turkenburg, W.C.; Kersten, H.H.; Colenbrander, B.G.; Jongh, A.P. de; Saris, F.W.

    1976-01-01

    A new UHV chamber for surface and surface layer analysis by collision spectroscopy of backscattered ions at medium energies is described. Experimental parameters like energy, angular and depth resolution, crystal alignment and background pressure are discussed. Formulae based on the use of an electrostatic energy analyser show that the analysis can be quantitative. Effects of beam induced build-up of a hydro-carbon layer, sputter cleaning and creation of radiation damage have been investigated for Cu (110) and Ni (110). Detection sensitivity for Carbon, Oxygen and Sulfur on Cu and Ni has been found to be 0.2, 0.1 and 0.03 of a monolayer respectively

  20. Low energy helium ion irradiation induced nanostructure formation on tungsten surface

    International Nuclear Information System (INIS)

    Al-Ajlony, A.; Tripathi, J.K.; Hassanein, A.

    2017-01-01

    We report on the low energy helium ion irradiation induced surface morphology changes on tungsten (W) surfaces under extreme conditions. Surface morphology changes on W surfaces were monitored as a function of helium ion energy (140–300 eV), fluence (2.3 × 10 24 –1.6 × 10 25 ions m −2 ), and flux (2.0 × 10 20 –5.5 × 10 20 ion m −2 s −1 ). All the experiments were performed at 900° C. Our study shows significant effect of all the three ion irradiation parameters (ion flux, fluence, and energy) on the surface morphology. However, the effect of ion flux is more pronounced. Variation of helium ion fluence allows to capture the very early stages of fuzz growth. The observed fuzz growth and morphology changes were understood in the realm of various possible phenomena. The study has relevance and important impact in the current and future nuclear fusion applications. - Highlights: •Reporting formation of W nanostructure (fuzz) due to low energy He ion beam irradiation. •Observing the very early stages for the W-Fuzz formation. •Tracking the surface morphological evolution during the He irradiation. •Discussing in depth our observation and drawing a possible scenario that explain this phenomenon. •Studying various ions irradiation parameters such as flux, fluence, and ions energy.

  1. Low energy helium ion irradiation induced nanostructure formation on tungsten surface

    Energy Technology Data Exchange (ETDEWEB)

    Al-Ajlony, A., E-mail: montaserajlony@yahoo.com; Tripathi, J.K.; Hassanein, A.

    2017-05-15

    We report on the low energy helium ion irradiation induced surface morphology changes on tungsten (W) surfaces under extreme conditions. Surface morphology changes on W surfaces were monitored as a function of helium ion energy (140–300 eV), fluence (2.3 × 10{sup 24}–1.6 × 10{sup 25} ions m{sup −2}), and flux (2.0 × 10{sup 20}–5.5 × 10{sup 20} ion m{sup −2} s{sup −1}). All the experiments were performed at 900° C. Our study shows significant effect of all the three ion irradiation parameters (ion flux, fluence, and energy) on the surface morphology. However, the effect of ion flux is more pronounced. Variation of helium ion fluence allows to capture the very early stages of fuzz growth. The observed fuzz growth and morphology changes were understood in the realm of various possible phenomena. The study has relevance and important impact in the current and future nuclear fusion applications. - Highlights: •Reporting formation of W nanostructure (fuzz) due to low energy He ion beam irradiation. •Observing the very early stages for the W-Fuzz formation. •Tracking the surface morphological evolution during the He irradiation. •Discussing in depth our observation and drawing a possible scenario that explain this phenomenon. •Studying various ions irradiation parameters such as flux, fluence, and ions energy.

  2. Potential energy surface from spectroscopic data in the photodissociation of polyatomic molecules

    International Nuclear Information System (INIS)

    Kim, Hwa Joong; Kim, Young Sik

    2001-01-01

    The time-dependent tracking inversion method is studied to extract the potential energy surface of the electronic excited state in the photodissociation of triatomic molecules. Based on the relay of the regularized inversion procedure and time-dependent wave packet propagation, the algorithm extracts the underlying potential energy surface piece by tracking the time-dependent data, which can be synthesized from Raman excitation profiles. We have demonstrated the algorithm to extract the potential energy surface of electronic excited state for NO 2 molecule where the wave packet split on a saddle-shaped surface. Finally, we describe the merits of the time-dependent tracking inversion method compared with the time-dependent inversion method and discussed several extensions of the algorithm

  3. Energy storage and dispersion of surface acoustic waves trapped in a periodic array of mechanical resonators

    DEFF Research Database (Denmark)

    Dühring, Maria Bayard; Laude, Vincent; Khelif, Abdelkrim

    2009-01-01

    It has been shown previously that surface acoustic waves can be efficiently trapped and slowed by steep ridges on a piezoelectric substrate, giving rise to two families of shear-horizontal and vertically polarized surface waves. The mechanisms of energy storage and dispersion are explored by using...... the finite element method to model surface acoustic waves generated by high aspect ratio electrodes. A periodic model is proposed including a perfectly matched layer to simulate radiation conditions away from the sources, from which the modal distributions are found. The ratio of the mechanical energy...... confined to the electrode as compared to the total mechanical energy is calculated and is found to be increasing for increasing aspect ratio and to tend to a definite limit for the two families of surface waves. This observation is in support of the interpretation that high aspect ratio electrodes act...

  4. Modification of the surface energy in isovalent nano-oxides prepared by chemical synthesis

    International Nuclear Information System (INIS)

    Miagava, J.; Gouvea, D.

    2011-01-01

    The phase stability of the nano-oxides depends on the bulk energy but it also depends on the surface energy. The difference of surface energy of the rutile and anatase phases result in a change of phase stability: TiO_2 without additives is stable as anatase when particles have nanometric size and a high specific surface area whereas rutile is stable when particles are larger. But this stability can be modified through the use of additives. Different studies demonstrate that additives segregate on the particle surface modifying the surface energy. In this work (1-X)TiO_2-XSnO_2 powders were synthesized by the polymeric precursor method with concentrations of 0 ≤ X ≤ 1. The specific surface area measurements demonstrate that the modification of the composition change the specific surface areas and it reaches a maximum at X = 0.005. The Raman spectroscopy demonstrates that a modification on the stability of the TiO_2 polymorphs occurs and the phase rutile is stabilized when SnO_2 is added to the nano powders.(author)

  5. Calculation of the surface energy of hcp-metals with the empirical electron theory

    International Nuclear Information System (INIS)

    Fu Baoqin; Liu Wei; Li Zhilin

    2009-01-01

    A brief introduction of the surface model based on the empirical electron theory (EET) and the dangling bond analysis method (DBAM) is presented in this paper. The anisotropy of spatial distribution of covalent bonds of hexagonal close-packed (hcp) metals such as Be, Mg, Sc, Ti, Co, Zn, Y, Zr, Tc, Cd, Hf, and Re, has been analyzed. And under the first-order approximation, the calculated surface energy values for low index surfaces of these hcp-metals are in agreement with experimental and other theoretical values. Correlated analysis showed that the anisotropy of surface energy of hcp-metals was related with the ratio of lattice constants (c/a). The calculation method for the research of surface energy provides a good basis for models of surface science phenomena, and the model may be extended to the surface energy estimation of more metals, alloys, ceramics, and so on, since abundant information about the valence electronic structure (VES) is generated from EET.

  6. Different secondary structure elements as scaffolds for protein folding transition states of two homologous four-helix bundles.

    Science.gov (United States)

    Teilum, Kaare; Thormann, Thorsten; Caterer, Nigel R; Poulsen, Heidi I; Jensen, Peter H; Knudsen, Jens; Kragelund, Birthe B; Poulsen, Flemming M

    2005-04-01

    Comparison of the folding processes for homologue proteins can provide valuable information about details in the interactions leading to the formation of the folding transition state. Here the folding kinetics of 18 variants of yACBP and 3 variants of bACBP have been studied by Phi-value analysis. In combination with Phi-values from previous work, detailed insight into the transition states for folding of both yACBP and bACBP has been obtained. Of the 16 sequence positions that have been studied in both yACBP and bACBP, 5 (V12, I/L27, Y73, V77, and L80) have high Phi-values and appear to be important for the transition state formation in both homologues. Y31, A34, and A69 have high Phi-values only in yACBP, while F5, A9, and I74 have high Phi-values only in bACBP. Thus, additional interactions between helices A2 and A4 appear to be important for the transition state of yACBP, whereas additional interactions between helices A1 and A4 appear to be important for the transition state of bACBP. To examine whether these differences could be assigned to different packing of the residues in the native state, a solution structure of yACBP was determined by NMR. Small changes in the packing of the hydrophobic side-chains, which strengthen the interactions between helices A2 and A4, are observed in yACBP relative to bACBP. It is suggested that different structure elements serve as scaffolds for the folding of the 2 ACBP homologues. (c) 2005 Wiley-Liss, Inc.

  7. Dynamics of very low energy photoelectrons interacting with image charge of Cs/Cu(111) surface

    International Nuclear Information System (INIS)

    Hayashi, K.; Arafune, R.; Ueda, S.; Uehara, Y.; Ushioda, S.

    2005-01-01

    We have measured the very low energy photoelectron spectra of Cs-covered Cu(111) surfaces, and determined the mechanism for the appearance of a spike structure due to the interaction of emitted electron with its image charge. At high Cs coverage of 0.10 and 0.14 monolayers (ML), the spike structure appeared at the vacuum level. No such structure was found at low coverage of 0.06 ML. The vacuum level at high coverage lies in the energy gap at the Γ point in the surface Brillouin zone of the Cu(111) surface, while it lies outside the energy gap at low coverage. These results confirm the validity of our proposed mechanism that the spike structure appears when the vacuum level lies in the energy gap

  8. Full charge-density calculation of the surface energy of metals

    DEFF Research Database (Denmark)

    Vitos, Levente; Kollár, J..; Skriver, Hans Lomholt

    1994-01-01

    of a spherically symmetrized charge density, while the Coulomb and exchange-correlation contributions are calculated by means of the complete, nonspherically symmetric charge density within nonoverlapping, space-filling Wigner-Seitz cells. The functional is used to assess the convergence and the accuracy......We have calculated the surface energy and the work function of the 4d metals by means of an energy functional based on a self-consistent, spherically symmetric atomic-sphere potential. In this approach the kinetic energy is calculated completely within the atomic-sphere approximation (ASA) by means...... of the linear-muffin-tin-orbitals (LMTO) method and the ASA in surface calculations. We find that the full charge-density functional improves the agreement with recent full-potential LMTO calculations to a level where the average deviation in surface energy over the 4d series is down to 10%....

  9. Effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interface temperature and surface energy

    Directory of Open Access Journals (Sweden)

    Tong Wen

    Full Text Available The microwave-assisted leaching was a new approach to intensify the copper recovery from chalcopyrite by hydrometallurgy. In this work, the effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interfacial reaction temperature and surface energy were investigated. The activation energy of chalcopyrite leaching was affected indistinctively by the microwave-assisted heating (39.1 kJ/mol compared with the conventional heating (43.9 kJ/mol. However, the boiling point of the leaching system increased through microwave-assisted heating. Because of the improved boiling point and the selective heating of microwave, the interfacial reaction temperature increased significantly, which gave rise to the increase of the leaching recovery of copper. Moreover, the surface energy of the chalcopyrite through microwave-assisted heating was also enhanced, which was beneficial to strengthen the leaching of chalcopyrite. Keywords: Microwave-assisted heating, Chalcopyrite, Leaching kinetics, Interface temperature, Surface energy

  10. Active surface model improvement by energy function optimization for 3D segmentation.

    Science.gov (United States)

    Azimifar, Zohreh; Mohaddesi, Mahsa

    2015-04-01

    This paper proposes an optimized and efficient active surface model by improving the energy functions, searching method, neighborhood definition and resampling criterion. Extracting an accurate surface of the desired object from a number of 3D images using active surface and deformable models plays an important role in computer vision especially medical image processing. Different powerful segmentation algorithms have been suggested to address the limitations associated with the model initialization, poor convergence to surface concavities and slow convergence rate. This paper proposes a method to improve one of the strongest and recent segmentation algorithms, namely the Decoupled Active Surface (DAS) method. We consider a gradient of wavelet edge extracted image and local phase coherence as external energy to extract more information from images and we use curvature integral as internal energy to focus on high curvature region extraction. Similarly, we use resampling of points and a line search for point selection to improve the accuracy of the algorithm. We further employ an estimation of the desired object as an initialization for the active surface model. A number of tests and experiments have been done and the results show the improvements with regards to the extracted surface accuracy and computational time of the presented algorithm compared with the best and recent active surface models. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Surface effects on sputtered atoms and their angular and energy dependence

    International Nuclear Information System (INIS)

    Hassanein, A.M.

    1985-04-01

    A comprehensive three-dimensional Monte Carlo computer code, Ion Transport in Materials and Compounds (ITMC), has been developed to study in detail the surfaces related phenomena that affect the amount of sputtered atoms and back-scattered ions and their angular and energy dependence. A number of important factors that can significantly affect the sputtering behavior of a surface can be studied in detail, such as having different surface properties and composition than the bulk and synergistic effects due to surface segregation of alloys. These factors can be important in determining and lifetime of fusion reactor first walls and limiters. The ITMC Code is based on Monte Carlo methods to track down the path and the damage produced by charged particles as they slow down in solid metal surfaces or compounds. The major advantages of the ITMC code are its flexibility and ability to use and compare all existing models for energy losses, all known interatomic potentials, and to use different materials and compounds with different surface and bulk composition to allow for dynamic surface composition to allow for dynamic surface composition changes. There is good agreement between the code and available experimental results without using adjusting parameters for the energy losses mechanisms. The ITMC Code is highly optimized, very fast to run and easy to use

  12. Low-energy electron irradiation induced top-surface nanocrystallization of amorphous carbon film

    Science.gov (United States)

    Chen, Cheng; Fan, Xue; Diao, Dongfeng

    2016-10-01

    We report a low-energy electron irradiation method to nanocrystallize the top-surface of amorphous carbon film in electron cyclotron resonance plasma system. The nanostructure evolution of the carbon film as a function of electron irradiation density and time was examined by transmission electron microscope (TEM) and Raman spectroscopy. The results showed that the electron irradiation gave rise to the formation of sp2 nanocrystallites in the film top-surface within 4 nm thickness. The formation of sp2 nanocrystallite was ascribed to the inelastic electron scattering in the top-surface of carbon film. The frictional property of low-energy electron irradiated film was measured by a pin-on-disk tribometer. The sp2 nanocrystallized top-surface induced a lower friction coefficient than that of the original pure amorphous film. This method enables a convenient nanocrystallization of amorphous surface.

  13. Behavior of Rydberg atoms at surfaces: energy level shifts and ionization

    Energy Technology Data Exchange (ETDEWEB)

    Dunning, F.B. E-mail: fbd@rice.edu; Dunham, H.R.; Oubre, C.; Nordlander, P

    2003-04-01

    The ionization of xenon atoms excited to the extreme red and blue states in high-lying Xe(n) Stark manifolds at a metal surface is investigated. The data show that, despite their very different initial spatial characteristics, the extreme members of a given Stark manifold ionize at similar atom/surface separations. This is explained, with the aid of complex scaling calculations, in terms of the strong perturbations in the energies and structure of the atomic states induced by the presence of the surface which lead to avoided crossings between neighboring levels as the surface is approached.

  14. Behavior of Rydberg atoms at surfaces: energy level shifts and ionization

    CERN Document Server

    Dunning, F B; Oubre, C D; Nordlander, P

    2003-01-01

    The ionization of xenon atoms excited to the extreme red and blue states in high-lying Xe(n) Stark manifolds at a metal surface is investigated. The data show that, despite their very different initial spatial characteristics, the extreme members of a given Stark manifold ionize at similar atom/surface separations. This is explained, with the aid of complex scaling calculations, in terms of the strong perturbations in the energies and structure of the atomic states induced by the presence of the surface which lead to avoided crossings between neighboring levels as the surface is approached.

  15. Influences of biomass heat and biochemical energy storages on the land surface fluxes and radiative temperature

    Science.gov (United States)

    Gu, Lianhong; Meyers, Tilden; Pallardy, Stephen G.; Hanson, Paul J.; Yang, Bai; Heuer, Mark; Hosman, Kevin P.; Liu, Qing; Riggs, Jeffery S.; Sluss, Dan; Wullschleger, Stan D.

    2007-01-01

    The interest of this study was to develop an initial assessment on the potential importance of biomass heat and biochemical energy storages for land-atmosphere interactions, an issue that has been largely neglected so far. We conducted flux tower observations and model simulations at a temperate deciduous forest site in central Missouri in the summer of 2004. The model used was the comprehensive terrestrial ecosystem Fluxes and Pools Integrated Simulator (FAPIS). We first examined FAPIS performance by testing its predictions with and without the representation of biomass energy storages against measurements of surface energy and CO2 fluxes. We then evaluated the magnitudes and temporal patterns of the biomass energy storages calculated by FAPIS. Finally, the effects of biomass energy storages on land-atmosphere exchanges of sensible and latent heat fluxes and variations of land surface radiative temperature were investigated by contrasting FAPIS simulations with and without these storage terms. We found that with the representation of the two biomass energy storage terms, FAPIS predictions agreed with flux tower measurements fairly well; without the representation, however, FAPIS performance deteriorated for all predicted surface energy flux terms although the effect on the predicted CO2 flux was minimal. In addition, we found that the biomass heat storage and biochemical energy storage had clear diurnal patterns with typical ranges from -50 to 50 and -3 to 20 W m-2, respectively; these typical ranges were exceeded substantially when there were sudden changes in atmospheric conditions. Furthermore, FAPIS simulations without the energy storages produced larger sensible and latent heat fluxes during the day but smaller fluxes (more negative values) at night as compared with simulations with the energy storages. Similarly, without-storage simulations had higher surface radiative temperature during the day but lower radiative temperature at night, indicating that the

  16. Contribution of cutinase serine 42 side chain to the stabilization of the oxyanion transition state.

    Science.gov (United States)

    Nicolas, A; Egmond, M; Verrips, C T; de Vlieg, J; Longhi, S; Cambillau, C; Martinez, C

    1996-01-16

    Cutinase from the fungus Fusarium solani pisi is a lipolytic enzyme able to hydrolyze both aggregated and soluble substrates. It therefore provides a powerful tool for probing the mechanisms underlying lipid hydrolysis. Lipolytic enzymes have a catalytic machinery similar to those present in serine proteinases. It is characterized by the triad Ser, His, and Asp (Glu) residues, by an oxyanion binding site that stabilizes the transition state via hydrogen bonds with two main chain amide groups, and possibly by other determinants. It has been suggested on the basis of a covalently bond inhibitor that the cutinase oxyanion hole may consist not only of two main chain amide groups but also of the Ser42 O gamma side chain. Among the esterases and the serine and the cysteine proteases, only Streptomyces scabies esterase, subtilisin, and papain, respectively, have a side chain residue which is involved in the oxyanion hole formation. The position of the cutinase Ser42 side chain is structurally conserved in Rhizomucor miehei lipase with Ser82 O gamma, in Rhizopus delemar lipase with Thr83 O gamma 1, and in Candida antartica B lipase with Thr40 O gamma 1. To evaluate the increase in the tetrahedral intermediate stability provided by Ser42 O gamma, we mutated Ser42 into Ala. Furthermore, since the proper orientation of Ser42 O gamma is directed by Asn84, we mutated Asn84 into Ala, Leu, Asp, and Trp, respectively, to investigate the contribution of this indirect interaction to the stabilization of the oxyanion hole. The S42A mutation resulted in a drastic decrease in the activity (450-fold) without significantly perturbing the three-dimensional structure. The N84A and N84L mutations had milder kinetic effects and did not disrupt the structure of the active site, whereas the N84W and N84D mutations abolished the enzymatic activity due to drastic steric and electrostatic effects, respectively.

  17. High Pressure ZZ-Exchange NMR Reveals Key Features of Protein Folding Transition States.

    Science.gov (United States)

    Zhang, Yi; Kitazawa, Soichiro; Peran, Ivan; Stenzoski, Natalie; McCallum, Scott A; Raleigh, Daniel P; Royer, Catherine A

    2016-11-23

    Understanding protein folding mechanisms and their sequence dependence requires the determination of residue-specific apparent kinetic rate constants for the folding and unfolding reactions. Conventional two-dimensional NMR, such as HSQC experiments, can provide residue-specific information for proteins. However, folding is generally too fast for such experiments. ZZ-exchange NMR spectroscopy allows determination of folding and unfolding rates on much faster time scales, yet even this regime is not fast enough for many protein folding reactions. The application of high hydrostatic pressure slows folding by orders of magnitude due to positive activation volumes for the folding reaction. We combined high pressure perturbation with ZZ-exchange spectroscopy on two autonomously folding protein domains derived from the ribosomal protein, L9. We obtained residue-specific apparent rates at 2500 bar for the N-terminal domain of L9 (NTL9), and rates at atmospheric pressure for a mutant of the C-terminal domain (CTL9) from pressure dependent ZZ-exchange measurements. Our results revealed that NTL9 folding is almost perfectly two-state, while small deviations from two-state behavior were observed for CTL9. Both domains exhibited large positive activation volumes for folding. The volumetric properties of these domains reveal that their transition states contain most of the internal solvent excluded voids that are found in the hydrophobic cores of the respective native states. These results demonstrate that by coupling it with high pressure, ZZ-exchange can be extended to investigate a large number of protein conformational transitions.

  18. Effect of cocoa fat content on wetting and surface energy of chocolate

    Directory of Open Access Journals (Sweden)

    Lubomír Lapčík

    2017-01-01

    Full Text Available The aim of this study was the quantification of the effect of the cocoa fat content on the wetting characteristics and surface free energy of different chocolate compositions. On the market, there are many different types of chocolate products which differ both in the sensory and physico-chemical properties together with their raw material compositions and the contents of the individual components. This paper focuses on differences in the use of different types of fats - cocoa butter, milk fat, equivalents or cocoa butter substitutes in chocolate products. Studied samples (prepared at Carla, Ltd. Company were followed by static contact angles of wetting measurements and by calculated surface free energies. There were investigated the effects of fat content and used fat types of the chocolate products on their final wettabilities and resulting surface free energies. There was found a linear dependence between total fat content and the surface free energy, which was gradually increasing with increasing fat content. Additionally, there were performed TG DTG and NIR spectrometry measurements of the tested materials with the aim to determine the melting point of studied fats used, as well as to determine and identify individual fat components of chocolate products which may affect the resulting value of surface free energy.

  19. Relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives.

    Science.gov (United States)

    Nagura, Yuko; Tsujimoto, Akimasa; Barkmeier, Wayne W; Watanabe, Hidehiko; Johnson, William W; Takamizawa, Toshiki; Latta, Mark A; Miyazaki, Masashi

    2018-04-01

    The relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives was investigated. The initial shear bond strengths and shear fatigue strengths of five universal adhesives to enamel were determined with and without phosphoric acid pre-etching. The surface free-energy characteristics of adhesive-treated enamel with and without pre-etching were also determined. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were higher than those to ground enamel. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were material dependent, unlike those to ground enamel. The surface free-energy of the solid (γ S ) and the hydrogen-bonding force (γSh) of universal adhesive-treated enamel were different depending on the adhesive, regardless of the presence or absence of pre-etching. The bond fatigue durability of universal adhesives was higher to pre-etched enamel than to ground enamel. In addition, the bond fatigue durability to pre-etched enamel was material dependent, unlike that to ground enamel. The surface free-energy characteristics of universal adhesive-treated enamel were influenced by the adhesive type, regardless of the presence or absence of pre-etching. The surface free-energy characteristics of universal adhesive-treated enamel were related to the results of the bond fatigue durability. © 2018 Eur J Oral Sci.

  20. An optimized surface plasmon photovoltaic structure using energy transfer between discrete nano-particles.

    Science.gov (United States)

    Lin, Albert; Fu, Sze-Ming; Chung, Yen-Kai; Lai, Shih-Yun; Tseng, Chi-Wei

    2013-01-14

    Surface plasmon enhancement has been proposed as a way to achieve higher absorption for thin-film photovoltaics, where surface plasmon polariton(SPP) and localized surface plasmon (LSP) are shown to provide dense near field and far field light scattering. Here it is shown that controlled far-field light scattering can be achieved using successive coupling between surface plasmonic (SP) nano-particles. Through genetic algorithm (GA) optimization, energy transfer between discrete nano-particles (ETDNP) is identified, which enhances solar cell efficiency. The optimized energy transfer structure acts like lumped-element transmission line and can properly alter the direction of photon flow. Increased in-plane component of wavevector is thus achieved and photon path length is extended. In addition, Wood-Rayleigh anomaly, at which transmission minimum occurs, is avoided through GA optimization. Optimized energy transfer structure provides 46.95% improvement over baseline planar cell. It achieves larger angular scattering capability compared to conventional surface plasmon polariton back reflector structure and index-guided structure due to SP energy transfer through mode coupling. Via SP mediated energy transfer, an alternative way to control the light flow inside thin-film is proposed, which can be more efficient than conventional index-guided mode using total internal reflection (TIR).

  1. On the mechanics of continua with boundary energies and growing surfaces

    Science.gov (United States)

    Papastavrou, Areti; Steinmann, Paul; Kuhl, Ellen

    2013-06-01

    Many biological systems are coated by thin films for protection, selective absorption, or transmembrane transport. A typical example is the mucous membrane covering the airways, the esophagus, and the intestine. Biological surfaces typically display a distinct mechanical behavior from the bulk; in particular, they may grow at different rates. Growth, morphological instabilities, and buckling of biological surfaces have been studied intensely by approximating the surface as a layer of finite thickness; however, growth has never been attributed to the surface itself. Here, we establish a theory of continua with boundary energies and growing surfaces of zero thickness in which the surface is equipped with its own potential energy and is allowed to grow independently of the bulk. In complete analogy to the kinematic equations, the balance equations, and the constitutive equations of a growing solid body, we derive the governing equations for a growing surface. We illustrate their spatial discretization using the finite element method, and discuss their consistent algorithmic linearization. To demonstrate the conceptual differences between volume and surface growth, we simulate the constrained growth of the inner layer of a cylindrical tube. Our novel approach toward continua with growing surfaces is capable of predicting extreme growth of the inner cylindrical surface, which more than doubles its initial area. The underlying algorithmic framework is robust and stable; it allows to predict morphological changes due to surface growth during the onset of buckling and beyond. The modeling of surface growth has immediate biomedical applications in the diagnosis and treatment of asthma, gastritis, obstructive sleep apnoea, and tumor invasion. Beyond biomedical applications, the scientific understanding of growth-induced morphological instabilities and surface wrinkling has important implications in material sciences, manufacturing, and microfabrication, with applications in

  2. Controlled synthesis and photocatalytic properties of rhombic dodecahedral Ag3PO4 with high surface energy

    International Nuclear Information System (INIS)

    Xie, Yao; Huang, Zhaohui; Zhang, Zhijie; Zhang, Xiaoguang; Wen, Ruilong; Liu, Yangai; Fang, Minghao; Wu, Xiaowen

    2016-01-01

    Graphical abstract: The high amount of rhombic dodecahedral Ag 3 PO 4 particles with a high exposure of the {110} facets and high surface energy (the surface energy of the {110} facets was 1.31 J/m 2 , greater than that of the {100} facet (1.12 J/m 2 ).) exhibited excellent photocatalytic activity. - Highlights: • High contents of rhombic dodecahedral Ag 3 PO 4 photocatalysts are prepared. • Excessive EG can destroy the morphology of Ag 3 PO 4 in synthesis process. • The rhombic dodecahedral Ag 3 PO 4 exhibits high surface energy. • High surface energy implies high photocatalytic activity. - Abstract: In this study, a series of Ag 3 PO 4 photocatalysts with different contents of rhombic dodecahedral particles were prepared in one pot by a facile, novel hydrothermal method using ethylene glycol (EG), which served as both a morphology modifier and reducing agent. The effects of EG content on the morphologies of Ag 3 PO 4 photocatalysts were discussed. The photocatalytic activity of the Ag 3 PO 4 photocatalysts was evaluated by the degradation of methylene blue trihydrate under visible-light irradiation. With the use of 0.8% EG in the reaction solvent, the sample exhibited excellent photocatalytic activity, attributed to the high amount of rhombic dodecahedral Ag 3 PO 4 particles with a high exposure of the {110} facets and high surface energy. The surface energy of the {110} facets was 1.31 J/m 2 , greater than that of the {100} facet (1.12 J/m 2 ). However, with 1% EG in the reaction solvent, although the Ag 3 PO 4 photocatalysts were composed of a majority of rhombic dodecahedral Ag 3 PO 4 particles, tiny Ag particles formed from Ag + under the action of EG attached on the surface of the sample decreased the absorption of visible light, resulting in low photocatalytic activity.

  3. Effect of Collagen Matrix Saturation on the Surface Free Energy of Dentin using Different Agents.

    Science.gov (United States)

    de Almeida, Leopoldina de Fátima Dantas; Souza, Samilly Evangelista; Sampaio, Aline Araújo; Cavalcanti, Yuri Wanderley; da Silva, Wander José; Del Bel Cur, Altair A; Hebling, Josimeri

    2015-07-01

    The surface free energy of conditioned-dentin is one of the factors that interfere with monomeric infiltration of the interfibrillar spaces. Saturation of the tooth matrix with different substances may modulate this energy and, consequently, the wettability of the dentin. To evaluate the influence of different substances used to saturate conditioned-dentin on surface free energy (SFE) of this substrate. Dentin blocks (4 × 7 × 1 mm, n = 6/ group), obtained from the roots of bovine incisors, were etched using phosphoric acid for 15 seconds, rinsed and gently dried. The surfaces were treated for 60 seconds with: ultra-purified water (H20-control); ethanol (EtOH), acetone (ACT), chlorhexidine (CHX), ethylenediaminetetraacetic acid (EDTA); or sodium hypochlorite (NaOCl). The tooth surfaces were once again dried with absorbent paper and prepared for SFE evaluation using three standards: water, formamide and bromonaphthalene. Analysis of variance (ANOVA) and Dunnet's tests (a = 0.05) were applied to the data. Ethylenediaminetetraacetic acid was the only substance that caused a change to the contact angle for the standards water and formamide, while only EtOH influenced the angles formed between formamide and the dentin surface. None of the substances exerted a significant effect for bromonaphtha-lene. In comparison to the control, only EDTA and NaOCl altered both polar components of the SFE. Total SFE was increased by saturation of the collagen matrix by EDTA and reduced when NaOCl was used. Saturation of the collagen matrix by EDTA and EtOH changed the surface free energy of the dentin. In addition, the use of NaOCl negatively interfered with the properties evaluated. The increase of surface free energy and wettability of the dentin surface would allow higher penetration of the the adhesive system, which would be of importance to the clinical success of resin-dentin union.

  4. Metadyn View: Fast web-based viewer of free energy surfaces calculated by metadynamics

    Science.gov (United States)

    Hošek, Petr; Spiwok, Vojtěch

    2016-01-01

    Metadynamics is a highly successful enhanced sampling technique for simulation of molecular processes and prediction of their free energy surfaces. An in-depth analysis of data obtained by this method is as important as the simulation itself. Although there are several tools to compute free energy surfaces from metadynamics data, they usually lack user friendliness and a build-in visualization part. Here we introduce Metadyn View as a fast and user friendly viewer of bias potential/free energy surfaces calculated by metadynamics in Plumed package. It is based on modern web technologies including HTML5, JavaScript and Cascade Style Sheets (CSS). It can be used by visiting the web site and uploading a HILLS file. It calculates the bias potential/free energy surface on the client-side, so it can run online or offline without necessity to install additional web engines. Moreover, it includes tools for measurement of free energies and free energy differences and data/image export.

  5. Silver inkjet printing with control of surface energy and substrate temperature

    International Nuclear Information System (INIS)

    Lee, S-H; Shin, K-Y; Hwang, J Y; Kang, K T; Kang, H S

    2008-01-01

    The characteristics of silver inkjet printing were intensively investigated with control of surface energy and substrate temperature. A fluorocarbon (FC) film was spincoated on a silicon (Si) substrate to obtain a hydrophobic surface, and an ultraviolet (UV)/ozone (O 3 ) treatment was performed to control the surface wettability of the FC film surface. To characterize the surface changes, we performed measurements of the static and dynamic contact angles and calculated the surface energy by Wu's harmonic mean model. The surface energy of the FC film increased with the UV/O 3 treatment time, while the contact angles decreased. In silver inkjet printing, the hydrophobic FC film could reduce the diameter of the printed droplets. Merging of deposited droplets was observed when the substrate was kept at room temperature. Substrate heating was effective in preventing the merging phenomenon among the deposited droplets, and in reducing the width of printed lines. The merging phenomenon of deposited droplets was also prevented by increasing the UV/O 3 treatment time. Continuous silver lines in the width range of 48.04–139.21 µm were successfully achieved by inkjet printing on the UV/O 3 -treated hydrophobic FC films at substrate temperatures below 90 °C

  6. Modeling the Surface Energy Balance of the Core of an Old Mediterranean City: Marseille.

    Science.gov (United States)

    Lemonsu, A.; Grimmond, C. S. B.; Masson, V.

    2004-02-01

    The Town Energy Balance (TEB) model, which parameterizes the local-scale energy and water exchanges between urban surfaces and the atmosphere by treating the urban area as a series of urban canyons, coupled to the Interactions between Soil, Biosphere, and Atmosphere (ISBA) scheme, was run in offline mode for Marseille, France. TEB's performance is evaluated with observations of surface temperatures and surface energy balance fluxes collected during the field experiments to constrain models of atmospheric pollution and transport of emissions (ESCOMPTE) urban boundary layer (UBL) campaign. Particular attention was directed to the influence of different surface databases, used for input parameters, on model predictions. Comparison of simulated canyon temperatures with observations resulted in improvements to TEB parameterizations by increasing the ventilation. Evaluation of the model with wall, road, and roof surface temperatures gave good results. The model succeeds in simulating a sensible heat flux larger than heat storage, as observed. A sensitivity comparison using generic dense city parameters, derived from the Coordination of Information on the Environment (CORINE) land cover database, and those from a surface database developed specifically for the Marseille city center shows the importance of correctly documenting the urban surface. Overall, the TEB scheme is shown to be fairly robust, consistent with results from previous studies.

  7. Surface free energy predominates in cell adhesion to hydroxyapatite through wettability.

    Science.gov (United States)

    Nakamura, Miho; Hori, Naoko; Ando, Hiroshi; Namba, Saki; Toyama, Takeshi; Nishimiya, Nobuyuki; Yamashita, Kimihiro

    2016-05-01

    The initial adhesion of cells to biomaterials is critical in the regulation of subsequent cell behaviors. The purpose of this study was to investigate a mechanism through which the surface wettability of biomaterials can be improved and determine the effects of biomaterial surface characteristics on cellular behaviors. We investigated the surface characteristics of various types of hydroxyapatite after sintering in different atmospheres and examined the effects of various surface characteristics on cell adhesion to study cell-biomaterial interactions. Sintering atmosphere affects the polarization capacity of hydroxyapatite by changing hydroxide ion content and grain size. Compared with hydroxyapatite sintered in air, hydroxyapatite sintered in saturated water vapor had a higher polarization capacity that increased surface free energy and improved wettability, which in turn accelerated cell adhesion. We determined the optimal conditions of hydroxyapatite polarization for the improvement of surface wettability and acceleration of cell adhesion. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Inter-comparison of energy balance and hydrological models for land surface energy flux estimation over a whole river catchment

    DEFF Research Database (Denmark)

    Guzinski, R.; Nieto, H.; Stisen, S.

    2015-01-01

    Evapotranspiration (ET) is the main link between the natural water cycle and the land surface energy budget. Therefore water-balance and energy-balance approaches are two of the main methodologies for modelling this process. The water-balance approach is usually implemented as a complex....... The temporal patterns produced by the remote sensing and hydrological models are quite highly correlated (r ≈ 0.8). This indicates potential benefits to the hydrological modelling community of integrating spatial information derived through remote sensing methodology (contained in the ET maps...

  9. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  10. Near-surface energy transfers from internal tide beams to smaller vertical scale motions

    Science.gov (United States)

    Chou, S.; Staquet, C.; Carter, G. S.; Luther, D. S.

    2016-02-01

    Mechanical energy capable of causing diapycnal mixing in the ocean is transferred to the internal wave field when barotropic tides pass over underwater topography and generate internal tides. The resulting internal tide energy is confined in vertically limited structures, or beams. As internal tide beams (ITBs) propagate through regions of non-uniform stratification in the upper ocean, wave energy can be scattered through multiple reflections and refractions, be vertically trapped, or transferred to non-tidal frequencies through different nonlinear processes. Various observations have shown that ITBs are no longer detectable in horizontal kinetic energy beyond the first surface reflection. Importantly, this implies that some of the internal tide energy no longer propagates in to the abyssal ocean and consequently will not be available to maintain the density stratification. Using the NHM, a nonlinear and nonhydrostatic model based on the MITgcm, simulations of an ITB propagating up to the sea surface are examined in order to quantify the transformation of ITB energy to other motions. We compare and contrast the transformations enabled by idealized, smoothly-varying stratification with transformations enabled by realistic stratification containing a broad-band vertical wavenumber spectrum of variations. Preliminary two-dimensional results show that scattering due to small-scale structure in realistic stratification profiles from Hawaii can lead to energy being vertically trapped near the surface. Idealized simulations of "locally" generated internal solitary waves are analyzed in terms of energy flux transfers from the ITB to solitary waves, higher harmonics, and mean flow. The amount of internal tide energy which propagates back down after near-surface reflection of the ITB in different environments is quantified.

  11. Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks

    Energy Technology Data Exchange (ETDEWEB)

    Kolb, Brian [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Zhao, Bin; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Li, Jun [School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331 (China); Jiang, Bin [Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2016-06-14

    The applicability and accuracy of the Behler-Parrinello atomistic neural network method for fitting reactive potential energy surfaces is critically examined in three systems, H + H{sub 2} → H{sub 2} + H, H + H{sub 2}O → H{sub 2} + OH, and H + CH{sub 4} → H{sub 2} + CH{sub 3}. A pragmatic Monte Carlo method is proposed to make efficient choice of the atom-centered mapping functions. The accuracy of the potential energy surfaces is not only tested by fitting errors but also validated by direct comparison in dynamically important regions and by quantum scattering calculations. Our results suggest this method is both accurate and efficient in representing multidimensional potential energy surfaces even when dissociation continua are involved.

  12. Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks

    International Nuclear Information System (INIS)

    Kolb, Brian; Zhao, Bin; Guo, Hua; Li, Jun; Jiang, Bin

    2016-01-01

    The applicability and accuracy of the Behler-Parrinello atomistic neural network method for fitting reactive potential energy surfaces is critically examined in three systems, H + H 2 → H 2 + H, H + H 2 O → H 2 + OH, and H + CH 4 → H 2 + CH 3 . A pragmatic Monte Carlo method is proposed to make efficient choice of the atom-centered mapping functions. The accuracy of the potential energy surfaces is not only tested by fitting errors but also validated by direct comparison in dynamically important regions and by quantum scattering calculations. Our results suggest this method is both accurate and efficient in representing multidimensional potential energy surfaces even when dissociation continua are involved.

  13. Experimental determination of the thermal contact conductance between two solid surfaces by the energy pulse technique

    International Nuclear Information System (INIS)

    Rubin, Gerson Antonio

    1979-01-01

    An experimental procedure for the determination of the thermal contact conductance between two solid surfaces as a function of the contact pressure and the energy of the laser radiation has been developed using the laser pulse method. A rubi laser with variable energy levels was employed as a radiating pulse energy source. The laser beam was allowed to impinge perpendicularly on the front face of a electrolytic iron 73 4 . The temperature fluctuations resulting on the back surface of the sample was detected by a thermocouple, which Is coupled to a PDP-11/45 Computer 32 Kbytes of memory, through a Analog-Digital Converter. A theoretical function, derived exclusively for the problem mentioned in this work, was adjusted by a method of least square fitting of experimental results. This adjustment yielded the value of a parameter related to the contact conductance between two surfaces. The experimental error obtained for the thermal contact conductance was +- 4.9%. (author)

  14. The 1,5-H-shift in 1-butoxy: A case study in the rigorous implementation of transition state theory for a multirotamer system

    Science.gov (United States)

    Vereecken, Luc; Peeters, Jozef

    2003-09-01

    The rigorous implementation of transition state theory (TST) for a reaction system with multiple reactant rotamers and multiple transition state conformers is discussed by way of a statistical rate analysis of the 1,5-H-shift in 1-butoxy radicals, a prototype reaction for the important class of H-shift reactions in atmospheric chemistry. Several approaches for deriving a multirotamer TST expression are treated: oscillator versus (hindered) internal rotor models; distinguishable versus indistinguishable atoms; and direct count methods versus degeneracy factors calculated by (simplified) direct count methods or from symmetry numbers and number of enantiomers, where applicable. It is shown that the various treatments are fully consistent, even if the TST expressions themselves appear different. The 1-butoxy H-shift reaction is characterized quantum chemically using B3LYP-DFT; the performance of this level of theory is compared to other methods. Rigorous application of the multirotamer TST methodology in an harmonic oscillator approximation based on this data yields a rate coefficient of k(298 K,1 atm)=1.4×105 s-1, and an Arrhenius expression k(T,1 atm)=1.43×1011 exp(-8.17 kcal mol-1/RT) s-1, which both closely match the experimental recommendations in the literature. The T-dependence is substantially influenced by the multirotamer treatment, as well as by the tunneling and fall-off corrections. The present results are compared to those of simplified TST calculations based solely on the properties of the lowest energy 1-butoxy rotamer.

  15. Use of low energy alkali ion scattering as a probe of surface structure

    International Nuclear Information System (INIS)

    Overbury, S.H.

    1986-01-01

    An overview is given of the use of low energy ion scattering as a probe of surface structure with emphasis on work done using alkali ions. Various schemes for extracting structural information from the ion energy and angle distributions are discussed in terms of advantages and disadvantages of each. The scattering potential which is the primary non-structural parameter needed for analysis, is discussed in terms of recent experimental results. The structure of clean and reconstructed surfaces are discussed, with examples of measurements of layer relaxations on the Mo(111) surface and missing row reconstructions on the Au(110) and Pt(110) surfaces. Studies of adsorbate covered surfaces are presented with respect to location of the adsorbate and its effect on the structure of the underlying substrate. Finally, examples are given which demonstrate the sensitivity of ion scattering to surface defects and disordering on reconstructed Au(110) and Pt(110) surfaces and unreconstructed Mo(111) surfaces, and to ordering of adsorbates on Mo(001). 47 refs., 12 figs

  16. Enhancement of optical absorption of Si (100) surfaces by low energy N+ ion beam irradiation

    Science.gov (United States)

    Bhowmik, Dipak; Karmakar, Prasanta

    2018-05-01

    The increase of optical absorption efficiency of Si (100) surface by 7 keV and 8 keV N+ ions bombardment has been reported here. A periodic ripple pattern on surface has been observed as well as silicon nitride is formed at the ion impact zones by these low energy N+ ion bombardment [P. Karmakar et al., J. Appl. Phys. 120, 025301 (2016)]. The light absorption efficiency increases due to the presence of silicon nitride compound as well as surface nanopatterns. The Atomic Force Microscopy (AFM) study shows the formation of periodic ripple pattern and increase of surface roughness with N+ ion energy. The enhancement of optical absorption by the ion bombarded Si, compared to the bare Si have been measured by UV - visible spectrophotometer.

  17. Interaction of low energy electrons with surface lattice vibrations. Final report

    International Nuclear Information System (INIS)

    Tong, S.Y.

    1984-01-01

    In carrying out the DOE contract, we have succeeded in constructing a new microscopic theory, with multiple scattering, for the inelastic scattering of electrons by surface vibrations. We have applied the theory to detailed studies of angle and energy variations of the inelastic cross-section for two important systems in surface physics: carbon monoxide molecules adsorbed on the (100) surface of a nickel crystal, and hydrogen atoms adsorbed on a reconstructed tungsten (100) surface. These calculations have outlined general trends that we expect to apply to a wide variety of systems. Also, we have discovered a series of new selection rules that apply to off-specular scattering. Particularly interesting are pseudo-selection rules which are not group theoretical in origin, but approximate statements that hold well when the electron scattering amplitude exhibits a slow energy variation. We have found and defined conditions for which these selection rules would hold and break down

  18. Molar Surface Gibbs Energy of the Aqueous Solution of Ionic Liquid [C4mim][Oac

    Institute of Scientific and Technical Information of China (English)

    TONG Jing; ZHENG Xu; TONG Jian; QU Ye; LIU Lu; LI Hui

    2017-01-01

    The values of density and surface tension for aqueous solution of ionic liquid(IL) 1-butyl-3-methylimidazolium acetate([C4mim][OAc]) with various molalities were measured in the range of 288.15-318.15 K at intervals of 5 K.On the basis of thermodynamics,a semi-empirical model-molar surface Gibbs energy model of the ionic liquid solution that could be used to predict the surface tension or molar volume of solutions was put forward.The predicted values of the surface tension for aqueous [C4im][OAc] and the corresponding experimental ones were highly correlated and extremely similar.In terms of the concept of the molar Gibbs energy,a new E(o)tv(o)s equation was obtained and each parameter of the new equation has a clear physical meaning.

  19. Surface transformation hardening on steels treated with solar energy in central tower and heliostats field

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, G.P.; Lopez, V.; de Damborenea, J.J.; Vazquez, A.J. [Centro Nacional de Investigaciones Metalurgicas CENIM/CSIC, Madrid (Spain)

    1995-04-28

    The possibility of surface hardening on AISI 4140 steel treated with concentrated solar energy in solar installations for electricity production has been studied. The samples were slides from a 35 mm diameter steel bar and their height was 35 mm. The quenching was made in water but also was considered the possibility of self-quenching by cooling in air. The amount of the surface hardness and the different structures obtained in both cases are presented, and some discussion is made with reference to the surface hardness, the hardness profiles and the structures obtained. The heating of steel with concentrated solar energy may produce similar hardening to that obtained with more conventional techniques of surface hardening

  20. Surface free energy of CrN x films deposited using closed field unbalanced magnetron sputtering

    International Nuclear Information System (INIS)

    Sun, C.-C.; Lee, S.-C.; Dai, S.-B.; Fu, Y.-S.; Wang, Y.-C.; Lee, Y.-H.

    2006-01-01

    CrN x thin films have attracted much attention for semiconductor IC packaging molding dies and forming tools due to their excellent hardness, thermal stability and non-sticking properties (low surface free energy). However, few data has been published on the surface free energy (SFE) of CrN x films at temperatures in the range 20-170 deg. C. In this study CrN x thin films with CrN, Cr(N), Cr 2 N (and mixture of these phases) were prepared using closed field unbalanced magnetron sputtering at a wide range of Cr +2 emission intensity. The contact angles of water, di-iodomethane and ethylene glycol on the coated surfaces were measured at temperatures in the range 20-170 deg. C using a Dataphysics OCA-20 contact angle analyzer. The surface free energy of the CrN x films and their components (e.g., dispersion, polar) were calculated using the Owens-Wendt geometric mean approach. The influences of CrN x film surface roughness and microstructure on the surface free energy were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The experimental results showed that the lowest total SFE was obtained corresponding to CrN at temperature in 20 deg. C. This is lower than that of Cr(N), Cr 2 N (and mixture of these phases). The total SFE, dispersive SFE and polar SFE of CrN x films decreased with increasing surface temperature. The film roughness has an obvious effect on the SFE and there is tendency for the SFE to increase with increasing film surface roughness

  1. Surface modification of TA2 pure titanium by low energy high current pulsed electron beam treatments

    International Nuclear Information System (INIS)

    Gao Yukui

    2011-01-01

    Surface integrity changes of TA2 pure titanium including surface topography, microstructure and nanohardness distribution along surface layer were investigated by different techniques of low energy high current pulsed electron beam treatments (LEHCPEBTs). The surface topography was characterized by SEM. Moreover, the TEM observation and X-ray diffraction analysis were performed to reveal the surface modification mechanism of TA2 pure titanium by LEHCPEBTs. The surface roughness was modified by electron beam treatment and the polishing mechanism was analyzed by studying the cross section microstructure of electron beam treated specimens by SEM and TEM. The results show that the surface finish obtains good polishing quality and there is no phase transformation but the dislocations by LEHCPEBT. Furthermore, the nanohardness in the surface modified layer is improved. The remelt and fine-grain microstructure of surface layer caused by LEHCPEBTs are the main polishing mechanism and the reason of modification of surface topography and the increment in nanohardness is mainly due to the dislocations and fine grains in the modified layer induced by LEHCPEBT.

  2. Effect of nanoscale surface roughness on the bonding energy of direct-bonded silicon wafers

    Science.gov (United States)

    Miki, N.; Spearing, S. M.

    2003-11-01

    Direct wafer bonding of silicon wafers is a promising technology for manufacturing three-dimensional complex microelectromechanical systems as well as silicon-on-insulator substrates. Previous work has reported that the bond quality declines with increasing surface roughness, however, this relationship has not been quantified. This article explicitly correlates the bond quality, which is quantified by the apparent bonding energy, and the surface morphology via the bearing ratio, which describes the area of surface lying above a given depth. The apparent bonding energy is considered to be proportional to the real area of contact. The effective area of contact is defined as the area sufficiently close to contribute to the attractive force between the two bonding wafers. Experiments were conducted with silicon wafers whose surfaces were roughened by a buffered oxide etch solution (BOE, HF:NH4F=1:7) and/or a potassium hydroxide solution. The surface roughness was measured by atomic force microscopy. The wafers were direct bonded to polished "monitor" wafers following a standard RCA cleaning and the resulting bonding energy was measured by the crack-opening method. The experimental results revealed a clear correlation between the bonding energy and the bearing ratio. A bearing depth of ˜1.4 nm was found to be appropriate for the characterization of direct-bonded silicon at room temperature, which is consistent with the thickness of the water layer at the interface responsible for the hydrogen bonds that link the mating wafers.

  3. The relevance of rooftops: Analyzing the microscale surface energy balance in the Chicago region

    Science.gov (United States)

    Khosla, Radhika

    Spatial structure in climate variables often exist over very short length scales within an urban area, and this structure is a result of various site-specific features. In order to analyze the seasonal and diurnal energy flows that take place at a microclimatic surface, this work develops a semi-empirical energy balance model. For this, radiation fluxes and meteorological measurements are determined by direct observation; sensible heat and latent heat fluxes by parameterizations; and the heat storage flux by a 1-D mechanistic model that allows analysis of the temperature profile and heat storage within an underlying slab. Two sites receive detailed study: an anthropogenic site, being a University of Chicago building rooftop, and a natural site, outside Chicago in the open country. Two identical sets of instruments record measurements contemporaneously from these locations during June-November 2007, the entire period for which analyses are carried out. The study yields seasonal trends in surface temperature, surface-to-air temperature contrast and net radiation. At both sites, a temporal hysteresis between net radiation and heat storage flux indicates that surplus energy absorbed during daylight is released to the atmosphere later in the evening. The surface energy balance model responds well to site specific features for both locations. An analysis of the surface energy balance shows that the flux of sensible heat is the largest non-radiative contributor to the roof's surface cooling, while the flux of latent heat (also referred to as evaporative cooling) is the largest heat sink for the soil layer. In the latter part of the study, the surface energy balance model is upgraded by adding the capability to compute changes in surface temperature and non-radiative fluxes for any specified set of thermal and reflective roof properties. The results of this analysis allow an examination of the relationship between the roof temperature, the heat flux entering the building

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. The nanostructure formation on muscovite mica surface induced by intermediate-energy ions

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, P.; Zhang, HQ., E-mail: zhanghq@lzu.edu.cn; Zhang, Q.; Liu, Z.; Guan, S.; Wang, G.; Zhou, C.; Jia, J.; Lv, X.; Shao, J.; Cui, Y.; Chen, L.; Chen, X., E-mail: chenxm@lzu.edu.cn

    2013-07-15

    Muscovite mica sheets were bombarded by lithium, carbon and oxygen ions in the energy range from several hundred keV to several MeV. The induced surface structures were measured in the air with atomic force microscopy (AFM) in the tapping mode. The hillock-like structure on the mica surface was observed. The height of the hillock increases linearly when the energy loss is above 1.2 keV/nm. The induced structures are similar with the similar electronic stopping powers but different projectiles for muscovite mica.

  6. Search for high energy skimming neutrinos at a surface detector array

    International Nuclear Information System (INIS)

    Vo Van Thuan; Hoang Van Khanh; Pham Ngoc Diep

    2010-01-01

    In the present study we propose a new method for detection of high energy cosmological muon neutrinos by transition radiations at a medium interface. The emerging electro-magnetic radiations induced by earth-skimming heavy charged leptons are able to trigger a few of aligned neighboring local water Cherenkov stations at a surface detector array similar to the Pierre Auger Observatory. The estimation applied to the model of Gamma Ray Burst induced neutrino fluxes and the spherical earth surface shows a competitive rate of muon neutrino events in the energy range below the GZK cut-off. (author)

  7. Surface technology is essential for transition to a hydrogen-based energy system

    DEFF Research Database (Denmark)

    Nielsen, L. P.; Leisner, P.; Møller, P.

    2018-01-01

    The importance of advanced surface technology for the success of the ongoing energy turnaround in Germany has recently been discussed in this journal. The purpose of the present article is to add views based on the conditions valid for the Nordic region.......The importance of advanced surface technology for the success of the ongoing energy turnaround in Germany has recently been discussed in this journal. The purpose of the present article is to add views based on the conditions valid for the Nordic region....

  8. Surface absorption in the 32S+24Mg interactions at energies near the Coulomb barrier

    International Nuclear Information System (INIS)

    Pacheco, J.C.; Sanchez, F.; Diaz, J.; Ferrero, J.L.; Bilwes, B.; Kadi-Hanifi, D.

    1995-01-01

    Elastic scattering 32 S on 24 Mg has been measured at 65.0, 75.0, 86.3, 95.0 and 110.0 MeV-lab energies, and the data were systematically analysed with semi-phenomenological potentials. Using microscopic potentials we found similar results at the lowest incident energies, for which we have compared both the microscopic and semi-phenomenological potentials. It appears that the absorption takes place in a narrow range at the nuclear surface and is mainly due to the low lying collective surface states. (author). 41 refs., 11 figs., 4 tabs

  9. Trajectory-dependent energy loss for swift He atoms axially scattered off a silver surface

    Energy Technology Data Exchange (ETDEWEB)

    Ríos Rubiano, C.A. [Instituto de Astronomía y Física del Espacio (CONICET-UBA), Casilla de correo 67, sucursal 28, 1428 Buenos Aires (Argentina); Bocan, G.A. [Centro Atómico Bariloche, Comisión Nacional de Energía Ató mica, and Consejo Nacional de Investigaciones Científicas y Técnicas, S.C. de Bariloche, Río Negro (Argentina); Juaristi, J.I. [Departamento de Física de Materiales, Facultad de Químicas, UPV/EHU, 20018 San Sebastián (Spain); Donostia International Physics Center (DIPC) and Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), 20018 San Sebastián (Spain); Gravielle, M.S., E-mail: msilvia@iafe.uba.ar [Instituto de Astronomía y Física del Espacio (CONICET-UBA), Casilla de correo 67, sucursal 28, 1428 Buenos Aires (Argentina)

    2014-12-01

    Angle- and energy-loss-resolved distributions of helium atoms grazingly scattered from a Ag(110) surface along low indexed crystallographic directions are investigated considering impact energies in the few keV range. Final projectile distributions are evaluated within a semi-classical formalism that includes dissipative effects due to electron–hole excitations through a friction force. For mono-energetic beams impinging along the [11{sup ¯}0],[11{sup ¯}2] and [001] directions, the model predicts the presence of multiple peak structures in energy-loss spectra. Such structures provide detailed information about the trajectory-dependent energy loss. However, when the experimental dispersion of the incident beam is taken into account, these energy-loss peaks are completely washed out, giving rise to a smooth energy-loss distribution, in fairly good agreement with available experimental data.

  10. High-energy terahertz wave parametric oscillator with a surface-emitted ring-cavity configuration.

    Science.gov (United States)

    Yang, Zhen; Wang, Yuye; Xu, Degang; Xu, Wentao; Duan, Pan; Yan, Chao; Tang, Longhuang; Yao, Jianquan

    2016-05-15

    A surface-emitted ring-cavity terahertz (THz) wave parametric oscillator has been demonstrated for high-energy THz output and fast frequency tuning in a wide frequency range. Through the special optical design with a galvano-optical scanner and four-mirror ring-cavity structure, the maximum THz wave output energy of 12.9 μJ/pulse is achieved at 1.359 THz under the pump energy of 172.8 mJ. The fast THz frequency tuning in the range of 0.7-2.8 THz can be accessed with the step response of 600 μs. Moreover, the maximum THz wave output energy from this configuration is 3.29 times as large as that obtained from the conventional surface-emitted THz wave parametric oscillator with the same experimental conditions.

  11. An ab initio potential energy surface for the reaction N+ + H2→ NH+ + H

    International Nuclear Information System (INIS)

    Gittins, M.A.; Hirst, D.M.

    1975-01-01

    Preliminary results of ab initio unrestricted Hartree-Fock calculations for the potential energy surface for the reaction N + + H 2 →NH + + H are reported. For the collinear approach of N + to H 2 , the 3 Σ - surface has no activation barrier and has a shallow well (ca.1eV). For perpendicular approach (Csub(2V)symmetry) the 3 B 2 states is of high energy, the 3 A 2 state has a shallow well but as the bond angle increases the 3 B 1 states decreases in energy to become the state of lowest energy. Neither the collinear nor the perpendicular approaches give adiabatic pathways to the deep potential well of 3 B 1 (HNH) + . (auth.)

  12. Low energy ion scattering (LEIS) and the compositional and structural analysis of solid surfaces

    International Nuclear Information System (INIS)

    Berg, J.A. van den; Armour, D.G.

    1981-01-01

    The physics of Low Energy Ion Scattering (LEIS) and its application as a surface analytical technique are reviewed. It is shown that compositional and short-range structural information can be obtained by choosing experimental conditions which optimize the contributions of single and double (or multiple) collisions, respectively. The LEIS technique allows mass analysis in a straightforward way, possesses a high surface selectivity but is unable to provide quantitative information in isolation due to scattering cross-section uncertainties and not easily quantifiable charge exchange effects. Structural information regarding adsorbate positions on single crystal surfaces and the short-range substrate structure (including damaged and reconstructed surfaces) can be obtained by exploiting shadowing and/or multiple scattering phenomena. The progress made in recent years in this area is charted. It is shown that computer simulations often play an important role in this type of study. Effects, such as charge exchange, inelastic energy loss and ion beam surface perturbations, which complicate the use of low energy ion scattering for surface analysis are discussed in detail. The present status of the technique in the different areas of study is indicated. (author)

  13. Topography and surface free energy of DPPC layers deposited on a glass, mica, or PMMA support.

    Science.gov (United States)

    Jurak, Malgorzata; Chibowski, Emil

    2006-08-15

    An investigation of energetic properties of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, mica, and PMMA (poly(methyl methacrylate)) surfaces was carried out by means of contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide). DPPC was deposited on the surfaces from water (on glass and mica) or methanol (on PMMA) solutions. The topography of the tested surfaces was determined with a help of scanning electron microscopy (SEM) and atomic force microscopy (AFM). Using the measured contact angles, the total apparent surface free energy and its components of the studied layers were determined from van Oss et al.'s (Lifshitz-van der Waals and acid-base components, LWAB) and contact angle hysteresis (CAH) approaches. It allowed us to learn about changes in the surface free energy of the layers (hydrophobicity/hydrophilicity) depending on their number and kind of support. It was found that the changes in the energy greatly depended on the surface properties of the substrate as well as the statistical number of monolayers of DPPC. However, principal changes took place for first three monolayers.

  14. The Reaction Mechanism of Claisen Rearrangement Obtained by Transition State Spectroscopy and Single Direct-Dynamics Trajectory

    Directory of Open Access Journals (Sweden)

    Takayoshi Kobayashi

    2013-02-01

    Full Text Available Chemical bond breaking and formation during chemical reactions can be observed using “transition state spectroscopy”. Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.

  15. Spatial and energy distributions of satellite-speed helium atoms reflected from satellite-type surfaces

    International Nuclear Information System (INIS)

    Liu, S.M.; Rodgers, W.E.; Knuth, E.L.

    1977-01-01

    Interactions of satellite-speed helium atoms (accelerated in an expansion from an arc-heated supersonic-molecular-beam source) with practical satellite surfaces have been investigated experimentally. The density and energy distributions of the scattered atoms were measured using a detection system developed for this study. This detection system includes (a) a target positioning mechanism, (b) a detector rotating mechanism, and (c) a mass spectrometer and/or a retarding-field energy analyzer. (Auth.)

  16. Downscaling Satellite Land Surface Temperatures in Urban Regions for Surface Energy Balance Study and Heat Index Development

    Science.gov (United States)

    Norouzi, H.; Bah, A.; Prakash, S.; Nouri, N.; Blake, R.

    2017-12-01

    A great percentage of the world's population reside in urban areas that are exposed to the threats of global and regional climate changes and associated extreme weather events. Among them, urban heat islands have significant health and economic impacts due to higher thermal gradients of impermeable surfaces in urban regions compared to their surrounding rural areas. Therefore, accurate characterization of the surface energy balance in urban regions are required to predict these extreme events. High spatial resolution Land surface temperature (LST) in the scale of street level in the cities can provide wealth of information to study surface energy balance and eventually providing a reliable heat index. In this study, we estimate high-resolution LST maps using combination of LandSat 8 and infrared based satellite products such as Moderate Resolution Imaging Spectroradiometer (MODIS) and newly launched Geostationary Operational Environmental Satellite-R Series (GOES-R). Landsat 8 provides higher spatial resolution (30 m) estimates of skin temperature every 16 days. However, MODIS and GOES-R have lower spatial resolution (1km and 4km respectively) with much higher temporal resolution. Several statistical downscaling methods were investigated to provide high spatiotemporal LST maps in urban regions. The results reveal that statistical methods such as Principal Component Analysis (PCA) can provide reliable estimations of LST downscaling with 2K accuracy. Other methods also were tried including aggregating (up-scaling) the high-resolution data to a coarse one to examine the limitations and to build the model. Additionally, we deployed flux towers over distinct materials such as concrete, asphalt, and rooftops in New York City to monitor the sensible and latent heat fluxes through eddy covariance method. To account for the incoming and outgoing radiation, a 4-component radiometer is used that can observe both incoming and outgoing longwave and shortwave radiation. This

  17. Surface characterization of the cement for retention of implant supported dental prostheses: In vitro evaluation of cement roughness and surface free energy

    International Nuclear Information System (INIS)

    Brajkovic, Denis; Antonijevic, Djordje; Milovanovic, Petar; Kisic, Danilo; Zelic, Ksenija; Djuric, Marija; Rakocevic, Zlatko

    2014-01-01

    Graphical abstract: - Highlights: • Surface free energy and surface roughness influence bacterial adhesion. • Bacterial colonization causes periimplantitis and implant loss. • Zinc-based, glass-ionomers and resin-cements were investigated. • Glass-ionomers-cements present the lowest values of surface free energy and roughness. • Glass-ionomer-cements surface properties result with reduced bacterial adhesion. - Abstract: Background: Material surface free energy and surface roughness strongly influence the bacterial adhesion in oral cavity. The aim of this study was to analyze these two parameters in various commercial luting agents used for cementation of implant restorations. Materials and methods: Zinc-based, glass-ionomers, resin modified glass-ionomer and resin-cements were investigated. Contact angle and surface free energy were measured by contact angle analyzer using Image J software program. Materials’ average roughness and fractal dimension were calculated based on Atomic Force Microscope topography images. Results: Zinc phosphate cements presented significantly higher total surface free energy and significantly lower dispersive component of surface free energy compared to other groups, while resin-cements showed significantly lower polar component than other groups. The surface roughness and fractal dimension values were statistically the highest in the zinc phosphate cements and the lowest for the glass-ionomers cements. Conclusion: Glass-ionomers-cements presented lower values of surface free energy and surface roughness than zinc phosphate and resin cements, indicating that their surfaces are less prone to biofilm adhesion. Practical implications: Within limitations of an in vitro trial, our results indicate that glass-ionomers-cements could be the cements of choice for fixation of cement retained implant restorations due to superior surface properties compared to zinc phosphate and resin cements, which may result in reduced plaque formation

  18. Surface characterization of the cement for retention of implant supported dental prostheses: In vitro evaluation of cement roughness and surface free energy

    Energy Technology Data Exchange (ETDEWEB)

    Brajkovic, Denis [Clinic for Dentistry, Department of Maxillofacial Surgery, Faculty of Medical Sciences, University of Kragujevac, Svetozara Markovica 69, 34000 Kragujevac (Serbia); Antonijevic, Djordje; Milovanovic, Petar [Laboratory for Anthropology, Institute of Anatomy, School of Medicine, University of Belgrade, Dr. Subotica 4/2, 11000 Belgrade (Serbia); Kisic, Danilo [Laboratory for Atomic Physics, Institute of Nuclear Sciences “Vinca”, University of Belgrade, Belgrade (Serbia); Zelic, Ksenija; Djuric, Marija [Laboratory for Anthropology, Institute of Anatomy, School of Medicine, University of Belgrade, Dr. Subotica 4/2, 11000 Belgrade (Serbia); Rakocevic, Zlatko, E-mail: zlatkora@vinca.rs [Laboratory for Atomic Physics, Institute of Nuclear Sciences “Vinca”, University of Belgrade, Belgrade (Serbia)

    2014-08-30

    Graphical abstract: - Highlights: • Surface free energy and surface roughness influence bacterial adhesion. • Bacterial colonization causes periimplantitis and implant loss. • Zinc-based, glass-ionomers and resin-cements were investigated. • Glass-ionomers-cements present the lowest values of surface free energy and roughness. • Glass-ionomer-cements surface properties result with reduced bacterial adhesion. - Abstract: Background: Material surface free energy and surface roughness strongly influence the bacterial adhesion in oral cavity. The aim of this study was to analyze these two parameters in various commercial luting agents used for cementation of implant restorations. Materials and methods: Zinc-based, glass-ionomers, resin modified glass-ionomer and resin-cements were investigated. Contact angle and surface free energy were measured by contact angle analyzer using Image J software program. Materials’ average roughness and fractal dimension were calculated based on Atomic Force Microscope topography images. Results: Zinc phosphate cements presented significantly higher total surface free energy and significantly lower dispersive component of surface free energy compared to other groups, while resin-cements showed significantly lower polar component than other groups. The surface roughness and fractal dimension values were statistically the highest in the zinc phosphate cements and the lowest for the glass-ionomers cements. Conclusion: Glass-ionomers-cements presented lower values of surface free energy and surface roughness than zinc phosphate and resin cements, indicating that their surfaces are less prone to biofilm adhesion. Practical implications: Within limitations of an in vitro trial, our results indicate that glass-ionomers-cements could be the cements of choice for fixation of cement retained implant restorations due to superior surface properties compared to zinc phosphate and resin cements, which may result in reduced plaque formation

  19. Modeling Evolution of Hydrogen Bonding and Stabilization of Transition States in the Process of Cocaine Hydrolysis Catalyzed by Human Butyrylcholinesterase

    OpenAIRE

    Gao, Daquan; Zhan, Chang-Guo

    2006-01-01

    Molecular dynamics (MD) simulations and quantum mechanical/molecular mechanical (QM/MM) calculations were performed on the prereactive enzyme-substrate complex, transition states, intermediates, and product involved in the process of human butyrylcholinesterase (BChE)-catalyzed hydrolysis of (−)-cocaine. The computational results consistently reveal a unique role of the oxyanion hole (consisting of G116, G117, and A199) in BChE-catalyzed hydrolysis of cocaine, as compared to acetylcholinester...

  20. Effect of Groove Surface Texture on Tribological Characteristics and Energy Consumption under High Temperature Friction.

    Science.gov (United States)

    Wu, Wei; Chen, Guiming; Fan, Boxuan; Liu, Jianyou

    2016-01-01

    Energy consumption and tribological properties could be improved by proper design of surface texture in friction. However, some literature focused on investigating their performance under high temperature. In the study, different groove surface textures were fabricated on steels by a laser machine, and their tribological behaviors were experimentally studied with the employment of the friction and wear tester under distinct high temperature and other working conditions. The friction coefficient was recorded, and wear performance were characterized by double light interference microscope, scanning electron microscope (SEM) and x-ray energy dispersive spectrometry (EDS). Then, the performances of energy consumptions were carefully estimated. Results showed that friction coefficient, wear, and energy consumption could almost all be reduced by most textures under high temperature conditions, but to a different extent which depends on the experimental conditions and texture parameters. The main improvement mechanisms were analyzed, such as the hardness change, wear debris storage, thermal stress release and friction induced temperature reduction by the textures. Finally, a scattergram of the relatively reduced ratio of the energy consumption was drawn for different surface textures under four distinctive experimental conditions to illustrate the comprehensive energy consumption improving ability of textures, which was of benefit for the application of texture design.

  1. Surface atomic relaxation and magnetism on hydrogen-adsorbed Fe(110) surfaces from first principles

    Energy Technology Data Exchange (ETDEWEB)

    Chohan, Urslaan K.; Jimenez-Melero, Enrique [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Dalton Cumbrian Facility, The University of Manchester, Moor Row CA24 3HA (United Kingdom); Koehler, Sven P.K., E-mail: sven.koehler@manchester.ac.uk [Dalton Cumbrian Facility, The University of Manchester, Moor Row CA24 3HA (United Kingdom); School of Chemistry, The University of Manchester, Manchester M13 9PL (United Kingdom); Photon Science Institute, The University of Manchester, Manchester M13 9PL (United Kingdom)

    2016-11-30

    Highlights: • Potential energy surfaces for H diffusion on Fe(110) calculated. • Full vibrational analysis of surface modes performed. • Vibrational analysis establishes lb site as a transition state to the 3f site. • Pronounced buckling observed in the Fe surface layer. - Abstract: We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber–Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe–H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm{sup −1}, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.

  2. Derivation of Hamaker Dispersion Energy of Amorphous Carbon Surfaces in Contact with Liquids Using Photoelectron Energy-Loss Spectra

    Science.gov (United States)

    Godet, Christian; David, Denis

    2017-12-01

    Hamaker interaction energies and cutoff distances have been calculated for disordered carbon films, in contact with purely dispersive (diiodomethane) or polar (water) liquids, using their experimental dielectric functions ɛ ( q, ω) obtained over a broad energy range. In contrast with previous works, a q-averaged q is derived from photoelectron energy-loss spectroscopy (XPS-PEELS) where the energy loss function (ELF) q is a weighted average over allowed transferred wave vector values, q, given by the physics of bulk plasmon excitation. For microcrystalline diamond and amorphous carbon films with a wide range of (sp3/sp2 + sp3) hybridization, non-retarded Hamaker energies, A 132 ( L < 1 nm), were calculated in several configurations, and distance and wavenumber cutoff values were then calculated based on A 132 and the dispersive work of adhesion obtained from contact angles. A geometric average approximation, H 0 CVL = ( H 0 CVC H 0 LVL )1/2, holds for the cutoff separation distances obtained for carbon-vacuum-liquid (CVL), carbon-vacuum-carbon (CVC) and liquid-vacuum-liquid (LVL) equilibrium configurations. The linear dependence found for A CVL, A CLC and A CLV values as a function of A CVC, for each liquid, allows predictive relationships for Hamaker energies (in any configuration) using experimental determination of the dispersive component of the surface tension, {γ}_{CV}^d , and a guess value of the cutoff distance H 0 CVC of the solid. [Figure not available: see fulltext.

  3. Ab initio study on stacking sequences, free energy, dynamical stability and potential energy surfaces of graphite structures

    International Nuclear Information System (INIS)

    Anees, P; Valsakumar, M C; Chandra, Sharat; Panigrahi, B K

    2014-01-01

    Ab initio simulations have been performed to study the structure, energetics and stability of several plausible stacking sequences in graphite. These calculations suggest that in addition to the standard structures, graphite can also exist in AA-simple hexagonal, AB-orthorhombic and ABC-hexagonal type stacking. The free energy difference between these structures is very small (∼1 meV/atom), and hence all the structures can coexist from purely energetic considerations. Calculated x-ray diffraction patterns are similar to those of the standard structures for 2θ ⩽ 70°. Shear elastic constant C 44 is negative in AA-simple hexagonal, AB-orthorhombic and ABC-hexagonal structures, suggesting that these structures are mechanically unstable. Phonon dispersions show that the frequencies of some modes along the Γ–A direction in the Brillouin zone are imaginary in all of the new structures, implying that these structures are dynamically unstable. Incorporation of zero point vibrational energy via the quasi-harmonic approximation does not result in the restoration of dynamical stability. Potential energy surfaces for the unstable normal modes are seen to have the topography of a potential hill for all the new structures, confirming that all of the new structures are inherently unstable. The fact that the potential energy surface is not in the form of a double well implies that the structures are linearly as well as globally unstable. (paper)

  4. Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

    Science.gov (United States)

    Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

    2015-11-12

    Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

  5. Electron emission and energy loss in grazing collisions of protons with insulator surfaces

    International Nuclear Information System (INIS)

    Gravielle, M. S.; Miraglia, J. E.; Aldazabal, I.; Arnau, A.; Ponce, V. H.; Aumayr, F.; Lederer, S.; Winter, H.

    2007-01-01

    Electron emission from LiF, KCl, and KI crystal surfaces during grazing collisions of swift protons is studied using a first-order distorted-wave formalism. Owing to the localized character of the electronic structure of these surfaces, we propose a model that allows us to describe the process as a sequence of atomic transitions from different target ions. Experimental results are presented for electron emission from LiF and KI and energy loss from KI surfaces. Calculations show reasonable agreement with these experimental data. The role played by the charge of the incident particle is also investigated

  6. On the topography of sputtered or chemically etched crystals: surface energies minimised

    International Nuclear Information System (INIS)

    Chadderton, L.T.; Cope, J.O.

    1984-01-01

    The sputtering of single or polycrystalline metal surfaces by heavy ions gives rise to the characteristic topographical features of etch pits, ripples, and cones (pyramids). For cones and pyramids, in particular, no completely satisfactory explanation exists as to the origin of the basic geometry. Scanning electron micrographs are shown. It is proposed that for topographical features of both chemical etch and ion beam origin on single crystal surfaces, the presence of facets on cones and pyramids in particular, is due to the minimization of surface energy. (U.K.)

  7. SEMIC: an efficient surface energy and mass balance model applied to the Greenland ice sheet

    Directory of Open Access Journals (Sweden)

    M. Krapp

    2017-07-01

    Full Text Available We present SEMIC, a Surface Energy and Mass balance model of Intermediate Complexity for snow- and ice-covered surfaces such as the Greenland ice sheet. SEMIC is fast enough for glacial cycle applications, making it a suitable replacement for simpler methods such as the positive degree day (PDD method often used in ice sheet modelling. Our model explicitly calculates the main processes involved in the surface energy and mass balance, while maintaining a simple interface and requiring minimal data input to drive it. In this novel approach, we parameterise diurnal temperature variations in order to more realistically capture the daily thaw–freeze cycles that characterise the ice sheet mass balance. We show how to derive optimal model parameters for SEMIC specifically to reproduce surface characteristics and day-to-day variations similar to the regional climate model MAR (Modèle Atmosphérique Régional, version 2 and its incorporated multilayer snowpack model SISVAT (Soil Ice Snow Vegetation Atmosphere Transfer. A validation test shows that SEMIC simulates future changes in surface temperature and surface mass balance in good agreement with the more sophisticated multilayer snowpack model SISVAT included in MAR. With this paper, we present a physically based surface model to the ice sheet modelling community that is general enough to be used with in situ observations, climate model, or reanalysis data, and that is at the same time computationally fast enough for long-term integrations, such as glacial cycles or future climate change scenarios.

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

    Science.gov (United States)

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

    2012-10-09

    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.

  9. Benchmark Database of Transition Metal Surface and Adsorption Energies from Many-Body Perturbation Theory

    DEFF Research Database (Denmark)

    Schmidt, Per Simmendefeldt; Thygesen, Kristian Sommer

    2018-01-01

    (RPA) is found to yield high accuracy for both adsorption and surface energies. In contrast, all the considered density functionals fail to describe both quantities accurately. This establishes the RPA as a universally accurate method for surface science. In the second part, we use the RPA to construct...... be significant. RPA is compared to the more advanced renormalized adiabatic LDA (rALDA) method for a subset of the reactions, and they are found to describe the adsorbate-metal bond as well as adsorbate-adsorbate interactions similarly. The RPA results are compared to a range of standard density functional...... theory methods typically employed for surface reactions representing the various rungs on Jacob's ladder. The deviations are found to be highly functional, surface, and reaction dependent. Our work establishes the RPA and rALDA methods as universally accurate full ab initio methods for surface science...

  10. Low-energy electron diffraction experiment, theory and surface structure determination

    CERN Document Server

    Hove, Michel A; Chan, Chi-Ming

    1986-01-01

    Surface crystallography plays the same fundamental role in surface science which bulk crystallography has played so successfully in solid-state physics and chemistry. The atomic-scale structure is one of the most important aspects in the understanding of the behavior of surfaces in such widely diverse fields as heterogeneous catalysis, microelectronics, adhesion, lubrication, cor­ rosion, coatings, and solid-solid and solid-liquid interfaces. Low-Energy Electron Diffraction or LEED has become the prime tech­ nique used to determine atomic locations at surfaces. On one hand, LEED has yielded the most numerous and complete structural results to date (almost 200 structures), while on the other, LEED has been regarded as the "technique to beat" by a variety of other surface crystallographic methods, such as photoemission, SEXAFS, ion scattering and atomic diffraction. Although these other approaches have had impressive successes, LEED has remained the most productive technique and has shown the most versatility...

  11. Office buildings and energy from the environment. Cooling and heating using near-surface geothermal energy; Buerogebaeude und Umweltenergie. Kuehlen und Heizen mit oberflaechennaher Geothermie

    Energy Technology Data Exchange (ETDEWEB)

    Bohne, Dirk; Harhausen, Gunnar; Wohlfahrt, Matthias [Leibniz Univ. Hannover (Germany). Inst. fuer Entwerfen und Konstruieren

    2009-07-01

    Increasing energy prices, uncertainties relating to imported energy and the first signs of an impending global climate change have enhanced interest in renewable energy sources, whose wide-spread use is receiving much public interest. Three scientists of the Institute of Design and Construction of Leibniz University Hanover investigated the application of near-surface geothermal energy for heating and cooling of buildings. (orig.)

  12. Quantifying the Terrestrial Surface Energy Fluxes Using Remotely-Sensed Satellite Data

    Science.gov (United States)

    Siemann, Amanda Lynn

    The dynamics of the energy fluxes between the land surface and the atmosphere drive local and regional climate and are paramount to understand the past, present, and future changes in climate. Although global reanalysis datasets, land surface models (LSMs), and climate models estimate these fluxes by simulating the physical processes involved, they merely simulate our current understanding of these processes. Global estimates of the terrestrial, surface energy fluxes based on observations allow us to capture the dynamics of the full climate system. Remotely-sensed satellite data is the source of observations of the land surface which provide the widest spatial coverage. Although net radiation and latent heat flux global, terrestrial, surface estimates based on remotely-sensed satellite data have progressed, comparable sensible heat data products and ground heat flux products have not progressed at this scale. Our primary objective is quantifying and understanding the terrestrial energy fluxes at the Earth's surface using remotely-sensed satellite data with consistent development among all energy budget components [through the land surface temperature (LST) and input meteorology], including validation of these products against in-situ data, uncertainty assessments, and long-term trend analysis. The turbulent fluxes are constrained by the available energy using the Bowen ratio of the un-constrained products to ensure energy budget closure. All final products are within uncertainty ranges of literature values, globally. When validated against the in-situ estimates, the sensible heat flux estimates using the CFSR air temperature and constrained with the products using the MODIS albedo produce estimates closest to the FLUXNET in-situ observations. Poor performance over South America is consistent with the largest uncertainties in the energy budget. From 1984-2007, the longwave upward flux increase due to the LST increase drives the net radiation decrease, and the

  13. Evapotranspiration and surface energy balance across an agricultural-urban landscape gradient in Southern California, USA.

    Science.gov (United States)

    Shiflett, S. A.; Anderson, R. G.; Jenerette, D.

    2014-12-01

    Urbanization substantially affects energy, surface and air temperature, and hydrology due to extensive modifications in land surface properties such as vegetation, albedo, thermal capacity and soil moisture. The magnitude and direction of these alterations depends heavily on the type of urbanization that occurs. We investigated energy balance variation in a local network of agricultural and urban ecosystems using the eddy covariance method to better understand how vegetation fraction and degree of urbanization affects energy exchanges between the land surface and the atmosphere. We deployed eddy flux systems within a well-irrigated, agricultural citrus orchard, a moderately developed urban zone with a substantial amount of local vegetative cover, and an intensely developed urban zone with minimal vegetative cover and increased impervious surfaces relative to the other two sites. Latent energy (LE) fluxes in the agricultural area ranged from 7.9 ± 1.4 W m-2 (nighttime) to 168.7 ± 6.2 W m-2 (daytime) compared to 10.2 ± 3.5 W m-2 and 40.6 ± 4.1 W m-2, respectively, for the moderately developed urban area. Sensible energy (H) fluxes ranged from -9.1 ± 1.0 W m-2 (nighttime) to 119 ± 7.0 W m-2 (daytime) in the agricultural area compared to 9.6 ± 2.6 W m-2 and 134 ± 6.0 W m-2, respectively, for the moderately developed urban zone. Daytime LE is reduced with increasing urbanization; however, daily cycles of LE are less recognizable in urban areas compared to distinct daily cycles obtained above a mature citrus crop. In contrast, both daytime and nighttime H increases with increasing degree of urbanization. Reduction in vegetation and increases in impervious surfaces along an urbanization gradient leads to alterations in energy balance, which are associated with microclimate and water use changes.

  14. Performance of five surface energy balance models for estimating daily evapotranspiration in high biomass sorghum

    Science.gov (United States)

    Wagle, Pradeep; Bhattarai, Nishan; Gowda, Prasanna H.; Kakani, Vijaya G.

    2017-06-01

    Robust evapotranspiration (ET) models are required to predict water usage in a variety of terrestrial ecosystems under different geographical and agrometeorological conditions. As a result, several remote sensing-based surface energy balance (SEB) models have been developed to estimate ET over large regions. However, comparison of the performance of several SEB models at the same site is limited. In addition, none of the SEB models have been evaluated for their ability to predict ET in rain-fed high biomass sorghum grown for biofuel production. In this paper, we evaluated the performance of five widely used single-source SEB models, namely Surface Energy Balance Algorithm for Land (SEBAL), Mapping ET with Internalized Calibration (METRIC), Surface Energy Balance System (SEBS), Simplified Surface Energy Balance Index (S-SEBI), and operational Simplified Surface Energy Balance (SSEBop), for estimating ET over a high biomass sorghum field during the 2012 and 2013 growing seasons. The predicted ET values were compared against eddy covariance (EC) measured ET (ETEC) for 19 cloud-free Landsat image. In general, S-SEBI, SEBAL, and SEBS performed reasonably well for the study period, while METRIC and SSEBop performed poorly. All SEB models substantially overestimated ET under extremely dry conditions as they underestimated sensible heat (H) and overestimated latent heat (LE) fluxes under dry conditions during the partitioning of available energy. METRIC, SEBAL, and SEBS overestimated LE regardless of wet or dry periods. Consequently, predicted seasonal cumulative ET by METRIC, SEBAL, and SEBS were higher than seasonal cumulative ETEC in both seasons. In contrast, S-SEBI and SSEBop substantially underestimated ET under too wet conditions, and predicted seasonal cumulative ET by S-SEBI and SSEBop were lower than seasonal cumulative ETEC in the relatively wetter 2013 growing season. Our results indicate the necessity of inclusion of soil moisture or plant water stress

  15. Surface Energy Balance in Jakarta and Neighboring Regions As Simulated Using Fifth Mesoscale Model (MM5

    Directory of Open Access Journals (Sweden)

    Yopi Ilhamsyah

    2014-04-01

    Full Text Available The objective of the present research was to assess the surface energy balance particularly in terms of the computed surface energy and radiation balance and the development of boundary layer over Jakarta and Neighboring Regions (JNR by means of numerical model of fifth generation of Mesoscale Model (MM5. The MM5 with four domains of 9 kilometers in spatial resolution presenting the outermost and the innermost of JNR is utilized. The research focuses on the third and fourth domains covering the entire JNR. The description between radiation and energy balance at the surface is obtained from the model. The result showed that energy balance is higher in the city area during daytime. Meanwhile, energy components, e.g., surface sensible and latent heat flux showed that at the sea and in the city areas were higher than other areas. Moreover, ground flux showed eastern region was higher than others. In general, radiation and energy balance was higher in the daytime and lower in the nighttime for all regions. The calculation of Bowen Ratio, the ratio of surface sensible and latent heat fluxes, was also higher in the city area, reflecting the dominations of urban and built-up land in the region. Meanwhile, Bowen Ratio in the rural area dominated by irrigated cropland was lower. It is consistent with changes of land cover properties, e.g. albedo, soil moisture, and thermal characteristics. In addition, the boundary layer is also higher in the city. Meanwhile western region dominated by suburban showed higher boundary layer instead of eastern region.

  16. Comparison of tropical and subtropical glacier surface energy balance in Africa and South America

    Science.gov (United States)

    Nicholson, L.; Prinz, R.; Kinnard, C.; Mölg, T.; Winkler, M.; Kaser, G.

    2010-05-01

    Tropical glaciers exist only at high altitude, and meteorological and surface energy balance studies of these glaciers can tell us much about the conditions and changes occurring in the mid troposphere. Understanding the surface energy balance and resultant mass balance regime of tropical glaciers is prerequisite to predicting glacier evolution, and future meltwater contributions to local hydrological resources, in response to future climate scenarios. Tropical glacier mass balance variability is strongly linked to precipitation and, via this, to multi-annual climate oscillations such as ENSO and IOZM, so it is useful to understand what role these differing regional influences play in comparison to the similarities imposed by the overarching tropical climate conditions and seasonality. New surface energy balance and mass balance data is available from Lewis glacier (Kenya, 0°09' S; 37°18' E), and here we use an energy and mass balance model to determine the surface energy flux characteristics at this site through a wet and dry season. Results are compared with those from Kersten glacier (Tanzania, 3°04' S; 37°21' E) to understand how conditions at these two glaciers compare and thus what coherent and contrasting climatic information glaciological records from these two sites can be expected to deliver. Meteorological data available from glacier stations on Antizana (Ecuador, 0°25' S; 78°09' W), Artesonraju (Peru, 8°28' S; 77°38' W) Zongo (Bolivia, 16°39' S; 67°47' W) and Guanaco (Chile, 29°20' S; 70°00' W) glaciers in South America offer the opportunity to examine how the surface fluxes and seasonal variability of the energy balance compares to those of the African glaciers. We include the extra-tropical Chilean example for comparison with the similarly high altitude, cold ice of Kersten glacier.

  17. Specific grinding energy and surface roughness of nanoparticle jet minimum quantity lubrication in grinding

    Directory of Open Access Journals (Sweden)

    Zhang Dongkun

    2015-04-01

    Full Text Available Nanoparticles with the anti-wear and friction reducing features were applied as cooling lubricant in the grinding fluid. Dry grinding, flood grinding, minimal quantity of lubrication (MQL, and nanoparticle jet MQL were used in the grinding experiments. The specific grinding energy of dry grinding, flood grinding and MQL were 84, 29.8, 45.5 J/mm3, respectively. The specific grinding energy significantly decreased to 32.7 J/mm3 in nanoparticle MQL. Compared with dry grinding, the surface roughness values of flood grinding, MQL, and nanoparticle jet MQL were significantly reduced with the surface topography profile values reduced by 11%, 2.5%, and 10%, respectively, and the ten point height of microcosmic unflatness values reduced by 1.5%, 0.5%, and 1.3%, respectively. These results verified the satisfactory lubrication effects of nanoparticle MQL. MoS2, carbon nanotube (CNT, and ZrO2 nanoparticles were also added in the grinding fluid of nanoparticle jet MQL to analyze their grinding surface lubrication effects. The specific grinding energy of MoS2 nanoparticle was only 32.7 J/mm3, which was 8.22% and 10.39% lower than those of the other two nanoparticles. Moreover, the surface roughness of workpiece was also smaller with MoS2 nanoparticle, which indicated its remarkable lubrication effects. Furthermore, the role of MoS2 particles in the grinding surface lubrication at different nanoparticle volume concentrations was analyzed. MoS2 volume concentrations of 1%, 2%, and 3% were used. Experimental results revealed that the specific grinding energy and the workpiece surface roughness initially increased and then decreased as MoS2 nanoparticle volume concentration increased. Satisfactory grinding surface lubrication effects were obtained with 2% MoS2 nanoparticle volume concentration.

  18. Low energy Cu clusters slow deposition on a Fe (001) surface investigated by molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shixu [School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Laboratory of Advanced Nuclear Materials, Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Gong, Hengfeng [School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Division of Nuclear Materials Science and Engineering, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Chen, Xuanzhi [School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Li, Gongping, E-mail: ligp@lzu.edu.cn [School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Wang, Zhiguang, E-mail: zhgwang@impcas.ac.cn [Laboratory of Advanced Nuclear Materials, Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2014-09-30

    Highlights: • We study the deposition of low energy Cu clusters on Fe (001) surface by molecular dynamics. • The interaction between low energy cluster and substrate can be divided to the landing and the thermal diffusion phases. • The phenomenon of contact epitaxy of cluster occurred. • The thermal diffusion of cluster atoms was analyzed. - Abstract: The slow deposition of low energy Cu clusters on a Fe (001) surface was investigated by molecular dynamics simulation. A many-body potential based on Finnis–Sinclair model was used to describe the interactions among atoms. Three clusters comprising of 13, 55 and 147 atoms, respectively, were deposited with incident energies ranging from 0.0 to 1.0 eV/atom at various substrate temperatures (0, 300 and 800 K). The rearrangement and the diffusion of cluster can occur, only when the cluster atoms are activated and obtained enough migration energy. The interaction between low energy cluster and substrate can be divided to the landing and the thermal diffusion phases. In the former, the migration energy originates from the latent heat of binding energy for the soft deposition regime and primarily comes from the incident energy of cluster for the energetic cluster deposition regime. In the latter, the thermal vibration would result in some cluster atoms activated again at medium and high substrate temperatures. Also, the effects of incident energy, cluster size and substrate temperature on the interaction potential energy between cluster and substrate, the final deposition morphology of cluster, the spreading index and the structure parameter of cluster are analyzed.

  19. Energy dissipation of highly charged ions interacting with solid surfaces; Energieeintrag langsamer hochgeladener Ionen in Festkoerperoberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Kost, D.

    2006-07-01

    Motivated by the incomplete scientific description of the relaxation of highly charged ions in front of solid surfaces and their energy balance, this thesis describes an advanced complementary study of determining deposited fractions and re-emitted fractions of the potential energy of highly charged ions. On one side, a calorimetric measurement setup is used to determine the retained potential energy and on the other side, energy resolved electron spectroscopy is used for measuring the reemitted energy due to secondary electron emission. In order to study the mechanism of energy retention in detail, materials with different electronic structures are investigated: Cu, n-Si, p-Si and SiO{sub 2}. In the case of calorimetry, a linear relationship between the deposited potential energy and the inner potential energy of the ions was determined. The total potential energy which stays in the solid remains almost constant at about (80 {+-} 10) %. Comparing the results of the Cu, n-Si and p-Si targets, no significant difference could be shown. Therefore we conclude that the difference in energy deposition between copper, n-doped Si and p-doped Si is below 10 %, which is significantly lower than using SiO{sub 2} targets. For this purpose, electron spectroscopy provides a complementary result. For Cu and Si surfaces, an almost linear increase of the re-emitted energy with increasing potential energy of the ion up to Ar{sup 7+} was also observed. The ratio of the re-emitted energy is about (10 {+-} 5) % of the total potential energy of the incoming ion, almost independent of the ion charge state. In contrast, an almost vanishing electron emission was observed for SiO{sub 2} and for charge states below q=7. For Ar{sup 8+} and Ar{sup 9+}, the electron emission increased due to the contribution of the projectile LMM Auger electrons and the re-emitted energy amounts up to 20 % for Cu and Si and around 10 % for SiO{sub 2}. These results are in good agreement with the calorimetric

  20. Surface Modification of MXenes: A Pathway to Improve MXene Electrode Performance in Electrochemical Energy Storage Devices

    KAUST Repository

    Ahmed, Bilal

    2017-12-31

    The recent discovery of layered transition metal carbides (MXenes) is one of the most important developments in two-dimensional (2D) materials. Preliminary theoretical and experimental studies suggest a wide range of potential applications for MXenes. The MXenes are prepared by chemically etching ‘A’-layer element from layered ternary metal carbides, nitrides and carbonitrides (MAX phases) through aqueous acid treatment, which results in various surface terminations such as hydroxyl, oxygen or fluorine. It has been found that surface terminations play a critical role in defining MXene properties and affects MXene performance in different applications such as electrochemical energy storage, electromagnetic interference shielding, water purification, sensors and catalysis. Also, the electronic, thermoelectric, structural, plasmonic and optical properties of MXenes largely depend upon surface terminations. Thus, controlling the surface chemistry if MXenes can be an efficient way to improve their properties. This research mainly aims to perform surface modifications of two commonly studied MXenes; Ti2C and Ti3C2, via chemical, thermal or physical processes to enhance electrochemical energy storage properties. The as-prepared and surface modified MXenes have been studied as electrode materials in Li-ion batteries (LIBs) and supercapacitors (SCs). In pursuit of desirable MXene surface, we have developed an in-situ room temperature oxidation process, which resulted in TiO2/MXene nanocomposite and enhanced Li-ion storage. The idea of making metal oxide and MXene nanocomposites was taken to the next level by combining a high capacity anode materials – SnO2 – and MXene. By taking advantage of already existing surface functional groups (–OH), we have developed a composite of SnO2/MXene by atomic layer deposition (ALD) which showed enhanced capacity and excellent cyclic stability. Thermal annealing of MXene at elevated temperature under different atmospheres was

  1. Construction of diabatic energy surfaces for LiFH with artificial neural networks

    Science.gov (United States)

    Guan, Yafu; Fu, Bina; Zhang, Dong H.

    2017-12-01

    A new set of diabatic potential energy surfaces (PESs) for LiFH is constructed with artificial neural networks (NNs). The adiabatic PESs of the ground state and the first excited state are directly fitted with NNs. Meanwhile, the adiabatic-to-diabatic transformation (ADT) angles (mixing angles) are obtained by simultaneously fitting energy difference and interstate coupling gradients. No prior assumptions of the functional form of ADT angles are used before fitting, and the ab initio data including energy difference and interstate coupling gradients are well reproduced. Converged dynamical results show remarkable differences between adiabatic and diabatic PESs, which suggests the significance of non-adiabatic processes.

  2. The conditions for total reflection of low-energy atoms from crystal surfaces

    International Nuclear Information System (INIS)

    Hou, M.; Robinson, M.T.

    1978-01-01

    The critical angles for the total reflection of low-energy particles from Cu rows and (001) planes have been investigated, using the binary collision approximation computer simulation code MARLOWE Breakthrough angles were evaluated for H, N, Ne, Ar, Cu, Xe, and Au in the energy range from 0.1 to 7.5 keV. In both the axial and the planar cases, recoiling of the target atoms lowers the energy barrier which the target surface presents to the heavy projectiles. Consequently, the breakthrough angles are reduced for heavy projectiles below the values expected either from observations on light projectiles or from analytical channeling theory. (orig.) [de

  3. Resonance Energy Transfer in Hybrid Devices in the Presence of a Surface

    DEFF Research Database (Denmark)

    Kopylov, Oleksii; Huck, Alexander; Kadkhodazadeh, Shima

    2014-01-01

    to approximately 10 nm was observed. By comparing the carrier dynamics of the quantum wells and the nanocrystals, we found that nonradiative recombination via surface states, generated during dry etching of the wafer, counteracts the nonradiative energy-transfer process to the nanocrystals and therefore decreases......We have studied room-temperature, nonradiative resonant energy transfer from InGaN/GaN quantum wells to CdSe/ZnS nanocrystals separated by aluminum oxide layers of different thicknesses. Nonradiative energy transfer from the quantum wells to the nanocrystals at separation distances of up...

  4. Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

    Science.gov (United States)

    Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

    2015-06-09

    The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

  5. High resolution electron energy loss spectroscopy of clean and hydrogen covered Si(001) surfaces: first principles calculations.

    Science.gov (United States)

    Patterson, C H

    2012-09-07

    Surface phonons, conductivities, and loss functions are calculated for reconstructed (2×1), p(2×2) and c(4×2) clean Si(001) surfaces, and (2×1) H and D covered Si(001) surfaces. Surface conductivities perpendicular to the surface are significantly smaller than conductivities parallel to the surface. The surface loss function is compared to high resolution electron energy loss measurements. There is good agreement between calculated loss functions and experiment for H and D covered surfaces. However, agreement between experimental data from different groups and between theory and experiment is poor for clean Si(001) surfaces. Formalisms for calculating electron energy loss spectra are reviewed and the mechanism of electron energy losses to surface vibrations is discussed.

  6. Self-energy behavior away from the Fermi surface in doped Mott insulators.

    Science.gov (United States)

    Merino, J; Gunnarsson, O; Kotliar, G

    2016-02-03

    We analyze self-energies of electrons away from the Fermi surface in doped Mott insulators using the dynamical cluster approximation to the Hubbard model. For large onsite repulsion, U, and hole doping, the magnitude of the self-energy for imaginary frequencies at the top of the band ([Formula: see text]) is enhanced with respect to the self-energy magnitude at the bottom of the band ([Formula: see text]). The self-energy behavior at these two [Formula: see text]-points is switched for electron doping. Although the hybridization is much larger for (0, 0) than for [Formula: see text], we demonstrate that this is not the origin of this difference. Isolated clusters under a downward shift of the chemical potential, [Formula: see text], at half-filling reproduce the overall self-energy behavior at (0, 0) and [Formula: see text] found in low hole doped embedded clusters. This happens although there is no change in the electronic structure of the isolated clusters. Our analysis shows that a downward shift of the chemical potential which weakly hole dopes the Mott insulator can lead to a large enhancement of the [Formula: see text] self-energy for imaginary frequencies which is not associated with electronic correlation effects, even in embedded clusters. Interpretations of the strength of electronic correlations based on self-energies for imaginary frequencies are, in general, misleading for states away from the Fermi surface.

  7. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Greeley, Jeffrey Philip; Studt, Felix

    2007-01-01

    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 adsorp...

  8. Daily cycle of the surface energy balance in Antarctica and the influence of clouds

    NARCIS (Netherlands)

    van den Broeke, M.R.|info:eu-repo/dai/nl/073765643; Reijmer, C.H.|info:eu-repo/dai/nl/229345956; van As, D.; Boot, W.

    2006-01-01

    We present the summertime daily cycle of the Antarctic surface energy balance (SEB) and its sensitivity to cloud cover. We use data of automatic weather stations (AWS) located in four major Antarctic climate zones: the coastal ice shelf, the coastal and interior katabatic wind zone and the interior

  9. Impacts of Climate Change and Land use Changes on Land Surface Radiation and Energy Budgets

    Science.gov (United States)

    Land surface radiation and energy budgets are critical to address a variety of scientific and application issues related to climate trends, weather predictions, hydrologic and biogeophysical modeling, and the monitoring of ecosystem health and agricultural crops. This is an introductory paper to t...

  10. Modified-surface-energy methods for deriving heavy-ion potentials

    International Nuclear Information System (INIS)

    Sierk, A.J.

    1977-01-01

    The use of a modified-surface-energy approach for the calculation of heavy-ion interaction potentials is discussed. It is not possible to simultaneously fit elastic scattering, ion interaction barriers, and fission barriers with the same set of constants in this model. Possible explanations of this deficiency are discussed

  11. The desorption behaviour of implanted noble gases at low energy on silicon surfaces

    NARCIS (Netherlands)

    Holtslag, A.H.M.; van Silfhout, Arend

    1987-01-01

    Under UHV conditions, clean crystalline Si(111) surfaces have been bombarded mass-selectively at room temperature with noble gas ions, Ne+, Ar+, Kr+, at normal incidence. By means of stepwise heating up to 1050 K the activation energies and desorbed doses of the noble gases have been straight

  12. A high performance GPU implementation of Surface Energy Balance System (SEBS) based on CUDA-C

    NARCIS (Netherlands)

    Abouali, Mohammad; Timmermans, J.; Castillo, Jose E.; Su, Zhongbo

    2013-01-01

    This paper introduces a new implementation of the Surface Energy Balance System (SEBS) algorithm harnessing the many cores available on Graphics Processing Units (GPUs). This new implementation uses Compute Unified Device Architecture C (CUDA-C) programming model and is designed to be executed on a

  13. Calculation of high-dimensional fission-fusion potential-energy surfaces in the SHE region

    International Nuclear Information System (INIS)

    Moeller, Peter; Sierk, Arnold J.; Ichikawa, Takatoshi; Iwamoto, Akira

    2004-01-01

    We calculate in a macroscopic-microscopic model fission-fusion potential-energy surfaces relevant to the analysis of heavy-ion reactions employed to form heavy-element evaporation residues. We study these multidimensional potential-energy surfaces both inside and outside the touching point.Inside the point of contact we define the potential on a multi-million-point grid in 5D deformation space where elongation, merging projectile and target spheroidal shapes, neck radius and projectile/target mass asymmetry are independent shape variables. The same deformation space and the corresponding potential-energy surface also describe the shape evolution from the nuclear ground-state to separating fragments in fission, and the fast-fission trajectories in incomplete fusion.For separated nuclei we study the macroscopic-microscopic potential energy, that is the ''collision surface'' between a spheroidally deformed target and a spheroidally deformed projectile as a function of three coordinates which are: the relative location of the projectile center-of-mass with respect to the target center-of-mass and the spheroidal deformations of the target and the projectile. We limit our study to the most favorable relative positions of target and projectile, namely that the symmetry axes of the target and projectile are collinear

  14. A new analytical potential energy surface for the adsorption systemk CO/Cu(100)

    NARCIS (Netherlands)

    Marquardt, R.; Cuvelier, F.; Olsen, R.A.; Baerends, E.J.; Tremblay, J.C.; Saalfrank, P.

    2010-01-01

    Electronic structure data and analytical representations of the potential energy surface for the adsorption of carbon monoxide on a crystalline copper Cu(100) substrate are reviewed. It is found that a previously published and widely used analytical hypersurface for this process [J. C. Tully, M.

  15. A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface

    KAUST Repository

    Ng, Kim Choon; Burhan, Muhammad; Shahzad, Muhammad Wakil; Ismail, Azahar Bin

    2017-01-01

    The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

  16. Potential energy surfaces of adsorbates on periodic substrates: Application of the Morse theory

    Czech Academy of Sciences Publication Activity Database

    Pick, Štěpán

    2009-01-01

    Roč. 79, č. 4 (2009), 045403-1-5 ISSN 1098-0121 Institutional research plan: CEZ:AV0Z40400503 Keywords : adsorbed layers * Morse potential * potential energy surfaces * substrates Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.475, year: 2009

  17. A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface

    KAUST Repository

    Ng, Kim Choon

    2017-08-31

    The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

  18. Surface energy balance of fresh and saline waters : AquaSEBS

    NARCIS (Netherlands)

    Abdelrady, A.R.; Timmermans, J.; Vekerdy, Z.; Salama, M.S.

    2016-01-01

    Current earth observation models do not take into account the influence of water salinity on the evaporation rate, even though the salinity influences the evaporation rate by affecting the density and latent heat of vaporization. In this paper, we adapt the SEBS (Surface Energy Balance System) model

  19. Influence of drying method on the surface energy of cellulose nanofibrils determined by inverse gas chromatography

    Science.gov (United States)

    Yucheng Peng; Douglas J. Gardner; Yousoo Han; Zhiyong Cai; Mandla A. Tshabalala

    2013-01-01

    Research and development of the renewable nanomaterial cellulose nanofibrils (CNFs) has received considerable attention. The effect of drying on the surface energy of CNFs was investigated. Samples of nanofibrillated cellulose (NFC) and cellulose nanocrystals (CNC) were each subjected to four separate drying methods: air-drying, freeze-drying, spray-drying, and...

  20. Surface energy balance of seasonal snow cover for snow-melt ...

    Indian Academy of Sciences (India)

    This study describes time series analysis of snow-melt, radiation data and energy balance for a seasonal snow cover at Dhundi field station of SASE, which lies in Pir Panjal range of the. N–W Himalaya, for a winter season from 13 January to 12 April 2005. The analysis shows that mean snow surface temperature remains ...

  1. Impact of surface energy on the shock properties of granular explosives

    Science.gov (United States)

    Bidault, X.; Pineau, N.

    2018-01-01

    This paper presents the first part of a two-fold molecular dynamics study of the impact of the granularity on the shock properties of high explosives. Recent experimental studies show that the granularity can have a substantial impact on the properties of detonation products {i.e., variations in the size distributions of detonation nanodiamonds [V. Pichot et al., Sci. Rep. 3, 2159 (2013)]}. These variations can have two origins: the surface energy, which is a priori enhanced from micro- to nano-scale, and the porosity induced by the granular structure. In this first report, we study the impact of the surface-energy contribution on the inert shock compression of TATB, TNT, α-RDX, and β-HMX nano-grains (triaminotrinitrobenzene, trinitrotoluene, hexogen and octogen, respectively). We compute the radius-dependent surface energy and combine it with an ab initio-based equation of state in order to obtain the resulting shock properties through the Rankine-Hugoniot relations. We find that the enhancement of the surface energy results in a moderate overheating under shock compression. This contribution is minor with respect to porosity, when compared to a simple macroscopic model. This result motivates further atomistic studies on the impact of nanoporosity networks on the shock properties.

  2. Energy-separated sequential irradiation for ripple pattern tailoring on silicon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Tanuj [Department of Physics, Central University of Haryana, Jant-Pali, Mahendergarh 1123029 (India); Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067 (India); Kumar, Manish, E-mail: manishbharadwaj@gmail.com [Department of Physics, Central University of Rajasthan, Kishangarh 305801 (India); Panchal, Vandana [Department of Physics, National Institute of Technology, Kurukshetra 136119 (India); Sahoo, P.K. [School of Physical Sciences, National Institute of Science Education and Research, Bhubaneswar 751005 (India); Kanjilal, D. [Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067 (India)

    2015-12-01

    Highlights: • A new process for controlling the near-surface amorphization of ripples on Si surfaces. • Ripples generation by 100 KeV Ar{sup +} and amorphization control by 60 KeV Ar{sup +} irradiation. • Advantage of energy-separated irradiation demonstrated by detailed RBS and AFM studies. • Relevant mechanism is presented on the basis of DAMAGE and SIMNRA simulations. • Key role of solid flow towards the amorphous/crystalline interface is demonstrated. - Abstract: Nanoscale ripples on semiconductor surfaces have potential application in biosensing and optoelectronics, but suffer from uncontrolled surface-amorphization when prepared by conventional ion-irradiation methods. A two-step, energy-separated sequential-irradiation enables simultaneous control of surface-amorphization and ripple-dimensions on Si(1 0 0). The evolution of ripples using 100 keV Ar{sup +} bombardment and further tuning of the patterns using a sequential-irradiation by 60 keV Ar{sup +} at different fluences are demonstrated. The advantage of this approach as opposed to increased fluence at the same energy is clarified by atomic force microscopy and Rutherford backscattering spectroscopy investigations. The explanation of our findings is presented through DAMAGE simulation.

  3. Mechanisms for the reflection of light atoms from crystal surfaces at kilovolt energies

    International Nuclear Information System (INIS)

    Hou, M.; Robinson, M.T.

    1978-01-01

    The computer program MARLOWE was used to investigate the backscattering of protons from the (110) surface of a nickel crystal. Grazing incidence was considered so that anisotropic effects originated mainly from the surface region. The contribution of aligned scattering was studied by comparing the results with similar calculations for an amorphous target. Energy distributions of backscattered particles were investigated for incident energies ranging from 0.1 to 5 keV. The structure of these distributions was explained by making calculations for several target thickness. Specular reflection was found to depend on the structure of the first few atomic planes only. The (110) rows in the surface plane were responsible for focusing into surface semichannels. Focusing in these semichannels was found to be the strongest under total reflection conditions (below about 1.3 keV) while the scattering intensity from surface rows increased with increasing incident energy. The orientation of the plane of incidence was found to have large influence on the relative contributions of the reflection mechanisms involved. (orig.) [de

  4. Impact of dissipation on the energy spectrum of experimental turbulence of gravity surface waves

    Science.gov (United States)

    Campagne, Antoine; Hassaini, Roumaissa; Redor, Ivan; Sommeria, Joël; Valran, Thomas; Viboud, Samuel; Mordant, Nicolas

    2018-04-01

    We discuss the impact of dissipation on the development of the energy spectrum in wave turbulence of gravity surface waves with emphasis on the effect of surface contamination. We performed experiments in the Coriolis facility, which is a 13-m-diam wave tank. We took care of cleaning surface contamination as well as possible, considering that the surface of water exceeds 100 m2. We observe that for the cleanest condition the frequency energy spectrum shows a power-law decay extending up to the gravity capillary crossover (14 Hz) with a spectral exponent that is increasing with the forcing strength and decaying with surface contamination. Although slightly higher than reported previously in the literature, the exponent for the cleanest water remains significantly below the prediction from the weak turbulence theory. By discussing length and time scales, we show that weak turbulence cannot be expected at frequencies above 3 Hz. We observe with a stereoscopic reconstruction technique that the increase with the forcing strength of energy spectrum beyond 3 Hz is mostly due to the formation and strengthening of bound waves.

  5. Global potential energy surface of ground state singlet spin O4

    Science.gov (United States)

    Mankodi, Tapan K.; Bhandarkar, Upendra V.; Puranik, Bhalchandra P.

    2018-02-01

    A new global potential energy for the singlet spin state O4 system is reported using CASPT2/aug-cc-pVTZ ab initio calculations. The geometries for the six-dimensional surface are constructed using a novel point generation scheme that employs randomly generated configurations based on the beta distribution. The advantage of this scheme is apparent in the reduction of the number of required geometries for a reasonably accurate potential energy surface (PES) and the consequent decrease in the overall computational effort. The reported surface matches well with the recently published singlet surface by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. In addition to the O4 PES, the ground state N4 PES is also constructed using the point generation scheme and compared with the existing PES [Y. Paukku et al., J. Chem. Phys. 139, 044309 (2013)]. The singlet surface is constructed with the aim of studying high energy O2-O2 collisions and predicting collision induced dissociation cross section to be used in simulating non-equilibrium aerothermodynamic flows.

  6. U. K. surface passenger transport sector. Energy consumption and policy options for conservation

    Energy Technology Data Exchange (ETDEWEB)

    Maltby, D; Monteath, I G; Lawler, K A

    1978-12-01

    Forecasts of U.K. energy consumption in this sector for four future scenarios based on different economic growth rates, energy prices, and energy conservation policies, show that by the year 2000, private transport will probably account for 76-94% of total energy consumption in surface passenger transport. A 33% increase in the average miles-per-gallon fuel consumption through technological improvements in private vehicles, conversion of private vehicles to diesel oil, additional fuel taxation equivalent to 25 or 50% fuel price increase, a 10% reduction in average car engine size (encouraged by taxation), and changes in public transport technology offer energy savings of about 20, 5-10, 6.3 or 12.5, 2-4, and 2%, respectively. There is considerable uncertainty about the outcome of these options.

  7. Improved parametric fits for the HeH2 ab initio energy surface

    International Nuclear Information System (INIS)

    Muchnick, P.

    1992-01-01

    A brief history of the development of ab initio calculations for the HeH 2 quasi-molecule energy surface, and the parametric fits to these ab initio calculations, is presented. The concept of 'physical reasonableness' of the parametric fit is discussed. Several new improved parametric fits for the energy surface, meeting these requirements, are then proposed. One fit extends the Russek-Garcia parametric fit for the deep repulsion region to include r-dependent parameters, resulting in a more physically reasonable fit with smaller average error. This improved surface fit is applied to quasi-elastic collisions of He on H 2 in the impulse approximation. Previous classical calculations of the scaled inelastic vibrorotational excitation energy distributions are improved with this more accurate parametric fit of the energy surface and with the incorporation of quantum effects in vibrational excitation. It is shown that Sigmund's approach in developing his scaling law is incomplete in the contribution of the three-body interactions to vibrational excitation of the H 2 molecule is concerned. The Sigmund theory is extended to take into account for r-dependency of three-body interactions. A parametric fit for the entire energy surface from essentially 0 ≤R≤∞ and 1.2≤r≤1.6 a.u., where R is the intermolecular spacing and r is the hydrogen bonding length, is also presented. This fit is physically reasonable in all asymptotic limits. This first, full surface parametric fit is based primarily upon a composite of ab initio studies by Russek and Garcia and Meyer, Hariharan and Kutzelnigg. Parametric fits for the H 2 (1sσ g ) 2 , H 2 + (1sσ g ), H 2 + (2pσ u ) and (LiH 2 ) + energy surfaces are also presented. The new parametric fits for H 2 , H 2 + (1sσ g ) are shown to be improvements over the well-known Morse potentials for these surfaces

  8. Electrode surface engineering by atomic layer deposition: A promising pathway toward better energy storage

    KAUST Repository

    Ahmed, Bilal

    2016-04-29

    Research on electrochemical energy storage devices including Li ion batteries (LIBs), Na ion batteries (NIBs) and supercapacitors (SCs) has accelerated in recent years, in part because developments in nanomaterials are making it possible to achieve high capacities and energy and power densities. These developments can extend battery life in portable devices, and open new markets such as electric vehicles and large-scale grid energy storage. It is well known that surface reactions largely determine the performance and stability of electrochemical energy storage devices. Despite showing impressive capacities and high energy and power densities, many of the new nanostructured electrode materials suffer from limited lifetime due to severe electrode interaction with electrolytes or due to large volume changes. Hence control of the surface of the electrode material is essential for both increasing capacity and improving cyclic stability of the energy storage devices.Atomic layer deposition (ALD) which has become a pervasive synthesis method in the microelectronics industry, has recently emerged as a promising process for electrochemical energy storage. ALD boasts excellent conformality, atomic scale thickness control, and uniformity over large areas. Since ALD is based on self-limiting surface reactions, complex shapes and nanostructures can be coated with excellent uniformity, and most processes can be done below 200. °C. In this article, we review recent studies on the use of ALD coatings to improve the performance of electrochemical energy storage devices, with particular emphasis on the studies that have provided mechanistic insight into the role of ALD in improving device performance. © 2016 Elsevier Ltd.

  9. Formation of nanostructures on HOPG surface in presence of surfactant atom during low energy ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Ranjan, M., E-mail: ranjanm@ipr.res.in; Joshi, P.; Mukherjee, S.

    2016-07-15

    Low energy ions beam often develop periodic patterns on surfaces under normal or off-normal incidence. Formation of such periodic patterns depends on the substrate material, the ion beam parameters, and the processing conditions. Processing conditions introduce unwanted contaminant atoms, which also play strong role in pattern formation by changing the effective sputtering yield of the material. In this work we have analysed the effect of Cu, Fe and Al impurities introduced during low energy Ar{sup +} ion irradiation on HOPG substrate. It is observed that by changing the species of foreign atoms the surface topography changes drastically. The observed surface topography is co-related with the modified sputtering yield of HOPG. Presence of Cu and Fe amplify the effective sputtering yield of HOPG, so that the required threshold for the pattern formation is achieved with the given fluence, whereas Al does not lead to any significant change in the effective yield and hence no pattern formation occurs.

  10. Dynamic Electron Correlation Effects on the Ground State Potential Energy Surface of a Retinal Chromophore Model.

    Science.gov (United States)

    Gozem, Samer; Huntress, Mark; Schapiro, Igor; Lindh, Roland; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

    2012-11-13

    The ground state potential energy surface of the retinal chromophore of visual pigments (e.g., bovine rhodopsin) features a low-lying conical intersection surrounded by regions with variable charge-transfer and diradical electronic structures. This implies that dynamic electron correlation may have a large effect on the shape of the force fields driving its reactivity. To investigate this effect, we focus on mapping the potential energy for three paths located along the ground state CASSCF potential energy surface of the penta-2,4-dieniminium cation taken as a minimal model of the retinal chromophore. The first path spans the bond length alternation coordinate and intercepts a conical intersection point. The other two are minimum energy paths along two distinct but kinetically competitive thermal isomerization coordinates. We show that the effect of introducing the missing dynamic electron correlation variationally (with MRCISD) and perturbatively (with the CASPT2, NEVPT2, and XMCQDPT2 methods) leads, invariably, to a stabilization of the regions with charge transfer character and to a significant reshaping of the reference CASSCF potential energy surface and suggesting a change in the dominating isomerization mechanism. The possible impact of such a correction on the photoisomerization of the retinal chromophore is discussed.

  11. Trajectory resolved analysis of LEIS energy spectra: Neutralization and surface structure

    International Nuclear Information System (INIS)

    Beikler, Robert; Taglauer, Edmund

    2001-01-01

    For a quantitative evaluation of low-energy ion scattering (LEIS) data with respect to surface composition and structure a detailed analysis of the energy spectra is required. This includes the identification of multiple scattering processes and the determination of ion survival probabilities. We analyzed scattered ion energy spectra by using the computer code MARLOWE for which we developed a new analysis routine that allows to record energy distributions in dependence of the number of projectile-target atom collisions, in dependence of the distance of closest approach, or in dependence of the scattering crystalline layer. This procedure also permits the determination of ion survival probabilities by applying simple collision-dependent neutralization models. Experimental energy spectra for various projectile (He + , Ne + , Na + ) and target (transition metals, oxides) combinations are well reproduced and quantitative results for ion survival probabilities are obtained. These are largely in agreement with results obtained for bimetallic crystal surfaces obtained in a different way. Such MARLOWE calculations are also useful for the identification of structure relevant processes. This is shown exemplarily for the reconstructed Au(1 1 0) surface including a possibility to determine the (1x2)→(1x1) transition temperature

  12. THE COSMIC-RAY ENERGY SPECTRUM OBSERVED WITH THE SURFACE DETECTOR OF THE TELESCOPE ARRAY EXPERIMENT

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Zayyad, T.; Allen, M.; Anderson, R.; Barcikowski, E.; Belz, J. W.; Bergman, D. R.; Blake, S. A.; Cady, R.; Hanlon, W. [High Energy Astrophysics Institute and Department of Physics and Astronomy, University of Utah, Salt Lake City, Utah (United States); Aida, R. [University of Yamanashi, Interdisciplinary Graduate School of Medicine and Engineering, Kofu, Yamanashi (Japan); Azuma, R.; Fukuda, T. [Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro, Tokyo (Japan); Cheon, B. G.; Cho, E. J. [Department of Physics and Research Institute of Natural Science, Hanyang University, Seongdong-gu, Seoul (Korea, Republic of); Chiba, J. [Department of Physics, Tokyo University of Science, Noda, Chiba (Japan); Chikawa, M. [Department of Physics, Kinki University, Higashi Osaka, Osaka (Japan); Cho, W. R. [Department of Physics, Yonsei University, Seodaemun-gu, Seoul (Korea, Republic of); Fujii, H. [Institute of Particle and Nuclear Studies, KEK, Tsukuba, Ibaraki (Japan); Fujii, T. [Graduate School of Science, Osaka City University, Osaka, Osaka (Japan); Fukushima, M. [Institute for Cosmic Ray Research, University of Tokyo, Kashiwa, Chiba (Japan); and others

    2013-05-01

    The Telescope Array (TA) collaboration has measured the energy spectrum of ultra-high energy cosmic rays (UHECRs) with primary energies above 1.6 Multiplication-Sign 10{sup 18} eV. This measurement is based upon four years of observation by the surface detector component of TA. The spectrum shows a dip at an energy of 4.6 Multiplication-Sign 10{sup 18} eV and a steepening at 5.4 Multiplication-Sign 10{sup 19} eV which is consistent with the expectation from the GZK cutoff. We present the results of a technique, new to the analysis of UHECR surface detector data, that involves generating a complete simulation of UHECRs striking the TA surface detector. The procedure starts with shower simulations using the CORSIKA Monte Carlo program where we have solved the problems caused by use of the ''thinning'' approximation. This simulation method allows us to make an accurate calculation of the acceptance of the detector for the energies concerned.

  13. Plasma-Assisted Synthesis and Surface Modification of Electrode Materials for Renewable Energy.

    Science.gov (United States)

    Dou, Shuo; Tao, Li; Wang, Ruilun; El Hankari, Samir; Chen, Ru; Wang, Shuangyin

    2018-02-14

    Renewable energy technology has been considered as a "MUST" option to lower the use of fossil fuels for industry and daily life. Designing critical and sophisticated materials is of great importance in order to realize high-performance energy technology. Typically, efficient synthesis and soft surface modification of nanomaterials are important for energy technology. Therefore, there are increasing demands on the rational design of efficient electrocatalysts or electrode materials, which are the key for scalable and practical electrochemical energy devices. Nevertheless, the development of versatile and cheap strategies is one of the main challenges to achieve the aforementioned goals. Accordingly, plasma technology has recently appeared as an extremely promising alternative for the synthesis and surface modification of nanomaterials for electrochemical devices. Here, the recent progress on the development of nonthermal plasma technology is highlighted for the synthesis and surface modification of advanced electrode materials for renewable energy technology including electrocatalysts for fuel cells, water splitting, metal-air batteries, and electrode materials for batteries and supercapacitors, etc. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

    International Nuclear Information System (INIS)

    Frisch, M.J.; Binkley, J.S.; Schaefer, H.F. III

    1984-01-01

    The relative energies of the stationary points on the FH 2 and H 2 CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H 2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Moller--Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H 2 →FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol -1 of the experimental value using the largest basis set considered. The qualitative features of the H 2 CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended

  15. Low-energy particle interaction at carbon nanowalls on W surface

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, N., E-mail: nozomi.tanaka@ppl2.qse.tohoku.ac.j [Tohoku University, Aramaki 6-01-2, Aoba, Sendai 980-8579 (Japan); Yamaoka, H. [Harima Institute, RIKEN (The Institute of Physical and Chemical Research), Hyogo 679-5148 (Japan); Nishiura, M.; Tsumori, K. [National Institute for Fusion Science, Toki, Gifu 509-5292 (Japan); Nagamura, T.; Sasao, M. [Tohoku University, Aramaki 6-01-2, Aoba, Sendai 980-8579 (Japan); Kenmotsu, T. [Doshisha University, Kyotanabe, Kyoto 610-0321 (Japan); Matsumoto, Y. [Tokushima Bunri University, Yamashiro, Tokushima 770-8514 (Japan); Wada, M. [Doshisha University, Kyotanabe, Kyoto 610-0321 (Japan)

    2009-06-15

    We measured the characteristics of the reflected particles from a carbon nanowall (CNW) deposited on a W surface following the injection of 1-2 keV H{sup +} and O{sup +} ions. The reflected ion energies and intensities indicated a contribution from multiple scattering in the target. The reflection angular dependence of the reflected ion intensities reached the maximum around the mirror angle and showed a sharp distribution, which may be attributable to the effect due to the aligned structure of the CNW. The energies and intensities of the reflected ions decreased with the time of ion bombardment. The intensities and energies of the reflected ions were, however, recovered to some degree by baking the sample, indicating the surface modification due to retention of the injected particles during the injection. We used the Monte Carlo simulation code ACAT (Atomic Collision in Amorphous Target) to study these processes theoretically and the calculated results supported the experimental results.

  16. Energy loss of MeV protons specularly reflected from metal surfaces

    International Nuclear Information System (INIS)

    Juaristi, J.I.; Garcia de Abajo, F.J.; Echenique, P.M.

    1996-01-01

    A parameter-free model is presented to study the energy loss of fast protons specularly reflected from metal surfaces. The contributions to the energy loss from excitation of valence-band electrons and ionization of localized target-atom electronic states are calculated separately. The former is calculated from the induced surface wake potential using linear response theory and the specular-reflection model, while the latter is calculated in the first Born approximation. The results obtained are in good agreement with available experimental data. However, the experimental qualitative trend of the energy loss as a function of the angle of incidence is obtained when the valence-band electron model is replaced by localized target atom electron states, though with a worse quantitative agreement. copyright 1996 The American Physical Society

  17. Simulated Effects of Land Cover Conversion on the Surface Energy Budget in the Southwest of China

    Directory of Open Access Journals (Sweden)

    Jiangbo Gao

    2014-03-01

    Full Text Available In this paper, the coupled WRF/SSiB model, accompanied by a Karst Rocky Desertification (KRD map of the Guizhou Karst Plateau (GKP of China, was applied to detect how the changed vegetation and soil characteristics over the GKP modify the energy balance at the land surface. The results indicated that land degradation led to reduced net radiation by inducing more upward shortwave and longwave radiation, which were associated with increasing surface albedo and temperature, respectively. The KRD also resulted in changed surface energy partitioning into sensible and latent heat fluxes. The latent heat flux at land surface was reduced substantially due to the higher surface albedo and stomatal resistance, the lower Leaf Area Index (LAI and roughness length in the degradation experiment, while the sensible heat flux increased, mainly because of the higher surface temperature. Furthermore, the moisture flux convergence was reduced, owing to the lower atmospheric heating and the relative subsidence. However, compared with the reduced evaporation, the decrease in moisture flux convergence contributed much less to the reduced precipitation. Precipitation strongly affects soil moisture, vegetation growth and phenology, and thus evaporation and convective latent heating, so when precipitation was changed, a feedback loop was created.

  18. Energy transfer and photochemistry on a metal surface: Mo(CO)6 on Rh(100)

    International Nuclear Information System (INIS)

    Germer, T.A.; Ho, W.

    1989-01-01

    The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO) 6 on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO) 6 adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated first layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO) 6 adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface

  19. An intercomparison and validation of satellite-based surface radiative energy flux estimates over the Arctic

    Science.gov (United States)

    Riihelä, Aku; Key, Jeffrey R.; Meirink, Jan Fokke; Kuipers Munneke, Peter; Palo, Timo; Karlsson, Karl-Göran

    2017-05-01

    Accurate determination of radiative energy fluxes over the Arctic is of crucial importance for understanding atmosphere-surface interactions, melt and refreezing cycles of the snow and ice cover, and the role of the Arctic in the global energy budget. Satellite-based estimates can provide comprehensive spatiotemporal coverage, but the accuracy and comparability of the existing data sets must be ascertained to facilitate their use. Here we compare radiative flux estimates from Clouds and the Earth's Radiant Energy System (CERES) Synoptic 1-degree (SYN1deg)/Energy Balanced and Filled, Global Energy and Water Cycle Experiment (GEWEX) surface energy budget, and our own experimental FluxNet / Satellite Application Facility on Climate Monitoring cLoud, Albedo and RAdiation (CLARA) data against in situ observations over Arctic sea ice and the Greenland Ice Sheet during summer of 2007. In general, CERES SYN1deg flux estimates agree best with in situ measurements, although with two particular limitations: (1) over sea ice the upwelling shortwave flux in CERES SYN1deg appears to be underestimated because of an underestimated surface albedo and (2) the CERES SYN1deg upwelling longwave flux over sea ice saturates during midsummer. The Advanced Very High Resolution Radiometer-based GEWEX and FluxNet-CLARA flux estimates generally show a larger range in retrieval errors relative to CERES, with contrasting tendencies relative to each other. The largest source of retrieval error in the FluxNet-CLARA downwelling shortwave flux is shown to be an overestimated cloud optical thickness. The results illustrate that satellite-based flux estimates over the Arctic are not yet homogeneous and that further efforts are necessary to investigate the differences in the surface and cloud properties which lead to disagreements in flux retrievals.

  20. Microsolvation of the water cation in neon: Infrared spectra and potential energy surface of the H2O+-Ne open-shell ionic complex

    Science.gov (United States)

    Dopfer, Otto; Roth, Doris; Maier, John P.

    2001-04-01

    The intermolecular potential of the H2O+-Ne open-shell ionic dimer in its doublet electronic ground state has been investigated by infrared spectroscopy in the vicinity of the O-H stretch vibrations (ν1 and ν3) and ab initio calculations at the unrestricted Møller-Plesset second-order (MP2) level with a basis set of aug-cc-pVTZ quality. The rovibrational structure of the photodissociation spectrum is consistent with a proton-bound planar H-O-H-Ne structure and a Ne-H separation of R0=1.815(5) Å. The complexation-induced redshifts are Δν1=-69 cm-1 and Δν3=-6 cm-1, respectively. Tunneling splittings observed in the perpendicular component of the ν3 hybrid band of H2O+-Ne are attributed to hindered internal rotation between the two equivalent proton-bound equilibrium structures. The interpretation of the H2O+-Ne spectrum is supported by the spectrum of the monodeuterated species, for which both the proton-bound and the deuteron-bound isomers are observed (DOH+-Ne, HOD+-Ne). The equilibrium structure of the calculated potential energy surface of H2O+-Ne has a slightly translinear proton bond, which is characterized by a Ne-H separation of Re=1.77 Å, a bond angle of φe=174°, and dissociation energies of De=756 cm-1 and D0=476 cm-1. According to the calculated potential, the exchange tunneling between the two equivalent minima occurs via the planar bridged transition state with C2v symmetry and a barrier of 340 cm-1. In general, the calculated properties of H2O+-Ne show good agreement with the experimental data. Initial steps in the microsolvation of the water cation in neon are discussed by comparing the calculated and experimental properties of H2O+-Nen (n=0-2) with neon matrix isolation data (n→∞).

  1. An energy-filtering device coupled to a quadrupole mass spectrometer for soft-landing molecular ions on surfaces with controlled energy

    Energy Technology Data Exchange (ETDEWEB)

    Bodin, A.; Laloo, R.; Abeilhou, P.; Guiraud, L.; Gauthier, S.; Martrou, D. [Nanosciences Group, CEMES, CNRS UPR 8011 and University Toulouse III - Paul Sabatier, 29 rue Jeanne Marvig, BP94347, F-31055 Toulouse Cedex 4 (France)

    2013-09-15

    We have developed an energy-filtering device coupled to a quadrupole mass spectrometer to deposit ionized molecules on surfaces with controlled energy in ultra high vacuum environment. Extensive numerical simulations as well as direct measurements show that the ion beam flying out of a quadrupole exhibits a high-energy tail decreasing slowly up to several hundred eV. This energy distribution renders impossible any direct soft-landing deposition of molecular ions. To remove this high-energy tail by energy filtering, a 127° electrostatic sector and a specific triplet lenses were designed and added after the last quadrupole of a triple quadrupole mass spectrometer. The results obtained with this energy-filtering device show clearly the elimination of the high-energy tail. The ion beam that impinges on the sample surface satisfies now the soft-landing criterion for molecular ions, opening new research opportunities in the numerous scientific domains involving charges adsorbed on insulating surfaces.

  2. Fast exploration of an optimal path on the multidimensional free energy surface

    Science.gov (United States)

    Chen, Changjun

    2017-01-01

    In a reaction, determination of an optimal path with a high reaction rate (or a low free energy barrier) is important for the study of the reaction mechanism. This is a complicated problem that involves lots of degrees of freedom. For simple models, one can build an initial path in the collective variable space by the interpolation method first and then update the whole path constantly in the optimization. However, such interpolation method could be risky in the high dimensional space for large molecules. On the path, steric clashes between neighboring atoms could cause extremely high energy barriers and thus fail the optimization. Moreover, performing simulations for all the snapshots on the path is also time-consuming. In this paper, we build and optimize the path by a growing method on the free energy surface. The method grows a path from the reactant and extends its length in the collective variable space step by step. The growing direction is determined by both the free energy gradient at the end of the path and the direction vector pointing at the product. With fewer snapshots on the path, this strategy can let the path avoid the high energy states in the growing process and save the precious simulation time at each iteration step. Applications show that the presented method is efficient enough to produce optimal paths on either the two-dimensional or the twelve-dimensional free energy surfaces of different small molecules. PMID:28542475

  3. Proper surface channelling of low energy argon ions incident on a nickel (110) crystal

    International Nuclear Information System (INIS)

    Evdokimov, I.N.; Berg, J.A. van den; Armour, D.G.

    1979-01-01

    The scattering behaviour of 6 keV argon ions from a nickel (110) surface has been investigated for specular reflection under grazing incidence conditions. The occurrence of an anomalously high energy loss has been confirmed and the transition from chain scattering at large scattering angles to a distinctly different type of scattering at small angles has been investigated. The characteristics of the low angle scattering phenomena, which dominate the observed spectra at scattering angles below about 18 0 , may be explained in terms of a surface hyperchannelling model in which the incident ions are confined to move within the shallow 'potential valleys' between two atomic rows in the surface. The critical angle for occurrence of this phenomena which is distinctly different from surface semichannelling has been evaluated with Lindhard's standard string potential. The experimentally measured critical angles are in good agreement with the calculated ones. (author)

  4. Surface effects in the energy loss of ions passing through a thin foil

    International Nuclear Information System (INIS)

    Osma, J.; Garcia de Abajo, F.J.

    1997-01-01

    The role of surface plasmon excitation in the interaction of ions passing through thin films has been studied in both the Bloch hydrodynamic approximation and the local response approach for projectile velocities above the maximum of the stopping power curve. The effect of the surface is found to be much weaker when the dispersion of the modes is taken into consideration than in the case of nondispersive media, though qualitatively the main features of the hydrodynamic approach resemble those of the local one. A generalization of the Bothe-Landau convolution formula for the loss probability distribution is derived to take into account the scattering due to the surface. The effects of the surface in the energy-loss spectra are discussed. A comparison with experiment is given. copyright 1997 The American Physical Society

  5. Calculated energy distributions for light 0.25--18-keV ions scattered from solid surfaces

    International Nuclear Information System (INIS)

    Robinson, J.E.; Harms, A.A.; Karapetsas, S.K.

    1975-01-01

    Scattered energy distributions are calculated for light ions incident on Nb and Mo surfaces of interest for controlled nulcear fusion reactors. The scattered energy is found to vary as a function of the reflection coefficient between a multiple-collision limit at low energies and a single-collision Rutherford scattering limit at high energies. High-energy peaking of the scattered particle distributions is also found for low incident energies

  6. Changing surface-atmosphere energy exchange and refreezing capacity of the lower accumulation area, West Greenland

    Science.gov (United States)

    Charalampidis, C.; van As, D.; Box, J. E.; van den Broeke, M. R.; Colgan, W. T.; Doyle, S. H.; Hubbard, A. L.; MacFerrin, M.; Machguth, H.; Smeets, C. J. P. P.

    2015-11-01

    We present 5 years (2009-2013) of automatic weather station measurements from the lower accumulation area (1840 m a.s.l. - above sea level) of the Greenland ice sheet in the Kangerlussuaq region. Here, the summers of 2010 and 2012 were both exceptionally warm, but only 2012 resulted in a strongly negative surface mass budget (SMB) and surface meltwater run-off. The observed run-off was due to a large ice fraction in the upper 10 m of firn that prevented meltwater from percolating to available pore volume below. Analysis reveals an anomalously low 2012 summer-averaged albedo of 0.71 (typically ~ 0.78), as meltwater was present at the ice sheet surface. Consequently, during the 2012 melt season, the ice sheet surface absorbed 28 % (213 MJ m-2) more solar radiation than the average of all other years. A surface energy balance model is used to evaluate the seasonal and interannual variability of all surface energy fluxes. The model reproduces the observed melt rates as well as the SMB for each season. A sensitivity analysis reveals that 71 % of the additional solar radiation in 2012 was used for melt, corresponding to 36 % (0.64 m) of the 2012 surface lowering. The remaining 64 % (1.14 m) of surface lowering resulted from high atmospheric temperatures, up to a +2.6 °C daily average, indicating that 2012 would have been a negative SMB year at this site even without the melt-albedo feedback. Longer time series of SMB, regional temperature, and remotely sensed albedo (MODIS) show that 2012 was the first strongly negative SMB year, with the lowest albedo, at this elevation on record. The warm conditions of recent years have resulted in enhanced melt and reduction of the refreezing capacity in the lower accumulation area. If high temperatures continue, the current lower accumulation area will turn into a region with superimposed ice in coming years.

  7. Modelling surface energy fluxes over a Dehesa ecosystem using a two-source energy balance model.

    Science.gov (United States)

    Andreu, Ana; Kustas, William. P.; Anderson, Martha C.; Carrara, Arnaud; Patrocinio Gonzalez-Dugo, Maria

    2013-04-01

    The Dehesa is the most widespread agroforestry land-use system in Europe, covering more than 3 million hectares in the Iberian Peninsula and Greece (Grove and Rackham, 2001; Papanastasis, 2004). It is an agro-silvo-pastural ecosystem consisting of widely-spaced oak trees (mostly Quercus ilex L.), combined with crops, pasture and Mediterranean shrubs, and it is recognized as an example of sustainable land use and for his importance in the rural economy (Diaz et al., 1997; Plieninger and Wilbrand, 2001). The ecosystem is influenced by a Mediterranean climate, with recurrent and severe droughts. Over the last decades the Dehesa has faced multiple environmental threats, derived from intensive agricultural use and socio-economic changes, which have caused environmental degradation of the area, namely reduction in tree density and stocking rates, changes in soil properties and hydrological processes and an increase of soil erosion (Coelho et al. 2004; Schnabel and Ferreira, 2004; Montoya 1998; Pulido and Díaz, 2005). Understanding the hydrological, atmospheric and physiological processes that affect the functioning of the ecosystem will improve the management and conservation of the Dehesa. One of the key metrics in assessing ecosystem health, particularly in this water-limited environment, is the capability of monitoring evaporation (ET). To make large area assessments requires the use of remote sensing. Thermal-based energy balance techniques that distinguish soil/substrate and vegetation contributions to the radiative temperature and radiation/turbulent fluxes have proven to be reliable in such semi-arid sparse canopy-cover landscapes. In particular, the two-source energy balance (TSEB) model of Norman et al. (1995) and Kustas and Norman (1999) has shown to be robust for a wide range of partially-vegetated landscapes. The TSEB formulation is evaluated at a flux tower site located in center Spain (Majadas del Tietar, Caceres). Its application in this environment is

  8. Vibrational energy on surfaces: Ultrafast flash-thermal conductance of molecular monolayers

    Science.gov (United States)

    Dlott, Dana

    2008-03-01

    Vibrational energy flow through molecules remains a perennial problem in chemical physics. Usually vibrational energy dynamics are viewed through the lens of time-dependent level populations. This is natural because lasers naturally pump and probe vibrational transitions, but it is also useful to think of vibrational energy as being conducted from one location in a molecule to another. We have developed a new technique where energy is driven into a specific part of molecules adsorbed on a metal surface, and ultrafast nonlinear coherent vibrational spectroscopy is used to watch the energy arrive at another part. This technique is the analog of a flash thermal conductance apparatus, except it probes energy flow with angstrom spatial and femtosecond temporal resolution. Specific examples to be presented include energy flow along alkane chains, and energy flow into substituted benzenes. Ref: Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Ultrafast flash thermal conductance of molecular chains, Science 317, 787-790 (2007). This material is based upon work supported by the National Science Foundation under award DMR 0504038 and the Air Force Office of Scientific Research under award FA9550-06-1-0235.

  9. Determination of surface energies of hot-melt extruded sugar-starch pellets.

    Science.gov (United States)

    Yeung, Chi-Wah; Rein, Hubert

    2018-02-01

    Hot-melt extruded sugar-starch pellets are an alternative for commercial sugar spheres, but their coating properties remain to be studied. Both the European Pharmcopoeia 8.6 and the United States Pharmacopoeia 40 specify the composition of sugar-starch pellets without giving requirements for the manufacturing process. Due to various fabrication techniques, the physicochemical properties of pellets may differ. Therefore, the adhesion energies of three coating dispersions (sustained, enteric and immediate release) on different types of pellets were investigated. In this context, the surface energies of various kinds of corn starch (normal, waxy, high-amylose) and sucrose pellets were analyzed using the sessile drop method, whereas the surface tensions of the coating dispersions were examined using the pendant drop method. The adhesion forces were calculated from the results of these studies. Furthermore, sugar spheres were characterized in terms of particle size distribution, porosity and specific surface area. An increase of the pellets' sucrose content leads to a more porous surface structure, which gives them an enhanced wetting behavior with coating dispersions. The adhesion energies of extruded sugar-starch pellets are similar to those of commercial sugar spheres, which comply with pharmacopeial requirements. Both types of pellets are equally suited for coating.

  10. Energy-resolved attosecond interferometric photoemission from Ag(111) and Au(111) surfaces

    Science.gov (United States)

    Ambrosio, M. J.; Thumm, U.

    2018-04-01

    Photoelectron emission from solid surfaces induced by attosecond pulse trains into the electric field of delayed phase-coherent infrared (IR) pulses allows the surface-specific observation of energy-resolved electronic phase accumulations and photoemission delays. We quantum-mechanically modeled interferometric photoemission spectra from the (111) surfaces of Au and Ag, including background contributions from secondary electrons and direct emission by the IR pulse, and adjusted parameters of our model to energy-resolved photoelectron spectra recently measured at a synchrotron light source by Roth et al. [J. Electron Spectrosc. 224, 84 (2018), 10.1016/j.elspec.2017.05.008]. Our calculated spectra and photoelectron phase shifts are in fair agreement with the experimental data of Locher et al. [Optica 2, 405 (2015), 10.1364/OPTICA.2.000405]. Our model's not reproducing the measured energy-dependent oscillations of the Ag(111) photoemission phases may be interpreted as evidence for subtle band-structure effects on the final-state photoelectron-surface interaction not accounted for in our simulation.

  11. Nanometer-size surface modification produced by single, low energy, highly charged ions

    International Nuclear Information System (INIS)

    Stockli, M.P.

    1994-01-01

    Atomically flat surfaces of insulators have been bombarded with low energy, highly charged ions to search for nanometer-size surface modifications. It is expected that the high electron deficiency of highly charged ions will capture and/or remove many of the insulator's localized electrons when impacting on an insulating surface. The resulting local electron deficiency is expected to locally disintegrate the insulator through a open-quotes Coulomb explosionclose quotes forming nanometer-size craters. Xe ions with charge states between 10+ and 45+ and kinetic energies between 0 and 10 keV/q were obtained from the KSU-CRYEBIS, a CRYogenic Electron Beam Ion Source and directed onto various insulating materials. Mica was favored as target material as atomically flat surfaces can be obtained reliably through cleaving. However, the authors observations with an atomic force microscope have shown that mica tends to defoliate locally rather than disintegrate, most likely due to the small binding forces between adjacent layers. So far the authors measurements indicate that each ion produces one blister if the charge state is sufficiently high. The blistering does not seem to depend very much on the kinetic energy of the ions

  12. Influence of Cooling Lubricants on the Surface Roughness and Energy Efficiency of the Cutting Machine Tools

    Directory of Open Access Journals (Sweden)

    Jersák J.

    2017-08-01

    Full Text Available The Technical University of Liberec and Brandenburg University of Technology Cottbus-Senftenberg investigated the influence of cooling lubricants on the surface roughness and energy efficiency of cutting machine tools. After summarizing the achieved experimental results, the authors conclude that cooling lubricants extensively influence the cutting temperature, cutting forces and energy consumption. Also, it is recognizable that cooling lubricants affect the cutting tools lifetime and the workpiece surface quality as well. Furthermore, costs of these cooling lubricants and the related environmental burden need to be considered. A current trend is to reduce the amount of lubricants that are used, e.g., when the Minimum Quantity Lubrication (MQL technique is applied. The lubricant or process liquid is thereby transported by the compressed air in the form of an aerosol to the contact area between the tool and workpiece. The cutting process was monitored during testing by the three following techniques: lubricant-free cutting, cutting with the use of a lubricant with the MQL technique, and only utilizing finish-turning and finish-face milling. The research allowed the authors to monitor the cutting power and mark the achieved surface quality in relation to the electrical power consumption of the cutting machine. In conclusions, the coherence between energy efficiency of the cutting machine and the workpiece surface quality regarding the used cooling lubricant is described.

  13. Nitrogen ion induced nitridation of Si(111) surface: Energy and fluence dependence

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Praveen [Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064 (India); ISOM, Universidad Politecnia de Madrid, 28040 (Spain); Kumar, Mahesh [Physics and Energy Harvesting Group, National Physical Laboratory, New Delhi 110012 (India); Nötzel, R. [ISOM, Universidad Politecnia de Madrid, 28040 (Spain); Shivaprasad, S.M., E-mail: smsprasad@jncasr.ac.in [Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064 (India)

    2014-06-01

    We present the surface modification of Si(111) into silicon nitride by exposure to energetic N{sub 2}{sup +} ions. In-situ UHV experiments have been performed to optimize the energy and fluence of the N{sub 2}{sup +} ions to form silicon nitride at room temperature (RT) and characterized in-situ by X-ray photoelectron spectroscopy. We have used N{sub 2}{sup +} ion beams in the energy range of 0.2–5.0 keV of different fluence to induce surface reactions, which lead to the formation of Si{sub x}N{sub y} on the Si(111) surface. The XPS core level spectra of Si(2p) and N(1s) have been deconvoluted into different oxidation states to extract qualitative information, while survey scans have been used for quantifying of the silicon nitride formation, valence band spectra show that as the N{sub 2}{sup +} ion fluence increases, there is an increase in the band gap. The secondary electron emission spectra region of photoemission is used to evaluate the change in the work function during the nitridation process. The results show that surface nitridation initially increases rapidly with ion fluence and then saturates. - Highlights: • A systematic study for the formation of silicon nitride on Si(111). • Investigation of optimal energy and fluence for energetic N{sub 2}{sup +} ions. • Silicon nitride formation at room temperature on Si(111)

  14. Dose distribution considerations of medium energy electron beams at extended source-to-surface distance

    International Nuclear Information System (INIS)

    Saw, Cheng B.; Ayyangar, Komanduri M.; Pawlicki, Todd; Korb, Leroy J.

    1995-01-01

    Purpose: To determine the effects of extended source-to-surface distance (SSD) on dose distributions for a range of medium energy electron beams and cone sizes. Methods and Materials: The depth-dose curves and isodose distributions of 6 MeV, 10 MeV, and 14 MeV electron beams from a dual photon and multielectron energies linear accelerator were studied. To examine the influence of cone size, the smallest and the largest cone sizes available were used. Measurements were carried out in a water phantom with the water surface set at three different SSDs from 101 to 116 cm. Results: In the region between the phantom surface and the depth of maximum dose, the depth-dose decreases as the SSD increases for all electron beam energies. The effects of extended SSD in the region beyond the depth of maximum dose are unobservable and, hence, considered minimal. Extended SSD effects are apparent for higher electron beam energy with small cone size causing the depth of maximum dose and the rapid dose fall-off region to shift deeper into the phantom. However, the change in the depth-dose curve is small. On the other hand, the rapid dose fall-off region is essentially unaltered when the large cone is used. The penumbra enlarges and electron beam flatness deteriorates with increasing SSD

  15. Surface modification and metallization of polycarbonate using low energy ion beam

    International Nuclear Information System (INIS)

    Reheem, A.M. Abdel; Maksoud, M.I.A. Abdel; Ashour, A.H.

    2016-01-01

    The low energy argon ion is used for irradiation polycarbonate samples using cold cathode ion source. The surface of the PC substrates is examined using SEM, UV-spectroscopy and FTIR. It was found that the energy band gap decrease by increase argon ion fluence. Copper films are deposited onto polycarbonate (PC) substrates after irradiation by argon ion beam. The structure, surface morphology and the optical band gap are investigated using XRD, SEM and UV spectroscopy. It can be seen that the intensity increases with deposition time and band gap decreases from 3.45 eV for the pristine PC to ∼1.7 eV for copper thin film. - Highlights: • The low energy argon ion is used for irradiation polycarbonate samples. • The surface roughness increase from 9 µm to 23.5 µm after argon ion irradiated. • Copper films are deposited onto polycarbonate (PC) substrates. • Energy band gap decreases from 3.45 eV for pristine to 1.7 eV for copper thin film.

  16. Analysis of the free-energy surface of proteins from reversible folding simulations.

    Directory of Open Access Journals (Sweden)

    Lucy R Allen

    2009-07-01

    Full Text Available Computer generated trajectories can, in principle, reveal the folding pathways of a protein at atomic resolution and possibly suggest general and simple rules for predicting the folded structure of a given sequence. While such reversible folding trajectories can only be determined ab initio using all-atom transferable force-fields for a few small proteins, they can be determined for a large number of proteins using coarse-grained and structure-based force-fields, in which a known folded structure is by construction the absolute energy and free-energy minimum. Here we use a model of the fast folding helical lambda-repressor protein to generate trajectories in which native and non-native states are in equilibrium and transitions are accurately sampled. Yet, representation of the free-energy surface, which underlies the thermodynamic and dynamic properties of the protein model, from such a trajectory remains a challenge. Projections over one or a small number of arbitrarily chosen progress variables often hide the most important features of such surfaces. The results unequivocally show that an unprojected representation of the free-energy surface provides important and unbiased information and allows a simple and meaningful description of many-dimensional, heterogeneous trajectories, providing new insight into the possible mechanisms of fast-folding proteins.

  17. Advancing the Frontiers in Nanocatalysis, Biointerfaces, and Renewable Energy Conversion by Innovations of Surface Techniques

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.; Frei, H.; Park, J.Y.

    2009-07-23

    The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ('green chemistry') and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

  18. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-04-10

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  19. Adhesion Evaluation of Asphalt-Aggregate Interface Using Surface Free Energy Method

    Directory of Open Access Journals (Sweden)

    Jie Ji

    2017-02-01

    Full Text Available The influence of organic additives (Sasobit and RH and water on the adhesion of the asphalt-aggregate interface was studied according to the surface free energy theory. Two asphalt binders (SK-70 and SK-90, and two aggregate types (limestone and basalt were used in this study. The sessile drop method was employed to test surface free energy components of asphalt, organic additives and aggregates. The adhesion models of the asphalt-aggregate interface in dry and wet conditions were established, and the adhesion work was calculated subsequently. The energy ratios were built to evaluate the effect of organic additives and water on the adhesiveness of the asphalt-aggregate interface. The results indicate that the addition of organic additives can enhance the adhesion of the asphalt-aggregate interface in dry conditions, because organic additives reduced the surface free energy of asphalt. However, the organic additives have hydrophobic characteristics and are sensitive to water. As a result, the adhesiveness of the asphalt-aggregate interface of the asphalt containing organic additives in wet conditions sharply decreased due to water damage to asphalt and organic additives. Furthermore, the compatibility of asphalt, aggregate with organic additive was noted and discussed.

  20. Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2012-02-01

    The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).