Formulation of dynamical theory of X-ray diffraction for perfect crystals in the Laue case using the Riemann surface.

PubMed

Saka, Takashi

2016-05-01

The dynamical theory for perfect crystals in the Laue case was reformulated using the Riemann surface, as used in complex analysis. In the two-beam approximation, each branch of the dispersion surface is specified by one sheet of the Riemann surface. The characteristic features of the dispersion surface are analytically revealed using four parameters, which are the real and imaginary parts of two quantities specifying the degree of departure from the exact Bragg condition and the reflection strength. By representing these parameters on complex planes, these characteristics can be graphically depicted on the Riemann surface. In the conventional case, the absorption is small and the real part of the reflection strength is large, so the formulation is the same as the traditional analysis. However, when the real part of the reflection strength is small or zero, the two branches of the dispersion surface cross, and the dispersion relationship becomes similar to that of the Bragg case. This is because the geometrical relationships among the parameters are similar in both cases. The present analytical method is generally applicable, irrespective of the magnitudes of the parameters. Furthermore, the present method analytically revealed many characteristic features of the dispersion surface and will be quite instructive for further numerical calculations of rocking curves.

Complex Teichmüller Space below the Planck Length for the Interpretation of Quantum Mechanics

NASA Astrophysics Data System (ADS)

Winterberg, Friedwardt

2014-03-01

As Newton's mysterious action at a distance law of gravity was explained as a Riemannian geometry by Einstein, it is proposed that the likewise mysterious non-local quantum mechanics is explained by the analytic continuation below the Planck length into a complex Teichmüller space. Newton's theory worked extremely well, as does quantum mechanics, but no satisfactory explanation has been given for quantum mechanics. In one space dimension, sufficient to explain the EPR paradox, the Teichmüller space is reduced to a space of complex Riemann surfaces. Einstein's curved space-time theory of gravity was confirmed by a tiny departure from Newton's theory in the motion of the planet Mercury, and an experiment is proposed to demonstrate the possible existence of a Teichmüller space below the Planck length.

Higher dimensional curved domain walls on Kähler surfaces

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

Akbar, Fiki T., E-mail: ftakbar@fi.itb.ac.id; Gunara, Bobby E., E-mail: bobby@fi.itb.ac.id; Radjabaycolle, Flinn C.

In this paper we study some aspects of curved BPS-like domain walls in higher dimensional gravity theory coupled to scalars where the scalars span a complex Kähler surface with scalar potential turned on. Assuming that a fake superpotential has a special form which depends on Kähler potential and a holomorphic function, we prove that BPS-like equations have a local unique solution. Then, we analyze the vacuum structure of the theory including their stability using dynamical system and their existence in ultraviolet-infrared regions using renormalization group flow.

U-folds as K3 fibrations

NASA Astrophysics Data System (ADS)

Braun, Andreas P.; Fucito, Francesco; Morales, Jose Francisco

2013-10-01

We study four-dimensional flux vacua describing intrinsic non- perturbative systems of 3 and 7 branes in type IIB string theory. The solutions are described as compactifications of a G(ravity) theory on a Calabi Yau threefold which consists of a fibration of an auxiliary K3 surface over an S 2 base. In the spirit of F-theory, the complex structure of the K3 surface varying over the base codifies the details of the fluxes, the dilaton and the warp factors in type IIB string theory. We discuss in detail some simple examples of geometric and non-geometric solutions where the precise flux/geometry dictionary can be explicitly worked out. In particular, we describe non-geometric T-fold solutions exhibiting non-trivial T-duality monodromies exchanging 3- and 7-branes.

Electrostatic Rate Enhancement and Transient Complex of Protein-Protein Association

PubMed Central

Alsallaq, Ramzi; Zhou, Huan-Xiang

2012-01-01

The association of two proteins is bounded by the rate at which they, via diffusion, find each other while in appropriate relative orientations. Orientational constraints restrict this rate to ~105 – 106 M−1s−1. Proteins with higher association rates generally have complementary electrostatic surfaces; proteins with lower association rates generally are slowed down by conformational changes upon complex formation. Previous studies (Zhou, Biophys. J. 1997;73:2441–2445) have shown that electrostatic enhancement of the diffusion-limited association rate can be accurately modeled by kD = kD0 exp(−*/ kBT), where kD and kD0 are the rates in the presence and absence of electrostatic interactions, respectively, * is the average electrostatic interaction energy in a “transient-complex” ensemble, and kBT is thermal energy. The transient-complex ensemble separates the bound state from the unbound state. Predictions of the transient-complex theory on four protein complexes were found to agree well with experiment when the electrostatic interaction energy was calculated with the linearized Poisson-Boltzmann (PB) equation (Alsallaq and Zhou, Structure 2007, 15:215–224). Here we show that the agreement is further improved when the nonlinear PB equation is used. These predictions are obtained with the dielectric boundary defined as the protein van der Waals surface. When the dielectric boundary is instead specified as the molecular surface, electrostatic interactions in the transient complex become repulsive and are thus predicted to retard association. Together these results demonstrate that the transient-complex theory is predictive of electrostatic rate enhancement and can help parameterize PB calculations. PMID:17932929

Sensitivity of Precipitation in Coupled Land-Atmosphere Models

NASA Technical Reports Server (NTRS)

Neelin, David; Zeng, N.; Suarez, M.; Koster, R.

2004-01-01

The project objective was to understand mechanisms by which atmosphere-land-ocean processes impact precipitation in the mean climate and interannual variations, focusing on tropical and subtropical regions. A combination of modeling tools was used: an intermediate complexity land-atmosphere model developed at UCLA known as the QTCM and the NASA Seasonal-to-Interannual Prediction Program general circulation model (NSIPP GCM). The intermediate complexity model was used to develop hypotheses regarding the physical mechanisms and theory for the interplay of large-scale dynamics, convective heating, cloud radiative effects and land surface feedbacks. The theoretical developments were to be confronted with diagnostics from the more complex GCM to validate or modify the theory.

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Electrostatic rate enhancement and transient complex of protein-protein association.

PubMed

Alsallaq, Ramzi; Zhou, Huan-Xiang

2008-04-01

The association of two proteins is bounded by the rate at which they, via diffusion, find each other while in appropriate relative orientations. Orientational constraints restrict this rate to approximately 10(5)-10(6) M(-1) s(-1). Proteins with higher association rates generally have complementary electrostatic surfaces; proteins with lower association rates generally are slowed down by conformational changes upon complex formation. Previous studies (Zhou, Biophys J 1997;73:2441-2445) have shown that electrostatic enhancement of the diffusion-limited association rate can be accurately modeled by $k_{\\bf D}$ = $k_{D}0\\ {exp} ( - \\langle U_{el} \\rangle;{\\star}/k_{B} T),$ where k(D) and k(D0) are the rates in the presence and absence of electrostatic interactions, respectively, U(el) is the average electrostatic interaction energy in a "transient-complex" ensemble, and k(B)T is the thermal energy. The transient-complex ensemble separates the bound state from the unbound state. Predictions of the transient-complex theory on four protein complexes were found to agree well with the experiment when the electrostatic interaction energy was calculated with the linearized Poisson-Boltzmann (PB) equation (Alsallaq and Zhou, Structure 2007;15:215-224). Here we show that the agreement is further improved when the nonlinear PB equation is used. These predictions are obtained with the dielectric boundary defined as the protein van der Waals surface. When the dielectric boundary is instead specified as the molecular surface, electrostatic interactions in the transient complex become repulsive and are thus predicted to retard association. Together these results demonstrate that the transient-complex theory is predictive of electrostatic rate enhancement and can help parameterize PB calculations. (c) 2007 Wiley-Liss, Inc.

Identification of Au–S complexes on Au(100)

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2016-01-25

In this study, using a combination of scanning tunneling microscopy and density functional theory (DFT) calculations, we have identified a set of related Au–S complexes that form on Au(100), when sulfur adsorbs and lifts the hexagonal surface reconstruction. The predominant complex is diamond-shaped with stoichiometry Au 4S 5. All of the complexes can be regarded as combinations of S–Au–S subunits. The complexes exist within, or at the edges of, p(2 × 2) sulfur islands that cover the unreconstructed Au regions, and are observed throughout the range of S coverage examined in this study, 0.009 to 0.12 monolayers. A qualitative modelmore » is developed which incorporates competitive formation of complexes, Au rafts, and p(2 × 2) sulfur islands, as Au atoms are released by the surface structure transformation.« less

Nonlinear modulation near the Lighthill instability threshold in 2+1 Whitham theory

NASA Astrophysics Data System (ADS)

Bridges, Thomas J.; Ratliff, Daniel J.

2018-04-01

The dispersionless Whitham modulation equations in 2+1 (two space dimensions and time) are reviewed and the instabilities identified. The modulation theory is then reformulated, near the Lighthill instability threshold, with a slow phase, moving frame and different scalings. The resulting nonlinear phase modulation equation near the Lighthill surfaces is a geometric form of the 2+1 two-way Boussinesq equation. This equation is universal in the same sense as Whitham theory. Moreover, it is dispersive, and it has a wide range of interesting multi-periodic, quasi-periodic and multi-pulse localized solutions. For illustration the theory is applied to a complex nonlinear 2+1 Klein-Gordon equation which has two Lighthill surfaces in the manifold of periodic travelling waves. This article is part of the theme issue `Stability of nonlinear waves and patterns and related topics'.

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

Possibility of designing catalysts beyond the traditional volcano curve: a theoretical framework for multi-phase surfaces.

PubMed

Wang, Ziyun; Wang, Hai-Feng; Hu, P

2015-10-01

The current theory of catalyst activity in heterogeneous catalysis is mainly obtained from the study of catalysts with mono-phases, while most catalysts in real systems consist of multi-phases, the understanding of which is far short of chemists' expectation. Density functional theory (DFT) and micro-kinetics simulations are used to investigate the activities of six mono-phase and nine bi-phase catalysts, using CO hydrogenation that is arguably the most typical reaction in heterogeneous catalysis. Excellent activities that are beyond the activity peak of traditional mono-phase volcano curves are found on some bi-phase surfaces. By analyzing these results, a new framework to understand the unexpected activities of bi-phase surfaces is proposed. Based on the framework, several principles for the design of multi-phase catalysts are suggested. The theoretical framework extends the traditional catalysis theory to understand more complex systems.

Generalized Toda theory from six dimensions and the conifold

NASA Astrophysics Data System (ADS)

van Leuven, Sam; Oling, Gerben

2017-12-01

Recently, a physical derivation of the Alday-Gaiotto-Tachikawa correspondence has been put forward. A crucial role is played by the complex Chern-Simons theory arising in the 3d-3d correspondence, whose boundary modes lead to Toda theory on a Riemann surface. We explore several features of this derivation and subsequently argue that it can be extended to a generalization of the AGT correspondence. The latter involves codimension two defects in six dimensions that wrap the Riemann surface. We use a purely geometrical description of these defects and find that the generalized AGT setup can be modeled in a pole region using generalized conifolds. Furthermore, we argue that the ordinary conifold clarifies several features of the derivation of the original AGT correspondence.

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex

NASA Astrophysics Data System (ADS)

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C.

2017-08-01

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O2-O2, relevant for the theoretical description of collision-induced absorption in the forbidden X3Σg- → a1Δg and X3Σg- → b1Σg+ bands at 7883 cm-1 and 13 122 cm-1, respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O2-O2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex.

PubMed

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C

2017-08-28

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O 2 -O 2 , relevant for the theoretical description of collision-induced absorption in the forbidden X 3 Σ g -  → a 1 Δ g and X 3 Σ g -  → b 1 Σ g + bands at 7883 cm -1 and 13 122 cm -1 , respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O 2 -O 2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Mathematical Methods for Physics and Engineering Third Edition Paperback Set

NASA Astrophysics Data System (ADS)

Riley, Ken F.; Hobson, Mike P.; Bence, Stephen J.

2006-06-01

Prefaces; 1. Preliminary algebra; 2. Preliminary calculus; 3. Complex numbers and hyperbolic functions; 4. Series and limits; 5. Partial differentiation; 6. Multiple integrals; 7. Vector algebra; 8. Matrices and vector spaces; 9. Normal modes; 10. Vector calculus; 11. Line, surface and volume integrals; 12. Fourier series; 13. Integral transforms; 14. First-order ordinary differential equations; 15. Higher-order ordinary differential equations; 16. Series solutions of ordinary differential equations; 17. Eigenfunction methods for differential equations; 18. Special functions; 19. Quantum operators; 20. Partial differential equations: general and particular; 21. Partial differential equations: separation of variables; 22. Calculus of variations; 23. Integral equations; 24. Complex variables; 25. Application of complex variables; 26. Tensors; 27. Numerical methods; 28. Group theory; 29. Representation theory; 30. Probability; 31. Statistics; Index.

Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

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

Wang, Jun; McEntee, Monica; Tang, Wenjie

2016-01-12

Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

Ultraviolet complex refractive index of Martian dust Laboratory measurements of terrestrial analogs

NASA Technical Reports Server (NTRS)

Egan, W. G.; Hilgeman, T.; Pang, K.

1975-01-01

The optical complex index of refraction of four candidate Martian surface materials has been determined between 0.185 and 0.4 microns using a modified Kubelka-Munk scattering theory. The cadidate materials were limonite, andesite, montmorillonite, and basalt. The effect of scattering has been removed from the results. Also presented are diffuse reflection and transmission data on these samples.

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions.

PubMed

Zheng, Jingjing; Truhlar, Donald G

2012-01-01

Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.

Synchrotron x-ray imaging visualization study of capillary-induced flow and critical heat flux on surfaces with engineered micropillars

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

Yu, Dong In; Kwak, Ho Jae; Noh, Hyunwoo

Over the past several decades, phenomena related to critical heat flux (CHF) on structured surfaces have received a large amount of attention from the research community. The purpose of such research has been to enhance the safety and efficiency of a variety of thermal systems. A number of theories have been put forward to explain the key CHF enhancement mechanisms on structured surfaces. However, these theories have not been confirmed experimentally due to limitations in the available visualization techniques and the complexity of the phenomena. To overcome the limitations of the previous visualization techniques and elucidate the CHF enhancement mechanismmore » on the structured surfaces, we introduce synchrotron X-ray imaging with high spatial (~2 μm) and time (~20,000 Hz) resolutions. Lastly, this technique has enabled us to confirm that capillary-induced flow is the key CHF enhancement mechanism on structured surfaces.« less

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1988-01-01

Tribology, the study of adhesion, friction and wear of materials is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture and friction are discussed.

Synchrotron x-ray imaging visualization study of capillary-induced flow and critical heat flux on surfaces with engineered micropillars

DOE PAGES

Yu, Dong In; Kwak, Ho Jae; Noh, Hyunwoo; ...

2018-02-23

Over the past several decades, phenomena related to critical heat flux (CHF) on structured surfaces have received a large amount of attention from the research community. The purpose of such research has been to enhance the safety and efficiency of a variety of thermal systems. A number of theories have been put forward to explain the key CHF enhancement mechanisms on structured surfaces. However, these theories have not been confirmed experimentally due to limitations in the available visualization techniques and the complexity of the phenomena. To overcome the limitations of the previous visualization techniques and elucidate the CHF enhancement mechanismmore » on the structured surfaces, we introduce synchrotron X-ray imaging with high spatial (~2 μm) and time (~20,000 Hz) resolutions. Lastly, this technique has enabled us to confirm that capillary-induced flow is the key CHF enhancement mechanism on structured surfaces.« less

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1989-01-01

Tribology, the study of adhesion, friction and wear of materials, is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science, and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid-state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture, and friction are discussed.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface

NASA Astrophysics Data System (ADS)

Yang, J.; Qi, Y.; Kim, H. D.; Rappe, A. M.

2018-04-01

A tribopolymer formed on the contacts of microelectromechanical and nanoelectromechanical system (MEMS-NEMS) devices is a major concern hampering their practical use in information technology. Conductive metal oxides, such as RuO2 and ReO3 , have been regarded as promising candidate materials for MEMS-NEMS contacts due to their conductivity, hardness, and relatively chemically inert surfaces. However, recent experimental works demonstrate that trace amounts of a polymer could still form on RuO2 surfaces. We demonstrate the mechanism of this class of unexpected tribopolymer formation by conducting density-functional-theory-based computational compression experiments with benzene as the contamination gas. First, mechanical force during compression changes the benzene molecules from slightly physisorbed to strongly chemisorbed. Further compression causes deformation and chemical linkage of the benzene molecules. Finally, the two contacts detach, with one having a complex organic molecule attached and the other a more reactive surface. The complex organic molecule, which has an oxabicyclic segment, can be viewed as the rudiment of a tribopolymer, and the more reactive surface can trigger the next adsorption-reaction-tribopolymer formation cycle. Based on these results, we also predict tribopolymer formation rates by using transition-state theory and the second-order rate law. We promote a deeper understanding of tribopolymer formation (especially on metal oxides) and provide strategies for suppressing tribopolymerization.

The birth and evolution of surface science: child of the union of science and technology.

PubMed

Duke, C B

2003-04-01

This article is an account of the birth and evolution of surface science as an interdisciplinary research area. Surface science emanated from the confluence of concepts and tools in physics and chemistry with technological innovations that made it possible to determine the structure and properties of surfaces and interfaces and the dynamics of chemical reactions at surfaces. The combination in the 1960s and 1970s of ultra-high-vacuum (i.e., P < 10(-7) Pascal or 10(-9) Torr) technology with the recognition that electrons in the energy range from 50 to 500 eV exhibited inelastic collision mean free paths of the order of a few angstroms fostered an explosion of activity. The results were a reformulation of the theory of electron solid scattering, the nearly universal use of electron spectroscopies for surface characterization, the rise of surface science as an independent interdisciplinary research area, and the emergence of the American Vacuum Society (AVS) as a major international scientific society. The rise of microelectronics in the 1970s and 1980s resulted in huge increases in computational power. These increases enabled more complex experiments and the utilization of density functional theory for the quantitative prediction of surface structure and dynamics. Development of scanning-probe microscopies in the 1990s led to atomic-resolution images of macroscopic surfaces and interfaces as well as videos of atoms moving about on surfaces during growth and diffusion. Scanning probes have since brought solid-liquid interfaces into the realm of atomic-level surface science, expanding its scope to more complex systems, including fragile biological materials and processes.

Self-organizing biochemical cycles

NASA Technical Reports Server (NTRS)

Orgel, L. E.; Bada, J. L. (Principal Investigator)

2000-01-01

I examine the plausibility of theories that postulate the development of complex chemical organization without requiring the replication of genetic polymers such as RNA. One conclusion is that theories that involve the organization of complex, small-molecule metabolic cycles such as the reductive citric acid cycle on mineral surfaces make unreasonable assumptions about the catalytic properties of minerals and the ability of minerals to organize sequences of disparate reactions. Another conclusion is that data in the Beilstein Handbook of Organic Chemistry that have been claimed to support the hypothesis that the reductive citric acid cycle originated as a self-organized cycle can more plausibly be interpreted in a different way.

Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? like attracting like!

PubMed

Varadwaj, Arpita; Varadwaj, Pradeep R; Yamashita, Koichi

2018-03-15

Coulomb's law states that like charges repel, and unlike charges attract. However, it has recently been theoretically revealed that two similarly charged conducting spheres will almost always attract each other when both are in close proximity. Using multiscale first principles calculations, we illustrate practical examples of several intermolecular complexes that are formed by the consequences of attraction between positive atomic sites of similar or dissimilar electrostatic surface potential on interacting molecules. The results of the quantum theory of atoms in molecules and symmetry adapted perturbation theory support the attraction between the positive sites, characterizing the F•••X (X = F, Cl, Br) intermolecular interactions in a series of 20 binary complexes as closed-shell type, although the molecular electrostatic surface potential approach does not (a failure!). Dispersion that has an r -6 dependence, where r is the equilibrium distance of separation, is found to be the sole driving force pushing the two positive sites to attract. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Dispersion features of complex waves in a graphene-coated semiconductor nanowire

NASA Astrophysics Data System (ADS)

Yu, Pengchao; Fesenko, Volodymyr I.; Tuz, Vladimir R.

2018-05-01

The dispersion features of a graphene-coated semiconductor nanowire operating in the terahertz frequency band are consistently studied in the framework of a special theory of complex waves. Detailed classification of the waveguide modes was carried out based on the analysis of characteristics of the phase and attenuation constants obtained from the complex roots of characteristic equation. With such a treatment, the waves are attributed to the group of either "proper" or "improper" waves, wherein their type is determined as the trapped surface waves, fast and slow leaky waves, and surface plasmons. The dispersion curves of axially symmetric TM0n and TE0n modes, as well as nonsymmetric hybrid EH1n and HE1n modes, were plotted and analyzed in detail, and both radiative regime of leaky waves and guided regime of trapped surface waves are identified. The peculiarities of propagation of the TM modes of surface plasmons were revealed. Two subregions of existence of surface plasmons were found out where they appear as propagating and reactive waves. The cutoff conditions for higher-order TM modes of surface plasmons were correctly determined.

Antimalarials inhibit hematin crystallization by unique drug–surface site interactions

PubMed Central

Olafson, Katy N.; Nguyen, Tam Q.; Rimer, Jeffrey D.; Vekilov, Peter G.

2017-01-01

In malaria pathophysiology, divergent hypotheses on the inhibition of hematin crystallization posit that drugs act either by the sequestration of soluble hematin or their interaction with crystal surfaces. We use physiologically relevant, time-resolved in situ surface observations and show that quinoline antimalarials inhibit β-hematin crystal surfaces by three distinct modes of action: step pinning, kink blocking, and step bunch induction. Detailed experimental evidence of kink blocking validates classical theory and demonstrates that this mechanism is not the most effective inhibition pathway. Quinolines also form various complexes with soluble hematin, but complexation is insufficient to suppress heme detoxification and is a poor indicator of drug specificity. Collectively, our findings reveal the significance of drug–crystal interactions and open avenues for rationally designing antimalarial compounds. PMID:28559329

Characterisation of High Grazing Angle X-band Sea-clutter Doppler Spectra

DTIC Science & Technology

2013-08-01

0397 2 Background The ocean surface is a highly complex dynamical system and relating Doppler spectra to surface conditions is a difficult problem...1966] then extended this theory to water and classified it as a ‘slightly rough’ surface. He showed that the scattering elements of primary importance...incidence field. This is the definition for the Bragg water -wave propagation number defined in the spatial frequency domain as kw = 2k0 cos θ, where

Experimental and Theoretical Approaches for the Surface Interaction between Copper and Activated Sludge Microorganisms at Molecular Scale

NASA Astrophysics Data System (ADS)

Luo, Hong-Wei; Chen, Jie-Jie; Sheng, Guo-Ping; Su, Ji-Hu; Wei, Shi-Qiang; Yu, Han-Qing

2014-11-01

Interactions between metals and activated sludge microorganisms substantially affect the speciation, immobilization, transport, and bioavailability of trace heavy metals in biological wastewater treatment plants. In this study, the interaction of Cu(II), a typical heavy metal, onto activated sludge microorganisms was studied in-depth using a multi-technique approach. The complexing structure of Cu(II) on microbial surface was revealed by X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) analysis. EPR spectra indicated that Cu(II) was held in inner-sphere surface complexes of octahedral coordination with tetragonal distortion of axial elongation. XAFS analysis further suggested that the surface complexation between Cu(II) and microbial cells was the distorted inner-sphere coordinated octahedra containing four short equatorial bonds and two elongated axial bonds. To further validate the results obtained from the XAFS and EPR analysis, density functional theory calculations were carried out to explore the structural geometry of the Cu complexes. These results are useful to better understand the speciation, immobilization, transport, and bioavailability of metals in biological wastewater treatment plants.

Point source moving above a finite impedance reflecting plane - Experiment and theory

NASA Technical Reports Server (NTRS)

Norum, T. D.; Liu, C. H.

1978-01-01

A widely used experimental version of the acoustic monopole consists of an acoustic driver of restricted opening forced by a discrete frequency oscillator. To investigate the effects of forward motion on this source, it was mounted above an automobile and driven over an asphalt surface at constant speed past a microphone array. The shapes of the received signal were compared to results computed from an analysis of a fluctuating-mass-type point source moving above a finite impedance reflecting plane. Good agreement was found between experiment and theory when a complex normal impedance representative of a fairly hard acoustic surface was used in the analysis.

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

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

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

DOE PAGES

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.; ...

2018-02-08

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Student Solution Manual for Mathematical Methods for Physics and Engineering Third Edition

NASA Astrophysics Data System (ADS)

Riley, K. F.; Hobson, M. P.

2006-03-01

Preface; 1. Preliminary algebra; 2. Preliminary calculus; 3. Complex numbers and hyperbolic functions; 4. Series and limits; 5. Partial differentiation; 6. Multiple integrals; 7. Vector algebra; 8. Matrices and vector spaces; 9. Normal modes; 10. Vector calculus; 11. Line, surface and volume integrals; 12. Fourier series; 13. Integral transforms; 14. First-order ordinary differential equations; 15. Higher-order ordinary differential equations; 16. Series solutions of ordinary differential equations; 17. Eigenfunction methods for differential equations; 18. Special functions; 19. Quantum operators; 20. Partial differential equations: general and particular; 21. Partial differential equations: separation of variables; 22. Calculus of variations; 23. Integral equations; 24. Complex variables; 25. Application of complex variables; 26. Tensors; 27. Numerical methods; 28. Group theory; 29. Representation theory; 30. Probability; 31. Statistics.

Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

DOE PAGES

White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William; ...

2017-06-21

The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N 2 - , CO - , CO 2 - , and CH 2 O - . Analytic continuation of complex θ-trajectories is used to compute Siegert energies, and the θ-trajectories of energy differences are found to yield more consistent results than those of total energies.more » Furthermore, the ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.« less

Magnetic properties of the Fe{sup II} spin crossover complex in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol)

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

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.j; Iguchi, Motoi; Oku, Takeo

2010-04-15

Influence of chemical substitution in the Fe{sup II} spin crossover complex on magnetic properties in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol) as a protective colloid was investigated near its high spin/low spin (HS/LS) phase transition. The obvious bi-stability of the HS/LS phase transition was considered by the identification of multiple spin states between the quintet (S=2) states to single state (S=0) across the excited triplet state (S=1). Magnetic parameters of gradual shifts of anisotropy g-tensor supported by the molecular distortion of the spin crossover complex would arise from a Jahn-Teller effect regarding ligand field theory on the basis ofmore » a B3LYP density functional theory using electron spin resonance (ESR) spectrum and X-ray powder diffraction. - Graphical abstract: AFM surface image of the emulsion particles with the spin crossover complex.« less

Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

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

White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William

The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N 2 - , CO - , CO 2 - , and CH 2 O - . Analytic continuation of complex θ-trajectories is used to compute Siegert energies, and the θ-trajectories of energy differences are found to yield more consistent results than those of total energies.more » Furthermore, the ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.« less

Dielectric Response at THz Frequencies of Mg Water Complexes Interacting with O3 Calculated by Density Functional Theory

DTIC Science & Technology

2012-10-24

of the atoms in a chemical system , at the maximal peak of the energy surface separating reactants from products . In the transition state every normal...Hada, M. Ehara, K. Toyota , R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda , O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E...calculations of ground state resonance structure associated with water complexes of Mg and the interaction of these complexes with Ozone using DFT. The

Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase

NASA Astrophysics Data System (ADS)

Choi, Tae Su; Ko, Jae Yoon; Heo, Sung Woo; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I.

2012-10-01

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular SN2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular SN2 reaction of haloacetate, which correlate well with the experimental observation.

Thinking Forbidden Thoughts: The Oedipus Complex as a Complex of Knowing.

PubMed

Schein, Michael

2016-04-01

The Oedipus complex, considered by Freud the "nuclear complex of development," played a central role in the evolution of psychoanalytic thought. This paper returns to the point of transition from the seduction theory, Freud's initial theorem, to the oedipal model, and suggests that the Oedipus complex is first and foremost a text and as such contains a multiplicity of narratives. In particular, the author articulates the close relation between the Oedipus complex and the subject of knowing, postulating that underlying its surface level, the deep-level structure of this complex is one of knowing. As a complex of knowing it is of dual quality, both promoting and impeding the ability to know.

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

Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine

The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and themore » LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.« less

Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

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

Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.

The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

DOE PAGES

Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.; ...

2017-06-12

The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

Interplay between topology, gauge fields and gravity

NASA Astrophysics Data System (ADS)

Corichi Rodriguez Gil, Alejandro

In this thesis we consider several physical systems that illustrate an interesting interplay between quantum theory, connections and knot theory. It can be divided into two parts. In the first one, we consider the quantization of the free Maxwell field. We show that there is an important role played by knot theory, and in particular the Gauss linking number, in the quantum theory. This manifestation is twofold. The first occurs at the level of the algebra of observables given by fluxes of electric and magnetic field across surfaces. The commutator of the operators, and thus the basic uncertainty relations, are given in terms of the linking number of the loops that bound the surfaces. Next, we consider the quantization of the Maxwell field based on self-dual connections in the loop representation. We show that the measure which determines the quantum inner product can be expressed in terms of the self linking number of thickened loops. Therefore, the linking number manifests itself at two key points of the theory: the Heisenberg uncertainty principle and the inner product. In the second part, we bring gravity into play. First we consider quantum test particles on certain stationary space-times. We demonstrate that a geometric phase exists for those space-times and focus on the example of a rotating cosmic string. The geometric phase can be explicitly computed, providing a fully relativistic gravitational Aharonov-Bohm effect. Finally, we consider 3-dimensional gravity with non-vanishing cosmological constant in the connection dynamics formulation. We restrict our attention to Lorentzian gravity with positive cosmological constant and Euclidean signature with negative cosmological constant. A complex transformation is performed in phase space that makes the constraints simple. The reduced phase space is characterized as the moduli space of flat complex connections. We construct the quantization of the theory when the initial hyper-surface is a torus. Two important issues relevant to full 3 + 1 gravity are clarified, namely, the incorporation of the 'reality conditions' in the quantum theory and the role played by the signature of the classical metric in the quantum theory.

Surface Roughness Measurements Utilizing Long-Range Surface-Plasma Waves

DTIC Science & Technology

1984-11-01

8217 The theory dealt only with the depen- modes, one symmetric and one antisymmetric, dence of the real wave vector on the real part of that propagate...quantity, while the wave vector is complex. It is shown that for both the supported and unsup- From Eqs. (1) and (2) one obtains the real implic- ported...Opt. Soc. sabbatical leave from the University of Toledo. Am.). Optical feild enhancemeft by long-range surface- I" ouT In O’ in OUT way@, plasma waves

Universal moduli spaces of Riemann surfaces

NASA Astrophysics Data System (ADS)

Ji, Lizhen; Jost, Jürgen

2017-04-01

We construct a moduli space for Riemann surfaces that is universal in the sense that it represents compact Riemann surfaces of any finite genus. This moduli space is a connected complex subspace of an infinite dimensional complex space, and is stratified according to genus such that each stratum has a compact closure, and it carries a metric and a measure that induce a Riemannian metric and a finite volume measure on each stratum. Applications to the Plateau-Douglas problem for minimal surfaces of varying genus and to the partition function of Bosonic string theory are outlined. The construction starts with a universal moduli space of Abelian varieties. This space carries a structure of an infinite dimensional locally symmetric space which is of interest in its own right. The key to our construction of the universal moduli space then is the Torelli map that assigns to every Riemann surface its Jacobian and its extension to the Satake-Baily-Borel compactifications.

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

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

Hensley, Alyssa J.; Wockel, Claudia; Gleichweit, Christoph

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changesmore » to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.« less

Proton adsorption onto alumina: extension of multisite complexation (MUSIC) theory

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

Nagashima, K.; Blum, F.D.

1999-09-01

The adsorption isotherm of protons onto a commercial {gamma}-alumina sample was determined in aqueous nitric acid with sodium nitrate as a background electrolyte. Three discrete regions could be discerned in the log-log plots of the proton isotherm determined at the solution pH 5 to 2. The multisite complexation (MUSIC) model was modified to analyze the simultaneous adsorption of protons onto various kinds of surface species.

The birth and evolution of surface science: Child of the union of science and technology

PubMed Central

Duke, C. B.

2003-01-01

This article is an account of the birth and evolution of surface science as an interdisciplinary research area. Surface science emanated from the confluence of concepts and tools in physics and chemistry with technological innovations that made it possible to determine the structure and properties of surfaces and interfaces and the dynamics of chemical reactions at surfaces. The combination in the 1960s and 1970s of ultra-high-vacuum (i.e., P < 10−7 Pascal or 10−9 Torr) technology with the recognition that electrons in the energy range from 50 to 500 eV exhibited inelastic collision mean free paths of the order of a few angstroms fostered an explosion of activity. The results were a reformulation of the theory of electron solid scattering, the nearly universal use of electron spectroscopies for surface characterization, the rise of surface science as an independent interdisciplinary research area, and the emergence of the American Vacuum Society (AVS) as a major international scientific society. The rise of microelectronics in the 1970s and 1980s resulted in huge increases in computational power. These increases enabled more complex experiments and the utilization of density functional theory for the quantitative prediction of surface structure and dynamics. Development of scanning-probe microscopies in the 1990s led to atomic-resolution images of macroscopic surfaces and interfaces as well as videos of atoms moving about on surfaces during growth and diffusion. Scanning probes have since brought solid–liquid interfaces into the realm of atomic-level surface science, expanding its scope to more complex systems, including fragile biological materials and processes. PMID:12651946

Kinetic Isotope Effects as a Probe for the Protonolysis Mechanism of Alkylmetal Complexes: VTST/MT Calculations Based on DFT Potential Energy Surfaces.

PubMed

Mai, Binh Khanh; Kim, Yongho

2016-10-03

Protonolysis by platinum or palladium complexes has been extensively studied because it is the microscopic reverse of the C-H bond activation reaction. The protonolysis of (COD)Pt II Me 2 , which exhibits abnormally large kinetic isotope effects (KIEs), is proposed to occur via a concerted pathway (S E 2 mechanism) with large tunneling. However, further investigation of KIEs for the protonolysis of ZnMe 2 and others led to a conclusion that there is no noticeable correlation between the mechanism and magnitude of KIE. In this study, we demonstrated that variational transition state theory including multidimensional tunneling (VTST/MT) could accurately predict KIEs and Arrhenius parameters of the protonolysis of alkylmetal complexes based on the potential energy surfaces generated by density functional theory. The predicted KIEs, E a D - E a H values, and A H /A D ratios for the protonolysis of (COD)Pt II Me 2 and Zn II Me 2 by TFA agreed very well with experimental values. The protonolysis of ZnMe 2 with the concerted pathway has a very flat potential energy surface, which produces a very small tunneling effect and therefore a small KIE. The predicted KIE for the stepwise protonolysis (S E (ox) mechanism) of (COD)Pt II Me 2 was much smaller than that of the concerted pathway, but greater than the KIE of the concerted protonolysis of ZnMe 2 . A large KIE, which entails a significant tunneling effect, could be used as an experimental probe of the concerted pathway. However, a normal or small KIE should not be used as an indicator of the stepwise mechanism, and the interplay between experiments and reliable theory including tunneling would be essential to uncover the mechanism correctly.

Theory after experiment on sensing mechanism of a newly developed sensor molecule: Converging or diverging?

NASA Astrophysics Data System (ADS)

Paul, Suvendu; Karar, Monaj; Das, Biswajit; Mallick, Arabinda; Majumdar, Tapas

2017-12-01

Fluoride ion sensing mechanism of 3,3‧-bis(indolyl)-4-chlorophenylmethane has been analyzed with density functional and time-dependent density functional theories. Extensive theoretical calculations on molecular geometry & energy, charge distribution, orbital energies & electronic distribution, minima on potential energy surface confirmed strong hydrogen bonded sensor-anion complex with incomplete proton transfer in S0. In S1, strong hydrogen bonding extended towards complete ESDPT. The distinct and single minima on the PES of the sensor-anion complex for both ground and first singlet excited states confirmed the concerted proton transfer mechanism. Present study well reproduced the experimental spectroscopic data and provided ESDPT as probable fluoride sensing mechanism.

Organic/Inorganic Complex Pigments: Ancient Colors Maya Blue

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

Polette-Niewold, L.A.; Manciu, F.S.; Torres, B.

2009-06-04

Maya Blue is an ancient blue pigment composed of palygorskite clay and indigo. It was used by the ancient Maya and provides a dramatic background for some of the most impressive murals throughout Mesoamerica. Despite exposure to acids, alkalis, and chemical solvents, the color of the Maya Blue pigment remains unaltered. The chemical interaction between palygorskite and indigo form an organic/inorganic complex with the carbonyl oxygen of the indigo bound to a surface Al{sup 3+} in the Si-O lattice. In addition indigo will undergo an oxidation to dehydroindigo during preparation. The dehydro-indigo molecule forms a similar but stronger complex withmore » the Al{sup 3+}. Thus, Maya Blue varies in color due to the mixed indigo/dehydroindigo complex. The above conclusions are the result of application of multiple techniques (X-ray diffraction, differential thermal analysis/thermal gravimetric analysis, high resolution transmission electron microscopy, scanning electron microscopy, infrared and Raman spectroscopy) to the characterization of the organic/inorganic complex. A picture of the bonding of the organic molecule to the palygorskite surface forming a surface complex is developed and supported by the results of density functional theory calculations. We also report that other organic molecules such as thioindigo form similar organic/inorganic complexes thus, opening an entirely new class of complex materials for future applications.« less

Deming's Quality: Our Last but Best Hope.

ERIC Educational Resources Information Center

Schenkat, Randy

1993-01-01

If educators endorse Alfie Kohn's surface message about Total Quality Management, they may miss opportunity to professionalize education. Deming's system of profound knowledge (interaction of theories of systems, knowledge, psychology, and variation) is a model for educated people grappling with life's complexities. Moreover, gaining community…

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

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

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

DOE PAGES

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; ...

2017-03-06

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

Impact of viscous droplets on different wettable surfaces: Impact phenomena, the maximum spreading factor, spreading time and post-impact oscillation.

PubMed

Lin, Shiji; Zhao, Binyu; Zou, Song; Guo, Jianwei; Wei, Zheng; Chen, Longquan

2018-04-15

In this paper, we experimentally investigated the impact dynamics of different viscous droplets on solid surfaces with diverse wettabilities. We show that the outcome of an impinging droplet is dependent on the physical property of the droplet and the wettability of the surface. Whereas only deposition was observed on lyophilic surfaces, more impact phenomena were identified on lyophobic and superlyophobic surfaces. It was found that none of the existing theoretical models can well describe the maximum spreading factor, revealing the complexity of the droplet impact dynamics and suggesting that more factors need to be considered in the theory. By using the modified capillary-inertial time, which considers the effects of liquid viscosity and surface wettability on droplet spreading, a universal scaling law describing the spreading time was obtained. Finally, we analyzed the post-impact droplet oscillation with the theory for damped harmonic oscillators and interpreted the effects of liquid viscosity and surface wettability on the oscillation by simple scaling analyses. Copyright © 2017 Elsevier Inc. All rights reserved.

The Information Available to a Moving Observer on Shape with Unknown, Isotropic BRDFs.

PubMed

Chandraker, Manmohan

2016-07-01

Psychophysical studies show motion cues inform about shape even with unknown reflectance. Recent works in computer vision have considered shape recovery for an object of unknown BRDF using light source or object motions. This paper proposes a theory that addresses the remaining problem of determining shape from the (small or differential) motion of the camera, for unknown isotropic BRDFs. Our theory derives a differential stereo relation that relates camera motion to surface depth, which generalizes traditional Lambertian assumptions. Under orthographic projection, we show differential stereo may not determine shape for general BRDFs, but suffices to yield an invariant for several restricted (still unknown) BRDFs exhibited by common materials. For the perspective case, we show that differential stereo yields the surface depth for unknown isotropic BRDF and unknown directional lighting, while additional constraints are obtained with restrictions on the BRDF or lighting. The limits imposed by our theory are intrinsic to the shape recovery problem and independent of choice of reconstruction method. We also illustrate trends shared by theories on shape from differential motion of light source, object or camera, to relate the hardness of surface reconstruction to the complexity of imaging setup.

Controlled ionic condensation at the surface of a native extremophile membrane

NASA Astrophysics Data System (ADS)

Contera, Sonia Antoranz; Voïtchovsky, Kislon; Ryan, John F.

2010-02-01

At the nanoscale level biological membranes present a complex interface with the solvent. The functional dynamics and relative flexibility of membrane components together with the presence of specific ionic effects can combine to create exciting new phenomena that challenge traditional theories such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory or models interpreting the role of ions in terms of their ability to structure water (structure making/breaking). Here we investigate ionic effects at the surface of a highly charged extremophile membrane composed of a proton pump (bacteriorhodopsin) and archaeal lipids naturally assembled into a 2D crystal. Using amplitude-modulation atomic force microscopy (AM-AFM) in solution, we obtained sub-molecular resolution images of ion-induced surface restructuring of the membrane. We demonstrate the presence of a stiff cationic layer condensed at its extracellular surface. This layer cannot be explained by traditional continuum theories. Dynamic force spectroscopy experiments suggest that it is produced by electrostatic correlation mediated by a Manning-type condensation of ions. In contrast, the cytoplasmic surface is dominated by short-range repulsive hydration forces. These findings are relevant to archaeal bioenergetics and halophilic adaptation. Importantly, they present experimental evidence of a natural system that locally controls its interactions with the surrounding medium and challenges our current understanding of biological interfaces.At the nanoscale level biological membranes present a complex interface with the solvent. The functional dynamics and relative flexibility of membrane components together with the presence of specific ionic effects can combine to create exciting new phenomena that challenge traditional theories such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory or models interpreting the role of ions in terms of their ability to structure water (structure making/breaking). Here we investigate ionic effects at the surface of a highly charged extremophile membrane composed of a proton pump (bacteriorhodopsin) and archaeal lipids naturally assembled into a 2D crystal. Using amplitude-modulation atomic force microscopy (AM-AFM) in solution, we obtained sub-molecular resolution images of ion-induced surface restructuring of the membrane. We demonstrate the presence of a stiff cationic layer condensed at its extracellular surface. This layer cannot be explained by traditional continuum theories. Dynamic force spectroscopy experiments suggest that it is produced by electrostatic correlation mediated by a Manning-type condensation of ions. In contrast, the cytoplasmic surface is dominated by short-range repulsive hydration forces. These findings are relevant to archaeal bioenergetics and halophilic adaptation. Importantly, they present experimental evidence of a natural system that locally controls its interactions with the surrounding medium and challenges our current understanding of biological interfaces. Electronic supplementary information (ESI) available: Figs. S1 and S2: amplitude- and phase-extension curves used to derive the data presented in Figs. 2 and 4. See DOI: 10.1039/b9nr00248k

Excitation energy transfer in molecular complexes: transport processes, optical properties and effects of nearby placed metal nano-particles

NASA Astrophysics Data System (ADS)

May, Volkhard; Megow, Jörg; Zelinskyi, Iaroslav

2012-04-01

Excitation energy transfer (EET) in molecular systems is studied theoretically. Chromophore complexes are considered which are formed by a butanediamine dendrimer with four pheophorbide-a molecules. To achieve a description with an atomic resolution and to account for the effect of an ethanol solvent a mixed quantum classical methodology is utilized. Details of the EET and spectra of transient anisotropy showing signatures of EET are presented. A particular control of intermolecular EET is achieved by surface plasmons of nearby placed metal nanoparticles (MNP). To attain a quantum description of the molecule-MNP system a microscopic theory is introduced. As a particular application surface plasmon affected absorption spectra of molecular complexes placed in the proximity of a spherical MNP are discussed.

Meeting in New Orleans: An Assessment of the Fate of Metal Oxide Nanomaterials in Porous Media

EPA Science Inventory

This work assesses potential aqueous environmental metal oxide nanomaterial self-aggregation through the application of recent developments in surface complexation theory with historical DLVO procedures. Findings include: 1) nanomaterials with a Hamaker constant as large as 1E-1...

Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

PubMed

Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

2015-03-04

In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation.

PubMed

Escaño, Mary Clare Sison; Arevalo, Ryan Lacdao; Gyenge, Elod; Kasai, Hideaki

2014-09-03

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4(-) on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation

NASA Astrophysics Data System (ADS)

Sison Escaño, Mary Clare; Lacdao Arevalo, Ryan; Gyenge, Elod; Kasai, Hideaki

2014-09-01

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4- on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

Automatic Overset Grid Generation with Heuristic Feedback Control

NASA Technical Reports Server (NTRS)

Robinson, Peter I.

2001-01-01

An advancing front grid generation system for structured Overset grids is presented which automatically modifies Overset structured surface grids and control lines until user-specified grid qualities are achieved. The system is demonstrated on two examples: the first refines a space shuttle fuselage control line until global truncation error is achieved; the second advances, from control lines, the space shuttle orbiter fuselage top and fuselage side surface grids until proper overlap is achieved. Surface grids are generated in minutes for complex geometries. The system is implemented as a heuristic feedback control (HFC) expert system which iteratively modifies the input specifications for Overset control line and surface grids. It is developed as an extension of modern control theory, production rules systems and subsumption architectures. The methodology provides benefits over the full knowledge lifecycle of an expert system for knowledge acquisition, knowledge representation, and knowledge execution. The vector/matrix framework of modern control theory systematically acquires and represents expert system knowledge. Missing matrix elements imply missing expert knowledge. The execution of the expert system knowledge is performed through symbolic execution of the matrix algebra equations of modern control theory. The dot product operation of matrix algebra is generalized for heuristic symbolic terms. Constant time execution is guaranteed.

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

Structures and Properties of As(OH)3 Adsorption Complexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study

PubMed Central

2017-01-01

Reactive mineral–water interfaces exert control on the bioavailability of contaminant arsenic species in natural aqueous systems. However, the ability to accurately predict As surface complexation is limited by the lack of molecular-level understanding of As–water–mineral interactions. In the present study, we report the structures and properties of the adsorption complexes of arsenous acid (As(OH)3) on hydrated mackinawite (FeS) surfaces, obtained from density functional theory (DFT) calculations. The fundamental aspects of the adsorption, including the registries of the adsorption complexes, adsorption energies, and structural parameters are presented. The FeS surfaces are shown to be stabilized by hydration, as is perhaps to be expected because the adsorbed water molecules stabilize the low-coordinated surface atoms. As(OH)3 adsorbs weakly at the water–FeS(001) interface through a network of hydrogen-bonded interactions with water molecules on the surface, with the lowest-energy structure calculated to be an As–up outer-sphere complex. Compared to the water–FeS(001) interface, stronger adsorption was calculated for As(OH)3 on the water–FeS(011) and water–FeS(111) interfaces, characterized by strong hybridization between the S-p and O-p states of As(OH)3 and the surface Fe-d states. The As(OH)3 molecule displayed a variety of chemisorption geometries on the water–FeS(011) and water–FeS(111) interfaces, where the most stable configuration at the water–FeS(011) interface is a bidentate Fe–AsO–Fe complex, but on the water–FeS(111) interface, a monodentate Fe–O–Fe complex was found. Detailed information regarding the adsorption mechanisms has been obtained via projected density of states (PDOS) and electron density difference iso-surface analyses and vibrational frequency assignments of the adsorbed As(OH)3 molecule. PMID:28233994

Philosophy, history and sociology of science: interdisciplinary relations and complex social identities.

PubMed

Riesch, Hauke

2014-12-01

Sociology and philosophy of science have an uneasy relationship, while the marriage of history and philosophy of science has--on the surface at least--been more successful I will take a sociological look at the history of the relationships between philosophy and history as well as philosophy and sociology of science. Interdisciplinary relations between these disciplines will be analysed through social identity complexity theory in oider to draw out some conclusions on how the disciplines interact and how they might develop. I will use the relationships between the disciplines as a pointer for a more general social theory of interdisciplinarity which will then be used to sound a caution on how interdisciplinary relations between the three disciplines might be managed.

Backscatter analysis of dihedral corner reflectors using physical optics and the physical theory of diffraction

NASA Technical Reports Server (NTRS)

Griesser, Timothy; Balanis, Constantine A.

1987-01-01

The backscatter cross-sections of dihedral corner reflectors in the azimuthal plane are presently determined by both physical optics (PO) and the physical theory of diffraction (PTD), yielding results for the vertical and horizontal polarizations. In the first analysis method used, geometrical optics is used in place of PO at initial reflections in order to maintain the planar character of the reflected wave and reduce the complexity of the analysis. In the second method, PO is used at almost every reflection in order to maximize the accuracy of the PTD solution at the expense of a rapid increase in complexity. Induced surface current densities and resulting cross section patterns are illustrated for the two methods.

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

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

Song, Wentao; Leung, Kevin; Shao, Qian

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

DOE PAGES

Song, Wentao; Leung, Kevin; Shao, Qian; ...

2016-09-15

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Predictive Modeling in Actinide Chemistry and Catalysis

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

Yang, Ping

2016-05-16

These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

Exploiting the flexibility and the polarization of ferroelectric perovskite surfaces to achieve efficient photochemistry and enantiospecificity

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

Rappe, Andrew

This research project explored the catalytic properties of complex surfaces of functional materials. The PI used first-principles density functional theory (DFT) calculations to explore a tightly integrated set of properties. The physical properties of complex functional materials that influence surface chemistry were explored, including bulk and surface electric dipoles, and surface conductivity. The energetic, compositional, electronic, and chemical properties of the surfaces of these materials were explored in detail, and connections between material properties and chemical reactivity were established. This project led to 28 publications, including Nat. Comm., JACS, 3 PRL, 7 PRB, 2 ACS Nano, 2 Nano Lett., 4more » JPCL, 2 JCP, Chem. Mater., ACS Appl. Mater. Interfaces, Phys. Rev. Appl., and a U.S. Patent on surface catalysts. The key accomplishments in this project involved work in six coordinated areas: pioneering ways to control bulk dipoles in order to dynamically affect catalysis, exploring novel ways of bringing charge to the surface for redox catalysis, nonstoichiometric surfaces offering new sites for heterogeneous catalysis, illustrating how surface catalysis responds to applied pressure, catalytic growth of carbon-based materials, and new computational methods allowing more accurate exploration of molecule-surface interactions« less

Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

NASA Astrophysics Data System (ADS)

Wang, Hong-Fei

2016-12-01

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

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

Wang, Hong-Fei

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there has been significant progress in the development of methodology and instrumentation in the SFG-VS toolbox that has significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, somemore » of the controversial issues that have been puzzling the community are to be discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.« less

Analytic theory for the selection of 2-D needle crystal at arbitrary Peclet number

NASA Technical Reports Server (NTRS)

Tanveer, Saleh

1989-01-01

An accurate analytic theory is presented for the velocity selection of a two-dimensional needle crystal for arbitrary Peclet number for small values of the surface tension parameter. The velocity selection is caused by the effect of transcendentally small terms which are determined by analytic continuation to the complex plane and analysis of nonlinear equations. The work supports the general conclusion of previous small Peclet number analytical results of other investigators, though there are some discrepancies in details. It also addresses questions raised on the validity of selection theory owing to assumptions made on shape corrections at large distances from the tip.

TRIZ theory in NEA photocathode preparation system

NASA Astrophysics Data System (ADS)

Qiao, Jianliang; Huang, Dayong; Li, Xiangjiang; Gao, Youtang

2016-09-01

The solutions to the engineering problems were provided according to the innovation principle based on the theory of TRIZ. The ultra high vacuum test and evaluation system for the preparation of negative electron affinity (NEA) photocathode has the characteristics of complex structure and powerful functions. Segmentation principle, advance function principle, curved surface principle, dynamic characteristics principle and nested principle adopted by the design of ultra high vacuum test and evaluation system for cathode preparation were analyzed. The applications of the physical contradiction and the substance-field analysis method of the theory of TRIZ in the cathode preparation ultra high vacuum test and evaluation system were discussed.

On the performance of infrared sensors in earth observations

NASA Technical Reports Server (NTRS)

Johnson, L. F.

1972-01-01

The performance of infrared sensing systems is dependent upon the radiative properties of targets in addition to constraints imposed by system components. The unclassified state-of-the-art of infrared system performance figures is reviewed to indicate the relevance to system performance of target radiative properties. A theory of rough surface scattering is developed which allows the formulation of the reflective characteristics of extended targets. The thermal radiation emission from extended targets is formulated on the basis of internal radiation characteristics of natural materials and the transmissive scattering effects at the surface. Finally, the total radiative characteristics may be expressed as functions of material properties and incident and received directions, although the expressions are extremely complex functions and do not account for the effects of shadowing or multiple scattering. It is believed that the theory may be extended to include these effects and to incorporate the local radii of curvature of the surface.

Nuclear Fission: from more phenomenology and adjusted parameters to more fundamental theory and increased predictive power

NASA Astrophysics Data System (ADS)

Bulgac, Aurel; Jin, Shi; Magierski, Piotr; Roche, Kenneth; Schunck, Nicolas; Stetcu, Ionel

2017-11-01

Two major recent developments in theory and computational resources created the favorable conditions for achieving a microscopic description of fission dynamics in classically allowed regions of the collective potential energy surface, almost eighty years after its discovery in 1939 by Hahn and Strassmann [1]. The first major development was in theory, the extension of the Time-Dependent Density Functional Theory (TDDFT) [2-5] to superfluid fermion systems [6]. The second development was in computing, the emergence of powerful enough supercomputers capable of solving the complex systems of equations describing the time evolution in three dimensions without any restrictions of hundreds of strongly interacting nucleons. Thus the conditions have been created to renounce phenomenological models and incomplete microscopic treatments with uncontrollable approximations and/or assumptions in the description of the complex dynamics of fission. Even though the available nuclear energy density functionals (NEDFs) are phenomenological still, their accuracy is improving steadily and the prospects of being able to perform calculations of the nuclear fission dynamics and to predict many properties of the fission fragments, otherwise not possible to extract from experiments.

Focus Article: Theoretical aspects of vapor/gas nucleation at structured surfaces

NASA Astrophysics Data System (ADS)

Meloni, Simone; Giacomello, Alberto; Casciola, Carlo Massimo

2016-12-01

Heterogeneous nucleation is the preferential means of formation of a new phase. Gas and vapor nucleation in fluids under confinement or at textured surfaces is central for many phenomena of technological relevance, such as bubble release, cavitation, and biological growth. Understanding and developing quantitative models for nucleation is the key to control how bubbles are formed and to exploit them in technological applications. An example is the in silico design of textured surfaces or particles with tailored nucleation properties. However, despite the fact that gas/vapor nucleation has been investigated for more than one century, many aspects still remain unclear and a quantitative theory is still lacking; this is especially true for heterogeneous systems with nanoscale corrugations, for which experiments are difficult. The objective of this focus article is analyzing the main results of the last 10-20 years in the field, selecting few representative works out of this impressive body of the literature, and highlighting the open theoretical questions. We start by introducing classical theories of nucleation in homogeneous and in simple heterogeneous systems and then discuss their extension to complex heterogeneous cases. Then we describe results from recent theories and computer simulations aimed at overcoming the limitations of the simpler theories by considering explicitly the diffuse nature of the interfaces, atomistic, kinetic, and inertial effects.

Rb + adsorption at the quartz(101)-aqueous interface: comparison of resonant anomalous x-ray reflectivity with ab initio calculations

DOE PAGES

Bellucci, Francesco; Lee, Sang Soo; Kubicki, James D.; ...

2015-01-29

We study adsorption of Rb + to the quartz(101)–aqueous interface at room temperature with specular X-ray reflectivity, resonant anomalous X-ray reflectivity, and density functional theory. The interfacial water structures observed in deionized water and 10 mM RbCl solution at pH 9.8 were similar, having a first water layer at height of 1.7 ± 0.1 Å above the quartz surface and a second layer at 4.8 ± 0.1 Å and 3.9 ± 0.8 Å for the water and RbCl solutions, respectively. The adsorbed Rb + distribution is broad and consists of presumed inner-sphere (IS) and outer-sphere (OS) complexes at heights ofmore » 1.8 ± 0.1 and 6.4 ± 1.0 Å, respectively. Projector-augmented planewave density functional theory (DFT) calculations of potential configurations for neutral and negatively charged quartz(101) surfaces at pH 7 and 12, respectively, reveal a water structure in agreement with experimental results. These DFT calculations also show differences in adsorbed speciation of Rb + between these two conditions. At pH 7, the lowest energy structure shows that Rb + adsorbs dominantly as an IS complex, whereas at pH 12 IS and OS complexes have equivalent energies. The DFT results at pH 12 are generally consistent with the two site Rb distribution observed from the X-ray data at pH 9.8, albeit with some differences that are discussed. In conclusion, surface charge estimated on the basis of the measured total Rb + coverage was -0.11 C/m 2, in good agreement with the range of the surface charge magnitudes reported in the literature.« less

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.

PubMed

Finlayson-Pitts, Barbara J

2009-09-28

While particles have significant deleterious impacts on human health, visibility and climate, quantitative understanding of their formation, composition and fates remains problematic. Indeed, in many cases, even qualitative understanding is lacking. One area of particular uncertainty is the nature of particle surfaces and how this determines interactions with gases in the atmosphere, including water, which is important for cloud formation and properties. The focus in this Perspective article is on some chemistry relevant to airborne particles and especially to reactions occurring on their surfaces. The intent is not to provide a comprehensive review, but rather to highlight a few selected examples of interface chemistry involving inorganic and organic species that may be important in the lower atmosphere. This includes sea salt chemistry, nitrate and nitrite ion photochemistry, organics on surfaces and heterogeneous reactions of oxides of nitrogen on proxies for airborne mineral dust and boundary layer surfaces. Emphasis is on the molecular level understanding that can only be gained by fully integrating experiment and theory to elucidate these complex systems.

New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer-A Density Functional Theory Approach.

PubMed

Landeros-Martinez, Linda-Lucila; Glossman-Mitnik, Daniel; Orrantia-Borunda, Erasmo; Flores-Holguín, Norma

2017-10-19

The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR) spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski's rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6-31G (d); for the esterified nanodiamond-Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.

New theory for Mode I crack-tip dislocation emission

NASA Astrophysics Data System (ADS)

Andric, Predrag; Curtin, W. A.

2017-09-01

A material is intrinsically ductile under Mode I loading when the critical stress intensity KIe for dislocation emission is lower than the critical stress intensity KIc for cleavage. KIe is usually evaluated using the approximate Rice theory, which predicts a dependence on the elastic constants and the unstable stacking fault energy γusf for slip along the plane of dislocation emission. Here, atomistic simulations across a wide range of fcc metals show that KIe is systematically larger (10-30%) than predicted. However, the critical (crack tip) shear displacement is up to 40% smaller than predicted. The discrepancy arises because Mode I emission is accompanied by the formation of a surface step that is not considered in the Rice theory. A new theory for Mode I emission is presented based on the ideas that (i) the stress resisting step formation at the crack tip creates "lattice trapping" against dislocation emission such that (ii) emission is due to a mechanical instability at the crack tip. The new theory is formulated using a Peierls-type model, naturally includes the energy to form the step, and reduces to the Rice theory (no trapping) when the step energy is small. The new theory predicts a higher KIe at a smaller critical shear displacement, rationalizing deviations of simulations from the Rice theory. Specific predictions of KIe for the simulated materials, usually requiring use of the measured critical crack tip shear displacement due to complex material non-linearity, show very good agreement with simulations. An analytic model involving only γusf, the surface energy γs, and anisotropic elastic constants is shown to be quite accurate, serves as a replacement for the analytical Rice theory, and is used to understand differences between Rice theory and simulation in recent literature. The new theory highlights the role of surface steps created by dislocation emission in Mode I, which has implications not only for intrinsic ductility but also for crack tip twinning and fracture due to chemical interactions at the crack tip.

The role of mechanics during brain development

NASA Astrophysics Data System (ADS)

Budday, Silvia; Steinmann, Paul; Kuhl, Ellen

2014-12-01

Convolutions are a classical hallmark of most mammalian brains. Brain surface morphology is often associated with intelligence and closely correlated with neurological dysfunction. Yet, we know surprisingly little about the underlying mechanisms of cortical folding. Here we identify the role of the key anatomic players during the folding process: cortical thickness, stiffness, and growth. To establish estimates for the critical time, pressure, and the wavelength at the onset of folding, we derive an analytical model using the Föppl-von Kármán theory. Analytical modeling provides a quick first insight into the critical conditions at the onset of folding, yet it fails to predict the evolution of complex instability patterns in the post-critical regime. To predict realistic surface morphologies, we establish a computational model using the continuum theory of finite growth. Computational modeling not only confirms our analytical estimates, but is also capable of predicting the formation of complex surface morphologies with asymmetric patterns and secondary folds. Taken together, our analytical and computational models explain why larger mammalian brains tend to be more convoluted than smaller brains. Both models provide mechanistic interpretations of the classical malformations of lissencephaly and polymicrogyria. Understanding the process of cortical folding in the mammalian brain has direct implications on the diagnostics of neurological disorders including severe retardation, epilepsy, schizophrenia, and autism.

The role of mechanics during brain development

PubMed Central

Budday, Silvia; Steinmann, Paul; Kuhl, Ellen

2014-01-01

Convolutions are a classical hallmark of most mammalian brains. Brain surface morphology is often associated with intelligence and closely correlated to neurological dysfunction. Yet, we know surprisingly little about the underlying mechanisms of cortical folding. Here we identify the role of the key anatomic players during the folding process: cortical thickness, stiffness, and growth. To establish estimates for the critical time, pressure, and the wavelength at the onset of folding, we derive an analytical model using the Föppl-von-Kármán theory. Analytical modeling provides a quick first insight into the critical conditions at the onset of folding, yet it fails to predict the evolution of complex instability patterns in the post-critical regime. To predict realistic surface morphologies, we establish a computational model using the continuum theory of finite growth. Computational modeling not only confirms our analytical estimates, but is also capable of predicting the formation of complex surface morphologies with asymmetric patterns and secondary folds. Taken together, our analytical and computational models explain why larger mammalian brains tend to be more convoluted than smaller brains. Both models provide mechanistic interpretations of the classical malformations of lissencephaly and polymicrogyria. Understanding the process of cortical folding in the mammalian brain has direct implications on the diagnostics of neurological disorders including severe retardation, epilepsy, schizophrenia, and autism. PMID:25202162

Fermiology and Superconductivity of Topological Surface States in PdTe2

NASA Astrophysics Data System (ADS)

Clark, O. J.; Neat, M. J.; Okawa, K.; Bawden, L.; Marković, I.; Mazzola, F.; Feng, J.; Sunko, V.; Riley, J. M.; Meevasana, W.; Fujii, J.; Vobornik, I.; Kim, T. K.; Hoesch, M.; Sasagawa, T.; Wahl, P.; Bahramy, M. S.; King, P. D. C.

2018-04-01

We study the low-energy surface electronic structure of the transition-metal dichalcogenide superconductor PdTe2 by spin- and angle-resolved photoemission, scanning tunneling microscopy, and density-functional theory-based supercell calculations. Comparing PdTe2 with its sister compound PtSe2 , we demonstrate how enhanced interlayer hopping in the Te-based material drives a band inversion within the antibonding p -orbital manifold well above the Fermi level. We show how this mediates spin-polarized topological surface states which form rich multivalley Fermi surfaces with complex spin textures. Scanning tunneling spectroscopy reveals type-II superconductivity at the surface, and moreover shows no evidence for an unconventional component of its superconducting order parameter, despite the presence of topological surface states.

Quantitative analysis of valence photoemission spectra and quasiparticle excitations at chromophore-semiconductor interfaces.

PubMed

Patrick, Christopher E; Giustino, Feliciano

2012-09-14

Investigating quasiparticle excitations of molecules on surfaces through photoemission spectroscopy forms a major part of nanotechnology research. Resolving spectral features at these interfaces requires a comprehensive theory of electron removal and addition processes in molecules and solids which captures the complex interplay of image charges, thermal effects, and configurational disorder. Here, we develop such a theory and calculate the quasiparticle energy-level alignment and the valence photoemission spectrum for the prototype biomimetic solar cell interface between anatase TiO(2) and the N3 chromophore. By directly matching our calculated photoemission spectrum to experimental data, we clarify the atomistic origin of the chromophore peak at low binding energy. This case study sets a new standard in the interpretation of photoemission spectroscopy at complex chromophore-semiconductor interfaces.

Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

PubMed

Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P

2013-11-12

In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

The adhesion and hysteresis effect in friction skin with artificial materials

NASA Astrophysics Data System (ADS)

Subhi, K. A.; Tudor, A.; Hussein, E. K.; Wahad, H. S.

2017-02-01

Human skin is a soft biomaterial with a complex anatomical structure and it has a complex material behavior during the mechanical contact with objects and surfaces. The friction adhesion component is defined by means of the theories of Johnson-Kendall-Roberts (JKR), Derjaguin-Muller-Toporov (DMT) and Maugis - Dugdale (MD). We shall consider the human skin entering into contact with a rigid surface. The deformation (hysteresis) component of the skin friction is evaluated with Voigt rheological model for the spherical contact, with the original model, developed in MATHCAD software. The adhesive component of the skin friction is greater than the hysteresis component for all friction parameters (load, velocity, the strength of interface between skin and the artificial material).

Particle and surfactant interactions effected polar and dispersive components of interfacial energy in nanocolloids

NASA Astrophysics Data System (ADS)

Harikrishnan, A. R.; Das, Sarit K.; Agnihotri, Prabhat K.; Dhar, Purbarun

2017-08-01

We segregate and report experimentally for the first time the polar and dispersive interfacial energy components of complex nanocolloidal dispersions. In the present study, we introduce a novel inverse protocol for the classical Owens Wendt method to determine the constitutive polar and dispersive elements of surface tension in such multicomponent fluidic systems. The effect of nanoparticles alone and aqueous surfactants alone are studied independently to understand the role of the concentration of the dispersed phase in modulating the constitutive elements of surface energy in fluids. Surfactants are capable of altering the polar component, and the combined particle and surfactant nanodispersions are shown to be effective in modulating the polar and dispersive components of surface tension depending on the relative particle and surfactant concentrations as well as the morphological and electrostatic nature of the dispersed phases. We observe that the combined surfactant and particle colloid exhibits a similar behavior to that of the particle only case; however, the amount of modulation of the polar and dispersive constituents is found to be different from the particle alone case which brings to the forefront the mechanisms through which surfactants modulate interfacial energies in complex fluids. Accordingly, we are able to show that the observations can be merged into a form of quasi-universal trend in the trends of polar and dispersive components in spite of the non-universal character in the wetting behavior of the fluids. We analyze the different factors affecting the polar and dispersive interactions in such complex colloids, and the physics behind such complex interactions has been explained by appealing to the classical dispersion theories by London, Debye, and Keesom as well as by Derjaguin-Landau-Verwey-Overbeek theory. The findings shed light on the nature of wetting behavior of such complex fluids and help in predicting the wettability and the degree of interfacial interaction with a substrate in such multicomponent nanocolloidal systems.

Spectroscopic and DFT study of atenolol and metoprolol and their copper complexes

NASA Astrophysics Data System (ADS)

Cozar, O.; Szabó, L.; Cozar, I. B.; Leopold, N.; David, L.; Căinap, C.; Chiş, V.

2011-05-01

IR, Raman and surface-enhanced Raman scattering (SERS) spectra of atenolol (ATE) and metoprolol (MET) were recorded and assigned on the basis of density functional theory (DFT) calculations. A reliable assignment of vibrational IR and Raman bands of the two compounds was possible by a proper choice of models used in quantum chemical calculations. Both molecules are adsorbed to the silver surface mainly through the oxygen atoms and π-electrons of the phenyl ring. The coordination mode of the metal ions in Cu(II)-ATE and -MET compounds was also derived from IR and EPR spectra. EPR spectra give evidence for a square-planar arrangement around the copper (II) ion in the case of Cu-ATE complex, with a N 2O 2 chromophore. Only oxygen atoms are involved in the cooper coordination for Cu-MET complex, and two types of local symmetries with d and d as ground states for paramagnetic electron coexist.

Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

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

Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu

2015-11-07

We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaksmore » down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.« less

Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals.

PubMed

Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

2016-02-16

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Charge-transfer mechanism for electrophilic aromatic nitration and nitrosation via the convergence of (ab initio) molecular-orbital and Marcus-Hush theories with experiments.

PubMed

Gwaltney, Steven R; Rosokha, Sergiy V; Head-Gordon, Martin; Kochi, Jay K

2003-03-19

The highly disparate rates of aromatic nitrosation and nitration, despite the very similar (electrophilic) properties of the active species: NO(+) and NO(2)(+) in Chart 1, are quantitatively reconciled. First, the thorough mappings of the potential-energy surfaces by high level (ab initio) molecular-orbital methodologies involving extensive coupled-cluster CCSD(T)/6-31G optimizations establish the intervention of two reactive intermediates in nitration (Figure 8) but only one in nitrosation (Figure 7). Second, the same distinctive topologies involving double and single potential-energy minima (Figures 6 and 5) also emerge from the semiquantitative application of the Marcus-Hush theory to the transient spectral data. Such a striking convergence from quite different theoretical approaches indicates that the molecular-orbital and Marcus-Hush (potential-energy) surfaces are conceptually interchangeable. In the resultant charge-transfer mechanism, the bimolecular interactions of arene donors with both NO(+) and NO(2)(+) spontaneously lead (barrierless) to pi-complexes in which electron transfer is concurrent with complexation. Such a pi-complex in nitration is rapidly converted to the sigma-complex, whereas this Wheland adduct in nitrosation merely represents a high energy (transition-state) structure. Marcus-Hush analysis thus demonstrates how the strongly differentiated (arene) reactivities toward NO(+) and NO(2)(+) can actually be exploited in the quantitative development of a single coherent (electron-transfer) mechanism for both aromatic nitrosation and nitration.

Computer Aided Simulation Machining Programming In 5-Axis Nc Milling Of Impeller Leaf

NASA Astrophysics Data System (ADS)

Huran, Liu

At present, cad/cam (computer-aided design and manufacture) have fine wider and wider application in mechanical industry. For the complex surfaces, the traditional machine tool can no longer satisfy the requirement of such complex task. Only by the help of cad/cam can fulfill the requirement. The machining of the vane surface of the impeller leaf has been considered as the hardest challenge. Because of their complex shape, the 5-axis cnc machine tool is needed for the machining of such parts. The material is hard to cut, the requirement for the surface finish and clearance is very high, so that the manufacture quality of impeller leaf represent the level of 5-axis machining. This paper opened a new field in machining the complicated surface, based on a relatively more rigid mathematical basis. The theory presented here is relatively more systematical. Since the lack of theoretical guidance, in the former research, people have to try in machining many times. Such case will be changed. The movement of the cutter determined by this method is definite, and the residual is the smallest while the times of travel is the fewest. The criterion is simple and the calculation is easy.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules.

PubMed

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin; Huang, Yingzhou

2017-08-02

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-M x (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-M x complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules

PubMed Central

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin

2017-01-01

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-Mx complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS. PMID:28767053

A numerical algorithm for MHD of free surface flows at low magnetic Reynolds numbers

NASA Astrophysics Data System (ADS)

Samulyak, Roman; Du, Jian; Glimm, James; Xu, Zhiliang

2007-10-01

We have developed a numerical algorithm and computational software for the study of magnetohydrodynamics (MHD) of free surface flows at low magnetic Reynolds numbers. The governing system of equations is a coupled hyperbolic-elliptic system in moving and geometrically complex domains. The numerical algorithm employs the method of front tracking and the Riemann problem for material interfaces, second order Godunov-type hyperbolic solvers, and the embedded boundary method for the elliptic problem in complex domains. The numerical algorithm has been implemented as an MHD extension of FronTier, a hydrodynamic code with free interface support. The code is applicable for numerical simulations of free surface flows of conductive liquids or weakly ionized plasmas. The code has been validated through the comparison of numerical simulations of a liquid metal jet in a non-uniform magnetic field with experiments and theory. Simulations of the Muon Collider/Neutrino Factory target have also been discussed.

Becchi-Rouet-Stora-Tyutin formalism and zero locus reduction

NASA Astrophysics Data System (ADS)

Grigoriev, M. A.; Semikhatov, A. M.; Tipunin, I. Yu.

2001-08-01

In the Becchi-Rouet-Stora-Tyutin (BRST) quantization of gauge theories, the zero locus ZQ of the BRST differential Q carries an (anti)bracket whose parity is opposite to that of the fundamental bracket. Observables of the BRST theory are in a 1:1 correspondence with Casimir functions of the bracket on ZQ. For any constrained dynamical system with the phase space N0 and the constraint surface Σ, we prove its equivalence to the constrained system on the BFV-extended phase space with the constraint surface given by ZQ. Reduction to the zero locus of the differential gives rise to relations between bracket operations and differentials arising in different complexes (the Gerstenhaber, Schouten, Berezin-Kirillov, and Sklyanin brackets); the equation ensuring the existence of a nilpotent vector field on the reduced manifold can be the classical Yang-Baxter equation. We also generalize our constructions to the bi-QP manifolds which from the BRST theory viewpoint correspond to the BRST-anti-BRST-symmetric quantization.

Local structural ordering in surface-confined liquid crystals

NASA Astrophysics Data System (ADS)

Śliwa, I.; Jeżewski, W.; Zakharov, A. V.

2017-06-01

The effect of the interplay between attractive nonlocal surface interactions and attractive pair long-range intermolecular couplings on molecular structures of liquid crystals confined in thin cells with flat solid surfaces has been studied. Extending the McMillan mean field theory to include finite systems, it has been shown that confining surfaces can induce complex orientational and translational ordering of molecules. Typically, local smectic A, nematic, and isotropic phases have been shown to coexist in certain temperature ranges, provided that confining cells are sufficiently thick, albeit finite. Due to the nonlocality of surface interactions, the spatial arrangement of these local phases can display, in general, an unexpected complexity along the surface normal direction. In particular, molecules located in the vicinity of surfaces can still be organized in smectic layers, even though nematic and/or isotropic order can simultaneously appear in the interior of cells. The resulting surface freezing of smectic layers has been confirmed to occur even for rather weak surface interactions. The surface interactions cannot, however, prevent smectic layers from melting relatively close to system boundaries, even when molecules are still arranged in layers within the central region of the system. The internal interfaces, separating individual liquid-crystal phases, are demonstrated here to form fronts of local finite-size transitions that move across cells under temperature changes. Although the complex molecular ordering in surface confined liquid-crystal systems can essentially be controlled by temperature variations, specific thermal properties of these systems, especially the nature of the local transitions, are argued to be strongly conditioned to the degree of molecular packing.

Topological characterization of antireflective and hydrophobic rough surfaces: are random process theory and fractal modeling applicable?

NASA Astrophysics Data System (ADS)

Borri, Claudia; Paggi, Marco

2015-02-01

The random process theory (RPT) has been widely applied to predict the joint probability distribution functions (PDFs) of asperity heights and curvatures of rough surfaces. A check of the predictions of RPT against the actual statistics of numerically generated random fractal surfaces and of real rough surfaces has been only partially undertaken. The present experimental and numerical study provides a deep critical comparison on this matter, providing some insight into the capabilities and limitations in applying RPT and fractal modeling to antireflective and hydrophobic rough surfaces, two important types of textured surfaces. A multi-resolution experimental campaign using a confocal profilometer with different lenses is carried out and a comprehensive software for the statistical description of rough surfaces is developed. It is found that the topology of the analyzed textured surfaces cannot be fully described according to RPT and fractal modeling. The following complexities emerge: (i) the presence of cut-offs or bi-fractality in the power-law power-spectral density (PSD) functions; (ii) a more pronounced shift of the PSD by changing resolution as compared to what was expected from fractal modeling; (iii) inaccuracy of the RPT in describing the joint PDFs of asperity heights and curvatures of textured surfaces; (iv) lack of resolution-invariance of joint PDFs of textured surfaces in case of special surface treatments, not accounted for by fractal modeling.

Characterization of the surface charge distribution on kaolinite particles using high resolution atomic force microscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Zhao, Cunlu; Klaassen, Aram; van den Ende, Dirk; Mugele, Frieder; Siretanu, Igor

2016-02-01

Most solid surfaces, in particular clay minerals and rock surfaces, acquire a surface charge upon exposure to an aqueous environment due to adsorption and/or desorption of ionic species. Macroscopic techniques such as titration and electrokinetic measurements are commonly used to determine the surface charge and ζ -potential of these surfaces. However, because of the macroscopic averaging character these techniques cannot do justice to the role of local heterogeneities on the surfaces. In this work, we use dynamic atomic force microscopy (AFM) to determine the distribution of surface charge on the two (gibbsite-like and silica-like) basal planes of kaolinite nanoparticles immersed in aqueous electrolyte with a lateral resolution of approximately 30 nm. The surface charge density is extracted from force-distance curves using DLVO theory in combination with surface complexation modeling. While the gibbsite-like and the silica-like facet display on average positive and negative surface charge values as expected, our measurements reveal lateral variations of more than a factor of two on seemingly atomically smooth terraces, even if high resolution AFM images clearly reveal the atomic lattice on the surface. These results suggest that simple surface complexation models of clays that attribute a unique surface chemistry and hence homogeneous surface charge densities to basal planes may miss important aspects of real clay surfaces.

Digging beneath the Surface Behavioral and Neural Indices of Lexical Access during Idiom Comprehension in Aphasia: A Multi-Modal Approach

ERIC Educational Resources Information Center

Brumm, Kathleen Patricia

2011-01-01

This project examines spoken language comprehension in Broca's aphasia, a non-fluent language disorder acquired subsequent to stroke. Broca's aphasics demonstrate impaired comprehension for complex sentence constructions. To account for this deficit, one current processing theory claims that Broca's patients retain intrinsic linguistic knowledge,…

Comparison of stresses on homogeneous spheroids in the optical stretcher computed with geometrical optics and generalized Lorenz-Mie theory.

PubMed

Boyde, Lars; Ekpenyong, Andrew; Whyte, Graeme; Guck, Jochen

2012-11-20

We present two electromagnetic frameworks to compare the surface stresses on spheroidal particles in the optical stretcher (a dual-beam laser trap that can be used to capture and deform biological cells). The first model is based on geometrical optics (GO) and limited in its applicability to particles that are much greater than the incident wavelength. The second framework is more sophisticated and hinges on the generalized Lorenz-Mie theory (GLMT). Despite the difference in complexity between both theories, the stress profiles computed with GO and GLMT are in good agreement with each other (relative errors are on the order of 1-10%). Both models predict a diminishing of the stresses for larger wavelengths and a strong increase of the stresses for shorter laser-cell distances. Results indicate that surface stresses on a spheroid with an aspect ratio of 1.2 hardly differ from the stresses on a sphere of similar size. Knowledge of the surface stresses and whether or not they redistribute during the stretching process is of crucial importance in real-time applications of the stretcher that aim to discern the viscoelastic properties of cells for purposes of cell characterization, sorting, and medical diagnostics.

Lineshape theory of pigment-protein complexes: How the finite relaxation time of nuclei influences the exciton relaxation-induced lifetime broadening.

PubMed

Dinh, Thanh-Chung; Renger, Thomas

2016-07-21

In pigment-protein complexes, often the excited states are partially delocalized and the exciton-vibrational coupling in the basis of delocalized states contains large diagonal and small off-diagonal elements. This inequality may be used to introduce potential energy surfaces (PESs) of exciton states and to treat the inter-PES coupling in Markov and secular approximations. The resulting lineshape function consists of a Lorentzian peak that is broadened by the finite lifetime of the exciton states caused by the inter-PES coupling and a vibrational sideband that results from the mutual displacement of the excitonic PESs with respect to that of the ground state. So far analytical expressions have been derived that relate the exciton relaxation-induced lifetime broadening to the Redfield [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)] or modified Redfield [M. Schröder, U. Kleinekathöfer, and M. Schreiber, J. Chem. Phys. 124, 084903 (2006)] rate constants of exciton relaxation, assuming that intra-PES nuclear relaxation is fast compared to inter-PES transfer. Here, we go beyond this approximation and provide an analytical expression, termed Non-equilibrium Modified Redfield (NeMoR) theory, for the lifetime broadening that takes into account the finite nuclear relaxation time. In an application of the theory to molecular dimers, we find that, for a widely used experimental spectral density of the exciton-vibrational coupling of pigment-protein complexes, the NeMoR spectrum at low-temperatures (T < 150 K) is better approximated by Redfield than by modified Redfield theory. At room temperature, the lifetime broadening obtained with Redfield theory underestimates the NeMoR broadening, whereas modified Redfield theory overestimates it by a similar amount. A fortuitous error compensation in Redfield theory is found to explain the good performance of this theory at low temperatures. Since steady state spectra of PPCs are often measured at low temperatures, Redfield theory still provides a numerically efficient alternative to NeMoR theory. At higher temperatures, we suggest to use NeMoR theory, because it has the same numerical costs as modified Redfield theory, but is more accurate.

Application of wavefield compressive sensing in surface wave tomography

NASA Astrophysics Data System (ADS)

Zhan, Zhongwen; Li, Qingyang; Huang, Jianping

2018-06-01

Dense arrays allow sampling of seismic wavefield without significant aliasing, and surface wave tomography has benefitted from exploiting wavefield coherence among neighbouring stations. However, explicit or implicit assumptions about wavefield, irregular station spacing and noise still limit the applicability and resolution of current surface wave methods. Here, we propose to apply the theory of compressive sensing (CS) to seek a sparse representation of the surface wavefield using a plane-wave basis. Then we reconstruct the continuous surface wavefield on a dense regular grid before applying any tomographic methods. Synthetic tests demonstrate that wavefield CS improves robustness and resolution of Helmholtz tomography and wavefield gradiometry, especially when traditional approaches have difficulties due to sub-Nyquist sampling or complexities in wavefield.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

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

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

An installed nacelle design code using a multiblock Euler solver. Volume 1: Theory document

NASA Technical Reports Server (NTRS)

Chen, H. C.

1992-01-01

An efficient multiblock Euler design code was developed for designing a nacelle installed on geometrically complex airplane configurations. This approach employed a design driver based on a direct iterative surface curvature method developed at LaRC. A general multiblock Euler flow solver was used for computing flow around complex geometries. The flow solver used a finite-volume formulation with explicit time-stepping to solve the Euler Equations. It used a multiblock version of the multigrid method to accelerate the convergence of the calculations. The design driver successively updated the surface geometry to reduce the difference between the computed and target pressure distributions. In the flow solver, the change in surface geometry was simulated by applying surface transpiration boundary conditions to avoid repeated grid generation during design iterations. Smoothness of the designed surface was ensured by alternate application of streamwise and circumferential smoothings. The capability and efficiency of the code was demonstrated through the design of both an isolated nacelle and an installed nacelle at various flow conditions. Information on the execution of the computer program is provided in volume 2.

Joint density-functional theory for energetics and spectroscopy in complex aqueous and nonaqueous solvents

NASA Astrophysics Data System (ADS)

Gunceler, Deniz

Solvents are of great importance in many technological applications, but are difficult to study using standard, off-the-shelf ab initio electronic structure methods. This is because a single configuration of molecular positions in the solvent (a "snapshot" of the fluid) is not necessarily representative of the thermodynamic average. To obtain any thermodynamic averages (e.g. free energies), the phase space of the solvent must be sampled, typically using molecular dynamics. This greatly increases the computational cost involved in studying solvated systems. Joint density-functional theory has made its mark by being a computationally efficient yet rigorous theory by which to study solvation. It replaces the need for thermodynamic sampling with an effective continuum description of the solvent environment that is in-principle exact, computationally efficient and intuitive (easier to interpret). It has been very successful in aqueous systems, with potential applications in (among others) energy materials discovery, catalysis and surface science. In this dissertation, we develop accurate and fast joint density functional theories for complex, non-aqueous solvent enviroments, including organic solvents and room temperature ionic liquids, as well as new methods for calculating electron excitation spectra in such systems. These theories are then applied to a range of physical problems, from dendrite formation in lithium-metal batteries to the optical spectra of solvated ions.

Designing molecular complexes using free-energy derivatives from liquid-state integral equation theory

NASA Astrophysics Data System (ADS)

Mrugalla, Florian; Kast, Stefan M.

2016-09-01

Complex formation between molecules in solution is the key process by which molecular interactions are translated into functional systems. These processes are governed by the binding or free energy of association which depends on both direct molecular interactions and the solvation contribution. A design goal frequently addressed in pharmaceutical sciences is the optimization of chemical properties of the complex partners in the sense of minimizing their binding free energy with respect to a change in chemical structure. Here, we demonstrate that liquid-state theory in the form of the solute-solute equation of the reference interaction site model provides all necessary information for such a task with high efficiency. In particular, computing derivatives of the potential of mean force (PMF), which defines the free-energy surface of complex formation, with respect to potential parameters can be viewed as a means to define a direction in chemical space toward better binders. We illustrate the methodology in the benchmark case of alkali ion binding to the crown ether 18-crown-6 in aqueous solution. In order to examine the validity of the underlying solute-solute theory, we first compare PMFs computed by different approaches, including explicit free-energy molecular dynamics simulations as a reference. Predictions of an optimally binding ion radius based on free-energy derivatives are then shown to yield consistent results for different ion parameter sets and to compare well with earlier, orders-of-magnitude more costly explicit simulation results. This proof-of-principle study, therefore, demonstrates the potential of liquid-state theory for molecular design problems.

Designing molecular complexes using free-energy derivatives from liquid-state integral equation theory.

PubMed

Mrugalla, Florian; Kast, Stefan M

2016-09-01

Complex formation between molecules in solution is the key process by which molecular interactions are translated into functional systems. These processes are governed by the binding or free energy of association which depends on both direct molecular interactions and the solvation contribution. A design goal frequently addressed in pharmaceutical sciences is the optimization of chemical properties of the complex partners in the sense of minimizing their binding free energy with respect to a change in chemical structure. Here, we demonstrate that liquid-state theory in the form of the solute-solute equation of the reference interaction site model provides all necessary information for such a task with high efficiency. In particular, computing derivatives of the potential of mean force (PMF), which defines the free-energy surface of complex formation, with respect to potential parameters can be viewed as a means to define a direction in chemical space toward better binders. We illustrate the methodology in the benchmark case of alkali ion binding to the crown ether 18-crown-6 in aqueous solution. In order to examine the validity of the underlying solute-solute theory, we first compare PMFs computed by different approaches, including explicit free-energy molecular dynamics simulations as a reference. Predictions of an optimally binding ion radius based on free-energy derivatives are then shown to yield consistent results for different ion parameter sets and to compare well with earlier, orders-of-magnitude more costly explicit simulation results. This proof-of-principle study, therefore, demonstrates the potential of liquid-state theory for molecular design problems.

Mechanism for chelated sulfate formation from SO2 and bis (triphenylphosphine) platinum

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

Structure and energy surface calculations using the atom superposition and electron delocalization molecular orbital theory show that the first step in the reaction between SO2 and the dioxygen complex (PPh3)2PtO2 is the coordination of SO2 with one oxygen atom of the complex, followed by metal-oxygen bond breaking and reorientation, leading to a five-membered cyclic structure. This then rearranges to form the bidentate coordinated sulfate. Alternative pathways are considered and are found to be less favorable.

Adsorption of the astatine species on a gold surface: A relativistic density functional theory study

NASA Astrophysics Data System (ADS)

Demidov, Yuriy; Zaitsevskii, Andréi

2018-01-01

We report first-principle based studies of the adsorption interaction of astatine species on a gold surface. These studies are aimed primarily at the support and interpretation of gas chromatographic experiments with superheavy elements, tennessine (Ts, Z = 117), a heavier homologue of At, and possibly its pseudo-homologue nihonium (Nh, Z = 113). We use gold clusters with up to 69 atoms to simulate the adsorption sites and estimate the desorption energies of At & AtOH from a stable gold (1 1 1) surface. To describe the electronic structure of At -Aun and AtOH -Aun complexes, we combine accurate shape-consistent relativistic pseudopotentials and non-collinear two-component relativistic density functional theory. The predicted desorption energies of At and AtOH on gold are 130 ± 10 kJ/mol and 90 ± 10 kJ/mol, respectively. These results confirm the validity of the estimates derived from chromatographic data (147 ± 15 kJ/mol for At, and 100-10+20 kJ/mol for AtOH).

Quantitative biological surface science: challenges and recent advances.

PubMed

Höök, Fredrik; Kasemo, Bengt; Grunze, Michael; Zauscher, Stefan

2008-12-23

Biological surface science is a broad, interdisciplinary subfield of surface science, where properties and processes at biological and synthetic surfaces and interfaces are investigated, and where biofunctional surfaces are fabricated. The need to study and to understand biological surfaces and interfaces in liquid environments provides sizable challenges as well as fascinating opportunities. Here, we report on recent progress in biological surface science that was described within the program assembled by the Biomaterial Interface Division of the Science and Technology of Materials, Interfaces and Processes (www.avs.org) during their 55th International Symposium and Exhibition held in Boston, October 19-24, 2008. The selected examples show that the rapid progress in nanoscience and nanotechnology, hand-in-hand with theory and simulation, provides increasingly sophisticated methods and tools to unravel the mechanisms and details of complex processes at biological surfaces and in-depth understanding of biomolecular surface interactions.

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

Method for the thermal characterization, visualization, and integrity evaluation of conducting material samples or complex structures

DOEpatents

Ortiz, Marcos G.

1992-01-01

A method for modeling a conducting material sample or structure (herein called a system) as at least two regions which comprise an electrical network of resistances, for measuring electric resistance between at least two selected pairs of external leads attached to the surface of the system, wherein at least one external lead is attached to the surface of each of the regions, and, using basic circuit theory, for translating measured resistances into temperatures or thermophysical properties in corresponding regions of the system.

Method for the thermal characterization, visualization, and integrity evaluation of conducting material samples or complex structures

DOEpatents

Ortiz, M.G.

1992-11-24

Disclosed is a method for modeling a conducting material sample or structure (herein called a system) as at least two regions which comprise an electrical network of resistances, for measuring electric resistance between at least two selected pairs of external leads attached to the surface of the system, wherein at least one external lead is attached to the surface of each of the regions, and, using basic circuit theory, for translating measured resistances into temperatures or thermophysical properties in corresponding regions of the system. 16 figs.

A DFT study on surface-enhanced Raman spectroscopy of aromatic dithiol derivatives adsorbed on gold nanojunctions

NASA Astrophysics Data System (ADS)

You, Tingting; Lang, Xiufeng; Huang, Anping; Yin, Penggang

2018-01-01

A computational study on aromatic dithiol derivatives (HS-Ar-X-Ar-SH, X = O, S, Se, NH, CH2, Ndbnd N, CHdbnd CH, Ctbnd C) interacting with gold cluster(s) was presented to investigate the chemical enhancement mechanism related to surface-enhanced Raman spectroscopy (SERS) for molecular junctions. Density functional theory (DFT) were performed on derivatives molecules as well as their single-end-linked (SEL) or double-end-linked (DEL) complexes for geometric, spectra, electronic and excitation properties, leading to discussions on dominant factor during SERS process. The resulted enhancement factors of SEL and DEL complexes exhibited specific dependency on linking atom or functional group between two phenyls, which was in accordance with the variation of polarizabilities and molecule-cluster transition energy.

Bird's eye view of black holes

NASA Astrophysics Data System (ADS)

Simien, Clayton

1998-03-01

Black hole theory can be quite complex, and from a mathematical point of view very abstract. However, from a bird's perspective its concepts and theories can be easily understood with the aid of a few fundamental ideas of physics. Black holes are just massive dead stars whose very existence originates from the ideas of the great mathematician and scientific pioneer, Pierre Laplace. These astrological wonders of the universe are currently governed by Einstein's General Theory of Relativity. It must be understood that the laws of the universe in accord with the black hole are only valid to its surface known as the horizon . After the horizon, the laws of physics are no longer valid. Consequently, science is replaced with imaginative ideas that are meaningfully probable through hypothetical assumptions.

Peptide interfaces with graphene: an emerging intersection of analytical chemistry, theory, and materials.

PubMed

Russell, Shane R; Claridge, Shelley A

2016-04-01

Because noncovalent interface functionalization is frequently required in graphene-based devices, biomolecular self-assembly has begun to emerge as a route for controlling substrate electronic structure or binding specificity for soluble analytes. The remarkable diversity of structures that arise in biological self-assembly hints at the possibility of equally diverse and well-controlled surface chemistry at graphene interfaces. However, predicting and analyzing adsorbed monolayer structures at such interfaces raises substantial experimental and theoretical challenges. In contrast with the relatively well-developed monolayer chemistry and characterization methods applied at coinage metal surfaces, monolayers on graphene are both less robust and more structurally complex, levying more stringent requirements on characterization techniques. Theory presents opportunities to understand early binding events that lay the groundwork for full monolayer structure. However, predicting interactions between complex biomolecules, solvent, and substrate is necessitating a suite of new force fields and algorithms to assess likely binding configurations, solvent effects, and modulations to substrate electronic properties. This article briefly discusses emerging analytical and theoretical methods used to develop a rigorous chemical understanding of the self-assembly of peptide-graphene interfaces and prospects for future advances in the field.

[Modeling and Simulation of Spectral Polarimetric BRDF].

PubMed

Ling, Jin-jiang; Li, Gang; Zhang, Ren-bin; Tang, Qian; Ye, Qiu

2016-01-01

Under the conditions of the polarized light, The reflective surface of the object is affected by many factors, refractive index, surface roughness, and so the angle of incidence. For the rough surface in the different wavelengths of light exhibit different reflection characteristics of polarization, a spectral polarimetric BRDF based on Kirchhof theory is proposee. The spectral model of complex refraction index is combined with refraction index and extinction coefficient spectral model which were got by using the known complex refraction index at different value. Then get the spectral model of surface roughness derived from the classical surface roughness measuring method combined with the Fresnel reflection function. Take the spectral model of refraction index and roughness into the BRDF model, then the spectral polarimetirc BRDF model is proposed. Compare the simulation results of the refractive index varies with wavelength, roughness is constant, the refraction index and roughness both vary with wavelength and origin model with other papers, it shows that, the spectral polarimetric BRDF model can show the polarization characteristics of the surface accurately, and can provide a reliable basis for the application of polarization remote sensing, and other aspects of the classification of substances.

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

Single metal catalysis: DFT and CAS modelling of species involved in the Fe cation assisted transformation of acetylene to benzene

NASA Astrophysics Data System (ADS)

Altun, Zikri; Bleda, Erdi; Trindle, Carl

2017-09-01

Gas phase conversion of acetylene to benzene, assisted by a single metal cation such as Fe(+), Ru(+) and Rh(+), offers an attractive prospect for application of computational modelling techniques to catalytic processes. Gas phase processes are not complicated by environmental effects and the participation of a single metal atom is a significant simplification. Still the process is complex, owing to the possibility of several low-energy spin states and the abundance of alternative structures. By density functional theory modelling using recently developed models with range and dispersion corrections, we locate and characterise a number of extreme points on the FeC6H6(+) surface, some of which have not been described previously. These include eta-1, eta-2 and eta-3 complexes of Fe(+) with the C4H4 ring. We identify new FeC6H6(+) structures as well, which may be landmarks for the Fe(+)-catalysed production of benzene from acetylene. The Fe(+) benzene complex is the most stable species on the FeC6H6 cation surface. With the abundant energy of complexation available in the isolated gas phase species, detachment of the Fe(+) and production of benzene can be efficient. We address the issue raised by other investigators whether multi-configurational self-consistent field methods are essential to the proper description of these systems. We find that the relative energy of intrinsically multi-determinant doublets is strongly affected, but judge that the density functional theory (DFT) description provides more accurate estimates of energetics and a more plausible reaction path.

Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water

DOE PAGES

Pham, Tuan Anh; Lee, Donghwa; Schwegler, Eric; ...

2014-11-17

By combining ab initio molecular dynamics simulations and many-body perturbation theory calculations of electronic energy levels, we determined the band edge positions of functionalized Si(111) surfaces in the presence of liquid water, with respect to vacuum and to water redox potentials. We considered surface terminations commonly used for Si photoelectrodes in water splitting experiments. We found that, when exposed to water, the semiconductor band edges were shifted by approximately 0.5 eV in the case of hydrophobic surfaces, irrespective of the termination. The effect of the liquid on band edge positions of hydrophilic surfaces was much more significant and determined bymore » a complex combination of structural and electronic effects. These include structural rearrangements of the semiconductor surfaces in the presence of water, changes in the orientation of interfacial water molecules with respect to the bulk liquid, and charge transfer at the interfaces, between the solid and the liquid. Our results showed that the use of many-body perturbation theory is key to obtain results in agreement with experiments; they also showed that the use of simple computational schemes that neglect the detailed microscopic structure of the solid–liquid interface may lead to substantial errors in predicting the alignment between the solid band edges and water redox potentials.« less

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H2

NASA Astrophysics Data System (ADS)

Denis-Alpizar, Otoniel; Kalugina, Yulia; Stoecklin, Thierry; Vera, Mario Hernández; Lique, François

2013-12-01

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H2. Ab initio calculations of the HCN-H2 van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN-H2 with the nitrogen pointing towards H2 at an intermolecular separation of 7.20 a0. The corresponding well depth is -195.20 cm-1. A secondary minimum of -183.59 cm-1 was found for a T-shape configuration with the H of HCN pointing to the center of mass of H2. We also determine the rovibrational energy levels of the HCN-para-H2 and HCN-ortho-H2 complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm-1 and 60.26 cm-1, respectively. The calculated ro-vibrational transitions in the HCN-H2 complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.

State-of-the-art thermochemical and kinetic computations for astrochemical complex organic molecules: formamide formation in cold interstellar clouds as a case study

PubMed Central

Vazart, Fanny; Calderini, Danilo; Puzzarini, Cristina; Skouteris, Dimitrios

2017-01-01

We propose an integrated computational strategy aimed at providing reliable thermochemical and kinetic information on the formation processes of astrochemical complex organic molecules. The approach involves state-of-the-art quantum-mechanical computations, second-order vibrational perturbation theory, and kinetic models based on capture and transition state theory together with the master equation approach. Notably, tunneling, quantum reflection, and leading anharmonic contributions are accounted for in our model. Formamide has been selected as a case study in view of its interest as a precursor in the abiotic amino acid synthesis. After validation of the level of theory chosen for describing the potential energy surface, we have investigated several pathways of the OH+CH2NH and NH2+HCHO reaction channels. Our results indicate that both reaction channels are essentially barrier-less (in the sense that all relevant transition states lie below or only marginally above the reactants) and can, therefore, occur under the low temperature conditions of interstellar objects provided that tunneling is taken into the proper account. PMID:27689448

Simulation of electron energy loss spectra of nanomaterials with linear-scaling density functional theory

DOE PAGES

Tait, E. W.; Ratcliff, L. E.; Payne, M. C.; ...

2016-04-20

Experimental techniques for electron energy loss spectroscopy (EELS) combine high energy resolution with high spatial resolution. They are therefore powerful tools for investigating the local electronic structure of complex systems such as nanostructures, interfaces and even individual defects. Interpretation of experimental electron energy loss spectra is often challenging and can require theoretical modelling of candidate structures, which themselves may be large and complex, beyond the capabilities of traditional cubic-scaling density functional theory. In this work, we present functionality to compute electron energy loss spectra within the onetep linear-scaling density functional theory code. We first demonstrate that simulated spectra agree withmore » those computed using conventional plane wave pseudopotential methods to a high degree of precision. The ability of onetep to tackle large problems is then exploited to investigate convergence of spectra with respect to supercell size. As a result, we apply the novel functionality to a study of the electron energy loss spectra of defects on the (1 0 1) surface of an anatase slab and determine concentrations of defects which might be experimentally detectable.« less

Global search in photoelectron diffraction structure determination using genetic algorithms

NASA Astrophysics Data System (ADS)

Viana, M. L.; Díez Muiño, R.; Soares, E. A.; Van Hove, M. A.; de Carvalho, V. E.

2007-11-01

Photoelectron diffraction (PED) is an experimental technique widely used to perform structural determinations of solid surfaces. Similarly to low-energy electron diffraction (LEED), structural determination by PED requires a fitting procedure between the experimental intensities and theoretical results obtained through simulations. Multiple scattering has been shown to be an effective approach for making such simulations. The quality of the fit can be quantified through the so-called R-factor. Therefore, the fitting procedure is, indeed, an R-factor minimization problem. However, the topography of the R-factor as a function of the structural and non-structural surface parameters to be determined is complex, and the task of finding the global minimum becomes tough, particularly for complex structures in which many parameters have to be adjusted. In this work we investigate the applicability of the genetic algorithm (GA) global optimization method to this problem. The GA is based on the evolution of species, and makes use of concepts such as crossover, elitism and mutation to perform the search. We show results of its application in the structural determination of three different systems: the Cu(111) surface through the use of energy-scanned experimental curves; the Ag(110)-c(2 × 2)-Sb system, in which a theory-theory fit was performed; and the Ag(111) surface for which angle-scanned experimental curves were used. We conclude that the GA is a highly efficient method to search for global minima in the optimization of the parameters that best fit the experimental photoelectron diffraction intensities to the theoretical ones.

Electrostatic theory of the assembly of PAMAM dendrimers and DNA.

PubMed

Perico, Angelo

2016-05-01

The electrostatic interactions mediated by counterions between a cationic PAMAM dendrimer, modelized as a sphere of radius and cationic surface charge highly increasing with generation, and a DNA, modelized as an anionic elastic line, are analytically calculated in the framework of condensation theory. Under these interactions the DNA is wrapped around the sphere. For excess phosphates relative to dendrimer primary amines, the free energy of the DNA-dendrimer complex displays an absolute minimum when the complex is weakly negatively overcharged. This overcharging opposes gene delivery. For a highly positive dendrimer and a DNA fixed by experimental conditions to a number of phosphates less than the number of dendrimer primary amines, excess amine charges, the dendrimer may at the same time bind stably DNA and interact with negative cell membranes to activate cell transfection in fair agreement with molecular simulations and experiments. © 2016 Wiley Periodicals, Inc.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

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

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Symmetry, Contingency, Complexity: Accommodating Uncertainty in Public Relations Theory.

ERIC Educational Resources Information Center

Murphy, Priscilla

2000-01-01

Explores the potential of complexity theory as a unifying theory in public relations, where scholars have recently raised problems involving flux, uncertainty, adaptiveness, and loss of control. Describes specific complexity-based methodologies and their potential for public relations studies. Offers an account of complexity theory, its…

Application of index number theory to the construction of a water quality index: aggregated nutrient loadings related to the areal extent of hypoxia in the northern Gulf of Mexico

USDA-ARS?s Scientific Manuscript database

The development of an index for description and monitoring of surface water quality has received significant attention in the water resources literature in recent years, primarily because of the increasing need for assessing water quality and the complex, multidimensional data collected from water q...

Sensitivity of the ocean overturning circulation to wind and mixing: theoretical scalings and global ocean models

NASA Astrophysics Data System (ADS)

Nikurashin, Maxim; Gunn, Andrew

2017-04-01

The meridional overturning circulation (MOC) is a planetary-scale oceanic flow which is of direct importance to the climate system: it transports heat meridionally and regulates the exchange of CO2 with the atmosphere. The MOC is forced by wind and heat and freshwater fluxes at the surface and turbulent mixing in the ocean interior. A number of conceptual theories for the sensitivity of the MOC to changes in forcing have recently been developed and tested with idealized numerical models. However, the skill of the simple conceptual theories to describe the MOC simulated with higher complexity global models remains largely unknown. In this study, we present a systematic comparison of theoretical and modelled sensitivity of the MOC and associated deep ocean stratification to vertical mixing and southern hemisphere westerlies. The results show that theories that simplify the ocean into a single-basin, zonally-symmetric box are generally in a good agreement with a realistic, global ocean circulation model. Some disagreement occurs in the abyssal ocean, where complex bottom topography is not taken into account by simple theories. Distinct regimes, where the MOC has a different sensitivity to wind or mixing, as predicted by simple theories, are also clearly shown by the global ocean model. The sensitivity of the Indo-Pacific, Atlantic, and global basins is analysed separately to validate the conceptual understanding of the upper and lower overturning cells in the theory.

Stably Stratified Atmospheric Boundary Layers

NASA Astrophysics Data System (ADS)

Mahrt, L.

2014-01-01

Atmospheric boundary layers with weak stratification are relatively well described by similarity theory and numerical models for stationary horizontally homogeneous conditions. With common strong stratification, similarity theory becomes unreliable. The turbulence structure and interactions with the mean flow and small-scale nonturbulent motions assume a variety of scenarios. The turbulence is intermittent and may no longer fully satisfy the usual conditions for the definition of turbulence. Nonturbulent motions include wave-like motions and solitary modes, two-dimensional vortical modes, microfronts, intermittent drainage flows, and a host of more complex structures. The main source of turbulence may not be at the surface, but rather may result from shear above the surface inversion. The turbulence is typically not in equilibrium with the nonturbulent motions, sometimes preventing the formation of an inertial subrange. New observational and analysis techniques are expected to advance our understanding of the very stable boundary layer.

Modeling the free energy surfaces of electron transfer in condensed phases

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.; Voth, Gregory A.

2000-10-01

We develop a three-parameter model of electron transfer (ET) in condensed phases based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states (a classical limit of the quantum Kubo-Toyozawa model). The exact analytical solution for the ET free energy surfaces demonstrates the following features: (i) the range of ET reaction coordinates is limited by a one-sided fluctuation band, (ii) the ET free energies are infinite outside the band, and (iii) the free energy surfaces are parabolic close to their minima and linear far from the minima positions. The model provides an analytical framework to map physical phenomena conflicting with the Marcus-Hush two-parameter model of ET. Nonlinear solvation, ET in polarizable charge-transfer complexes, and configurational flexibility of donor-acceptor complexes are successfully mapped onto the model. The present theory leads to a significant modification of the energy gap law for ET reactions.

Simulations of Turbulent Flow Over Complex Terrain Using an Immersed-Boundary Method

NASA Astrophysics Data System (ADS)

DeLeon, Rey; Sandusky, Micah; Senocak, Inanc

2018-02-01

We present an immersed-boundary method to simulate high-Reynolds-number turbulent flow over the complex terrain of Askervein and Bolund Hills under neutrally-stratified conditions. We reconstruct both the velocity and the eddy-viscosity fields in the terrain-normal direction to produce turbulent stresses as would be expected from the application of a surface-parametrization scheme based on Monin-Obukhov similarity theory. We find that it is essential to be consistent in the underlying assumptions for the velocity reconstruction and the eddy-viscosity relation to produce good results. To this end, we reconstruct the tangential component of the velocity field using a logarithmic velocity profile and adopt the mixing-length model in the near-surface turbulence model. We use a linear interpolation to reconstruct the normal component of the velocity to enforce the impermeability condition. Our approach works well for both the Askervein and Bolund Hills when the flow is attached to the surface, but shows slight disagreement in regions of flow recirculation, despite capturing the flow reversal.

Simulations of Turbulent Flow Over Complex Terrain Using an Immersed-Boundary Method

NASA Astrophysics Data System (ADS)

DeLeon, Rey; Sandusky, Micah; Senocak, Inanc

2018-06-01

We present an immersed-boundary method to simulate high-Reynolds-number turbulent flow over the complex terrain of Askervein and Bolund Hills under neutrally-stratified conditions. We reconstruct both the velocity and the eddy-viscosity fields in the terrain-normal direction to produce turbulent stresses as would be expected from the application of a surface-parametrization scheme based on Monin-Obukhov similarity theory. We find that it is essential to be consistent in the underlying assumptions for the velocity reconstruction and the eddy-viscosity relation to produce good results. To this end, we reconstruct the tangential component of the velocity field using a logarithmic velocity profile and adopt the mixing-length model in the near-surface turbulence model. We use a linear interpolation to reconstruct the normal component of the velocity to enforce the impermeability condition. Our approach works well for both the Askervein and Bolund Hills when the flow is attached to the surface, but shows slight disagreement in regions of flow recirculation, despite capturing the flow reversal.

Preliminary study of the effect of the turbulent flow field around complex surfaces on their acoustic characteristics

NASA Technical Reports Server (NTRS)

Olsen, W. A.; Boldman, D.

1978-01-01

Fairly extensive measurements have been conducted of the turbulent flow around various surfaces as a basis for a study of the acoustic characteristics involved. In the experiments the flow from a nozzle was directed upon various two-dimensional surface configurations such as the three-flap model. A turbulent flow field description is given and an estimate of the acoustic characteristics is provided. The developed equations are based upon fundamental theories for simple configurations having simple flows. Qualitative estimates are obtained regarding the radiation pattern and the velocity power law. The effect of geometry and turbulent flow distribution on the acoustic emission from simple configurations are discussed.

Computational characterization of ordered nanostructured surfaces

NASA Astrophysics Data System (ADS)

Mohieddin Abukhdeir, Nasser

2016-08-01

A vital and challenging task for materials researchers is to determine relationships between material characteristics and desired properties. While the measurement and assessment of material properties can be complex, quantitatively characterizing their structure is frequently a more challenging task. This issue is magnified for materials researchers in the areas of nanoscience and nanotechnology, where material structure is further complicated by phenomena such as self-assembly, collective behavior, and measurement uncertainty. Recent progress has been made in this area for both self-assembled and nanostructured surfaces due to increasing accessibility of imaging techniques at the nanoscale. In this context, recent advances in nanomaterial surface structure characterization are reviewed including the development of new theory and image processing methods.

Surface-modified TiO2 powders with phenol derivatives: A comparative DFT and experimental study

NASA Astrophysics Data System (ADS)

Sredojević, Dušan N.; Kovač, Tijana; Džunuzović, Enis; Ðorđević, Vesna; Grgur, Branimir N.; Nedeljković, Jovan M.

2017-10-01

The charge transfer complex formation between TiO2 powder and variety of phenol derivatives (phenol, 4-nitrophenol, 4-bromophenol, 4-tert-butylphenol, hydroquinone) was achieved. The red-shift of optical absorption was observed upon surface modification of TiO2 powders with phenol derivatives. The influence of substituent functional groups in para position on the optical band gap and conduction band edge of inorganic/organic hybrids was studied using reflection spectroscopy and cyclic voltammetry. The experimental findings were supported by density functional theory calculations. The measured reflection spectra of surface-modified TiO2 powders with phenol derivatives were compared with calculated electronic excitation spectra of corresponding model systems.

Lineshape theory of pigment-protein complexes: How the finite relaxation time of nuclei influences the exciton relaxation-induced lifetime broadening

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

Dinh, Thanh-Chung; Renger, Thomas, E-mail: thomas.renger@jku.at

2016-07-21

In pigment-protein complexes, often the excited states are partially delocalized and the exciton-vibrational coupling in the basis of delocalized states contains large diagonal and small off-diagonal elements. This inequality may be used to introduce potential energy surfaces (PESs) of exciton states and to treat the inter-PES coupling in Markov and secular approximations. The resulting lineshape function consists of a Lorentzian peak that is broadened by the finite lifetime of the exciton states caused by the inter-PES coupling and a vibrational sideband that results from the mutual displacement of the excitonic PESs with respect to that of the ground state. Somore » far analytical expressions have been derived that relate the exciton relaxation-induced lifetime broadening to the Redfield [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)] or modified Redfield [M. Schröder, U. Kleinekathöfer, and M. Schreiber, J. Chem. Phys. 124, 084903 (2006)] rate constants of exciton relaxation, assuming that intra-PES nuclear relaxation is fast compared to inter-PES transfer. Here, we go beyond this approximation and provide an analytical expression, termed Non-equilibrium Modified Redfield (NeMoR) theory, for the lifetime broadening that takes into account the finite nuclear relaxation time. In an application of the theory to molecular dimers, we find that, for a widely used experimental spectral density of the exciton-vibrational coupling of pigment-protein complexes, the NeMoR spectrum at low-temperatures (T < 150 K) is better approximated by Redfield than by modified Redfield theory. At room temperature, the lifetime broadening obtained with Redfield theory underestimates the NeMoR broadening, whereas modified Redfield theory overestimates it by a similar amount. A fortuitous error compensation in Redfield theory is found to explain the good performance of this theory at low temperatures. Since steady state spectra of PPCs are often measured at low temperatures, Redfield theory still provides a numerically efficient alternative to NeMoR theory. At higher temperatures, we suggest to use NeMoR theory, because it has the same numerical costs as modified Redfield theory, but is more accurate.« less

Experimental analysis of bidirectional reflectance distribution function cross section conversion term in direction cosine space.

PubMed

Butler, Samuel D; Nauyoks, Stephen E; Marciniak, Michael A

2015-06-01

Of the many classes of bidirectional reflectance distribution function (BRDF) models, two popular classes of models are the microfacet model and the linear systems diffraction model. The microfacet model has the benefit of speed and simplicity, as it uses geometric optics approximations, while linear systems theory uses a diffraction approach to compute the BRDF, at the expense of greater computational complexity. In this Letter, nongrazing BRDF measurements of rough and polished surface-reflecting materials at multiple incident angles are scaled by the microfacet cross section conversion term, but in the linear systems direction cosine space, resulting in great alignment of BRDF data at various incident angles in this space. This results in a predictive BRDF model for surface-reflecting materials at nongrazing angles, while avoiding some of the computational complexities in the linear systems diffraction model.

Theories of how the school environment impacts on student health: systematic review and synthesis.

PubMed

Bonell, C P; Fletcher, A; Jamal, F; Wells, H; Harden, A; Murphy, S; Thomas, J

2013-11-01

Public-health interventions informed by theory can be more effective but complex interventions often use insufficiently complex theories. We systematically reviewed theories of how school environments influence health. We included 37 reports drawing on 24 theories. Narrative synthesis summarised and categorised theories. We then produced an integrated theory of school environment influences on student health. This integrated theory could inform complex interventions such as health promoting schools programmes. Using systematic reviews to develop theories of change might be useful for other types of 'complex' public-health interventions addressing risks at the individual and community levels. © 2013 Published by Elsevier Ltd.

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

PubMed

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S; Schott, Jacques

2010-08-03

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

A detailed study of intermolecular interactions, electronic and vibrational properties of the metal complex bis(uracilato)diammine copper(ii) dihydrate

NASA Astrophysics Data System (ADS)

Gramajo Feijoo, M.; Fernández-Liencres, M. P.; Gil, D. M.; Gómez, M. I.; Ben Altabef, A.; Navarro, A.; Tuttolomondo, M. E.

2018-03-01

Density Functional Theory (DFT) calculations were performed with the aim of investigating the vibrational, electronic and structural properties of [Cu(uracilato-N1)2 (NH3)2]ṡ2H2O complex. The IR and Raman spectra were recorded leading to a complete analysis of the normal modes of vibration of the metal complex. A careful study of the intermolecular interactions observed in solid state was performed by using the Hirshfeld surface analysis and their associated 2D fingerprint plots. The results indicated that the crystal packing is stabilized by Nsbnd H⋯O hydrogen bonds and π-stacking interactions. In addition, Csbnd H···π interactions were also observed. Time-dependent density functional theory (TD-DFT) calculations revealed that all the low-lying electronic states correspond to a mixture of intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions. Finally, Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analysis were performed to shed light on the intermolecular interactions in the coordination sphere.

Gauged Q-balls

NASA Technical Reports Server (NTRS)

Lee, Kimyeong; Stein-Schabes, Jaime A.; Watkins, Richard; Widrow, Lawrence M.

1988-01-01

Classical non-topological soliton configurations are considered within the theory of a complex scalar field with a gauged U symmetry. Their existence and stability against dispersion are demonstrated and some of their properties are investigated analytically and numerically. The soliton configuration is such that inside the soliton the local U symmetry is broken, the gauge field becomes massive and for a range of values of the coupling constants the soliton becomes a superconductor pushing the charge to the surface. Furthermore, because of the repulsive Coulomb force, there is a maximum size for these objects, making impossible the existence of Q-matter in bulk form. Also briefly discussed are solitons with fermions in a U gauge theory.

The contact sport of rough surfaces

NASA Astrophysics Data System (ADS)

Carpick, Robert W.

2018-01-01

Describing the way two surfaces touch and make contact may seem simple, but it is not. Fully describing the elastic deformation of ideally smooth contacting bodies, under even low applied pressure, involves second-order partial differential equations and fourth-rank elastic constant tensors. For more realistic rough surfaces, the problem becomes a multiscale exercise in surface-height statistics, even before including complex phenomena such as adhesion, plasticity, and fracture. A recent research competition, the “Contact Mechanics Challenge” (1), was designed to test various approximate methods for solving this problem. A hypothetical rough surface was generated, and the community was invited to model contact with this surface with competing theories for the calculation of properties, including contact area and pressure. A supercomputer-generated numerical solution was kept secret until competition entries were received. The comparison of results (2) provides insights into the relative merits of competing models and even experimental approaches to the problem.

Lead and selenite adsorption at water–goethite interfaces from first principles

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

Leung, Kevin; Criscenti, Louise J.

Here, the complexation of toxic and/or radioactive ions on to mineral surfaces is an important topic in geochemistry. We apply periodic-boundary-conditions density functional theory (DFT) molecular dynamics simulations to examine the coordination of Pb(II),more » $${\\rm SeO}_3^{2-}$$ , and their contact ion pairs to goethite (1 0 1) and (2 1 0) surfaces. The multitude of Pb(II) adsorption sites and possibility of Pb(II)-induced FeOH deprotonation make this a complex problem. At surface sites where Pb(II) is coordinated to three FeO and/or FeOH groups, and with judicious choices of FeOH surface group protonation states, the predicted Fe–Pb distances are in good agreement with EXAFS measurements. Trajectories where Pb(II) is in part coordinated to only two surface Fe–O groups exhibit larger fluctuations in Pb–O distances. Pb(II)/$${\\rm SeO}_3^{2-}$$ contact ion pairs are at least metastable on goethite (2 1 0) surfaces if the $${\\rm SeO}_3^{2-}$$ has a monodentate Se–O–Fe bond. Our DFT-based molecular dynamics calculations are a prerequisite for calculations of finite temperature equilibrium binding constants of Pb(II) and Pb(II)/$${\\rm SeO}_3^{2-}$$ ion pairs to goethite adsorption sites.« less

Lead and selenite adsorption at water–goethite interfaces from first principles

DOE PAGES

Leung, Kevin; Criscenti, Louise J.

2017-08-04

Here, the complexation of toxic and/or radioactive ions on to mineral surfaces is an important topic in geochemistry. We apply periodic-boundary-conditions density functional theory (DFT) molecular dynamics simulations to examine the coordination of Pb(II),more » $${\\rm SeO}_3^{2-}$$ , and their contact ion pairs to goethite (1 0 1) and (2 1 0) surfaces. The multitude of Pb(II) adsorption sites and possibility of Pb(II)-induced FeOH deprotonation make this a complex problem. At surface sites where Pb(II) is coordinated to three FeO and/or FeOH groups, and with judicious choices of FeOH surface group protonation states, the predicted Fe–Pb distances are in good agreement with EXAFS measurements. Trajectories where Pb(II) is in part coordinated to only two surface Fe–O groups exhibit larger fluctuations in Pb–O distances. Pb(II)/$${\\rm SeO}_3^{2-}$$ contact ion pairs are at least metastable on goethite (2 1 0) surfaces if the $${\\rm SeO}_3^{2-}$$ has a monodentate Se–O–Fe bond. Our DFT-based molecular dynamics calculations are a prerequisite for calculations of finite temperature equilibrium binding constants of Pb(II) and Pb(II)/$${\\rm SeO}_3^{2-}$$ ion pairs to goethite adsorption sites.« less

Achieving DFT accuracy with a machine-learning interatomic potential: Thermomechanics and defects in bcc ferromagnetic iron

NASA Astrophysics Data System (ADS)

Dragoni, Daniele; Daff, Thomas D.; Csányi, Gábor; Marzari, Nicola

2018-01-01

We show that the Gaussian Approximation Potential (GAP) machine-learning framework can describe complex magnetic potential energy surfaces, taking ferromagnetic iron as a paradigmatic challenging case. The training database includes total energies, forces, and stresses obtained from density-functional theory in the generalized-gradient approximation, and comprises approximately 150,000 local atomic environments, ranging from pristine and defected bulk configurations to surfaces and generalized stacking faults with different crystallographic orientations. We find the structural, vibrational, and thermodynamic properties of the GAP model to be in excellent agreement with those obtained directly from first-principles electronic-structure calculations. There is good transferability to quantities, such as Peierls energy barriers, which are determined to a large extent by atomic configurations that were not part of the training set. We observe the benefit and the need of using highly converged electronic-structure calculations to sample a target potential energy surface. The end result is a systematically improvable potential that can achieve the same accuracy of density-functional theory calculations, but at a fraction of the computational cost.

Application of simplified Complexity Theory concepts for healthcare social systems to explain the implementation of evidence into practice.

PubMed

Chandler, Jacqueline; Rycroft-Malone, Jo; Hawkes, Claire; Noyes, Jane

2016-02-01

To examine the application of core concepts from Complexity Theory to explain the findings from a process evaluation undertaken in a trial evaluating implementation strategies for recommendations about reducing surgical fasting times. The proliferation of evidence-based guidance requires a greater focus on its implementation. Theory is required to explain the complex processes across the multiple healthcare organizational levels. This social healthcare context involves the interaction between professionals, patients and the organizational systems in care delivery. Complexity Theory may provide an explanatory framework to explain the complexities inherent in implementation in social healthcare contexts. A secondary thematic analysis of qualitative process evaluation data informed by Complexity Theory. Seminal texts applying Complexity Theory to the social context were annotated, key concepts extracted and core Complexity Theory concepts identified. These core concepts were applied as a theoretical lens to provide an explanation of themes from a process evaluation of a trial evaluating the implementation of strategies to reduce surgical fasting times. Sampled substantive texts provided a representative spread of theoretical development and application of Complexity Theory from late 1990's-2013 in social science, healthcare, management and philosophy. Five Complexity Theory core concepts extracted were 'self-organization', 'interaction', 'emergence', 'system history' and 'temporality'. Application of these concepts suggests routine surgical fasting practice is habituated in the social healthcare system and therefore it cannot easily be reversed. A reduction to fasting times requires an incentivised new approach to emerge in the surgical system's priority of completing the operating list. The application of Complexity Theory provides a useful explanation for resistance to change fasting practice. Its utility in implementation research warrants further attention and evaluation. © 2015 John Wiley & Sons Ltd.

Operational Shock Complexity Theory

DTIC Science & Technology

2005-05-26

Theory : Recommendations For The National Strategy To Defeat Terrorism.” Student Issue Paper, Center for Strategic Leadership , US Army War College, July...Lens of Complexity Theory : Recommendations For The National Strategy To Defeat Terrorism.” (Student Issue Paper, Center for Strategic Leadership , US... Leadership Complexity theory affects the training of leaders. With the enemy system able to develop its complexity either through interaction with US

Turbulence structure of the near-surface boundary layer in complex terrain

NASA Astrophysics Data System (ADS)

Sfyri, Eleni; Rotach, Mathias Walter; Stiperski, Ivana; Bosveld, Fred; Lehner, Manuela; Obleitner, Friedrich

2017-04-01

Monin-Obukhov Similarity Theory (MOST) is evaluated in two cases: truly complex terrain (CT) and horizontally inhomogeneous and flat (HIF) terrain. CT data are derived from 5 measurement sites, which differ in terms of slope, orientation and surface roughness at the Inn Valley of Austria (i-Box) and HIF data come from one measurement site at the Cabauw experimental site (Netherlands). The applicability of the surface-layer, 'ideal' similarity relations is examined for both data-sets and the non-dimensional variances of temperature and humidity as a function of stability (z/L, where L is the Obukhov length) are compared for each type of terrain. Large deviations from the reference curves in case of temperature are observed in both CT and HIF, leading to the conclusion that these deviations are not due to the complex terrain but due to inappropriate near-neutral description of the reference curves. It is found here that the non-dimensional temperature variance exhibits a -1 slope in the near-neutral region, for both CT and HIF datasets. In addition, the constant-fluxes hypothesis of the MOST is evaluated at one i-Box site. It is found that only about 1% of the data show constant momentum, sensible and latent heat fluxes with height. Therefore, local scaling instead of surface layer scaling is being used in this study.

Dannie Heineman Prize for Mathematical Physics: Applying mathematical techniques to solve important problems in quantum theory

NASA Astrophysics Data System (ADS)

Bender, Carl

2017-01-01

The theory of complex variables is extremely useful because it helps to explain the mathematical behavior of functions of a real variable. Complex variable theory also provides insight into the nature of physical theories. For example, it provides a simple and beautiful picture of quantization and it explains the underlying reason for the divergence of perturbation theory. By using complex-variable methods one can generalize conventional Hermitian quantum theories into the complex domain. The result is a new class of parity-time-symmetric (PT-symmetric) theories whose remarkable physical properties have been studied and verified in many recent laboratory experiments.

Surface field theories of point group symmetry protected topological phases

NASA Astrophysics Data System (ADS)

Huang, Sheng-Jie; Hermele, Michael

2018-02-01

We identify field theories that describe the surfaces of three-dimensional bosonic point group symmetry protected topological (pgSPT) phases. The anomalous nature of the surface field theories is revealed via a dimensional reduction argument. Specifically, we study three different surface field theories. The first field theory is quantum electrodynamics in three space-time dimensions (QED3) with four flavors of fermions. We show this theory can describe the surfaces of a majority of bosonic pgSPT phases protected by a single mirror reflection, or by Cn v point group symmetry for n =2 ,3 ,4 ,6 . The second field theory is a variant of QED3 with charge-1 and charge-3 Dirac fermions. This field theory can describe the surface of a reflection symmetric pgSPT phase built by placing an E8 state on the mirror plane. The third field theory is an O (4 ) nonlinear sigma model with a topological theta term at θ =π , or, equivalently, a noncompact CP1 model. Using a coupled wire construction, we show this is a surface theory for bosonic pgSPT phases with U (1 ) ×Z2P symmetry. For the latter two field theories, we discuss the connection to gapped surfaces with topological order. Moreover, we conjecture that the latter two field theories can describe surfaces of more general bosonic pgSPT phases with Cn v point group symmetry.

Visual complexity: a review.

PubMed

Donderi, Don C

2006-01-01

The idea of visual complexity, the history of its measurement, and its implications for behavior are reviewed, starting with structuralism and Gestalt psychology at the beginning of the 20th century and ending with visual complexity theory, perceptual learning theory, and neural circuit theory at the beginning of the 21st. Evidence is drawn from research on single forms, form and texture arrays and visual displays. Form complexity and form probability are shown to be linked through their reciprocal relationship in complexity theory, which is in turn shown to be consistent with recent developments in perceptual learning and neural circuit theory. Directions for further research are suggested.

Selective adsorption of a supramolecular structure on flat and stepped gold surfaces

NASA Astrophysics Data System (ADS)

Peköz, Rengin; Donadio, Davide

2018-04-01

Halogenated aromatic molecules assemble on surfaces forming both hydrogen and halogen bonds. Even though these systems have been intensively studied on flat metal surfaces, high-index vicinal surfaces remain challenging, as they may induce complex adsorbate structures. The adsorption of 2,6-dibromoanthraquinone (2,6-DBAQ) on flat and stepped gold surfaces is studied by means of van der Waals corrected density functional theory. Equilibrium geometries and corresponding adsorption energies are systematically investigated for various different adsorption configurations. It is shown that bridge sites and step edges are the preferred adsorption sites for single molecules on flat and stepped surfaces, respectively. The role of van der Waals interactions, halogen bonds and hydrogen bonds are explored for a monolayer coverage of 2,6-DBAQ molecules, revealing that molecular flexibility and intermolecular interactions stabilize two-dimensional networks on both flat and stepped surfaces. Our results provide a rationale for experimental observation of molecular carpeting on high-index vicinal surfaces of transition metals.

The Characterization of Atmospheric Boundary Layer Depth and Turbulence in a Mixed Rural and Urban Convective Environment

NASA Astrophysics Data System (ADS)

Hicks, Micheal M.

A comprehensive analysis of surface-atmosphere flux exchanges over a mixed rural and urban convective environment is conducted at Howard University Beltsville, MD Research Campus. This heterogeneous site consists of rural, suburban and industrial surface covers to its south, east and west, within a 2 km radius of a flux sensor. The eddy covariance method is utilized to estimate surface-atmosphere flux exchanges of momentum, heat and moisture. The attributes of these surface flux exchanges are contrasted to those of classical homogeneous sites and assessed for accuracy, to evaluate the following: (I) their similarity to conventional convective boundary layer (CBL) processes and (II) their representativeness of the surrounding environment's turbulent properties. Both evaluations are performed as a function of upwind surface conditions. In particular, the flux estimates' obedience to spectrum power laws and similarity theory relationships is used for performing the first evaluation, and their ability to close the surface energy balance and accurately model CBL heights is used for the latter. An algorithm that estimates atmospheric boundary layer heights from observed lidar extinction backscatter was developed, tested and applied in this study. The derived lidar based CBL heights compared well with those derived from balloon borne soundings, with an overall Pearson correlation coefficient and standard deviation of 0.85 and 223 m, respectively. This algorithm assisted in the evaluation of the response of CBL processes to surface heterogeneity, by deriving high temporal CBL heights and using them as independent references of the surrounding area averaged sensible heat fluxes. This study found that the heterogeneous site under evaluation was rougher than classical homogeneous sites, with slower dissipation rates of turbulent kinetic energy. Flux measurements downwind of the industrial complexes exhibited enhanced efficiency in surface-atmosphere momentum, heat, and moisture transport relative to their similarity theory predictions. In addition, these enhanced heat flux estimates ingested into the CBL slab model overestimated observed CBL heights. More spatial flux observations are needed to better understand the role that the industrial complexes are playing in enhancing the efficiency of turbulent processes, which may have important implications on the role humans are assuming in regional climate change.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

PRODUCTION OF SOUND BY UNSTEADY THROTTLING OF FLOW INTO A RESONANT CAVITY, WITH APPLICATION TO VOICED SPEECH

PubMed Central

Howe, M. S.; McGowan, R. S.

2011-01-01

An analysis is made of the sound generated by the time-dependent throttling of a nominally steady stream of air through a small orifice into a flow-through resonant cavity. This is exemplified by the production of voiced speech, where air from the lungs enters the vocal tract through the glottis at a time variable volume flow rate Q(t) controlled by oscillations of the glottis cross-section. Voicing theory has hitherto determined Q from a heuristic, reduced complexity ‘Fant’ differential equation (G. Fant, Acoustic Theory of Speech Production, 1960). A new self-consistent, integro-differential form of this equation is derived in this paper using the theory of aerodynamic sound, with full account taken of the back-reaction of the resonant tract on the glottal flux Q. The theory involves an aeroacoustic Green’s function (G) for flow-surface interactions in a time-dependent glottis, so making the problem non-self-adjoint. In complex problems of this type it is not usually possible to obtain G in an explicit analytic form. The principal objective of the paper is to show how the Fant equation can still be derived in such cases from a consideration of the equation of aerodynamic sound and from the adjoint of the equation governing G in the neighbourhood of the ‘throttle’. The theory is illustrated by application to the canonical problem of throttled flow into a Helmholtz resonator. PMID:21666824

Theoretical insights of proton transfer and hydrogen bonded charge transfer complex of 1,2-dimethylimidazolium-3,5-dinitrobenzoate crystal

NASA Astrophysics Data System (ADS)

Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-04-01

Proton transfer (PT) and hydrogen bonded charge transfer (HBCT) 1:1 complex of 1,2-dimethylimidazole (DMI) and 3,5-dinitrobenzoic acid (DNBA) have been theoretically analyzed and compared with reported experimental results. Both the structures in the isolated gaseous state have been optimized at DFT/B3LYP/6-311G(d,p) level of theory and further, the PT energy barrier has been calculated from potential energy surface scan. Along with structural investigations, theoretical vibrational spectra have been inspected and compared with the FTIR spectrum. Moreover, frontier molecular analysis has also been carried out.

[Analysis of Conformational Features of Watson-Crick Duplex Fragments by Molecular Mechanics and Quantum Mechanics Methods].

PubMed

Poltev, V I; Anisimov, V M; Sanchez, C; Deriabina, A; Gonzalez, E; Garcia, D; Rivas, F; Polteva, N A

2016-01-01

It is generally accepted that the important characteristic features of the Watson-Crick duplex originate from the molecular structure of its subunits. However, it still remains to elucidate what properties of each subunit are responsible for the significant characteristic features of the DNA structure. The computations of desoxydinucleoside monophosphates complexes with Na-ions using density functional theory revealed a pivotal role of DNA conformational properties of single-chain minimal fragments in the development of unique features of the Watson-Crick duplex. We found that directionality of the sugar-phosphate backbone and the preferable ranges of its torsion angles, combined with the difference between purines and pyrimidines. in ring bases, define the dependence of three-dimensional structure of the Watson-Crick duplex on nucleotide base sequence. In this work, we extended these density functional theory computations to the minimal' fragments of DNA duplex, complementary desoxydinucleoside monophosphates complexes with Na-ions. Using several computational methods and various functionals, we performed a search for energy minima of BI-conformation for complementary desoxydinucleoside monophosphates complexes with different nucleoside sequences. Two sequences are optimized using ab initio method at the MP2/6-31++G** level of theory. The analysis of torsion angles, sugar ring puckering and mutual base positions of optimized structures demonstrates that the conformational characteristic features of complementary desoxydinucleoside monophosphates complexes with Na-ions remain within BI ranges and become closer to the corresponding characteristic features of the Watson-Crick duplex crystals. Qualitatively, the main characteristic features of each studied complementary desoxydinucleoside monophosphates complex remain invariant when different computational methods are used, although the quantitative values of some conformational parameters could vary lying within the limits typical for the corresponding family. We observe that popular functionals in density functional theory calculations lead to the overestimated distances between base pairs, while MP2 computations and the newer complex functionals produce the structures that have too close atom-atom contacts. A detailed study of some complementary desoxydinucleoside monophosphate complexes with Na-ions highlights the existence of several energy minima corresponding to BI-conformations, in other words, the complexity of the relief pattern of the potential energy surface of complementary desoxydinucleoside monophosphate complexes. This accounts for variability of conformational parameters of duplex fragments with the same base sequence. Popular molecular mechanics force fields AMBER and CHARMM reproduce most of the conformational characteristics of desoxydinucleoside monophosphates and their complementary complexes with Na-ions but fail to reproduce some details of the dependence of the Watson-Crick duplex conformation on the nucleotide sequence.

Tribology theory versus experiment

NASA Technical Reports Server (NTRS)

Ferrante, John

1987-01-01

Tribology, the study of friction and wear of materials, has achieved a new interest because of the need for energy conservation. Fundamental understanding of this field is very complex and requires a knowledge of solid-state physics, material science, chemistry, and mechanical engineering. This paper is meant to be didactic in nature and outlines some of the considerations needed for a tribology research program. The approach is first to present a simple model, a field emission tip in contact with a flat surface, in order to elucidate important considerations, such as contact area, mechanical deformations, and interfacial bonding. Then examples from illustrative experiments are presented. Finally, the current status of physical theories concerning interfacial bonding are presented.

Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components.

PubMed

Makarewicz, Jan; Shirkov, Leonid

2016-05-28

The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy De of 392 cm(-1) is close to that of 387 cm(-1) calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, De for PAr becomes slightly lower than De for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

Setting the Context for Using Complexity Theory in Evaluation: Boundaries, Governance and Utilisation

ERIC Educational Resources Information Center

Walton, Mat

2016-01-01

Recent literature has usefully explored the application of complexity theory to evaluation. However, there is little discussion of the contextual conditions in applying complexity theory. Drawing upon a single complexity-consistent public health programme evaluation and subsequent policy decisions, this paper considers how programme framing and…

Optimal Mass Transport for Shape Matching and Comparison

PubMed Central

Su, Zhengyu; Wang, Yalin; Shi, Rui; Zeng, Wei; Sun, Jian; Luo, Feng; Gu, Xianfeng

2015-01-01

Surface based 3D shape analysis plays a fundamental role in computer vision and medical imaging. This work proposes to use optimal mass transport map for shape matching and comparison, focusing on two important applications including surface registration and shape space. The computation of the optimal mass transport map is based on Monge-Brenier theory, in comparison to the conventional method based on Monge-Kantorovich theory, this method significantly improves the efficiency by reducing computational complexity from O(n2) to O(n). For surface registration problem, one commonly used approach is to use conformal map to convert the shapes into some canonical space. Although conformal mappings have small angle distortions, they may introduce large area distortions which are likely to cause numerical instability thus resulting failures of shape analysis. This work proposes to compose the conformal map with the optimal mass transport map to get the unique area-preserving map, which is intrinsic to the Riemannian metric, unique, and diffeomorphic. For shape space study, this work introduces a novel Riemannian framework, Conformal Wasserstein Shape Space, by combing conformal geometry and optimal mass transport theory. In our work, all metric surfaces with the disk topology are mapped to the unit planar disk by a conformal mapping, which pushes the area element on the surface to a probability measure on the disk. The optimal mass transport provides a map from the shape space of all topological disks with metrics to the Wasserstein space of the disk and the pullback Wasserstein metric equips the shape space with a Riemannian metric. We validate our work by numerous experiments and comparisons with prior approaches and the experimental results demonstrate the efficiency and efficacy of our proposed approach. PMID:26440265

Anisotropic surface physicochemical properties of spodumene and albite crystals: Implications for flotation separation

NASA Astrophysics Data System (ADS)

Xu, Longhua; Peng, Tiefeng; Tian, Jia; Lu, Zhongyuan; Hu, Yuehua; Sun, Wei

2017-12-01

Aluminosilicate minerals (e.g., spodumene, albite) have complex crystal structures and similar surface chemistries, but they have poor selectivity compared to traditional fatty acid collectors, making flotation separation difficult. Previous research has mainly considered the mineral crystal structure as a whole. In contrast, the surface characteristics at the atomic level and the effects of different crystal interfaces on the flotation behavior have rarely been investigated. This study focuses on investigating the surface anisotropy quantitatively, including the chemical bond characteristics, surface energies, and broken bond densities, using density functional theory and classical theoretical calculations. In addition, the anisotropy of the surface wettability and adsorption characteristics were examined using contact angle, zeta potential, and Fourier-transform infrared measurements. Finally, these surface anisotropies with different flotation behaviors were investigated and interpreted using molecular dynamics simulations, scanning electron microscopy, and X-ray photoelectron spectroscopy. This systematic research offers new ideas concerning the selective grinding and stage flotation of aluminosilicate minerals based on the crystal characteristics.

Intercalation of Transition Metals into Stacked Benzene Rings: A Model Study of the Intercalation of Transition Metals into Bilayered Graphene.

PubMed

Youn, Il Seung; Kim, Dong Young; Singh, N Jiten; Park, Sung Woo; Youn, Jihee; Kim, Kwang S

2012-01-10

Structures of neutral metal-dibenzene complexes, M(C6H6)2 (M = Sc-Zn), are investigated by using Møller-Plesset second order perturbation theory (MP2). The benzene molecules change their conformation and shape upon complexation with the transition metals. We find two types of structures: (i) stacked forms for early transition metal complexes and (ii) distorted forms for late transition metal ones. The benzene molecules and the metal atom are bound together by δ bonds which originate from the interaction of π-MOs and d orbitals. The binding energy shows a maximum for Cr(C6H6)2, which obeys the 18-electron rule. It is noticeable that Mn(C6H6)2, a 19-electron complex, manages to have a stacked structure with an excess electron delocalized. For other late transition metal complexes having more than 19 electrons, the benzene molecules are bent or stray away from each other to reduce the electron density around a metal atom. For the early transition metals, the M(C6H6) complexes are found to be more weakly bound than M(C6H6)2. This is because the M(C6H6) complexes do not have enough electrons to satisfy the 18-electron rule, and so the M(C6H6)2 complexes generally tend to have tighter binding with a shorter benzene-metal length than the M(C6H6) complexes, which is quite unusual. The present results could provide a possible explanation of why on the Ni surface graphene tends to grow in a few layers, while on the Cu surface the weak interaction between the copper surface and graphene allows for the formation of a single layer of graphene, in agreement with chemical vapor deposition experiments.

Supersymmetric Casimir energy and SL(3,Z) transformations

NASA Astrophysics Data System (ADS)

Brünner, Frederic; Regalado, Diego; Spiridonov, Vyacheslav P.

2017-07-01

We provide a recipe to extract the supersymmetric Casimir energy of theories defined on primary Hopf surfaces directly from the superconformal index. It involves an SL(3,Z) transformation acting on the complex structure moduli of the background geometry. In particular, the known relation between Casimir energy, index and partition function emerges naturally from this framework, allowing rewriting of the latter as a modified elliptic hypergeometric integral. We show this explicitly for N=1 SQCD and N=4 supersymmetric Yang-Mills theory for all classical gauge groups, and conjecture that it holds more generally. We also use our method to derive an expression for the Casimir energy of the nonlagrangian N=2 SCFT with E6 flavour symmetry. Furthermore, we predict an expression for Casimir energy of the N=1 SP(2N) theory with SU(8) × U(1) flavour symmetry that is part of a multiple duality network, and for the doubled N=1 theory with enhanced E7 flavour symmetry.

Analysis of current-driven oscillatory dynamics of single-layer homoepitaxial islands on crystalline conducting substrates

NASA Astrophysics Data System (ADS)

Dasgupta, Dwaipayan; Kumar, Ashish; Maroudas, Dimitrios

2018-03-01

We report results of a systematic study on the complex oscillatory current-driven dynamics of single-layer homoepitaxial islands on crystalline substrate surfaces and the dependence of this driven dynamical behavior on important physical parameters, including island size, substrate surface orientation, and direction of externally applied electric field. The analysis is based on a nonlinear model of driven island edge morphological evolution that accounts for curvature-driven edge diffusion, edge electromigration, and edge diffusional anisotropy. Using a linear theory of island edge morphological stability, we calculate a critical island size at which the island's equilibrium edge shape becomes unstable, which sets a lower bound for the onset of time-periodic oscillatory dynamical response. Using direct dynamical simulations, we study the edge morphological dynamics of current-driven single-layer islands at larger-than-critical size, and determine the actual island size at which the migrating islands undergo a transition from steady to time-periodic asymptotic states through a subcritical Hopf bifurcation. At the highest symmetry of diffusional anisotropy examined, on {111} surfaces of face-centered cubic crystalline substrates, we find that more complex stable oscillatory states can be reached through period-doubling bifurcation at island sizes larger than those at the Hopf points. We characterize in detail the island morphology and dynamical response at the stable time-periodic asymptotic states, determine the range of stability of these oscillatory states terminated by island breakup, and explain the morphological features of the stable oscillating islands on the basis of linear stability theory.

Complexity, Chaos, and Nonlinear Dynamics: A New Perspective on Career Development Theory

ERIC Educational Resources Information Center

Bloch, Deborah P.

2005-01-01

The author presents a theory of career development drawing on nonlinear dynamics and chaos and complexity theories. Career is presented as a complex adaptive entity, a fractal of the human entity. Characteristics of complex adaptive entities, including (a) autopiesis, or self-regeneration; (b) open exchange; (c) participation in networks; (d)…

Taxonomy for complexity theory in the context of maternity care.

PubMed

Nieuwenhuijze, Marianne; Downe, Soo; Gottfreðsdóttir, Helga; Rijnders, Marlies; du Preez, Antoinette; Vaz Rebelo, Piedade

2015-09-01

The linear focus of 'normal science' is unable to adequately take account of the complex interactions that direct health care systems. There is a turn towards complexity theory as a more appropriate framework for understanding system behaviour. However, a comprehensive taxonomy for complexity theory in the context of health care is lacking. This paper aims to build a taxonomy based on the key complexity theory components that have been used in publications on complexity theory and health care, and to explore their explanatory power for health care system behaviour, specifically for maternity care. A search strategy was devised in PubMed and 31 papers were identified as relevant for the taxonomy. The final taxonomy for complexity theory included and defined 11 components. The use of waterbirth and the impact of the Term Breech trial showed that each of the components of our taxonomy has utility in helping to understand how these techniques became widely adopted. It is not just the components themselves that characterise a complex system but also the dynamics between them. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adsorption of Aqueous Crude Oil Components on the Basal Surfaces of Clay Minerals: Molecular Simulations Including Salinity and Temperature Effects

DOE PAGES

Greathouse, J. A.; Cygan, R. T.; Fredrich, J. T.; ...

2017-09-28

Molecular simulations of the adsorption of representative organic molecules onto the basal surfaces of various clay minerals were used to assess the mechanisms of enhanced oil recovery associated with salinity changes and water flooding. Simulations at the density functional theory (DFT) and classical levels provide insights into the molecular structure, binding energy, and interfacial behavior of saturate, aromatic, and resin molecules near clay mineral surfaces. Periodic DFT calculations reveal binding geometries and ion pairing mechanisms at mineral surfaces while also providing a basis for validating the classical force field approach. Through classical molecular dynamics simulations, the influence of aqueous cationsmore » at the interface and the role of water solvation are examined to better evaluate the dynamical nature of cation-organic complexes and their co-adsorption onto the clay surfaces. The extent of adsorption is controlled by the hydrophilic nature and layer charge of the clay mineral. All organic species studied showed preferential adsorption on hydrophobic mineral surfaces. However, the anionic form of the resin (decahydro-2-naphthoic acid)—expected to be prevalent at near-neutral pH conditions in petroleum reservoirs—readily adsorbs to the hydrophilic kaolinite surface through a combination of cation pairing and hydrogen bonding with surface hydroxyl groups. Analysis of cation-organic pairing in both the adsorbed and desorbed states reveals a strong preference for organic anions to coordinate with divalent calcium ions rather than monovalent sodium ions, lending support to current theories regarding low-salinity water flooding.« less

Adsorption of Aqueous Crude Oil Components on the Basal Surfaces of Clay Minerals: Molecular Simulations Including Salinity and Temperature Effects

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

Greathouse, J. A.; Cygan, R. T.; Fredrich, J. T.

Molecular simulations of the adsorption of representative organic molecules onto the basal surfaces of various clay minerals were used to assess the mechanisms of enhanced oil recovery associated with salinity changes and water flooding. Simulations at the density functional theory (DFT) and classical levels provide insights into the molecular structure, binding energy, and interfacial behavior of saturate, aromatic, and resin molecules near clay mineral surfaces. Periodic DFT calculations reveal binding geometries and ion pairing mechanisms at mineral surfaces while also providing a basis for validating the classical force field approach. Through classical molecular dynamics simulations, the influence of aqueous cationsmore » at the interface and the role of water solvation are examined to better evaluate the dynamical nature of cation-organic complexes and their co-adsorption onto the clay surfaces. The extent of adsorption is controlled by the hydrophilic nature and layer charge of the clay mineral. All organic species studied showed preferential adsorption on hydrophobic mineral surfaces. However, the anionic form of the resin (decahydro-2-naphthoic acid)—expected to be prevalent at near-neutral pH conditions in petroleum reservoirs—readily adsorbs to the hydrophilic kaolinite surface through a combination of cation pairing and hydrogen bonding with surface hydroxyl groups. Analysis of cation-organic pairing in both the adsorbed and desorbed states reveals a strong preference for organic anions to coordinate with divalent calcium ions rather than monovalent sodium ions, lending support to current theories regarding low-salinity water flooding.« less

A Theory of Complex Adaptive Inquiring Organizations: Application to Continuous Assurance of Corporate Financial Information

ERIC Educational Resources Information Center

Kuhn, John R., Jr.

2009-01-01

Drawing upon the theories of complexity and complex adaptive systems and the Singerian Inquiring System from C. West Churchman's seminal work "The Design of Inquiring Systems" the dissertation herein develops a systems design theory for continuous auditing systems. The dissertation consists of discussion of the two foundational theories,…

Being pragmatic about healthcare complexity: our experiences applying complexity theory and pragmatism to health services research.

PubMed

Long, Katrina M; McDermott, Fiona; Meadows, Graham N

2018-06-20

The healthcare system has proved a challenging environment for innovation, especially in the area of health services management and research. This is often attributed to the complexity of the healthcare sector, characterized by intersecting biological, social and political systems spread across geographically disparate areas. To help make sense of this complexity, researchers are turning towards new methods and frameworks, including simulation modeling and complexity theory. Herein, we describe our experiences implementing and evaluating a health services innovation in the form of simulation modeling. We explore the strengths and limitations of complexity theory in evaluating health service interventions, using our experiences as examples. We then argue for the potential of pragmatism as an epistemic foundation for the methodological pluralism currently found in complexity research. We discuss the similarities between complexity theory and pragmatism, and close by revisiting our experiences putting pragmatic complexity theory into practice. We found the commonalities between pragmatism and complexity theory to be striking. These included a sensitivity to research context, a focus on applied research, and the valuing of different forms of knowledge. We found that, in practice, a pragmatic complexity theory approach provided more flexibility to respond to the rapidly changing context of health services implementation and evaluation. However, this approach requires a redefinition of implementation success, away from pre-determined outcomes and process fidelity, to one that embraces the continual learning, evolution, and emergence that characterized our project.

Implementation of Complexity Analyzing Based on Additional Effect

NASA Astrophysics Data System (ADS)

Zhang, Peng; Li, Na; Liang, Yanhong; Liu, Fang

According to the Complexity Theory, there is complexity in the system when the functional requirement is not be satisfied. There are several study performances for Complexity Theory based on Axiomatic Design. However, they focus on reducing the complexity in their study and no one focus on method of analyzing the complexity in the system. Therefore, this paper put forth a method of analyzing the complexity which is sought to make up the deficiency of the researches. In order to discussing the method of analyzing the complexity based on additional effect, this paper put forth two concepts which are ideal effect and additional effect. The method of analyzing complexity based on additional effect combines Complexity Theory with Theory of Inventive Problem Solving (TRIZ). It is helpful for designers to analyze the complexity by using additional effect. A case study shows the application of the process.

Anomalous transport and stochastic processes

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

Balescu, R.

1996-03-01

The relation between kinetic transport theory and theory of stochastic processes is reviewed. The Langevin equation formalism provides important, but rather limited information about diffusive processes. A quite promising new approach to modeling complex situations, such as transport in incompletely destroyed magnetic surfaces, is provided by the theory of Continuous Time Random Walks (CTRW), which is presented in some detail. An academic test problem is discussed in great detail: transport of particles in a fluctuating magnetic field, in the limit of infinite perpendicular correlation length. The well-known subdiffusive behavior of the Mean Square Displacement (MSD), proportional to t{sup 1/2}, ismore » recovered by a CTRW, but the complete density profile is not. However, the quasilinear approximation of the kinetic equation has the form of a non-Markovian diffusion equation and can thus be generated by a CTRW. 16 refs., 3 figs.« less

Renormalized charge in a two-dimensional model of colloidal suspension from hypernetted chain approach.

PubMed

Camargo, Manuel; Téllez, Gabriel

2008-04-07

The renormalized charge of a simple two-dimensional model of colloidal suspension was determined by solving the hypernetted chain approximation and Ornstein-Zernike equations. At the infinite dilution limit, the asymptotic behavior of the correlation functions is used to define the effective interactions between the components of the system and these effective interactions were compared to those derived from the Poisson-Boltzmann theory. The results we obtained show that, in contrast to the mean-field theory, the renormalized charge does not saturate, but exhibits a maximum value and then decays monotonically as the bare charge increases. The results also suggest that beyond the counterion layer near to the macroion surface, the ionic cloud is not a diffuse layer which can be handled by means of the linearized theory, as the two-state model claims, but a more complex structure is settled by the correlations between microions.

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H{sub 2}

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

Denis-Alpizar, Otoniel, E-mail: otonieldenisalpizar@gmail.com; Departamento de Física, Universidad de Matanzas, Matanzas 40100; Kalugina, Yulia

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H{sub 2}. Ab initio calculations of the HCN–H{sub 2} van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H{sub 2} with the nitrogen pointing towards H{sub 2} at an intermolecular separation of 7.20 a{sub 0}. The corresponding well depth is −195.20 cm{sup −1}. A secondary minimum of −183.59 cm{sup −1}more » was found for a T-shape configuration with the H of HCN pointing to the center of mass of H{sub 2}. We also determine the rovibrational energy levels of the HCN–para-H{sub 2} and HCN–ortho-H{sub 2} complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm{sup −1} and 60.26 cm{sup −1}, respectively. The calculated ro-vibrational transitions in the HCN–H{sub 2} complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.« less

Complexity growth in massive gravity theories, the effects of chirality, and more

NASA Astrophysics Data System (ADS)

Ghodrati, Mahdis

2017-11-01

To study the effect of parity violation on the rate of complexity growth, by using "complexity=action " conjecture, we find the complexity growth rates in different solutions of the chiral theory of topologically massive gravity (TMG) and parity-preserving theory of new massive gravity (NMG). Using the results, one can see that decreasing the parameter μ , which increases the effect of the Chern-Simons term and increases chirality, would increase the rate of growth of complexity. Also one can observe a stronger correlation between complexity growth and temperature rather than complexity growth and entropy. At the end we comment on the possible meaning of the deforming term of chiral Liouville action for the rate of complexity growth of warped conformal field theories in the tensor network renormalization picture.

Growth of carbon structured over Pd, Pt and Ni: A comparative DFT study

NASA Astrophysics Data System (ADS)

Quiroga, Matías Abel

2013-03-01

To elucidate the graphene-like structures mechanisms growth over the M(1 1 1) surface (M = Pd, Pt and Ni) we performed ab initio calculus in the frame of density functional theory with the exchange-correlation functional treated according to the Generalized Gradient Approximation (GGA). In order to avoid the problem that represent the complex interaction between the well formed graphene layer and the metallic surface, we recreate the carbon rings formation initial steps, by adding one by one carbon atoms over M(1 1 1) surface. With this strategy, the chemical bonding is always present until the graphene layer is well formed, in which case the GGA neglects van der Waals dispersive forces. We investigate the electronic properties by studying the band structure and the density of states.

Topological String Theory and Enumerative Geometry

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

Song, Y. S

In this thesis we investigate several problems which have their roots in both topological string theory and enumerative geometry. In the former case, underlying theories are topological field theories, whereas the latter case is concerned with intersection theories on moduli spaces. A permeating theme in this thesis is to examine the close interplay between these two complementary fields of study. The main problems addressed are as follows: In considering the Hurwitz enumeration problem of branched covers of compact connected Riemann surfaces, we completely solve the problem in the case of simple Hurwitz numbers. In addition, utilizing the connection between Hurwitzmore » numbers and Hodge integrals, we derive a generating function for the latter on the moduli space {bar M}{sub g,2} of 2-pointed, genus-g Deligne-Mumford stable curves. We also investigate Givental's recent conjecture regarding semisimple Frobenius structures and Gromov-Witten invariants, both of which are closely related to topological field theories; we consider the case of a complex projective line P{sup 1} as a specific example and verify his conjecture at low genera. In the last chapter, we demonstrate that certain topological open string amplitudes can be computed via relative stable morphisms in the algebraic category.« less

Mechanistic Insights into Photocatalyzed Hydrogen Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon Resonances.

PubMed

Spata, Vincent A; Carter, Emily A

2018-04-24

Nanoparticles synthesized from plasmonic metals can absorb low-energy light, producing an oscillation/excitation of their valence electron density that can be utilized in chemical conversions. For example, heterogeneous photocatalysis can be achieved within heterometallic antenna-reactor complexes (HMARCs), by coupling a reactive center at which a chemical reaction occurs to a plasmonic nanoparticle that acts as a light-absorbing antenna. For example, HMARCs composed of aluminum antennae and palladium (Pd) reactive centers have been demonstrated recently to catalyze selective hydrogenation of acetylene to ethylene. Here, we explore within a theoretical framework the rate-limiting step of hydrogen photodesorption from a Pd surface-crucial to achieving partial rather than full hydrogenation of acetylene-to understand the mechanism behind the photodesorption process within the HMARC assembly. To properly describe electronic excited states of the metal-molecule system, we employ embedded complete active space self-consistent field and n-electron valence state perturbation theory to second order within density functional embedding theory. The results of these calculations reveal that the photodesorption mechanism does not create a frequently invoked transient negative ion species but instead enhances population of available excited-state, low-barrier pathways that exhibit negligible charge-transfer character.

Well Conditioned Formulations for Open Surface Scattering

DTIC Science & Technology

2008-08-01

region on the negative real half of the com- plex plane and tend to cluster about a few points. With few exceptions12, the eigenvalues have converged...a relatively small region on the negative real half of the complex plane and they tend to cluster about a few points. We were surprised, however, to...theory and the results from a numerical implementation. We also discuss a 2d extension of the Poincare -Bertrand identity could be used to develop an

Radiative decay engineering 5: metal-enhanced fluorescence and plasmon emission

PubMed Central

Lakowicz, Joseph R.

2009-01-01

Metallic particles and surfaces display diverse and complex optical properties. Examples include the intense colors of noble metal colloids, surface plasmon resonance absorption by thin metal films, and quenching of excited fluorophores near the metal surfaces. Recently, the interactions of fluorophores with metallic particles and surfaces (metals) have been used to obtain increased fluorescence intensities, to develop assays based on fluorescence quenching by gold colloids, and to obtain directional radiation from fluorophores near thin metal films. For metal-enhanced fluorescence it is difficult to predict whether a particular metal structure, such as a colloid, fractal, or continuous surface, will quench or enhance fluorescence. In the present report we suggest how the effects of metals on fluorescence can be explained using a simple concept, based on radiating plasmons (RPs). The underlying physics may be complex but the concept is simple to understand. According to the RP model, the emission or quenching of a fluorophore near the metal can be predicted from the optical properties of the metal structures as calculated from electrodynamics, Mie theory, and/or Maxwell’s equations. For example, according to Mie theory and the size and shape of the particle, the extinction of metal colloids can be due to either absorption or scattering. Incident energy is dissipated by absorption. Far-field radiation is created by scattering. Based on our model small colloids are expected to quench fluorescence because absorption is dominant over scattering. Larger colloids are expected to enhance fluorescence because the scattering component is dominant over absorption. The ability of a metal’s surface to absorb or reflect light is due to wavenumber matching requirements at the metal–sample interface. Wavenumber matching considerations can also be used to predict whether fluorophores at a given distance from a continuous planar surface will be emitted or quenched. These considerations suggest that the so called “lossy surface waves” which quench fluorescence are due to induced electron oscillations which cannot radiate to the far-field because wavevector matching is not possible. We suggest that the energy from the fluorophores thought to be lost by lossy surface waves can be recovered as emission by adjustment of the sample to allow wavevector matching. The RP model provides a rational approach for designing fluorophore–metal configurations with the desired emissive properties and a basis for nanophotonic fluorophore technology. PMID:15691498

Syntheses, structures and photoelectric properties of a series of Cd(II)/Zn(II) coordination polymers and coordination supramolecules

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

Jin Jing; Han Xiao; Meng Qin

2013-01-15

Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz){sub 2}(H{sub 2}O)]{sub n} (1), [Cd1Cd2(btec)(H{sub 2}O){sub 6}]{sub n} (2), [Cd(3,4-pdc) (H{sub 2}O)]{sub n} (3), [Zn(2,5-pdc)(H{sub 2}O){sub 4}]{center_dot}2H{sub 2}O (4) and {l_brace} [Zn(2,5-pdc)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (5) (H{sub 2}bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, H{sub 2}pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV-vis spectra and elemental analysis. Structural analyses show that complexes 1-3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexesmore » were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300-600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response. - Graphical abstract: Five Cd(II)/Zn(II) complexes have been hydrothermally synthesized and characterized. The photoelectric properties were studied with SPS. The species and coordination micro-environment of central metal ion, the species and property of ligands all affect the photoelectric responses. Highlights: Black-Right-Pointing-Pointer Five Cd/Zn complexes have been synthesized and characterized. Black-Right-Pointing-Pointer The SPS results indicate they possess obvious photoelectric conversion property. Black-Right-Pointing-Pointer The species and coordination environment of central metal ion affect SPS. Black-Right-Pointing-Pointer The species and property of ligands affect SPS. Black-Right-Pointing-Pointer By the energy-band theory and the crystal filed theory, the SPS are analyzed and assigned.« less

Periodic density functional theory calculations of bulk and the (010) surface of goethite

PubMed Central

Kubicki, James D; Paul, Kristian W; Sparks, Donald L

2008-01-01

Background Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP). Results Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer) and solvated (three H2O layers) (010) surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Conclusion Surface Fe-O and (Fe)O-H bond lengths are reported that may be useful in surface complexation models (SCM) of the goethite (010) surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface), indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces. PMID:18477389

Statistics of multi-look AIRSAR imagery: A comparison of theory with measurements

NASA Technical Reports Server (NTRS)

Lee, J. S.; Hoppel, K. W.; Mango, S. A.

1993-01-01

The intensity and amplitude statistics of SAR images, such as L-Band HH for SEASAT and SIR-B, and C-Band VV for ERS-1 have been extensively investigated for various terrain, ground cover and ocean surfaces. Less well-known are the statistics between multiple channels of polarimetric of interferometric SAR's, especially for the multi-look processed data. In this paper, we investigate the probability density functions (PDF's) of phase differences, the magnitude of complex products and the amplitude ratios, between polarization channels (i.e. HH, HV, and VV) using 1-look and 4-look AIRSAR polarimetric data. Measured histograms are compared with theoretical PDF's which were recently derived based on a complex Gaussian model.

Groundwater–surface water mixing shifts ecological assembly processes and stimulates organic carbon turnover

PubMed Central

Stegen, James C.; Fredrickson, James K.; Wilkins, Michael J.; Konopka, Allan E.; Nelson, William C.; Arntzen, Evan V.; Chrisler, William B.; Chu, Rosalie K.; Danczak, Robert E.; Fansler, Sarah J.; Kennedy, David W.; Resch, Charles T.; Tfaily, Malak

2016-01-01

Environmental transitions often result in resource mixtures that overcome limitations to microbial metabolism, resulting in biogeochemical hotspots and moments. Riverine systems, where groundwater mixes with surface water (the hyporheic zone), are spatially complex and temporally dynamic, making development of predictive models challenging. Spatial and temporal variations in hyporheic zone microbial communities are a key, but understudied, component of riverine biogeochemical function. Here, to investigate the coupling among groundwater–surface water mixing, microbial communities and biogeochemistry, we apply ecological theory, aqueous biogeochemistry, DNA sequencing and ultra-high-resolution organic carbon profiling to field samples collected across times and locations representing a broad range of mixing conditions. Our results indicate that groundwater–surface water mixing in the hyporheic zone stimulates heterotrophic respiration, alters organic carbon composition, causes ecological processes to shift from stochastic to deterministic and is associated with elevated abundances of microbial taxa that may degrade a broad suite of organic compounds. PMID:27052662

Groundwater-surface water mixing shifts ecological assembly processes and stimulates organic carbon turnover.

PubMed

Stegen, James C; Fredrickson, James K; Wilkins, Michael J; Konopka, Allan E; Nelson, William C; Arntzen, Evan V; Chrisler, William B; Chu, Rosalie K; Danczak, Robert E; Fansler, Sarah J; Kennedy, David W; Resch, Charles T; Tfaily, Malak

2016-04-07

Environmental transitions often result in resource mixtures that overcome limitations to microbial metabolism, resulting in biogeochemical hotspots and moments. Riverine systems, where groundwater mixes with surface water (the hyporheic zone), are spatially complex and temporally dynamic, making development of predictive models challenging. Spatial and temporal variations in hyporheic zone microbial communities are a key, but understudied, component of riverine biogeochemical function. Here, to investigate the coupling among groundwater-surface water mixing, microbial communities and biogeochemistry, we apply ecological theory, aqueous biogeochemistry, DNA sequencing and ultra-high-resolution organic carbon profiling to field samples collected across times and locations representing a broad range of mixing conditions. Our results indicate that groundwater-surface water mixing in the hyporheic zone stimulates heterotrophic respiration, alters organic carbon composition, causes ecological processes to shift from stochastic to deterministic and is associated with elevated abundances of microbial taxa that may degrade a broad suite of organic compounds.

New five coordinated supramolecular structured cadmium complex as precursor for CdO nanoparticles: Synthesis, crystal structure, theoretical and 3D Hirshfeld surface analyses

NASA Astrophysics Data System (ADS)

Ghanbari Niyaky, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

2017-03-01

In this paper, a combined experimental and theoretical study on a new CdLBr2 complex (L = N1-(2-bromobenzylidene)-N2-(2-((E)-(2-bromobenzylidene) amino)ethyl) ethane-1,2-diamine) synthesized via template method, is described. The crystal structure analysis of the complex indicates that, the Cd(II) ion is centered in a distorted square pyramidal space constructed by three iminic nitrogens of the ligand as well as two bromide anions. More analysis of crystal packing proposed a supramolecular structure stabilized by some non-covalent interactions such as Br⋯Br and Xsbnd H⋯Br (X = N and C) in solid state. Furthermore, 3D Hirshfeld surface analyses and DFT studies were applied for theoretical investigation of the complexes. Theoretical achievements were found in a good agreement with respect to the experimental data. To evaluate the nature of bonding and the strength of the intra and inter-molecular interactions a natural bond orbital (NBO) analysis on the complex structure was performed. Time dependent density functional theory (TD-DFT) was also applied to predict the electronic spectral data of the complex as compared with the experimental ones. CdLBr2 complex as nano-structure compound was also prepared under ultrasonic conditions and characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). Finally, it was found that the cadmium complex can be used as a suitable precursor for preparation of CdO nanoparticles via calcination process at 600 °C under air atmosphere.

An introduction to orbit dynamics and its application to satellite-based earth monitoring systems

NASA Technical Reports Server (NTRS)

Brooks, D. R.

1977-01-01

The long term behavior of satellites is studied at a level of complexity suitable for the initial planning phases of earth monitoring missions. First-order perturbation theory is used to describe in detail the basic orbit dynamics of satellite motion around the earth and relative to the sun. Surface coverage capabilities of satellite orbits are examined. Several examples of simulated observation and monitoring missions are given to illustrate representative applications of the theory. The examples stress the need for devising ways of maximizing total mission output in order to make the best possible use of the resultant data base as input to those large-scale, long-term earth monitoring activities which can best justify the use of satellite systems.

Some elements of a theory of multidimensional complex variables. I - General theory. II - Expansions of analytic functions and application to fluid flows

NASA Technical Reports Server (NTRS)

Martin, E. Dale

1989-01-01

The paper introduces a new theory of N-dimensional complex variables and analytic functions which, for N greater than 2, is both a direct generalization and a close analog of the theory of ordinary complex variables. The algebra in the present theory is a commutative ring, not a field. Functions of a three-dimensional variable were defined and the definition of the derivative then led to analytic functions.

Probing Nitrosyl Ligation of Surface-Confined Metalloporphyrins by Inelastic Electron Tunneling Spectroscopy

PubMed Central

2013-01-01

Complexes obtained by the ligation of nitric oxide (NO) to metalloporphyrins represent important model systems with biological relevance. Herein we report a molecular-level investigation of surface-confined cobalt tetraphenyl porphyrin (Co-TPP) species and their interaction with NO under ultrahigh vacuum conditions. It is demonstrated that individual NO adducts can be desorbed using the atomically sharp tip of a scanning tunneling microscope, whereby a writing process is implemented for fully saturated regular metalloporphyrin arrays. The low-energy vibrational characteristics of individual Co-TPP-nitrosyl complexes probed by inelastic electron tunneling spectroscopy (IETS) reveal a prominent signature at an energy of ≃31 meV. Using density functional theory-based IETS simulations—the first to be performed on such an extensive interfacial nanosystem—we succeed to reproduce the low-frequency spectrum for the NO-ligated complex and explain the absence of IETS activity for bare Co-TPP. Moreover, we can conclusively assign the IETS peak of NO-Co-TPP to a unique vibration mode involving the NO complexation site, namely, the in-plane Co–N–O rocking mode. In addition, we verify that the propensity rules previously designed on small aromatic systems and molecular fragments hold true for a metal–organic entity. This work notably permits one to envisage IETS spectroscopy as a sensitive tool to chemically characterize hybrid interfaces formed by complex metal–organic units and gaseous adducts. PMID:23718257

Isometric immersions and self-similar buckling in elastic sheets.

NASA Astrophysics Data System (ADS)

Gemmer, John

The edges of torn elastic sheets and growing leaves often display hierarchical self-similar like buckling patterns. On the one hand, such complex, self similar patterns are usually associated with a competition between two distinct energy scales, e.g. elastic sheets with boundary conditions that preclude the possibility of relieving in plane strains, or at alloy-alloy interfaces between distinct crystal structures. On the other hand, within the non-Euclidean plate theory this complex morphology can be understood as low bending energy isometric immersions of hyperbolic Riemannian metrics. In particular, many growth patterns generate residual in-plane strains which can be entirely relieved by the sheet forming part of a surface of revolution or a helix. In this talk we will show that this complex morphology (i) arises from isometric immersions (ii) is driven by a competition between the two principal curvatures, rather than between bending and stretching. We identify the key role of branch-point (or monkey-saddle) singularities, in complex wrinkling patterns within the class of finite bending energy isometric immersions. Using these defects we will give an explicit construction of strain-free embeddings of hyperbolic surfaces that are fractal like and have lower elastic energy than their smooth counterparts US-Israel BSF Grant 2008432. NSF Grant DMS-0807501. NSF-RTG Grant DMS-1148284.

Complexity theory, time series analysis and Tsallis q-entropy principle part one: theoretical aspects

NASA Astrophysics Data System (ADS)

Pavlos, George P.

2017-12-01

In this study, we present the highlights of complexity theory (Part I) and significant experimental verifications (Part II) and we try to give a synoptic description of complexity theory both at the microscopic and at the macroscopic level of the physical reality. Also, we propose that the self-organization observed macroscopically is a phenomenon that reveals the strong unifying character of the complex dynamics which includes thermodynamical and dynamical characteristics in all levels of the physical reality. From this point of view, macroscopical deterministic and stochastic processes are closely related to the microscopical chaos and self-organization. The scientific work of scientists such as Wilson, Nicolis, Prigogine, Hooft, Nottale, El Naschie, Castro, Tsallis, Chang and others is used for the development of a unified physical comprehension of complex dynamics from the microscopic to the macroscopic level. Finally, we provide a comprehensive description of the novel concepts included in the complexity theory from microscopic to macroscopic level. Some of the modern concepts that can be used for a unified description of complex systems and for the understanding of modern complexity theory, as it is manifested at the macroscopic and the microscopic level, are the fractal geometry and fractal space-time, scale invariance and scale relativity, phase transition and self-organization, path integral amplitudes, renormalization group theory, stochastic and chaotic quantization and E-infinite theory, etc.

FASTER 3: A generalized-geometry Monte Carlo computer program for the transport of neutrons and gamma rays. Volume 1: Summary report

NASA Technical Reports Server (NTRS)

Jordan, T. M.

1970-01-01

The theory used in FASTER-III, a Monte Carlo computer program for the transport of neutrons and gamma rays in complex geometries, is outlined. The program includes the treatment of geometric regions bounded by quadratic and quadric surfaces with multiple radiation sources which have specified space, angle, and energy dependence. The program calculates, using importance sampling, the resulting number and energy fluxes at specified point, surface, and volume detectors. It can also calculate minimum weight shield configuration meeting a specified dose rate constraint. Results are presented for sample problems involving primary neutron, and primary and secondary photon, transport in a spherical reactor shield configuration.

Visual Complexity: A Review

ERIC Educational Resources Information Center

Donderi, Don C.

2006-01-01

The idea of visual complexity, the history of its measurement, and its implications for behavior are reviewed, starting with structuralism and Gestalt psychology at the beginning of the 20th century and ending with visual complexity theory, perceptual learning theory, and neural circuit theory at the beginning of the 21st. Evidence is drawn from…

Complexity Leadership: A Theoretical Perspective

ERIC Educational Resources Information Center

Baltaci, Ali; Balci, Ali

2017-01-01

Complex systems are social networks composed of interactive employees interconnected through collaborative, dynamic ties such as shared goals, perspectives and needs. Complex systems are largely based on "the complex system theory". The complex system theory focuses mainly on finding out and developing strategies and behaviours that…

Modeling of thin-walled structures interacting with acoustic media as constrained two-dimensional continua

NASA Astrophysics Data System (ADS)

Rabinskiy, L. N.; Zhavoronok, S. I.

2018-04-01

The transient interaction of acoustic media and elastic shells is considered on the basis of the transition function approach. The three-dimensional hyperbolic initial boundary-value problem is reduced to a two-dimensional problem of shell theory with integral operators approximating the acoustic medium effect on the shell dynamics. The kernels of these integral operators are determined by the elementary solution of the problem of acoustic waves diffraction at a rigid obstacle with the same boundary shape as the wetted shell surface. The closed-form elementary solution for arbitrary convex obstacles can be obtained at the initial interaction stages on the background of the so-called “thin layer hypothesis”. Thus, the shell–wave interaction model defined by integro-differential dynamic equations with analytically determined kernels of integral operators becomes hence two-dimensional but nonlocal in time. On the other hand, the initial interaction stage results in localized dynamic loadings and consequently in complex strain and stress states that require higher-order shell theories. Here the modified theory of I.N.Vekua–A.A.Amosov-type is formulated in terms of analytical continuum dynamics. The shell model is constructed on a two-dimensional manifold within a set of field variables, Lagrangian density, and constraint equations following from the boundary conditions “shifted” from the shell faces to its base surface. Such an approach allows one to construct consistent low-order shell models within a unified formal hierarchy. The equations of the N th-order shell theory are singularly perturbed and contain second-order partial derivatives with respect to time and surface coordinates whereas the numerical integration of systems of first-order equations is more efficient. Such systems can be obtained as Hamilton–de Donder–Weyl-type equations for the Lagrangian dynamical system. The Hamiltonian formulation of the elementary N th-order shell theory is here briefly described.

F-theory and AdS3/CFT2 (2, 0)

NASA Astrophysics Data System (ADS)

Couzens, Christopher; Martelli, Dario; Schäfer-Nameki, Sakura

2018-06-01

We continue to develop the program initiated in [1] of studying supersymmetric AdS3 backgrounds of F-theory and their holographic dual 2d superconformal field theories, which are dimensional reductions of theories with varying coupling. Imposing 2d N=(0,2) supersymmetry,wederivethegeneralconditionsonthegeometryforTypeIIB AdS3 solutions with varying axio-dilaton and five-form flux. Locally the compact part of spacetime takes the form of a circle fibration over an eight-fold Y_8^{τ } , which is elliptically fibered over a base \\tilde{M}_6 . We construct two classes of solutions given in terms of a product ansatz \\tilde{M}_6}=Σ × {M}_4 , where Σ is a complex curve and \\tilde{M}_4 is locally a Kähler surface. In the first class \\tilde{M}_4 is globally a Kähler surface and we take the elliptic fibration to vary non-trivially over either of these two factors, where in both cases the metrics on the total space of the elliptic fibrations are not Ricci-flat. In the second class the metric on the total space of the elliptic fibration over either curve or surface are Ricci-flat. This results in solutions of the type AdS3 × K3 × ℳ 5 τ , dual to 2d (0, 2) SCFTs, and AdS3 × S 3/Γ × CY 3, dual to 2d (0, 4) SCFTs, respectively. In all cases we compute the charges for the dual field theories with varying coupling and find agreement with the holographic results. We also show that solutions with enhanced 2d N=(2,2) supersymmetry must have constant axio-dilaton. Allowing the internal geometry to be non-compact leads to the most general class of Type IIB AdS5 solutions with varying axio-dilaton, i.e. F-theoretic solutions, that are dual to 4d N=1 SCFTs.

Adsorption of various types of amino acids on the graphene and boron-nitride nano-sheet, a DFT-D3 study

NASA Astrophysics Data System (ADS)

Zhiani, Rahele

2017-07-01

The binding properties of the adsorption of five different classes of amino acids, namely, alanine (Ala), arginine (Arg), asparagine (Asn), histidine (His) and cysteine (Cys) on the surface of the graphene (Gra) and the born-nitride (BN) nano-sheet structures were studied from molecular viewpoint using quantum mechanics methods. Density functional theory (DFT) and DFT-D3 calculations were carried out to investigate the electronic properties and the dispersion interaction of the amino acid/adsorbent complexes. Several parameters affecting the interactions between the amino acids and the adsorbent surfaces such as solvent effect, adsorption energy and separation distance were investigated. Findings show that Arg forms the most stable complexes with the graphene and the BN nano-sheet compare to the other amino acids used in this study. The observed frequency results which were related to the band gap energies were consistent with the above statement. Results exhibit that adsorption of the amino acids on the surface of the BN nano-sheet and the graphene accompanied with the release of the energy. Calculations show that there are no bonded interactions between the amino acids and adsorbent surfaces. The polarity of the BN nano-sheet provides the more affinity towards the amino acids. These results were proved by the quantum chemistry studies.

Cytosolic proteins can exploit membrane localization to trigger functional assembly

PubMed Central

2018-01-01

Cell division, endocytosis, and viral budding would not function without the localization and assembly of protein complexes on membranes. What is poorly appreciated, however, is that by localizing to membranes, proteins search in a reduced space that effectively drives up concentration. Here we derive an accurate and practical analytical theory to quantify the significance of this dimensionality reduction in regulating protein assembly on membranes. We define a simple metric, an effective equilibrium constant, that allows for quantitative comparison of protein-protein interactions with and without membrane present. To test the importance of membrane localization for driving protein assembly, we collected the protein-protein and protein-lipid affinities, protein and lipid concentrations, and volume-to-surface-area ratios for 46 interactions between 37 membrane-targeting proteins in human and yeast cells. We find that many of the protein-protein interactions between pairs of proteins involved in clathrin-mediated endocytosis in human and yeast cells can experience enormous increases in effective protein-protein affinity (10–1000 fold) due to membrane localization. Localization of binding partners thus triggers robust protein complexation, suggesting that it can play an important role in controlling the timing of endocytic protein coat formation. Our analysis shows that several other proteins involved in membrane remodeling at various organelles have similar potential to exploit localization. The theory highlights the master role of phosphoinositide lipid concentration, the volume-to-surface-area ratio, and the ratio of 3D to 2D equilibrium constants in triggering (or preventing) constitutive assembly on membranes. Our simple model provides a novel quantitative framework for interpreting or designing in vitro experiments of protein complexation influenced by membrane binding. PMID:29505559

The interaction of mercury with halogenated graphene

NASA Astrophysics Data System (ADS)

Kirchofer, Abigail; Sasmaz, Erdem; Wilcox, Jennifer

2011-03-01

The interaction of mercury with halogenated graphene was studied using plane-wave density functional theory. Various configurations of H, Hg, O and Br or Cl on the zigzag edge sites of graphene were investigated. Although Hg-Br (or -Cl) complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The surface atoms Hg, O, and Br tend to repel each other during geometric optimization, moving towards an H atom nearest-neighbor where possible. The strength of the Hg-graphene interaction is very sensitive to the local environment. The Hg-graphene binding energy is strongest when the Hg is located next to a surface O but not immediately next to a bound Br. DOS analysis revealed that Hg adsorption involves a gain in Hg 6 p-states and a loss in Hg 5 s electron density, resulting in an oxidized surface-bound Hg complex. DOS analysis suggests that Br strengthens the Hg-graphene interaction by modifying the surface carbon electron density; however, when Br is adjacent to Hg, a direct Hg-Br interaction weakens the Hg-C bond. These investigations provide insight into the mechanism associated with enhanced Hg adsorption on Br-functionalized carbon materials for Hg emissions reductions from coal-fired power plant applications. The authors acknowledge the financial support by Electric Power Research Institute (EPRI).

International Conference on Mathematical Methods in Electromagnetic Theory (MMET 2000), Volume 2 Held in Kharkov, Ukraine on September 12-15, 2000

DTIC Science & Technology

2000-09-01

frequencies of the WG-modes of the resonator are determined as the points on the complex frequency plane for which nontrivial solutions of (3) exist...allow to determine a surface impedance of end-walls using the experimentally measured frequencies and basic Q-factors of resonance oscillations of a...Y0 = Y,. The com- plex eigen frequencies K’ = Re< + i. Im< (v is the number of the resonance in the zones

Dielectric Response at THz Frequencies of Fe Water Complexes and Their Interaction with O3 Calculated by Density Functional Theory

DTIC Science & Technology

2012-10-24

geometric arrangement of the atoms in a chemical system , at the maximal peak of the energy surface separating reactants from products . In the...Sonnenberg, M. Hada, M. Ehara, K. Toyota , R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda , O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery... using DFT. The calculation of ground state resonance structure is for the construction of parameterized dielectric response functions for excitation

Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation.

PubMed

Zhu, Mengqiang; Paul, Kristian W; Kubicki, James D; Sparks, Donald L

2009-09-01

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Study on interfacial stability and internal flow of a droplet levitated by ultrasonic wave.

PubMed

Abe, Yutaka; Yamamoto, Yuji; Hyuga, Daisuke; Awazu, Shigeru; Aoki, Kazuyoshi

2009-04-01

For a microgravity environment, new and high-quality material is expected to be manufactured. However, the effect of surface instability and the internal flow become significant when the droplet becomes large. Elucidation of internal flow and surface instability on a levitated droplet is required for the quality improvement of new material manufacturing in a microgravity environment. The objectives of this study are to clarify the interfacial stability and internal flow of a levitated droplet. Surface instability and internal flow are investigated with a large droplet levitated by the ultrasonic acoustic standing wave. The experiment with a large droplet is conducted both under normal gravity and microgravity environments. In the experiment, at first, the characteristics of the levitated droplet are investigated; that is, the relationships among the levitated droplet diameter, the droplet aspect ratio, the displacement of the antinode of the standing wave, and the sound pressure are experimentally measured. As a result, it is clarified that the levitated droplet tends to be located at an optimal position with an optimal shape and diameter. Second, the border condition between the stable and the unstable levitation of the droplet is evaluated by using the existing stability theory. The experimental results qualitatively agree with the theory. It is suggested that the stability of the droplet can be evaluated with the stability theory. Finally, multidimensional visual measurement is conducted to investigate the internal flow structure in a levitated droplet. It is suggested that complex flow with the vortex is generated in the levitated droplet. Moreover, the effect of physical properties of the test fluid on the internal flow structure of the levitated droplet is investigated. As a result, the internal flow structure of the levitated droplet is affected by the surface tension and viscosity.

Semiclassical multi-phonon theory for atom-surface scattering: Application to the Cu(111) system

NASA Astrophysics Data System (ADS)

Daon, Shauli; Pollak, Eli

2015-05-01

The semiclassical perturbation theory of Hubbard and Miller [J. Chem. Phys. 80, 5827 (1984)] is further developed to include the full multi-phonon transitions in atom-surface scattering. A practically applicable expression is developed for the angular scattering distribution by utilising a discretized bath of oscillators, instead of the continuum limit. At sufficiently low surface temperature good agreement is found between the present multi-phonon theory and the previous one-, and two-phonon theory derived in the continuum limit in our previous study [Daon, Pollak, and Miret-Artés, J. Chem. Phys. 137, 201103 (2012)]. The theory is applied to the measured angular distributions of Ne, Ar, and Kr scattered from a Cu(111) surface. We find that the present multi-phonon theory substantially improves the agreement between experiment and theory, especially at the higher surface temperatures. This provides evidence for the importance of multi-phonon transitions in determining the angular distribution as the surface temperature is increased.

Current use was established and Cochrane guidance on selection of social theories for systematic reviews of complex interventions was developed.

PubMed

Noyes, Jane; Hendry, Maggie; Booth, Andrew; Chandler, Jackie; Lewin, Simon; Glenton, Claire; Garside, Ruth

2016-07-01

To identify examples of how social theories are used in systematic reviews of complex interventions to inform production of Cochrane guidance. Secondary analysis of published/unpublished examples of theories of social phenomena for use in reviews of complex interventions identified through scoping searches, engagement with key authors and methodologists supplemented by snowballing and reference searching. Theories were classified (low-level, mid-range, grand). Over 100 theories were identified with evidence of proliferation over the last 5 years. New low-level theories (tools, taxonomies, etc) have been developed for classifying and reporting complex interventions. Numerous mid-range theories are used; one example demonstrated how control theory had changed the review's findings. Review-specific logic models are increasingly used, but these can be challenging to develop. New low-level and mid-range psychological theories of behavior change are evolving. No reviews using grand theory (e.g., feminist theory) were identified. We produced a searchable Wiki, Mendeley Inventory, and Cochrane guidance. Use of low-level theory is common and evolving; incorporation of mid-range theory is still the exception rather than the norm. Methodological work is needed to evaluate the contribution of theory. Choice of theory reflects personal preference; application of theory is a skilled endeavor. Crown Copyright © 2016. Published by Elsevier Inc. All rights reserved.

Differential Geometry Based Multiscale Models

PubMed Central

Wei, Guo-Wei

2010-01-01

Large chemical and biological systems such as fuel cells, ion channels, molecular motors, and viruses are of great importance to the scientific community and public health. Typically, these complex systems in conjunction with their aquatic environment pose a fabulous challenge to theoretical description, simulation, and prediction. In this work, we propose a differential geometry based multiscale paradigm to model complex macromolecular systems, and to put macroscopic and microscopic descriptions on an equal footing. In our approach, the differential geometry theory of surfaces and geometric measure theory are employed as a natural means to couple the macroscopic continuum mechanical description of the aquatic environment with the microscopic discrete atom-istic description of the macromolecule. Multiscale free energy functionals, or multiscale action functionals are constructed as a unified framework to derive the governing equations for the dynamics of different scales and different descriptions. Two types of aqueous macromolecular complexes, ones that are near equilibrium and others that are far from equilibrium, are considered in our formulations. We show that generalized Navier–Stokes equations for the fluid dynamics, generalized Poisson equations or generalized Poisson–Boltzmann equations for electrostatic interactions, and Newton's equation for the molecular dynamics can be derived by the least action principle. These equations are coupled through the continuum-discrete interface whose dynamics is governed by potential driven geometric flows. Comparison is given to classical descriptions of the fluid and electrostatic interactions without geometric flow based micro-macro interfaces. The detailed balance of forces is emphasized in the present work. We further extend the proposed multiscale paradigm to micro-macro analysis of electrohydrodynamics, electrophoresis, fuel cells, and ion channels. We derive generalized Poisson–Nernst–Planck equations that are coupled to generalized Navier–Stokes equations for fluid dynamics, Newton's equation for molecular dynamics, and potential and surface driving geometric flows for the micro-macro interface. For excessively large aqueous macromolecular complexes in chemistry and biology, we further develop differential geometry based multiscale fluid-electro-elastic models to replace the expensive molecular dynamics description with an alternative elasticity formulation. PMID:20169418

Biomass-derived oxygenate reforming on Pt(111): A demonstration of surface science using D-glucose and its model surrogate glycolaldehyde

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Yu, Weiting; Salciccioli, Michael; Vlachos, Dionisios G.; Chen, Jingguang G.; Vohs, John M.

2012-12-01

Molecules derived from cellulosic biomass, such as glucose, represent an important renewable feedstock for the production of hydrogen and hydrocarbon-based fuels and chemicals. Development of efficient catalysts for their reformation into useful products is needed; however, this requires a detailed understanding of their adsorption and reaction on catalytically active transition metal surfaces. In this paper we demonstrate that the standard surface science techniques routinely used to characterize the reaction of small molecules on metals are also amenable for use in studying the adsorption and reaction of complex biomass-derivatives on single crystal metal surfaces. In particular, Temperature Programmed Desorption (TPD) and High Resolution Electron Energy Loss Spectroscopy (HREELS) combined with Density Functional Theory (DFT) calculations were used to elucidate the adsorption configuration of D-glucose and glycolaldehye on Pt(111). Both molecules were found to adsorb in an η1 aldehyde configuration partially validating the use of simple, functionally-equivalent model compounds for surface studies of cellulosic oxygenates.

Fluid Mechanics and Complex Variable Theory: Getting Past the 19th Century

ERIC Educational Resources Information Center

Newton, Paul K.

2017-01-01

The subject of fluid mechanics is a rich, vibrant, and rapidly developing branch of applied mathematics. Historically, it has developed hand-in-hand with the elegant subject of complex variable theory. The Westmont College NSF-sponsored workshop on the revitalization of complex variable theory in the undergraduate curriculum focused partly on…

A topological study of gravity free-surface waves generated by bluff bodies using the method of steepest descents

PubMed Central

2016-01-01

The standard analytical approach for studying steady gravity free-surface waves generated by a moving body often relies upon a linearization of the physical geometry, where the body is considered asymptotically small in one or several of its dimensions. In this paper, a methodology that avoids any such geometrical simplification is presented for the case of steady-state flows at low speeds. The approach is made possible through a reduction of the water-wave equations to a complex-valued integral equation that can be studied using the method of steepest descents. The main result is a theory that establishes a correspondence between different bluff-bodied free-surface flow configurations, with the topology of the Riemann surface formed by the steepest descent paths. Then, when a geometrical feature of the body is modified, a corresponding change to the Riemann surface is observed, and the resultant effects to the water waves can be derived. This visual procedure is demonstrated for the case of two-dimensional free-surface flow past a surface-piercing ship and over an angled step in a channel. PMID:27493559

On Complex Nuclei Energetics in LENR

NASA Astrophysics Data System (ADS)

Miley, George H.; Hora, Heinz

2005-03-01

Swimming Electron Layer (SEL) theory plus fission of ``complex nuclei'' were proposed earlier to explain reaction products observed in electrolysis with multi-layer thin-film metallic electrodesootnotetext1.G.H. Miley, and J.A. Patterson, J. New Energy, Vol. 1, pp.11-15, (1996).. SEL was then extended to treat gas-diffusion driven transmutation experimentsootnotetextG. H. Miley and H. Hora, ``Nuclear Reactions in Solids,'' APS DNP Mtg., East Lansing, MI, Oct (2002).. It is also consistent with measured charged-particle emission during thin-film electrolysis and x-ray emission during plasma bombardment experimentsootnotetextA. Karabut, ``X-ray emission in high-current glow discharge,'' Proc., ICCF-9, Beijing China, May (2002).. The binding energy per complex nucleon can be estimated by an energy balance combined with identification of products for each complex e.g. complexes of A 39 have ˜ 0.05 MeV/Nucleon, etc, in thin film electrolysis. Energies in gas diffusion experiments are lower due to the reduced trap site potential at the multi-atom surface. In the case of x-ray emission, complexes involve subsurface defect center traps, giving only a few keV/Nucleon, consistent with experiments^3.

Time evolution of complexity in Abelian gauge theories

NASA Astrophysics Data System (ADS)

Hashimoto, Koji; Iizuka, Norihiro; Sugishita, Sotaro

2017-12-01

Quantum complexity is conjectured to probe inside of black hole horizons (or wormholes) via gauge gravity correspondence. In order to have a better understanding of this correspondence, we study time evolutions of complexities for Abelian pure gauge theories. For this purpose, we discretize the U (1 ) gauge group as ZN and also the continuum spacetime as lattice spacetime, and this enables us to define a universal gate set for these gauge theories and to evaluate time evolutions of the complexities explicitly. We find that to achieve a large complexity ˜exp (entropy), which is one of the conjectured criteria necessary to have a dual black hole, the Abelian gauge theory needs to be maximally nonlocal.

Abrasive slurry jet cutting model based on fuzzy relations

NASA Astrophysics Data System (ADS)

Qiang, C. H.; Guo, C. W.

2017-12-01

The cutting process of pre-mixed abrasive slurry or suspension jet (ASJ) is a complex process affected by many factors, and there is a highly nonlinear relationship between the cutting parameters and cutting quality. In this paper, guided by fuzzy theory, the fuzzy cutting model of ASJ was developed. In the modeling of surface roughness, the upper surface roughness prediction model and the lower surface roughness prediction model were established respectively. The adaptive fuzzy inference system combines the learning mechanism of neural networks and the linguistic reasoning ability of the fuzzy system, membership functions, and fuzzy rules are obtained by adaptive adjustment. Therefore, the modeling process is fast and effective. In this paper, the ANFIS module of MATLAB fuzzy logic toolbox was used to establish the fuzzy cutting model of ASJ, which is found to be quite instrumental to ASJ cutting applications.

Surface Charge-Transfer Doping of Graphene Nanoflakes Containing Double-Vacancy (5-8-5) and Stone-Wales (55-77) Defects through Molecular Adsorption.

PubMed

Shakourian-Fard, Mehdi; Jamshidi, Zahra; Kamath, Ganesh

2016-10-18

The adsorption of six electron donor-acceptor (D/A) organic molecules on various sizes of graphene nanoflakes (GNFs) containing two common defects, double-vacancy (5-8-5) and Stone-Wales (55-77), are investigated by means of ab initio DFT [M06-2X(-D3)/cc-pVDZ]. Different D/A molecules adsorb on a defect graphene (DG) surface with binding energies (ΔE b ) of about -12 to -28 kcal mol -1 . The ΔE b values for adsorption of molecules on the Stone-Wales GNF surface are higher than those on the double vacancy GNF surface. Moreover, binding energies increase by about 10 % with an increase in surface size. The nature of cooperative weak interactions is analyzed based on quantum theory of atoms in molecules, noncovalent interactions plot, and natural bond order analyses, and the dominant interaction is compared for different molecules. Electron density population analysis is used to explain the n- and p-type character of defect graphene nanoflakes (DGNFs) and also the change in electronic properties and reactivity parameters of DGNFs upon adsorption of different molecules and with increasing DGNF size. Results indicate that the HOMO-LUMO energy gap (E g ) of DGNFs decreases upon adsorption of molecules. However, by increasing the size of DGNFs, the E g and chemical hardness of all complexes decrease and the electrophilicity index increases. Furthermore, the values of the chemical potential of acceptor-DGNF complexes decrease with increasing size, whereas those of donor-DGNF complexes increase. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Femtosecond Laser Surface Structuring with Optical Vortex Beams Generated by a q-plate

PubMed Central

JJ Nivas, Jijil; He, Shutong; Rubano, Andrea; Vecchione, Antonio; Paparo, Domenico; Marrucci, Lorenzo; Bruzzese, Riccardo; Amoruso, Salvatore

2015-01-01

Creation of patterns and structures on surfaces at the micro- and nano-scale is a field of growing interest. Direct femtosecond laser surface structuring with a Gaussian-like beam intensity profile has already distinguished itself as a versatile method to fabricate surface structures on metals and semiconductors. Here we present an approach for direct femtosecond laser surface structuring based on optical vortex beams with different spatial distributions of the state of polarization, which are easily generated by means of a q-plate. The different states of an optical vortex beam carrying an orbital angular momentum ℓ = ±1 are used to demonstrate the fabrication of various regular surface patterns on silicon. The spatial features of the regular rippled and grooved surface structures are correlated with the state of polarization of the optical vortex beam. Moreover, scattered surface wave theory approach is used to rationalize the dependence of the surface structures on the local state of the laser beam characteristics (polarization and fluence). The present approach can be further extended to fabricate even more complex and unconventional surface structures by exploiting the possibilities offered by femtosecond optical vector fields. PMID:26658307

Simulation of surface processes

PubMed Central

Jónsson, Hannes

2011-01-01

Computer simulations of surface processes can reveal unexpected insight regarding atomic-scale structure and transitions. Here, the strengths and weaknesses of some commonly used approaches are reviewed as well as promising avenues for improvements. The electronic degrees of freedom are usually described by gradient-dependent functionals within Kohn–Sham density functional theory. Although this level of theory has been remarkably successful in numerous studies, several important problems require a more accurate theoretical description. It is important to develop new tools to make it possible to study, for example, localized defect states and band gaps in large and complex systems. Preliminary results presented here show that orbital density-dependent functionals provide a promising avenue, but they require the development of new numerical methods and substantial changes to codes designed for Kohn–Sham density functional theory. The nuclear degrees of freedom can, in most cases, be described by the classical equations of motion; however, they still pose a significant challenge, because the time scale of interesting transitions, which typically involve substantial free energy barriers, is much longer than the time scale of vibrations—often 10 orders of magnitude. Therefore, simulation of diffusion, structural annealing, and chemical reactions cannot be achieved with direct simulation of the classical dynamics. Alternative approaches are needed. One such approach is transition state theory as implemented in the adaptive kinetic Monte Carlo algorithm, which, thus far, has relied on the harmonic approximation but could be extended and made applicable to systems with rougher energy landscape and transitions through quantum mechanical tunneling. PMID:21199939

In situ synthesis and surface functionalization of gold nanoparticles with curcumin and their antioxidant properties: an experimental and density functional theory investigation.

PubMed

Singh, Dheeraj K; Jagannathan, Ramya; Khandelwal, Puneet; Abraham, Priya Mary; Poddar, Pankaj

2013-03-07

Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl(4) using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au(3+) ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au(3+) ions are reduced to Au(0). Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules.

Uniform and Janus-like nanoparticles in contact with vesicles: energy landscapes and curvature-induced forces.

PubMed

Agudo-Canalejo, Jaime; Lipowsky, Reinhard

2017-03-15

Biological membranes and lipid vesicles often display complex shapes with non-uniform membrane curvature. When adhesive nanoparticles with chemically uniform surfaces come into contact with such membranes, they exhibit four different engulfment regimes as recently shown by a systematic stability analysis. Depending on the local curvature of the membrane, the particles either remain free, become partially or completely engulfed by the membrane, or display bistability between free and completely engulfed states. Here, we go beyond stability analysis and develop an analytical theory to leading order in the ratio of particle-to-vesicle size. This theory allows us to determine the local and global energy landscapes of uniform nanoparticles that are attracted towards membranes and vesicles. While the local energy landscape depends only on the local curvature of the vesicle membrane and not on the overall membrane shape, the global energy landscape describes the variation of the equilibrium state of the particle as it probes different points along the membrane surface. In particular, we find that the binding energy of a partially engulfed particle depends on the 'unperturbed' local curvature of the membrane in the absence of the particle. This curvature dependence leads to local forces that pull the partially engulfed particles towards membrane segments with lower and higher mean curvature if the particles originate from the exterior and interior solution, respectively, corresponding to endo- and exocytosis. Thus, for partial engulfment, endocytic particles undergo biased diffusion towards the membrane segments with the lowest membrane curvature, whereas exocytic particles move towards segments with the highest curvature. The curvature-induced forces are also effective for Janus particles with one adhesive and one non-adhesive surface domain. In fact, Janus particles with a strongly adhesive surface domain are always partially engulfed which implies that they provide convenient probes for experimental studies of the curvature-induced forces that arise for complex-shaped membranes.

Equivariant Verlinde Formula from Fivebranes and Vortices

NASA Astrophysics Data System (ADS)

Gukov, Sergei; Pei, Du

2017-10-01

We study complex Chern-Simons theory on a Seifert manifold M 3 by embedding it into string theory. We show that complex Chern-Simons theory on M 3 is equivalent to a topologically twisted supersymmetric theory and its partition function can be naturally regularized by turning on a mass parameter. We find that the dimensional reduction of this theory to 2d gives the low energy dynamics of vortices in four-dimensional gauge theory, the fact apparently overlooked in the vortex literature. We also generalize the relations between (1) the Verlinde algebra, (2) quantum cohomology of the Grassmannian, (3) Chern-Simons theory on {Σ× S^1} and (4) index of a spin c Dirac operator on the moduli space of flat connections to a new set of relations between (1) the "equivariant Verlinde algebra" for a complex group, (2) the equivariant quantum K-theory of the vortex moduli space, (3) complex Chern-Simons theory on {Σ × S^1} and (4) the equivariant index of a spin c Dirac operator on the moduli space of Higgs bundles.

Catalytic Activity and Proton Translocation of Reconstituted Respiratory Complex I Monitored by Surface-Enhanced Infrared Absorption Spectroscopy.

PubMed

Gutiérrez-Sanz, Oscar; Forbrig, Enrico; Batista, Ana P; Pereira, Manuela M; Salewski, Johannes; Mroginski, Maria A; Götz, Robert; De Lacey, Antonio L; Kozuch, Jacek; Zebger, Ingo

2018-05-22

Respiratory complex I (CpI) is a key player in the way organisms obtain energy, being an energy transducer, which couples nicotinamide adenine dinucleotide (NADH)/quinone oxidoreduction with proton translocation by a mechanism that remains elusive so far. In this work, we monitored the function of CpI in a biomimetic, supported lipid membrane system assembled on a 4-aminothiophenol (4-ATP) self-assembled monolayer by surface-enhanced infrared absorption spectroscopy. 4-ATP serves not only as a linker molecule to a nanostructured gold surface but also as pH sensor, as indicated by concomitant density functional theory calculations. In this way, we were able to monitor NADH/quinone oxidoreduction-induced transmembrane proton translocation via the protonation state of 4-ATP, depending on the net orientation of CpI molecules induced by two complementary approaches. An associated change of the amide I/amide II band intensity ratio indicates conformational modifications upon catalysis which may involve movements of transmembrane helices or other secondary structural elements, as suggested in the literature [ Di Luca , Proc. Natl. Acad. Sci. U.S.A. , 2017 , 114 , E6314 - E6321 ].

A Multiscale Model for Virus Capsid Dynamics

PubMed Central

Chen, Changjun; Saxena, Rishu; Wei, Guo-Wei

2010-01-01

Viruses are infectious agents that can cause epidemics and pandemics. The understanding of virus formation, evolution, stability, and interaction with host cells is of great importance to the scientific community and public health. Typically, a virus complex in association with its aquatic environment poses a fabulous challenge to theoretical description and prediction. In this work, we propose a differential geometry-based multiscale paradigm to model complex biomolecule systems. In our approach, the differential geometry theory of surfaces and geometric measure theory are employed as a natural means to couple the macroscopic continuum domain of the fluid mechanical description of the aquatic environment from the microscopic discrete domain of the atomistic description of the biomolecule. A multiscale action functional is constructed as a unified framework to derive the governing equations for the dynamics of different scales. We show that the classical Navier-Stokes equation for the fluid dynamics and Newton's equation for the molecular dynamics can be derived from the least action principle. These equations are coupled through the continuum-discrete interface whose dynamics is governed by potential driven geometric flows. PMID:20224756

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Understanding the biological underpinnings of ecohydrological processes

NASA Astrophysics Data System (ADS)

Huxman, T. E.; Scott, R. L.; Barron-Gafford, G. A.; Hamerlynck, E. P.; Jenerette, D.; Tissue, D. T.; Breshears, D. D.; Saleska, S. R.

2012-12-01

Climate change presents a challenge for predicting ecosystem response, as multiple factors drive both the physical and life processes happening on the land surface and their interactions result in a complex, evolving coupled system. For example, changes in surface temperature and precipitation influence near-surface hydrology through impacts on system energy balance, affecting a range of physical processes. These changes in the salient features of the environment affect biological processes and elicit responses along the hierarchy of life (biochemistry to community composition). Many of these structural or process changes can alter patterns of soil water-use and influence land surface characteristics that affect local climate. Of the many features that affect our ability to predict the future dynamics of ecosystems, it is this hierarchical response of life that creates substantial complexity. Advances in the ability to predict or understand aspects of demography help describe thresholds in coupled ecohydrological system. Disentangling the physical and biological features that underlie land surface dynamics following disturbance are allowing a better understanding of the partitioning of water in the time-course of recovery. Better predicting the timing of phenology and key seasonal events allow for a more accurate description of the full functional response of the land surface to climate. In addition, explicitly considering the hierarchical structural features of life are helping to describe complex time-dependent behavior in ecosystems. However, despite this progress, we have yet to build an ability to fully account for the generalization of the main features of living systems into models that can describe ecohydrological processes, especially acclimation, assembly and adaptation. This is unfortunate, given that many key ecosystem services are functions of these coupled co-evolutionary processes. To date, both the lack of controlled measurements and experimentation has precluded determination of sufficient theoretical development. Understanding the land-surface response and feedback to climate change requires a mechanistic understanding of the coupling of ecological and hydrological processes and an expansion of theory from the life sciences to appropriately contribute to the broader Earth system science goal.

Complexity-action duality of the shock wave geometry in a massive gravity theory

NASA Astrophysics Data System (ADS)

Miao, Yan-Gang; Zhao, Long

2018-01-01

On the holographic complexity dual to the bulk action, we investigate the action growth for a shock wave geometry in a massive gravity theory within the Wheeler-DeWitt (WDW) patch at the late time limit. For a global shock wave, the graviton mass does not affect the action growth in the bulk, i.e., the complexity on the boundary, showing that the action growth (complexity) is the same for both the Einstein gravity and the massive gravity. Nevertheless, for a local shock wave that depends on transverse coordinates, the action growth (complexity) caused by the boundary disturbance (perturbation) is proportional to the butterfly velocity for the two gravity theories, but the butterfly velocity of the massive gravity theory is smaller than that of the Einstein gravity theory, indicating that the action growth (complexity) of the massive gravity is depressed by the graviton mass. In addition, we extend the black hole thermodynamics of the massive gravity and obtain the right Smarr formula.

Theory and Application of Photoelectron Diffraction for Complex Oxide Systems

NASA Astrophysics Data System (ADS)

Chassé, Angelika; Chassé, Thomas

2018-06-01

X-ray photoelectron diffraction (XPD) has been used to investigate film structures and local sites of surface and dopant atoms in complex oxide materials. We have performed angular-resolved measurements of intensity distribution curves (ADCs) and patterns (ADPs) of elemental core level intensities from binary to quaternary mixed oxide samples and compared them to multiple-scattering cluster (MSC) calculations in order to derive information on structural models and related parameters. MSC calculations permitted to describe both bulk diffraction features of binary oxide MnO(001) and the thickness-dependence of the tetragonal distortion of epitaxial MnO films on Ag(001). XPD was further used to investigate the surface termination of perovskite SrTiO3 and BaTiO3 substrates in order to evaluate influence of different ex situ and in situ preparation procedures on the surface layers, which are crucial for quality of following film growth. Despite the similarity of local environments of Sr (Ba) and Ti atoms in the perovskite film structure an angular region in the ADCs was identified as a fingerprint with the help of MSC simulations which provided clear conclusions on the perovskite oxide surfaces. Dopant sites in quaternary perovskite manganites La1-xCaxMnO3, La1-xSrxMnO3, and La1-xCexMnO3 were studied with polar angle scans of the photoemission intensities of host and dopant atoms. Both direct comparison of experimental ADCs and to the simulations within MSC models confirm the occupation of A sites by the dopants and the structural quality of the complex oxide films.

An analytical method for computing atomic contact areas in biomolecules.

PubMed

Mach, Paul; Koehl, Patrice

2013-01-15

We propose a new analytical method for detecting and computing contacts between atoms in biomolecules. It is based on the alpha shape theory and proceeds in three steps. First, we compute the weighted Delaunay triangulation of the union of spheres representing the molecule. In the second step, the Delaunay complex is filtered to derive the dual complex. Finally, contacts between spheres are collected. In this approach, two atoms i and j are defined to be in contact if their centers are connected by an edge in the dual complex. The contact areas between atom i and its neighbors are computed based on the caps formed by these neighbors on the surface of i; the total area of all these caps is partitioned according to their spherical Laguerre Voronoi diagram on the surface of i. This method is analytical and its implementation in a new program BallContact is fast and robust. We have used BallContact to study contacts in a database of 1551 high resolution protein structures. We show that with this new definition of atomic contacts, we generate realistic representations of the environments of atoms and residues within a protein. In particular, we establish the importance of nonpolar contact areas that complement the information represented by the accessible surface areas. This new method bears similarity to the tessellation methods used to quantify atomic volumes and contacts, with the advantage that it does not require the presence of explicit solvent molecules if the surface of the protein is to be considered. © 2012 Wiley Periodicals, Inc. Copyright © 2012 Wiley Periodicals, Inc.

Classical theory of atom-surface scattering: The rainbow effect

NASA Astrophysics Data System (ADS)

Miret-Artés, Salvador; Pollak, Eli

2012-07-01

The scattering of heavy atoms and molecules from surfaces is oftentimes dominated by classical mechanics. A large body of experiments have gathered data on the angular distributions of the scattered species, their energy loss distribution, sticking probability, dependence on surface temperature and more. For many years these phenomena have been considered theoretically in the framework of the “washboard model” in which the interaction of the incident particle with the surface is described in terms of hard wall potentials. Although this class of models has helped in elucidating some of the features it left open many questions such as: true potentials are clearly not hard wall potentials, it does not provide a realistic framework for phonon scattering, and it cannot explain the incident angle and incident energy dependence of rainbow scattering, nor can it provide a consistent theory for sticking. In recent years we have been developing a classical perturbation theory approach which has provided new insight into the dynamics of atom-surface scattering. The theory includes both surface corrugation as well as interaction with surface phonons in terms of harmonic baths which are linearly coupled to the system coordinates. This model has been successful in elucidating many new features of rainbow scattering in terms of frictions and bath fluctuations or noise. It has also given new insight into the origins of asymmetry in atomic scattering from surfaces. New phenomena deduced from the theory include friction induced rainbows, energy loss rainbows, a theory of super-rainbows, and more. In this review we present the classical theory of atom-surface scattering as well as extensions and implications for semiclassical scattering and the further development of a quantum theory of surface scattering. Special emphasis is given to the inversion of scattering data into information on the particle-surface interactions.

Classical theory of atom-surface scattering: The rainbow effect

NASA Astrophysics Data System (ADS)

Miret-Artés, Salvador; Pollak, Eli

The scattering of heavy atoms and molecules from surfaces is oftentimes dominated by classical mechanics. A large body of experiments have gathered data on the angular distributions of the scattered species, their energy loss distribution, sticking probability, dependence on surface temperature and more. For many years these phenomena have been considered theoretically in the framework of the "washboard model" in which the interaction of the incident particle with the surface is described in terms of hard wall potentials. Although this class of models has helped in elucidating some of the features it left open many questions such as: true potentials are clearly not hard wall potentials, it does not provide a realistic framework for phonon scattering, and it cannot explain the incident angle and incident energy dependence of rainbow scattering, nor can it provide a consistent theory for sticking. In recent years we have been developing a classical perturbation theory approach which has provided new insight into the dynamics of atom-surface scattering. The theory includes both surface corrugation as well as interaction with surface phonons in terms of harmonic baths which are linearly coupled to the system coordinates. This model has been successful in elucidating many new features of rainbow scattering in terms of frictions and bath fluctuations or noise. It has also given new insight into the origins of asymmetry in atomic scattering from surfaces. New phenomena deduced from the theory include friction induced rainbows, energy loss rainbows, a theory of super-rainbows, and more. In this review we present the classical theory of atom-surface scattering as well as extensions and implications for semiclassical scattering and the further development of a quantum theory of surface scattering. Special emphasis is given to the inversion of scattering data into information on the particle-surface interactions.

Predicting surface scatter using a linear systems formulation of non-paraxial scalar diffraction

NASA Astrophysics Data System (ADS)

Krywonos, Andrey

Scattering effects from rough surfaces are non-paraxial diffraction phenomena resulting from random phase variations in the reflected wavefront. The ability to predict these effects is important in a variety of applications including x-ray and EUV imaging, the design of stray light rejection systems, and reflection modeling for rendering realistic scenes and animations of physical objects in computer graphics. Rayleigh-Rice (small perturbation method) and Beckmann-Kirchoff (Kirchhoff approximation) theories are commonly used to predict surface scatter effects. In addition, Harvey and Shack developed a linear systems formulation of surface scatter phenomena in which the scattering behavior is characterized by a surface transfer function. This treatment provided insight and understanding not readily gleaned from the two previous theories, and has been incorporated into a variety of computer software packages (ASAP, Zemax, Tracepro). However, smooth surface and paraxial approximations have severely limited the range of applicability of each of the above theoretical treatments. In this dissertation, a linear systems formulation of non-paraxial scalar diffraction theory is first developed and then applied to sinusoidal phase gratings, resulting in diffraction efficiency predictions far more accurate than those provided by classical scalar theories. The application of the theory to these gratings was motivated by the fact that rough surfaces are frequently modeled as a superposition of sinusoidal surfaces of different amplitudes, periods, and orientations. The application of the non-paraxial scalar diffraction theory to surface scatter phenomena resulted first in a modified Beckmann-Kirchhoff surface scattering model, then a generalized Harvey-Shack theory, both of which produce accurate results for rougher surfaces than the Rayleigh-Rice theory and for larger incident and scattering angles than the classical Beckmann-Kirchhoff theory. These new developments enable the analysis and simplify the understanding of wide-angle scattering behavior from rough surfaces illuminated at large incident angles. In addition, they provide an improved BRDF (Bidirectional Reflectance Distribution Function) model, particularly for the smooth surface inverse scattering problem of determining surface power spectral density (PSD) curves from BRDF measurements.

Divergences in holographic complexity

NASA Astrophysics Data System (ADS)

Reynolds, Alan; Ross, Simon F.

2017-05-01

We study the UV divergences in the action of the ‘Wheeler-de Witt patch’ in asymptotically AdS spacetimes, which has been conjectured to be dual to the computational complexity of the state of the dual field theory on a spatial slice of the boundary. We show that including a surface term in the action on the null boundaries which ensures invariance under coordinate transformations has the additional virtue of removing a stronger than expected divergence, making the leading divergence proportional to the proper volume of the boundary spatial slice. We compare the divergences in the action to divergences in the volume of a maximal spatial slice in the bulk, finding that the qualitative structure is the same, but subleading divergences have different relative coefficients in the two cases.

A New Reynolds Stress Algebraic Equation Model

NASA Technical Reports Server (NTRS)

Shih, Tsan-Hsing; Zhu, Jiang; Lumley, John L.

1994-01-01

A general turbulent constitutive relation is directly applied to propose a new Reynolds stress algebraic equation model. In the development of this model, the constraints based on rapid distortion theory and realizability (i.e. the positivity of the normal Reynolds stresses and the Schwarz' inequality between turbulent velocity correlations) are imposed. Model coefficients are calibrated using well-studied basic flows such as homogeneous shear flow and the surface flow in the inertial sublayer. The performance of this model is then tested in complex turbulent flows including the separated flow over a backward-facing step and the flow in a confined jet. The calculation results are encouraging and point to the success of the present model in modeling turbulent flows with complex geometries.

Surface plasticity: theory and computation

NASA Astrophysics Data System (ADS)

Esmaeili, A.; Steinmann, P.; Javili, A.

2017-11-01

Surfaces of solids behave differently from the bulk due to different atomic rearrangements and processes such as oxidation or aging. Such behavior can become markedly dominant at the nanoscale due to the large ratio of surface area to bulk volume. The surface elasticity theory (Gurtin and Murdoch in Arch Ration Mech Anal 57(4):291-323, 1975) has proven to be a powerful strategy to capture the size-dependent response of nano-materials. While the surface elasticity theory is well-established to date, surface plasticity still remains elusive and poorly understood. The objective of this contribution is to establish a thermodynamically consistent surface elastoplasticity theory for finite deformations. A phenomenological isotropic plasticity model for the surface is developed based on the postulated elastoplastic multiplicative decomposition of the surface superficial deformation gradient. The non-linear governing equations and the weak forms thereof are derived. The numerical implementation is carried out using the finite element method and the consistent elastoplastic tangent of the surface contribution is derived. Finally, a series of numerical examples provide further insight into the problem and elucidate the key features of the proposed theory.

A continuum state variable theory to model the size-dependent surface energy of nanostructures.

PubMed

Jamshidian, Mostafa; Thamburaja, Prakash; Rabczuk, Timon

2015-10-14

We propose a continuum-based state variable theory to quantify the excess surface free energy density throughout a nanostructure. The size-dependent effect exhibited by nanoplates and spherical nanoparticles i.e. the reduction of surface energy with reducing nanostructure size is well-captured by our continuum state variable theory. Our constitutive theory is also able to predict the reducing energetic difference between the surface and interior (bulk) portions of a nanostructure with decreasing nanostructure size.

Why did the apple fall? A new model to explain Einstein’s gravity

NASA Astrophysics Data System (ADS)

Stannard, Warren; Blair, David; Zadnik, Marjan; Kaur, Tejinder

2017-01-01

Newton described gravity as an attractive force between two masses but Einstein’s General Theory of Relativity provides a very different explanation. Implicit in Einstein’s theory is the idea that gravitational effects are the result of a distortion in the shape of space-time. Despite its elegance, Einstein’s concept of gravity is rarely encountered outside of an advanced physics course as it is often considered to be too complex and too mathematical. This paper describes a new conceptual and quantitative model of gravity based on General Relativity at a level most science students should be able to understand. The model illustrates geodesics using analogies with paths of navigation on the surface of the Earth. This is extended to space and time maps incorporating the time warping effects of General Relativity. Using basic geometry, the geodesic path of a falling object near the surface of the Earth is found. From this the acceleration of an object in free fall is calculated. The model presented in this paper can answer the question, ‘Why do things fall?’ without resorting to Newton’s gravitational force.

Imaging of Formaldehyde Adsorption and Diffusion on TiO2(110)

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

Zhang, Zhenrong; Tang, Miru; Wang, Zhitao

2015-03-01

Surface reactions of formaldehyde with reduced TiO2(110) surfaces have been studied using variable-temperature scanning tunneling microscopy (STM) and density functional theory (DFT). STM results show that formaldehyde preferably adsorbs on the bridging bonded oxygen (Ob) vacancy (VO) defect site. Bias-dependent STM images show that both the Ti-bound CH2O and the VO-bound CH2O are positioned between the Ob row and the Ti row. The VO-bound formaldehyde rotates at 95 K. It starts to diffuse along the Ob row as –CH2– at ~170 K and starts to diffuse along the Ti row as a molecule at ~215 K. However, the stabilities andmore » the configurations of the Ti-bound and the VO-bound formaldehyde calculated using DFT are not in line with the experimental results. The values of diffusion barriers determined experimentally and theoretically are also different. The discrepancy between the experiment and theory indicates the presence of a complex charge distribution related to the defects.« less

First-principles density functional theory (DFT) study of gold nanorod and its interaction with alkanethiol ligands.

PubMed

Hu, Hang; Reven, Linda; Rey, Alejandro

2013-10-17

The structure and mechanical properties of gold nanorods and their interactions with alkenthiolate self-assembled monolayers have been determined using a novel first-principle density functional theory simulation approach. The multifaceted, 1-dimensional, octagonal nanorod has alternate Au100 and Au110 surfaces. The structural optimization of the gold nanorods was performed with a mixed basis: the outermost layer of gold atoms used double-ζ plus polarization (DZP), the layer below used double-ζ (DZ), and the inner layers used single-ζ (SZ). The final structure compares favorably with simulations using DZP for all atoms. Phonon dispersion calculations and ab initio molecular dynamics (AIMD) were used to establish the dynamic and thermal stability of the system. From the AIMD simulations it was found that the nanorod system will undergo significant surface reconstruction at 300 K. In addition, when subjected to mechanical stress in the axial direction, the nanorod responds as an orthotropic material, with uniform expansion along the radial direction. The Young's moduli are 207 kbar in the axial direction and 631 kbar in the radial direction. The binding of alkanethiolates, ranging from methanethiol to pentanethiol, caused formation of surface point defects on the Au110 surfaces. On the Au100 surfaces, the defects occurred in the inner layer, creating a small surface island. These defects make positive and negative concavities on the gold nanorod surface, which helps the ligand to achieve a more stable state. The simulation results narrowed significant knowledge gaps on the alkanethiolate adsorption process and on their mutual interactions on gold nanorods. The mechanical characterization offers a new dimension to understand the physical chemistry of these complex nanoparticles.

Potassium-induced effect on structure and chemical activity of Cu xO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study

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

Liu, Ping; An, Wei; Stacchiola, Dario

2015-10-16

Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of Cu xO/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on Cu xO/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on themore » Cu xO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of Cu xO/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on Cu xO/Cu(111), but being able to accelerate the activation of CO 2. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.« less

DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages

NASA Astrophysics Data System (ADS)

Jouypazadeh, Hamidreza; Farrokhpour, Hossein

2018-07-01

In the present research, the interaction of sulfur mustard, a chemical warfare agent, with the surface of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages was studied using the dispersion corrected density function theory (DFT-D3) method. The calculated adsorption energies of sulfur mustard on the surface of the nanocages showed that the Al12N12, C12Si12 and Mg12O12 are useful for the adsorption of the sulfur mustard. The quantum theory atom in molecule (QTAIM) analysis was used to study the nature of interactions of sulfur mustard with the surface of the selected nanocages. Based on QTAIM analysis, the majority of interactions of sulfur and chlorine atoms of sulfur mustard with the surface of the considered nanocages are covalent and quasi covalent whereas the interactions of hydrogen atoms of sulfur mustard with the surface of the nanocages are generally non-covalent. The charge transfer between sulfur mustard and the nanocages as well as chemical quantum descriptors of complexes were calculated using natural bond orbital (NBO) method. The most electron charge transfers from the sulfur mustard to B12N12 nanocage where the S atom of sulfur mustard donor a chemical bond to B atom of the nanocage. The ability of the considered nanocages for detecting sulfur mustard was studied using time-dependent density function theory (TD-DFT) and density of state (DOS) diagram. It is found that the C24, Al12P12, Be12O12 and B12N12 nanocages are useful sensors for this chemical agent.

New Communitarianism Movements and Complex Utopia

NASA Astrophysics Data System (ADS)

Akdeniz, K. Gediz

Simulation is a rapidly growing field in social sciences. Simulation theories in social sciences are considered to critique social dynamics and societies which are mostly simulated by media, cinema, TV, internet, etc. Recently we (Akdeniz KG, Disorder in complex human system. In: Fritzsch H, Phua KK (eds) Singapore: proceedings of the conference in Honour of Murray Gell-Mann's 80th birthday quantum mechanics, elementary particles, quantum cosmology and complexity. World Scientific Publishing, Hackensack, pp 630-637, 2009) purposed a simulation theory as a critique theory to investigate disordered human behaviors. In this theory, "Disorder-Sensitive Human Behaviors (DSHB) Simulation Theory", chaotic awareness is also considered as a reality principle in simulation world to complete Baudrillard Simulation Theory (Baudrillard J, Simulacra and simulation. University of Michigan Press, Michigan, 1995). We call the emergence of this reality as zuhur which is different than simulacra. More recently we proposed the complex utopia (Akdeniz KG, From Simulacra to Zuhur in Complex Utopia. 11th International Conference of the Utopian Studies Society, Lublin, 2010; Akdeniz KG, The new identities of the physicist: cyborg-physicist and post-physicist. In: Proceedings of the conference of world international conference of technology and education, Beirut, 2010) to critique the complex societies and communities in simulation world. The challenging agents in the complex utopia are both simulacra and zuhur. In this paper we would like to review "What is the complex utopia?" And we shall critique some global events in framework of complex utopia with particular examples in socio-economic and political contexts.

Single-photon test of hyper-complex quantum theories using a metamaterial.

PubMed

Procopio, Lorenzo M; Rozema, Lee A; Wong, Zi Jing; Hamel, Deny R; O'Brien, Kevin; Zhang, Xiang; Dakić, Borivoje; Walther, Philip

2017-04-21

In standard quantum mechanics, complex numbers are used to describe the wavefunction. Although this has so far proven sufficient to predict experimental results, there is no theoretical reason to choose them over real numbers or generalizations of complex numbers, that is, hyper-complex numbers. Experiments performed to date have proven that real numbers are insufficient, but the need for hyper-complex numbers remains an open question. Here we experimentally probe hyper-complex quantum theories, studying one of their deviations from complex quantum theory: the non-commutativity of phases. We do so by passing single photons through a Sagnac interferometer containing both a metamaterial with a negative refractive index, and a positive phase shifter. To accomplish this we engineered a fishnet metamaterial to have a negative refractive index at 780 nm. We show that the metamaterial phase commutes with other phases with high precision, allowing us to place limits on a particular prediction of hyper-complex quantum theories.

Single-photon test of hyper-complex quantum theories using a metamaterial

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

Procopio, Lorenzo M.; Rozema, Lee A.; Wong, Zi Jing

In standard quantum mechanics, complex numbers are used to describe the wavefunction. Although this has so far proven sufficient to predict experimental results, there is no theoretical reason to choose them over real numbers or generalizations of complex numbers, that is, hyper-complex numbers. Experiments performed to date have proven that real numbers are insufficient, but the need for hyper-complex numbers remains an open question. Here we experimentally probe hyper-complex quantum theories, studying one of their deviations from complex quantum theory: the non-commutativity of phases. We do so by passing single photons through a Sagnac interferometer containing both a metamaterial withmore » a negative refractive index, and a positive phase shifter. In order to accomplish this we engineered a fishnet metamaterial to have a negative refractive index at 780 nm. Here, we show that the metamaterial phase commutes with other phases with high precision, allowing us to place limits on a particular prediction of hyper-complex quantum theories.« less

Single-photon test of hyper-complex quantum theories using a metamaterial

DOE PAGES

Procopio, Lorenzo M.; Rozema, Lee A.; Wong, Zi Jing; ...

2017-04-21

In standard quantum mechanics, complex numbers are used to describe the wavefunction. Although this has so far proven sufficient to predict experimental results, there is no theoretical reason to choose them over real numbers or generalizations of complex numbers, that is, hyper-complex numbers. Experiments performed to date have proven that real numbers are insufficient, but the need for hyper-complex numbers remains an open question. Here we experimentally probe hyper-complex quantum theories, studying one of their deviations from complex quantum theory: the non-commutativity of phases. We do so by passing single photons through a Sagnac interferometer containing both a metamaterial withmore » a negative refractive index, and a positive phase shifter. In order to accomplish this we engineered a fishnet metamaterial to have a negative refractive index at 780 nm. Here, we show that the metamaterial phase commutes with other phases with high precision, allowing us to place limits on a particular prediction of hyper-complex quantum theories.« less

Single-photon test of hyper-complex quantum theories using a metamaterial

PubMed Central

Procopio, Lorenzo M.; Rozema, Lee A.; Wong, Zi Jing; Hamel, Deny R.; O'Brien, Kevin; Zhang, Xiang; Dakić, Borivoje; Walther, Philip

2017-01-01

In standard quantum mechanics, complex numbers are used to describe the wavefunction. Although this has so far proven sufficient to predict experimental results, there is no theoretical reason to choose them over real numbers or generalizations of complex numbers, that is, hyper-complex numbers. Experiments performed to date have proven that real numbers are insufficient, but the need for hyper-complex numbers remains an open question. Here we experimentally probe hyper-complex quantum theories, studying one of their deviations from complex quantum theory: the non-commutativity of phases. We do so by passing single photons through a Sagnac interferometer containing both a metamaterial with a negative refractive index, and a positive phase shifter. To accomplish this we engineered a fishnet metamaterial to have a negative refractive index at 780 nm. We show that the metamaterial phase commutes with other phases with high precision, allowing us to place limits on a particular prediction of hyper-complex quantum theories. PMID:28429711

Origins of life: a comparison of theories and application to Mars

NASA Technical Reports Server (NTRS)

Davis, W. L.; McKay, C. P.

1996-01-01

The field of study that deals with the origins of life does not have a consensus for a theory of life's origin. An analysis of the range of theories offered shows that they share some common features that may be reliable predictors when considering the possible origins of life on another planet. The fundamental datum dealing with the origins of life is that life appeared early in the history of the Earth, probably before 3.5 Ga and possibly before 3.8 Ga. What might be called the standard theory (the Oparin-Haldane theory) posits the production of organic molecules on the early Earth followed by chemical reactions that produced increased organic complexity leading eventually to organic life capable of reproduction, mutation, and selection using organic material as nutrients. A distinct class of other theories (panspermia theories) suggests that life was carried to Earth from elsewhere--these theories receive some support from recent work on planetary impact processes. Other alternatives to the standard model suggest that life arose as an inorganic (clay) form and/or that the initial energy source was not organic material but chemical energy or sunlight. We find that the entire range of current theories suggests that liquid water is the quintessential environmental criterion for both the origin and sustenance of life. It is therefore of interest that during the time that life appeared on Earth we have evidence for liquid water present on the surface of Mars.

A Combined Theoretical and Experimental Study for Silver Electroplating

PubMed Central

Liu, Anmin; Ren, Xuefeng; An, Maozhong; Zhang, Jinqiu; Yang, Peixia; Wang, Bo; Zhu, Yongming; Wang, Chong

2014-01-01

A novel method combined theoretical and experimental study for environmental friendly silver electroplating was introduced. Quantum chemical calculations and molecular dynamic (MD) simulations were employed for predicting the behaviour and function of the complexing agents. Electronic properties, orbital information, and single point energies of the 5,5-dimethylhydantoin (DMH), nicotinic acid (NA), as well as their silver(I)-complexes were provided by quantum chemical calculations based on density functional theory (DFT). Adsorption behaviors of the agents on copper and silver surfaces were investigated using MD simulations. Basing on the data of quantum chemical calculations and MD simulations, we believed that DMH and NA could be the promising complexing agents for silver electroplating. The experimental results, including of electrochemical measurement and silver electroplating, further confirmed the above prediction. This efficient and versatile method thus opens a new window to study or design complexing agents for generalized metal electroplating and will vigorously promote the level of this research region. PMID:24452389

Ab initio theory of point defects in oxide materials: structure, properties, chemical reactivity

NASA Astrophysics Data System (ADS)

Pacchioni, Gianfranco

2000-05-01

Point defects play a fundamental role in determining the physical and chemical properties of inorganic materials. This holds not only for the bulk properties but also for the surface of oxides where several kinds of point defects exist and exhibit a rich and complex chemistry. A particularly important defect in oxides is the oxygen vacancy. Depending on the electronic structure of the material the nature of oxygen vacancies changes dramatically. In this article we provide a rationalization of the very different electronic structure of neutral and charged oxygen vacancies in SiO 2 and MgO, two oxide materials with completely different electronic structure (from very ionic, MgO, to largely covalent, SiO 2). We used methods of ab initio quantum chemistry, from density functional theory (DFT) to configuration interaction (CI), to determine the ground and excited state properties of these defects. The theoretical results are combined with recent spectroscopic measurements. A series of observable properties has been determined in this way: defect formation energies, hyperfine interactions in electron paramagnetic resonance (EPR) spectra of paramagnetic centers, optical spectra, surface chemical reactivity. The interplay between experimental and theoretical information allows one to unambiguously identify the structure of oxygen vacancies in these binary oxides and on their surfaces.

On the theory of drainage area for regular and non-regular points.

PubMed

Bonetti, S; Bragg, A D; Porporato, A

2018-03-01

The drainage area is an important, non-local property of a landscape, which controls surface and subsurface hydrological fluxes. Its role in numerous ecohydrological and geomorphological applications has given rise to several numerical methods for its computation. However, its theoretical analysis has lagged behind. Only recently, an analytical definition for the specific catchment area was proposed (Gallant & Hutchinson. 2011 Water Resour. Res. 47 , W05535. (doi:10.1029/2009WR008540)), with the derivation of a differential equation whose validity is limited to regular points of the watershed. Here, we show that such a differential equation can be derived from a continuity equation (Chen et al. 2014 Geomorphology 219 , 68-86. (doi:10.1016/j.geomorph.2014.04.037)) and extend the theory to critical and singular points both by applying Gauss's theorem and by means of a dynamical systems approach to define basins of attraction of local surface minima. Simple analytical examples as well as applications to more complex topographic surfaces are examined. The theoretical description of topographic features and properties, such as the drainage area, channel lines and watershed divides, can be broadly adopted to develop and test the numerical algorithms currently used in digital terrain analysis for the computation of the drainage area, as well as for the theoretical analysis of landscape evolution and stability.

On the theory of drainage area for regular and non-regular points

NASA Astrophysics Data System (ADS)

Bonetti, S.; Bragg, A. D.; Porporato, A.

2018-03-01

The drainage area is an important, non-local property of a landscape, which controls surface and subsurface hydrological fluxes. Its role in numerous ecohydrological and geomorphological applications has given rise to several numerical methods for its computation. However, its theoretical analysis has lagged behind. Only recently, an analytical definition for the specific catchment area was proposed (Gallant & Hutchinson. 2011 Water Resour. Res. 47, W05535. (doi:10.1029/2009WR008540)), with the derivation of a differential equation whose validity is limited to regular points of the watershed. Here, we show that such a differential equation can be derived from a continuity equation (Chen et al. 2014 Geomorphology 219, 68-86. (doi:10.1016/j.geomorph.2014.04.037)) and extend the theory to critical and singular points both by applying Gauss's theorem and by means of a dynamical systems approach to define basins of attraction of local surface minima. Simple analytical examples as well as applications to more complex topographic surfaces are examined. The theoretical description of topographic features and properties, such as the drainage area, channel lines and watershed divides, can be broadly adopted to develop and test the numerical algorithms currently used in digital terrain analysis for the computation of the drainage area, as well as for the theoretical analysis of landscape evolution and stability.

Using activity theory to study cultural complexity in medical education.

PubMed

Frambach, Janneke M; Driessen, Erik W; van der Vleuten, Cees P M

2014-06-01

There is a growing need for research on culture, cultural differences and cultural effects of globalization in medical education, but these are complex phenomena to investigate. Socio-cultural activity theory seems a useful framework to study cultural complexity, because it matches current views on culture as a dynamic process situated in a social context, and has been valued in diverse fields for yielding rich understandings of complex issues and key factors involved. This paper explains how activity theory can be used in (cross-)cultural medical education research. We discuss activity theory's theoretical background and principles, and we show how these can be applied to the cultural research practice by discussing the steps involved in a cross-cultural study that we conducted, from formulating research questions to drawing conclusions. We describe how the activity system, the unit of analysis in activity theory, can serve as an organizing principle to grasp cultural complexity. We end with reflections on the theoretical and practical use of activity theory for cultural research and note that it is not a shortcut to capture cultural complexity: it is a challenge for researchers to determine the boundaries of their study and to analyze and interpret the dynamics of the activity system.

Anharmonic vibrational spectroscopy, NBO charges and global chemical reactivity studies on the charge transfer PDCA-.AHMP+ single crystal using DFT calculations

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Afroz, Ziya; Bhat, Sheeraz Ahmad; Alam, Mohamad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-04-01

The charge transfer (CT) complex of the 2-amino-4-hydroxy-6-methylpyrimidine and 2,3 pyrazinedicarboxylic acid (PDCA-.AHMP+) was synthesized and its single crystal was grown by solution method. The structure of the crystalline complex has been investigated by single crystal X-ray diffraction (SCXRD). The vibrational features of the complex have been studied with the help of FTIR spectra and DFT computation. The anharmonic corrections in vibrational frequencies are made using the GVPT2 method at B3LYP/6-311++G(d,p) level of theory. The frontier molecular orbitals and global chemical reactivity have been calculated to understand the pharmacological aspect of the synthesized crystal. Furthermore, Hirshfeld electrostatic potential (ESP) surface, void space in the crystal structure and natural as well as Mulliken atomic charges are studied.

Nearside-farside, local angular momentum and resummation theories: Useful tools for understanding the dynamics of complex-mode reactions

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

Hankel, Marlies, E-mail: m.hankel@uq.edu.au, E-mail: j.n.l.connor@manchester.ac.uk; Connor, J. N. L., E-mail: m.hankel@uq.edu.au, E-mail: j.n.l.connor@manchester.ac.uk

2015-07-15

A valuable tool for understanding the dynamics of direct reactions is Nearside-Farside (NF) scattering theory. It makes a decomposition of the (resummed) partial wave series for the scattering amplitude, both for the differential cross section (DCS) and the Local Angular Momentum (LAM). This paper makes the first combined application of these techniques to complex-mode reactions. We ask if NF theory is a useful tool for their identification, in particular, can it distinguish complex-mode from direct-mode reactions? We also ask whether NF theory can identify NF interference oscillations in the full DCSs of complex-mode reactions. Our investigation exploits the fact thatmore » accurate quantum scattering matrix elements have recently become available for complex-mode reactions. We first apply NF theory to two simple models for the scattering amplitude of a complex-mode reaction: One involves a single Legendre polynomial; the other involves a single Legendre function of the first kind, whose form is suggested by complex angular momentum theory. We then study, at fixed translational energies, four state-to-state complex-mode reactions. They are: S({sup 1}D) + HD → SH + D, S({sup 1}D) + DH → SD + H, N({sup 2}D) +H{sub 2} → NH + H, and H{sup +} + D{sub 2} → HD + D{sup +}. We compare the NF results for the DCSs and LAMs with those for a state-to-state direct reaction, namely, F + H{sub 2} → FH + H. We demonstrate that NF theory is a valuable tool for identifying and analyzing the dynamics of complex-mode reactions.« less

Dissociation of water and Acetic acid on PbS from first principles

NASA Astrophysics Data System (ADS)

Satta, Alessandra; Ruggerone, Paolo; de Giudici, Giovanni

2008-03-01

The adsorption of complex molecules at mineral surfaces are crucial ingredients for understanding the mechanisms that rule the interaction between minerals and the biosphere and for predicting both the stability and the reactivity of minerals. The present work focuses mainly on the early stages of different adsorption reactions occurring at both the cleavage surface and a high-index vicinal surface of galena (PbS). We have studied the dissociation mechanism of water and acetic acid on the galena surfaces by means of ab initio calculations within the framework of the density functional theory in the generalized gradient approximation and of pseudopotential approach. The calculated adsorption energies of the molecules indicate the stepped surface as the most reactive, as expected. The free energy surface during the reaction process has been explored via metadynamics[1]. The optimized configurations of both reactants and products obtained, were then used to accurately calculate the dissociation energy via the Nudge Elastic Band method[2]. [1] A. Laio and M. Parrinello, PNAS 99, 12562 (2002). [2] G. Mills and H. Jonsson, Phys. Rev. Lett. 72, 1124 (1994).

Comparison of microfacet BRDF model to modified Beckmann-Kirchhoff BRDF model for rough and smooth surfaces.

PubMed

Butler, Samuel D; Nauyoks, Stephen E; Marciniak, Michael A

2015-11-02

A popular class of BRDF models is the microfacet models, where geometric optics is assumed. In contrast, more complex physical optics models may more accurately predict the BRDF, but the calculation is more resource intensive. These seemingly disparate approaches are compared in detail for the rough and smooth surface approximations of the modified Beckmann-Kirchhoff BRDF model, assuming Gaussian surface statistics. An approximation relating standard Fresnel reflection with the semi-rough surface polarization term, Q, is presented for unpolarized light. For rough surfaces, the angular dependence of direction cosine space is shown to be identical to the angular dependence in the microfacet distribution function. For polished surfaces, the same comparison shows a breakdown in the microfacet models. Similarities and differences between microfacet BRDF models and the modified Beckmann-Kirchhoff model are identified. The rationale for the original Beckmann-Kirchhoff F(bk)(2) geometric term relative to both microfacet models and generalized Harvey-Shack model is presented. A modification to the geometric F(bk)(2) term in original Beckmann-Kirchhoff BRDF theory is proposed.

Control of Orientation and Morphology of Crystals Grown Under Organic Templates

NASA Astrophysics Data System (ADS)

Stripe, Benjamin

Living creatures demonstrate an extraordinary ability to both grow and control the growth of inorganic crystals. These biominerals are found almost everywhere in nature from simple plants and plankton to our own teeth and bones. A great deal of research has been focused on how living creatures are able to achieve such control over the shape, size, orientation, and arrangement of these biominerals. Many studies have been done demonstrating the effects the presence of organic molecules can have on the morphology of nucleating inorganic crystals. These studies have led to the use of ordered arrays of biological molecules as templates to select the orientation of the crystals. Such experiments have had amazing success cataloging monolayers, orientations and morphologies of crystals grown beneath them. However, despite several decades of work, the exact mechanisms by which the orientation and morphology of crystals is selected by organic templates are still not known. The present study attempts to explain the complex interactions that take place at the template surface and decide the orientations and morphologies of the crystals that nucleate there. To do this, scanning electron microscopy (SEM), grazing incidence x-ray diffraction (GID), and x-ray reflectivity have been used to probe the templates and nucleating crystals in situ. The experiments described here seek to move beyond the well-studied two-component systems. In many of these two-component systems a single template and a single type of crystal are grown, and often many claims and comparisons are made about monolayer charge, crystal surface energies, stereochemical recognition, and lattice matches. However, almost all of the claims and comparisons are between systems that are different enough that assumptions about relative charge, strain, recognition, and lattice dynamics are either unfounded or poorly supported. To bridge this gap in the comparison of these different two-component systems the studies presented here are tunable three-component systems. These experiments allow for either continuously adjusting the template by means of two miscible monolayers or adjusting the growing crystals by incorporation of secondary ions. In either case, the idea is the same: we can more accurately compare two-component systems and isolate the controlling factor in the selection of orientation and morphology of the nucleating crystals. The results of these studies have shown that there is a complex interplay of charge, lattice parameters and kinetics. Despite this, we have been able to show that well-oriented growth of single non-dendritic crystals is limited to a fairly small range of surface charges and relative growth kinetics. Within this range, variations in the growing crystals can be seen based on changes in the average lattice parameters despite there being no evidence of direct epitaxy. Theories have evolved around the idea of stereochemical matching between the template and nucleating surface. These theories correlate the template molecular tilt to the orientation relative to the nucleation plane. However, these theories are not supported by the results presented in this manuscript. The data presented in this manuscript are suggestive of far more complex interfacial interactions involving an intermediary amorphous precursor, or possible networks of hydrated or hydrogen bonded ions than has been suggested in previous studies. Excitingly, it appears to be possible to control the selection of orientation using these multicomponent systems despite the complex interactions at the surface.

Studying complex interventions: reflections from the FEMHealth project on evaluating fee exemption policies in West Africa and Morocco.

PubMed

Marchal, Bruno; Van Belle, Sara; De Brouwere, Vincent; Witter, Sophie

2013-11-08

The importance of complexity in health care policy-making and interventions, as well as research and evaluation is now widely acknowledged, but conceptual confusion reigns and few applications of complexity concepts in research design have been published. Taking user fee exemption policies as an entry point, we explore the methodological consequences of 'complexity' for health policy research and evaluation. We first discuss the difference between simple, complicated and complex and introduce key concepts of complex adaptive systems theory. We then apply these to fee exemption policies. We describe how the FEMHealth research project attempts to address the challenges of complexity in its evaluation of fee exemption policies for maternal care. We present how the development of a programme theory for fee exemption policies was used to structure the overall design. This allowed for structured discussions on the hypotheses held by the researchers and helped to structure, integrate and monitor the sub-studies. We then show how the choice of data collection methods and tools for each sub-study was informed by the overall design. Applying key concepts from complexity theory proved useful in broadening our view on fee exemption policies and in developing the overall research design. However, we encountered a number of challenges, including maintaining adaptiveness of the design during the evaluation, and ensuring cohesion in the disciplinary diversity of the research teams. Whether the programme theory can fulfil its claimed potential to help making sense of the findings is yet to be tested. Experience from other studies allows for some moderate optimism. However, the biggest challenge complexity throws at health system researchers may be to deal with the unknown unknowns and the consequence that complex issues can only be understood in retrospect. From a complexity theory point of view, only plausible explanations can be developed, not predictive theories. Yet here, theory-driven approaches may help.

Arsenic interactions with a fullerene-like BN cage in the vacuum and aqueous phase.

PubMed

Beheshtian, Javad; Peyghan, Ali Ahmadi; Bagheri, Zargham

2013-02-01

Adsorption of arsenic ions, As (III and V), on the surface of fullerene-like B(12)N(12) cage has been explored in vacuum and aqueous phase using density functional theory in terms of Gibbs free energies, enthalpies, geometry, and density of state analysis. It was found that these ions can be strongly chemisorbed on the surface of the cluster in both vacuum and aqueous phase, resulting in significant changes in its electronic properties so that the cluster transforms from a semi-insulator to a semiconductor. The solvent significantly affects the geometry parameters and electronic properties of the As/B(12)N(12) complexes and the interaction between components is considerably weaker in the aqueous phase than that in the vacuum.

Nanoparticle heterodimers: The role of size and interparticle gap distance on the optical response

NASA Astrophysics Data System (ADS)

Mokkath, Junais Habeeb

2018-05-01

Composite plasmonic nanostructures with controlled size, shape and relative arrangement is a subject of significant current research interest. Much of this is stimulated by the prospects by generating enormous near-field enhancements of the surface and interparticle gap regions for potential applications in surface-enhanced spectroscopies. In this manuscript, using time-dependent density functional theory (TDDFT) calculations, we investigate how the optical response in size matched homodimers and size mismatched heterodimers composed of Aluminum modify while varying the size and interparticle gap distances in the sub-nanometer range. Both systems show interesting optical response evolution. In particular, the size mismatched heterodimers show even more complex optical response evolution due to a symmetry-breaking in the system.

Effective elastic properties of a van der Waals molecular monolayer at a metal surface

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Dae-Ho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jonathan; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat S.; Hyldgaard, Per; Bartels, Ludwig

2010-11-01

Adsorbing anthracene on a Cu(111) surface results in a wide range of complex and intriguing superstructures spanning a coverage range from 1 per 17 to 1 per 15 substrate atoms. In accompanying first-principles density-functional theory calculations we show the essential role of van der Waals interactions in estimating the variation in anthracene adsorption energy and height across the sample. We can thereby evaluate the compression of the anthracene film in terms of continuum elastic properties, which results in an effective Young’s modulus of 1.5 GPa and a Poisson ratio ≈0.1 . These values suggest interpretation of the molecular monolayer as a porous material—in marked congruence with our microscopic observations.

The CFVib Experiment: Control of Fluids in Microgravity with Vibrations

NASA Astrophysics Data System (ADS)

Fernandez, J.; Sánchez, P. Salgado; Tinao, I.; Porter, J.; Ezquerro, J. M.

2017-10-01

The Control of Fluids in Microgravity with Vibrations (CFVib) experiment was selected for the 2016 Fly Your Thesis! programme as part of the 65th ESA Parabolic Flight Campaign. The aim of the project is to observe the potentially complex behaviour of vibrated liquids in weightless environments and to investigate the extent to which small-amplitude vibrations can be used to influence and control this behaviour. Piezoelectric materials are used to generate high-frequency vibrations to drive surface waves and large-scale reorientation of the interface. The theory of vibroequilibria, which treats the quasi-stationary surface configurations achieved by this reorientation, was used to predict interesting parameter regimes and interpret fluid behaviour. Here we describe the scientific motivation, objectives, and design of the experiment.

Advances in the Theory of Complex Networks

NASA Astrophysics Data System (ADS)

Peruani, Fernando

An exhaustive and comprehensive review on the theory of complex networks would imply nowadays a titanic task, and it would result in a lengthy work containing plenty of technical details of arguable relevance. Instead, this chapter addresses very briefly the ABC of complex network theory, visiting only the hallmarks of the theoretical founding, to finally focus on two of the most interesting and promising current research problems: the study of dynamical processes on transportation networks and the identification of communities in complex networks.

In situ synthesis and surface functionalization of gold nanoparticles with curcumin and their antioxidant properties: an experimental and density functional theory investigation

NASA Astrophysics Data System (ADS)

Singh, Dheeraj K.; Jagannathan, Ramya; Khandelwal, Puneet; Abraham, Priya Mary; Poddar, Pankaj

2013-02-01

Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl4 using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au3+ ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au3+ ions are reduced to Au0. Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules.Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl4 using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au3+ ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au3+ ions are reduced to Au0. Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33776b

Applicability of Complexity Theory to Martian Fluvial Systems: A Preliminary Analysis

NASA Technical Reports Server (NTRS)

Rosenshein, E. B.

2003-01-01

In the last 15 years, terrestrial geomorphology has been revolutionized by the theories of chaotic systems, fractals, self-organization, and selforganized criticality. Except for the application of fractal theory to the analysis of lava flows and rampart craters on Mars, these theories have not yet been applied to problems of Martian landscape evolution. These complexity theories are elucidated below, along with the methods used to relate these theories to the realities of Martian fluvial systems.

Phased Array Imaging of Complex-Geometry Composite Components.

PubMed

Brath, Alex J; Simonetti, Francesco

2017-10-01

Progress in computational fluid dynamics and the availability of new composite materials are driving major advances in the design of aerospace engine components which now have highly complex geometries optimized to maximize system performance. However, shape complexity poses significant challenges to traditional nondestructive evaluation methods whose sensitivity and selectivity rapidly decrease as surface curvature increases. In addition, new aerospace materials typically exhibit an intricate microstructure that further complicates the inspection. In this context, an attractive solution is offered by combining ultrasonic phased array (PA) technology with immersion testing. Here, the water column formed between the complex surface of the component and the flat face of a linear or matrix array probe ensures ideal acoustic coupling between the array and the component as the probe is continuously scanned to form a volumetric rendering of the part. While the immersion configuration is desirable for practical testing, the interpretation of the measured ultrasonic signals for image formation is complicated by reflection and refraction effects that occur at the water-component interface. To account for refraction, the geometry of the interface must first be reconstructed from the reflected signals and subsequently used to compute suitable delay laws to focus inside the component. These calculations are based on ray theory and can be computationally intensive. Moreover, strong reflections from the interface can lead to a thick dead zone beneath the surface of the component which limits sensitivity to shallow subsurface defects. This paper presents a general approach that combines advanced computing for rapid ray tracing in anisotropic media with a 256-channel parallel array architecture. The full-volume inspection of complex-shape components is enabled through the combination of both reflected and transmitted signals through the part using a pair of arrays held in a yoke configuration. Experimental results are provided for specimens of increasing complexity relevant to aerospace applications such as fan blades. It is shown that PA technology can provide a robust solution to detect a variety of defects including porosity and waviness in composite parts.

Dual emission behavior of phenyleneethynylene gold(I) complexes dictated by intersystem crossing: a theoretical perspective.

PubMed

Wang, Li; Li, Yuanyuan; Zhang, Yanxin; He, Hongqing; Zhang, Jinglai

2015-02-25

In commonly studied gold(I) complexes with oligo (o-, p-, or m-phenyleneethynylene) (PE) ligands, an intriguing photophysical behavior is dual emission composed of fluorescence from S1 and phosphorescence from T1 which is dictated by effective intersystem crossing (ISC) process. In order to explore the salient photodynamics of such oligo-PE gold(I) complexes effectively, we have deliberately chosen three model complexes, namely, Ph-C≡C-Au(PMe3) (1a') and Ph-C≡C-(1,m)C6H4-C≡C-Au(PMe3) (m=4, 2a'; m=3, 3a') in place of the real system. Firstly, electronic structure methods based on DFT and TD-DFT are utilized to perform optimization calculations for the ground- and lowest-lying excited states, respectively. Next, basic photophysical properties including absorption and emission spectra are investigated by TD-DFT under the optimized geometries. Besides, on the basis of the electronic spectra herein, we succeed in searching for surface intersections as the minima on the seam of singlet-triplet surface crossings (SCs) at the CASSCF level of theory. By integration of the results available, the process of delayed fluorescence of triplet-triplet annihilation (TTA) and phosphorescence was displayed in detail with SCs playing the lead in monitoring the ISC. Copyright © 2014 Elsevier B.V. All rights reserved.

Programming of the complex logarithm function in the solution of the cracked anisotropic plate loaded by a point force

NASA Astrophysics Data System (ADS)

Zaal, K. J. J. M.

1991-06-01

In programming solutions of complex function theory, the complex logarithm function is replaced by the complex logarithmic function, introducing a discontinuity along the branch cut into the programmed solution which was not present in the mathematical solution. Recently, Liaw and Kamel presented their solution of the infinite anisotropic centrally cracked plate loaded by an arbitrary point force, which they used as Green's function in a boundary element method intended to evaluate the stress intensity factor at the tip of a crack originating from an elliptical home. Their solution may be used as Green's function of many more numerical methods involving anisotropic elasticity. In programming applications of Liaw and Kamel's solution, the standard definition of the logarithmic function with the branch cut at the nonpositive real axis cannot provide a reliable computation of the displacement field for Liaw and Kamel's solution. Either the branch cut should be redefined outside the domain of the logarithmic function, after proving that the domain is limited to a part of the plane, or the logarithmic function should be defined on its Riemann surface. A two dimensional line fractal can provide the link between all mesh points on the plane essential to evaluate the logarithm function on its Riemann surface. As an example, a two dimensional line fractal is defined for a mesh once used by Erdogan and Arin.

Using complexity theory to analyse the organisational response to resurgent tuberculosis across London.

PubMed

Trenholm, Susan; Ferlie, Ewan

2013-09-01

We employ complexity theory to analyse the English National Health Service (NHS)'s organisational response to resurgent tuberculosis across London. Tennison (2002) suggests that complexity theory could fruitfully explore a healthcare system's response to this complex and emergent phenomenon: we explore this claim here. We also bring in established New Public Management principles to enhance our empirical analysis, which is based on data collected between late 2009 and mid-2011. We find that the operation of complexity theory based features, especially self-organisation, are significantly impacted by the macro context of a New Public Management-based regime which values control, measurement and risk management more than innovation, flexibility and lateral system building. We finally explore limitations and suggest perspectives for further research. Copyright © 2012 Elsevier Ltd. All rights reserved.

Complexity Theory

USGS Publications Warehouse

Lee, William H K.

2016-01-01

A complex system consists of many interacting parts, generates new collective behavior through self organization, and adaptively evolves through time. Many theories have been developed to study complex systems, including chaos, fractals, cellular automata, self organization, stochastic processes, turbulence, and genetic algorithms.

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

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Trajectory fitting in function space with application to analytic modeling of surfaces

NASA Technical Reports Server (NTRS)

Barger, Raymond L.

1992-01-01

A theory for representing a parameter-dependent function as a function trajectory is described. Additionally, a theory for determining a piecewise analytic fit to the trajectory is described. An example is given that illustrates the application of the theory to generating a smooth surface through a discrete set of input cross-section shapes. A simple procedure for smoothing in the parameter direction is discussed, and a computed example is given. Application of the theory to aerodynamic surface modeling is demonstrated by applying it to a blended wing-fuselage surface.

A numerical assessment of rough surface scattering theories. I - Horizontal polarization. II - Vertical polarization

NASA Technical Reports Server (NTRS)

Rodriguez, Ernesto; Kim, Yunjin; Durden, Stephen L.

1992-01-01

A numerical evaluation is presented of the regime of validity for various rough surface scattering theories against numerical results obtained by employing the method of moments. The contribution of each theory is considered up to second order in the perturbation expansion for the surface current. Considering both vertical and horizontal polarizations, the unified perturbation method provides best results among all theories weighed.

Path-Integration Computation of the Transport Properties of Polymers Nanoparticles and Complex Biological Structures

NASA Astrophysics Data System (ADS)

Douglas, Jack

2014-03-01

One of the things that puzzled me when I was a PhD student working under Karl Freed was the curious unity between the theoretical descriptions of excluded volume interactions in polymers, the hydrodynamic properties of polymers in solution, and the critical properties of fluid mixtures, gases and diverse other materials (magnets, superfluids,etc.) when these problems were formally expressed in terms of Wiener path integration and the interactions treated through a combination of epsilon expansion and renormalization group (RG) theory. It seemed that only the interaction labels changed from one problem to the other. What do these problems have in common? Essential clues to these interrelations became apparent when Karl Freed, myself and Shi-Qing Wang together began to study polymers interacting with hyper-surfaces of continuously variable dimension where the Feynman perturbation expansions could be performed through infinite order so that we could really understand what the RG theory was doing. It is evidently simply a particular method for resuming perturbation theory, and former ambiguities no longer existed. An integral equation extension of this type of exact calculation to ``surfaces'' of arbitrary fixed shape finally revealed the central mathematical object that links these diverse physical models- the capacity of polymer chains, whose value vanishes at the critical dimension of 4 and whose magnitude is linked to the friction coefficient of polymer chains, the virial coefficient of polymers and the 4-point function of the phi-4 field theory,...Once this central object was recognized, it then became possible solve diverse problems in material science through the calculation of capacity, and related ``virials'' properties, through Monte Carlo sampling of random walk paths. The essential ideas of this computational method are discussed and some applications given to non-trivial problems: nanotubes treated as either rigid rods or ensembles worm-like chains having finite cross-section, DNA, nanoparticles with grafted chain layers and knotted polymers. The path-integration method, which grew up from research in Karl Freed's group, is evidently a powerful tool for computing basic transport properties of complex-shaped objects and should find increasing application in polymer science, nanotechnological applications and biology.

QCM-D study of nanoparticle interactions.

PubMed

Chen, Qian; Xu, Shengming; Liu, Qingxia; Masliyah, Jacob; Xu, Zhenghe

2016-07-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been proven to be a powerful research tool to investigate in situ interactions between nanoparticles and different functionalized surfaces in liquids. QCM-D can also be used to quantitatively determine adsorption kinetics of polymers, DNA and proteins from solutions on various substrate surfaces while providing insights into conformations of adsorbed molecules. This review aims to provide a comprehensive overview on various important applications of QCM-D, focusing on deposition of nanoparticles and attachment-detachment of nanoparticles on model membranes in complex fluid systems. We will first describe the working principle of QCM-D and DLVO theory pertinent to understanding nanoparticle deposition phenomena. The interactions between different nanoparticles and functionalized surfaces for different application areas are then critically reviewed. Finally, the potential applications of QCM-D in other important fields are proposed and knowledge gaps are identified. Copyright © 2015 Elsevier B.V. All rights reserved.

The fall of a viscous thread onto a moving surface: a ‘fluid-mechanical sewing machine’

NASA Astrophysics Data System (ADS)

Chiu-Webster, S.; Lister, J. R.

2006-12-01

A viscous thread falling onto a steadily moving horizontal belt shows a surprisingly complex range of behaviour in experiments. Low belt speeds produce coiling, as might be expected from the behaviour of a thread falling onto a stationary surface. High belt speeds produce a steady thread, whose shape is predicted well by theory developed to describe a stretching viscous catenary with surface tension and inertia. Intermediate belt speeds show several novel modes of oscillation, which lay down a wide variety of patterns on the belt. The patterns include meanders, side kicks, slanted loops, braiding, figures-of-eight, Ws, and also period-doubled versions of figures-of-eight, meanders and coiling. The experimental boundary between steady and unsteady behaviour occurs at a slightly lower belt speed than the loss of the steady solution for a stretching catenary.

The syntactic complexity of Russian relative clauses

PubMed Central

Fedorenko, Evelina; Gibson, Edward

2012-01-01

Although syntactic complexity has been investigated across dozens of studies, the available data still greatly underdetermine relevant theories of processing difficulty. Memory-based and expectation-based theories make opposite predictions regarding fine-grained time course of processing difficulty in syntactically constrained contexts, and each class of theory receives support from results on some constructions in some languages. Here we report four self-paced reading experiments on the online comprehension of Russian relative clauses together with related corpus studies, taking advantage of Russian’s flexible word order to disentangle predictions of competing theories. We find support for key predictions of memory-based theories in reading times at RC verbs, and for key predictions of expectation-based theories in processing difficulty at RC-initial accusative noun phrase (NP) objects, which corpus data suggest should be highly unexpected. These results suggest that a complete theory of syntactic complexity must integrate insights from both expectation-based and memory-based theories. PMID:24711687

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

PubMed

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Emergent "Quantum" Theory in Complex Adaptive Systems.

PubMed

Minic, Djordje; Pajevic, Sinisa

2016-04-30

Motivated by the question of stability, in this letter we argue that an effective quantum-like theory can emerge in complex adaptive systems. In the concrete example of stochastic Lotka-Volterra dynamics, the relevant effective "Planck constant" associated with such emergent "quantum" theory has the dimensions of the square of the unit of time. Such an emergent quantum-like theory has inherently non-classical stability as well as coherent properties that are not, in principle, endangered by thermal fluctuations and therefore might be of crucial importance in complex adaptive systems.

Emergent “Quantum” Theory in Complex Adaptive Systems

PubMed Central

Minic, Djordje; Pajevic, Sinisa

2017-01-01

Motivated by the question of stability, in this letter we argue that an effective quantum-like theory can emerge in complex adaptive systems. In the concrete example of stochastic Lotka-Volterra dynamics, the relevant effective “Planck constant” associated with such emergent “quantum” theory has the dimensions of the square of the unit of time. Such an emergent quantum-like theory has inherently non-classical stability as well as coherent properties that are not, in principle, endangered by thermal fluctuations and therefore might be of crucial importance in complex adaptive systems. PMID:28890591

Ordered hydroxyls on Ca 3Ru 2O 7(001)

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

Halwidl, Daniel; Mayr-Schmölzer, Wernfried; Fobes, David

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3Ru 2O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygenmore » atom, O surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.« less

First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces

DOE PAGES

Leung, Kevin

2016-12-10

The density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn–O bonds forming mobile OH – surface groups; and chemicalmore » reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. Our findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Ordered hydroxyls on Ca 3Ru 2O 7(001)

DOE PAGES

Halwidl, Daniel; Mayr-Schmölzer, Wernfried; Fobes, David; ...

2017-06-20

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3Ru 2O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygenmore » atom, O surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.« less

Spin polarized electronic states and spin textures at the surface of oxygen-deficient SrTiO3

NASA Astrophysics Data System (ADS)

Jeschke, Harald O.; Altmeyer, Michaela; Rozenberg, Marcelo; Gabay, Marc; Valenti, Roser

We investigate the electronic structure and spin texture at the (001) surface of SrTiO3 in the presence of oxygen vacancies by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic non-magnetic DFT calculations exhibit Rashba-like spin winding with a characteristic energy scale ~ 10 meV. However, when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ~ 100 meV at the Γ point. This energy scale is comparable to the observations in SARPES experiments performed on the two-dimensional electronic states confined near the (001) surface of SrTiO3. We find the spin polarized state to be the ground state of the system, and while magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. We gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft through grants SFB/TR 49 and FOR 1346.

Groundwater–surface water mixing shifts ecological assembly processes and stimulates organic carbon turnover

DOE PAGES

Stegen, James C.; Fredrickson, James K.; Wilkins, Michael J.; ...

2016-04-07

Environmental transition zones are associated with geochemical gradients that overcome energy limitations to microbial metabolism, resulting in biogeochemical hot spots and moments. Riverine systems where groundwater mixes with surface water (the hyporheic zone) are spatially complex and temporally dynamic, making development of predictive models challenging. Spatial and temporal variations in hyporheic zone microbial communities are a key, but understudied, component of riverine biogeochemical function. To investigate the coupling among groundwater-surface water mixing, microbial communities, and biogeochemistry we applied ecological theory, aqueous biogeochemistry, DNA sequencing, and ultra-high resolution organic carbon profiling to field samples collected across times and locations representing amore » broad range of mixing conditions. Mixing of groundwater and surface water resulted in a shift from transport-driven stochastic dynamics to a deterministic microbial structure associated with elevated biogeochemical rates. While the dynamics of the hyporheic make predictive modeling a challenge, we provide new knowledge that can improve the tractability of such models.« less

Coherence solution for bidirectional reflectance distributions of surfaces with wavelength-scale statistics.

PubMed

Hoover, Brian G; Gamiz, Victor L

2006-02-01

The scalar bidirectional reflectance distribution function (BRDF) due to a perfectly conducting surface with roughness and autocorrelation width comparable with the illumination wavelength is derived from coherence theory on the assumption of a random reflective phase screen and an expansion valid for large effective roughness. A general quadratic expansion of the two-dimensional isotropic surface autocorrelation function near the origin yields representative Cauchy and Gaussian BRDF solutions and an intermediate general solution as the sum of an incoherent component and a nonspecular coherent component proportional to an integral of the plasma dispersion function in the complex plane. Plots illustrate agreement of the derived general solution with original bistatic BRDF data due to a machined aluminum surface, and comparisons are drawn with previously published data in the examination of variations with incident angle, roughness, illumination wavelength, and autocorrelation coefficients in the bistatic and monostatic geometries. The general quadratic autocorrelation expansion provides a BRDF solution that smoothly interpolates between the well-known results of the linear and parabolic approximations.

Charge-transfer complex formation between TiO2 nanoparticles and thiosalicylic acid: A comprehensive experimental and DFT study

NASA Astrophysics Data System (ADS)

Milićević, Bojana; Đorđević, Vesna; Lončarević, Davor; Dostanić, Jasmina M.; Ahrenkiel, S. Phillip; Dramićanin, Miroslav D.; Sredojević, Dušan; Švrakić, Nenad M.; Nedeljković, Jovan M.

2017-11-01

Under normal conditions, titanium dioxide does not absorb visible light photons due to large band gap. Nevertheless, when titanium dioxide nanoparticles (TiO2 NPs) are surface-modified with thiosalicylic acid (TSA), their optical properties are altered owing to the formation of charge transfer complex that initiates absorption in the visible spectral range. Colloidal and sol-gel techniques were used to synthesize uniform TiO2 NPs of different sizes (average diameters in the range 4-15 nm), and effects of their subsequent modification by TSA molecules were compared with effect of modification of commercial Degussa TiO2 powder. Thorough microstructural characterization of TiO2 nanoparticulates was performed including transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis, as well as nitrogen adsorption-desorption isotherms. Optical measurements revealed that all surface-modified TiO2 samples with TSA have similar spectral features independent of their morphological differences, and, more importantly, absorption onset of modified TiO2 samples was found to be red-shifted by 1.0 eV compared to the unmodified ones. The mode of binding between TSA and surface Ti atoms was analyzed by infrared spectroscopy. Finally, the quantum chemical calculations, based on density functional theory, were performed to support optical characterization of surface-modified TiO2 with TSA.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

Zero-point corrections and temperature dependence of HD spin-spin coupling constants of heavy metal hydride and dihydrogen complexes calculated by vibrational averaging.

PubMed

Mort, Brendan C; Autschbach, Jochen

2006-08-09

Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence.

Minimization of Dependency Length in Written English

ERIC Educational Resources Information Center

Temperley, David

2007-01-01

Gibson's Dependency Locality Theory (DLT) [Gibson, E. 1998. "Linguistic complexity: locality of syntactic dependencies." "Cognition," 68, 1-76; Gibson, E. 2000. "The dependency locality theory: A distance-based theory of linguistic complexity." In A. Marantz, Y. Miyashita, & W. O'Neil (Eds.), "Image,…

Complexity, Connections, and Soul-Work

ERIC Educational Resources Information Center

Bloch, Deborah P.

2008-01-01

Organizational theory and personal behaviors are both shaped by contemporary thinking and theories regarding spirituality, history, and the order, shape, and direction of modern culture. Complexity theory, discussed in this article, offers some helpful insights into appreciating the relationships and connections often overlooked in today's…

An Automated Method to Identify Mesoscale Convective Complexes (MCCs) Implementing Graph Theory

NASA Astrophysics Data System (ADS)

Whitehall, K. D.; Mattmann, C. A.; Jenkins, G. S.; Waliser, D. E.; Rwebangira, R.; Demoz, B.; Kim, J.; Goodale, C. E.; Hart, A. F.; Ramirez, P.; Joyce, M. J.; Loikith, P.; Lee, H.; Khudikyan, S.; Boustani, M.; Goodman, A.; Zimdars, P. A.; Whittell, J.

2013-12-01

Mesoscale convective complexes (MCCs) are convectively-driven weather systems with a duration of ~10 - 12 hours and contributions of large amounts to the rainfall daily and monthly totals. More than 400 MCCs occur annually over various locations on the globe. In West Africa, ~170 MCCs occur annually during the 180 days representing the summer months (June - November), and contribute ~75% of the annual wet season rainfall. The main objective of this study is to improve automatic identification of MCC over West Africa. The spatial expanse of MCCs and the spatio-temporal variability in their convective characteristics make them difficult to characterize even in dense networks of radars and/or surface gauges. As such there exist criteria for identifying MCCs with satellite images - mostly using infrared (IR) data. Automated MCC identification methods are based on forward and/or backward in time spatial-temporal analysis of the IR satellite data and characteristically incorporate a manual component as these algorithms routinely falter with merging and splitting cloud systems between satellite images. However, these algorithms are not readily transferable to voluminous data or other satellite-derived datasets (e.g. TRMM), thus hindering comprehensive studies of these features both at weather and climate timescales. Recognizing the existing limitations of automated methods, this study explores the applicability of graph theory to creating a fully automated method for deriving a West African MCC dataset from hourly infrared satellite images between 2001- 2012. Graph theory, though not heavily implemented in the atmospheric sciences, has been used for the predicting (nowcasting) of thunderstorms from radar and satellite data by considering the relationship between atmospheric variables at a given time, or for the spatial-temporal analysis of cloud volumes. From these few studies, graph theory appears to be innately applicable to the complexity, non-linearity and inherent chaos of the atmospheric system. Our preliminary results show that the use of graph theory improves data management thus allowing for longer periods to be studied, and creates a transferable method that allows for other data to be utilized.

Holographic complexity and noncommutative gauge theory

NASA Astrophysics Data System (ADS)

Couch, Josiah; Eccles, Stefan; Fischler, Willy; Xiao, Ming-Lei

2018-03-01

We study the holographic complexity of noncommutative field theories. The four-dimensional N=4 noncommutative super Yang-Mills theory with Moyal algebra along two of the spatial directions has a well known holographic dual as a type IIB supergravity theory with a stack of D3 branes and non-trivial NS-NS B fields. We start from this example and find that the late time holographic complexity growth rate, based on the "complexity equals action" conjecture, experiences an enhancement when the non-commutativity is turned on. This enhancement saturates a new limit which is exactly 1/4 larger than the commutative value. We then attempt to give a quantum mechanics explanation of the enhancement. Finite time behavior of the complexity growth rate is also studied. Inspired by the non-trivial result, we move on to more general setup in string theory where we have a stack of D p branes and also turn on the B field. Multiple noncommutative directions are considered in higher p cases.

DFT description of the magnetic properties and electron localization in dinuclear di-mu-oxo-bridged manganese complexes.

PubMed

Barone, Vincenzo; Bencini, Alessandro; Gatteschi, Dante; Totti, Federico

2002-11-04

Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed.

Complex Refractive Index of Ice Fog at a Radio Wavelength of 3 mm

DTIC Science & Technology

1974-10-01

particles on mirror surface 55 41. Liberally dusting mirror with 3-// polystyrene dust produces almost no effect 56 —" -.-.—-- ■ .■..^„^-^aa...spheres, as Debye (1929) did in his original theory. The rotation of these spheres in a viscous medium is opposed by forces related by Stoke’s law to...given by a relation of the form ,_ C „D/kT E/RT Z 0 where R k ■ M.C \\s only slightly temperature dependent, and n/w is the average time required by

Three-gradient regular solution model for simple liquids wetting complex surface topologies

PubMed Central

Akerboom, Sabine; Kamperman, Marleen

2016-01-01

Summary We use regular solution theory and implement a three-gradient model for a liquid/vapour system in contact with a complex surface topology to study the shape of a liquid drop in advancing and receding wetting scenarios. More specifically, we study droplets on an inverse opal: spherical cavities in a hexagonal pattern. In line with experimental data, we find that the surface may switch from hydrophilic (contact angle on a smooth surface θY < 90°) to hydrophobic (effective advancing contact angle θ > 90°). Both the Wenzel wetting state, that is cavities under the liquid are filled, as well as the Cassie–Baxter wetting state, that is air entrapment in the cavities under the liquid, were observed using our approach, without a discontinuity in the water front shape or in the water advancing contact angle θ. Therefore, air entrapment cannot be the main reason why the contact angle θ for an advancing water front varies. Rather, the contact line is pinned and curved due to the surface structures, inducing curvature perpendicular to the plane in which the contact angle θ is observed, and the contact line does not move in a continuous way, but via depinning transitions. The pinning is not limited to kinks in the surface with angles θkink smaller than the angle θY. Even for θkink > θY, contact line pinning is found. Therefore, the full 3D-structure of the inverse opal, rather than a simple parameter such as the wetting state or θkink, determines the final observed contact angle. PMID:27826512

Nonadiabatic molecular dynamics simulations: synergies between theory and experiments.

PubMed

Tavernelli, Ivano

2015-03-17

Recent developments in nonadiabatic dynamics enabled ab inito simulations of complex ultrafast processes in the condensed phase. These advances have opened new avenues in the study of many photophysical and photochemical reactions triggered by the absorption of electromagnetic radiation. In particular, theoretical investigations can be combined with the most sophisticated femtosecond experimental techniques to guide the interpretation of measured time-resolved observables. At the same time, the availability of experimental data at high (spatial and time) resolution offers a unique opportunity for the benchmarking and the improvement of those theoretical models used to describe complex molecular systems in their natural environment. The established synergy between theory and experiments can produce a better understanding of new ultrafast physical and chemical processes at atomistic scale resolution. Furthermore, reliable ab inito molecular dynamics simulations can already be successfully employed as predictive tools to guide new experiments as well as the design of novel and better performing materials. In this paper, I will give a concise account on the state of the art of molecular dynamics simulations of complex molecular systems in their excited states. The principal aim of this approach is the description of a given system of interest under the most realistic ambient conditions including all environmental effects that influence experiments, for instance, the interaction with the solvent and with external time-dependent electric fields, temperature, and pressure. To this end, time-dependent density functional theory (TDDFT) is among the most efficient and accurate methods for the representation of the electronic dynamics, while trajectory surface hopping gives a valuable representation of the nuclear quantum dynamics in the excited states (including nonadiabatic effects). Concerning the environment and its effects on the dynamics, the quantum mechanics/molecular mechanics (QM/MM) approach has the advantage of providing an atomistic (even though approximated) description of the solvent molecules, which is crucial for the characterization of all ultrafast relaxation phenomena that depend on the geometrical arrangement at the interface between a molecule and the solvent, for example, the hydrogen bond network. After a short description of the TDDFT-based implementation of Ehrenfest and trajectory surface hopping dynamics, I will present applications in different domains of molecular chemistry and physics: the analysis and the understanding of (time-resolved) X-ray absorption spectra, the interpretation of the ultrafast relaxation dynamics of photoexcited dyes in solution, and the design of specific laser pulses (capable of inducing desired chemical reactions) using local control theory.

Microwave backscattering theory and active remote sensing of the ocean surface

NASA Technical Reports Server (NTRS)

Brown, G. S.; Miller, L. S.

1977-01-01

The status is reviewed of electromagnetic scattering theory relative to the interpretation of microwave remote sensing data acquired from spaceborne platforms over the ocean surface. Particular emphasis is given to the assumptions which are either implicit or explicit in the theory. The multiple scale scattering theory developed during this investigation is extended to non-Gaussian surface statistics. It is shown that the important statistic for the case is the probability density function of the small scale heights conditioned on the large scale slopes; this dependence may explain the anisotropic scattering measurements recently obtained with the AAFE Radscat. It is noted that present surface measurements are inadequate to verify or reject the existing scattering theories. Surface measurements are recommended for qualifying sensor data from radar altimeters and scatterometers. Additional scattering investigations are suggested for imaging type radars employing synthetically generated apertures.

Distributed collaborative response surface method for mechanical dynamic assembly reliability design

NASA Astrophysics Data System (ADS)

Bai, Guangchen; Fei, Chengwei

2013-11-01

Because of the randomness of many impact factors influencing the dynamic assembly relationship of complex machinery, the reliability analysis of dynamic assembly relationship needs to be accomplished considering the randomness from a probabilistic perspective. To improve the accuracy and efficiency of dynamic assembly relationship reliability analysis, the mechanical dynamic assembly reliability(MDAR) theory and a distributed collaborative response surface method(DCRSM) are proposed. The mathematic model of DCRSM is established based on the quadratic response surface function, and verified by the assembly relationship reliability analysis of aeroengine high pressure turbine(HPT) blade-tip radial running clearance(BTRRC). Through the comparison of the DCRSM, traditional response surface method(RSM) and Monte Carlo Method(MCM), the results show that the DCRSM is not able to accomplish the computational task which is impossible for the other methods when the number of simulation is more than 100 000 times, but also the computational precision for the DCRSM is basically consistent with the MCM and improved by 0.40˜4.63% to the RSM, furthermore, the computational efficiency of DCRSM is up to about 188 times of the MCM and 55 times of the RSM under 10000 times simulations. The DCRSM is demonstrated to be a feasible and effective approach for markedly improving the computational efficiency and accuracy of MDAR analysis. Thus, the proposed research provides the promising theory and method for the MDAR design and optimization, and opens a novel research direction of probabilistic analysis for developing the high-performance and high-reliability of aeroengine.

Effects of temperature and surface orientation on migration behaviours of helium atoms near tungsten surfaces

NASA Astrophysics Data System (ADS)

Wang, Xiaoshuang; Wu, Zhangwen; Hou, Qing

2015-10-01

Molecular dynamics simulations were performed to study the dependence of migration behaviours of single helium atoms near tungsten surfaces on the surface orientation and temperature. For W{100} and W{110} surfaces, He atoms can quickly escape out near the surface without accumulation even at a temperature of 400 K. The behaviours of helium atoms can be well-described by the theory of continuous diffusion of particles in a semi-infinite medium. For a W{111} surface, the situation is complex. Different types of trap mutations occur within the neighbouring region of the W{111} surface. The trap mutations hinder the escape of He atoms, resulting in their accumulation. The probability of a He atom escaping into vacuum from a trap mutation depends on the type of the trap mutation, and the occurrence probabilities of the different types of trap mutations are dependent on the temperature. This finding suggests that the escape rate of He atoms on the W{111} surface does not show a monotonic dependence on temperature. For instance, the escape rate at T = 1500 K is lower than the rate at T = 1100 K. Our results are useful for understanding the structural evolution and He release on tungsten surfaces and for designing models in other simulation methods beyond molecular dynamics.

Magnetic order at a single-crystal surface in the diffuse-scattering theory

NASA Astrophysics Data System (ADS)

Zasada, I.

2003-06-01

A theoretical description of incoherent spin-dependent multiple scattering of electrons at a magnetically disordered single-crystal surface is reported. A formalism in which the spin operators specify the magnetic state of a surface atom is used for the description of magnetic order at the surface. The theory is based upon the concepts used in multiple scattering spin-dependent diffuse LEED theory (DSPLEED) theory. In the present considerations, this theory is extended to the case of magnetic materials by using the time-independent Dirac equation with an effective magnetic field. Thus, an expression for incoherent spin-dependent intensity for magnetic material is obtained. It depends on the Fourier transform on the surface lattice of the spin-pair correlation function and, as a consequence, on the magnetic properties of the surface. The equations for the description of magnetization and various correlation functions in the frame of effective field theory are derived and the results of the numerical calculations are presented for the particular case of Ni(1 0 0) surface. The spin-orbit induced and exchange asymmetries are calculated. It is found that the magnetic DSPLEED is sensitive to the properties of the surface characterized by the spin-pair correlation functions. Thus, it is demonstrated that the magnetic DSPLEED can be an effective method in the investigation of critical behaviour of magnetic surfaces.

Evolution of the transfer function characterization of surface scatter phenomena

NASA Astrophysics Data System (ADS)

Harvey, James E.; Pfisterer, Richard N.

2016-09-01

Based upon the empirical observation that BRDF measurements of smooth optical surfaces exhibited shift-invariant behavior when plotted versus    o , the original Harvey-Shack (OHS) surface scatter theory was developed as a scalar linear systems formulation in which scattered light behavior was characterized by a surface transfer function (STF) reminiscent of the optical transfer function (OTF) of modern image formation theory (1976). This shift-invariant behavior combined with the inverse power law behavior when plotting log BRDF versus log   o was quickly incorporated into several optical analysis software packages. Although there was no explicit smooth-surface approximation in the OHS theory, there was a limitation on both the incident and scattering angles. In 1988 the modified Harvey-Shack (MHS) theory removed the limitation on the angle of incidence; however, a moderate-angle scattering limitation remained. Clearly for large incident angles the BRDF was no longer shift-invariant as a different STF was now required for each incident angle. In 2011 the generalized Harvey-Shack (GHS) surface scatter theory, characterized by a two-parameter family of STFs, evolved into a practical modeling tool to calculate BRDFs from optical surface metrology data for situations that violate the smooth surface approximation inherent in the Rayleigh-Rice theory and/or the moderate-angle limitation of the Beckmann-Kirchhoff theory. And finally, the STF can be multiplied by the classical OTF to provide a complete linear systems formulation of image quality as degraded by diffraction, geometrical aberrations and surface scatter effects from residual optical fabrication errors.

Spectral determinants for twist field correlators

NASA Astrophysics Data System (ADS)

Belitsky, A. V.

2018-04-01

Twist fields were introduced a few decades ago as a quantum counterpart to classical kink configurations and disorder variables in low dimensional field theories. In recent years they received a new incarnation within the framework of geometric entropy and strong coupling limit of four-dimensional scattering amplitudes. In this paper, we study their two-point correlation functions in a free massless scalar theory, namely, twist-twist and twist-antitwist correlators. In spite of the simplicity of the model in question, the properties of the latter are far from being trivial. The problem is reduced, within the formalism of the path integral, to the study of spectral determinants on surfaces with conical points, which are then computed exactly making use of the zeta function regularization. We also provide an insight into twist correlators for a massive complex scalar by means of the Lifshitz-Krein trace formula.

Theoretical Modeling of Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Charnley, Steven

2009-01-01

The chemistry of complex interstellar organic molecules will be described. Gas phase processes that may build large carbon-chain species in cold molecular clouds will be summarized. Catalytic reactions on grain surfaces can lead to a large variety of organic species, and models of molecule formation by atom additions to multiply-bonded molecules will be presented. The subsequent desorption of these mixed molecular ices can initiate a distinctive organic chemistry in hot molecular cores. The general ion-molecule pathways leading to even larger organics will be outlined. The predictions of this theory will be compared with observations to show how possible organic formation pathways in the interstellar medium may be constrained. In particular, the success of the theory in explaining trends in the known interstellar organics, in predicting recently-detected interstellar molecules, and, just as importantly, non-detections, will be discussed.

Morphometric approach to thermodynamic quantities of solvation of complex molecules: Extension to multicomponent solvent

NASA Astrophysics Data System (ADS)

Kodama, Ryota; Roth, Roland; Harano, Yuichi; Kinoshita, Masahiro

2011-07-01

The morphometric approach (MA) is a powerful tool for calculating a solvation free energy (SFE) and related quantities of solvation thermodynamics of complex molecules. Here, we extend it to a solvent consisting of m components. In the integral equation theories, the SFE is expressed as the sum of m terms each of which comprises solute-component j correlation functions (j = 1, …, m). The MA is applied to each term in a formally separate manner: The term is expressed as a linear combination of the four geometric measures, excluded volume, solvent-accessible surface area, and integrated mean and Gaussian curvatures of the accessible surface, which are calculated for component j. The total number of the geometric measures or the coefficients in the linear combinations is 4m. The coefficients are determined in simple geometries, i.e., for spherical solutes with various diameters in the same multicomponent solvent. The SFE of the spherical solutes are calculated using the radial-symmetric integral equation theory. The extended version of the MA is illustrated for a protein modeled as a set of fused hard spheres immersed in a binary mixture of hard spheres. Several mixtures of different molecular-diameter ratios and compositions and 30 structures of the protein with a variety of radii of gyration are considered for the illustration purpose. The SFE calculated by the MA is compared with that by the direct application of the three-dimensional integral equation theory (3D-IET) to the protein. The deviations of the MA values from the 3D-IET values are less than 1.5%. The computation time required is over four orders of magnitude shorter than that in the 3D-IET. The MA thus developed is expected to be best suited to analyses concerning the effects of cosolvents such as urea on the structural stability of a protein.

Light Makes a Surface Banana-Bond Split: Photodesorption of Molecular Hydrogen from RuO 2 (110)

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

Henderson, Michael A.; Mu, Rentao; Dahal, Arjun

The coordination of H2 to a metal center via polarization of its bond electron density, known as a Kubas complex, is the means by which H2 chemisorbs at Ru4+ sites on the rutile RuO2(110) surface. This distortion of electron density off an interatomic axis is often described as a ‘banana-bond.’ We show that the Ru-H2 banana-bond can be destabilized, and split, using visible light. Photodesorption of H2 (or D2) is evident by mass spectrometry and scanning tunneling microscopy. From time-dependent density functional theory, the key optical excitation splitting the Ru-H2 banana-bond involves an interband transition in RuO2 which effectively diminishesmore » its Lewis acidity, and thereby weakening the Kubas complex. Such excitations are not expected to affect adsorbates on RuO2 given its metallic properties. Therefore, this common thermal co-catalyst employed in promoting water splitting is, itself, photo-active in the visible.« less

Homogenous Surface Nucleation of Solid Polar Stratospheric Cloud Particles

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Hamill, P.; Salcedo, D.; Gore, Warren J. (Technical Monitor)

2002-01-01

A general surface nucleation rate theory is presented for the homogeneous freezing of crystalline germs on the surfaces of aqueous particles. While nucleation rates in a standard classical homogeneous freezing rate theory scale with volume, the rates in a surface-based theory scale with surface area. The theory is used to convert volume-based information on laboratory freezing rates (in units of cu cm, seconds) of nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD) aerosols into surface-based values (in units of sq cm, seconds). We show that a surface-based model is capable of reproducing measured nucleation rates of NAT and NAD aerosols from concentrated aqueous HNO3 solutions in the temperature range of 165 to 205 K. Laboratory measured nucleation rates are used to derive free energies for NAT and NAD germ formation in the stratosphere. NAD germ free energies range from about 23 to 26 kcal mole, allowing for fast and efficient homogeneous NAD particle production in the stratosphere. However, NAT germ formation energies are large (greater than 26 kcal mole) enough to prevent efficient NAT particle production in the stratosphere. We show that the atmospheric NAD particle production rates based on the surface rate theory are roughly 2 orders of magnitude larger than those obtained from a standard volume-based rate theory. Atmospheric volume and surface production of NAD particles will nearly cease in the stratosphere when denitrification in the air exceeds 40 and 78%, respectively. We show that a surface-based (volume-based) homogeneous freezing rate theory gives particle production rates, which are (not) consistent with both laboratory and atmospheric data on the nucleation of solid polar stratospheric cloud particles.

Educational Philosophy and the Challenge of Complexity Theory

ERIC Educational Resources Information Center

Morrison, Keith

2008-01-01

Complexity theory challenges educational philosophy to reconsider accepted paradigms of teaching, learning and educational research. However, though attractive, not least because of its critique of positivism, its affinity to Dewey and Habermas, and its arguments for openness, diversity, relationships, agency and creativity, the theory is not…

Structure, Agency, Complexity Theory and Interdisciplinary Research in Education Studies

ERIC Educational Resources Information Center

Smith, John A.

2013-01-01

This article argues that Education Studies needs to develop its existing interdisciplinarity understanding of structures and agencies by giving greater attention to the modern process theories of self-organisation in the physical, biological, psychological and social sciences, sometimes given the umbrella term "complexity theory". The…

Slow dynamics in glasses: A comparison between theory and experiment

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

Phillips, J. C.

Minimalist theories of complex systems are broadly of two kinds: mean field and axiomatic. So far, all theories of complex properties absent from simple systems and intrinsic to glasses are axiomatic. Stretched Exponential Relaxation (SER) is the prototypical complex temporal property of glasses, discovered by Kohlrausch 150 years ago, and now observed almost universally in microscopically homogeneous, complex nonequilibrium materials, including luminescent electronic Coulomb glasses. A critical comparison of alternative axiomatic theories with both numerical simulations and experiments strongly favors channeled dynamical trap models over static percolative or energy landscape models. The topics discussed cover those reported since the author'smore » review article in 1996, with an emphasis on parallels between channel bifurcation in electronic and molecular relaxation.« less

Transition operators in acoustic-wave diffraction theory. I - General theory. II - Short-wavelength behavior, dominant singularities of Zk0 and Zk0 exp -1

NASA Technical Reports Server (NTRS)

Hahne, G. E.

1991-01-01

A formal theory of the scattering of time-harmonic acoustic scalar waves from impenetrable, immobile obstacles is established. The time-independent formal scattering theory of nonrelativistic quantum mechanics, in particular the theory of the complete Green's function and the transition (T) operator, provides the model. The quantum-mechanical approach is modified to allow the treatment of acoustic-wave scattering with imposed boundary conditions of impedance type on the surface (delta-Omega) of an impenetrable obstacle. With k0 as the free-space wavenumber of the signal, a simplified expression is obtained for the k0-dependent T operator for a general case of homogeneous impedance boundary conditions for the acoustic wave on delta-Omega. All the nonelementary operators entering the expression for the T operator are formally simple rational algebraic functions of a certain invertible linear radiation impedance operator which maps any sufficiently well-behaved complex-valued function on delta-Omega into another such function on delta-Omega. In the subsequent study, the short-wavelength and the long-wavelength behavior of the radiation impedance operator and its inverse (the 'radiation admittance' operator) as two-point kernels on a smooth delta-Omega are studied for pairs of points that are close together.

Spectroscopic Studies of Molecular Systems relevant in Astrobiology

NASA Astrophysics Data System (ADS)

Fornaro, Teresa

2016-01-01

In the Astrobiology context, the study of the physico-chemical interactions involving "building blocks of life" in plausible prebiotic and space-like conditions is fundamental to shed light on the processes that led to emergence of life on Earth as well as to molecular chemical evolution in space. In this PhD Thesis, such issues have been addressed both experimentally and computationally by employing vibrational spectroscopy, which has shown to be an effective tool to investigate the variety of intermolecular interactions that play a key role in self-assembling mechanisms of nucleic acid components and their binding to mineral surfaces. In particular, in order to dissect the contributions of the different interactions to the overall spectroscopic signals and shed light on the intricate experimental data, feasible computational protocols have been developed for the characterization of the spectroscopic properties of such complex systems. This study has been carried out through a multi-step strategy, starting the investigation from the spectroscopic properties of the isolated nucleobases, then studying the perturbation induced by the interaction with another molecule (molecular dimers), towards condensed phases like the molecular solid, up to the case of nucleic acid components adsorbed on minerals. A proper modeling of these weakly bound molecular systems has required, firstly, a validation of dispersion-corrected Density Functional Theory methods for simulating anharmonic vibrational properties. The isolated nucleobases and some of their dimers have been used as benchmark set for identifying a general, reliable and effective computational procedure based on fully anharmonic quantum mechanical computations of the vibrational wavenumbers and infrared intensities within the generalized second order vibrational perturbation theory (GVPT2) approach, combined with the cost-effective dispersion-corrected density functional B3LYP-D3, in conjunction with basis sets of double-ζ quality such as N07D and SNSD. Such a protocol has been then applied to the dimers of nucleobases in order to study the perturbation on the vibrational frequencies and infrared intensities induced by the intermolecular hydrogen-bonding interactions. Efforts have been made to challenge the problems of simulating strongly anharmonic vibrations within hydrogen-bonded bridges, focusing on the requirement of a very accurate description of the underlying potential energy surface. Improvements for such vibrations have been achieved by means of hybrid models, where the harmonic part of the force-field is computed at a higher level of theory like B2PLYP, or by application of the less demanding ONIOM B2PLYP:B3LYP scheme, which is a focused model where only the part of the molecular system forming the hydrogen bonds is treated at B2PLYP level of theory. Moreover, for improving the vibrational frequencies of modes like the stretching of C=O and N-H functional groups, which are particularly sensitive to hydrogen-bonding, correction parameters for the B3LYP-D3/N07D frequencies have been determined. Afterwards, the treatment of the vibrational properties of nucleobases in condensed phases has been faced, focusing on uracil in the solid state. In particular, a heptamer cluster of uracil molecules has been considered as model to represent the properties in the solid state. The relative vibrational frequencies have been computed at anharmonic level within the VPT2 framework, combining two cost-effective approaches, namely the hybrid B3LYP-D3/N07D:DFTBA model, where the harmonic frequencies are computed with B3LYP-D3/N07D method and the anharmonic corrections are evaluated with the less expensive DFTBA method, and the reduced dimensionality VPT2 (RD-VPT2) approach, in which only selected vibrational modes are calculated anharmonically (including the couplings with the other modes) while the remaining modes are treated at the harmonic level, using the B3LYP-D3/N07D method only. The reliability of such theoretical results has been validated with respect to experiments, by performing infrared measurements of uracil in the solid state through the Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) technique. The good performance in predicting the experimental shifts of the vibrational frequencies of uracil due to the intermolecular hydrogen bonds in the solid state with respect to uracil isolated in Argon matrix, has allowed also to provide some new assignments of the experimental spectrum of uracil in the solid state. Finally, the study of molecule-mineral interactions has been addressed, investigating experimentally the thermodynamics of the adsorption process of nucleic acid components on brucite, a serpentinite-hosted hydrothermal mineral, through determination of the equilibrium adsorption isotherms. Additionally, surface complexation studies have been carried out to get the stoichiometry of surface reactions and the associated electrical work. Such surface complexation modeling has provided reasonable inferences for the possible surface complexes, determining the number of inner/outer-sphere linkages for the adsorbates and the number of surface sites involved in the reaction stoichiometry. However, to distinguish the specific functional groups which constitute the points of attachment to the surface, further quantum mechanical simulations on the energetics of these complexes and spectroscopic characterizations are in progress.

Dynamics of Defects and Dopants in Complex Systems: Si and Oxide Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

Kirichenko, Taras; Yu, Decai; Banarjee, Sanjay; Hwang, Gyeong

2004-10-01

Fabrication of forthcoming nanometer scale electronic devices faces many difficulties including formation of extremely shallow and highly doped junctions. At present, ultra-low-energy ion implantation followed by high-temperature thermal annealing is most widely used to fabricate such ultra-shallow junctions. In the process, a great challenge lies in achieving precise control of redistribution and electrical activation of dopant impurities. Native defects (such as vacancies and interstitials) generated during implantation are known to be mainly responsible for the TED and also influence significantly the electrical activation/deactivation. Defect-dopant dynamics is rather well understood in crystalline Si and SiO2. However, little is known about their diffusion and annihilation (or precipitation) at the surfaces and interfaces, despite its growing importance in determining junction profiles as device dimensions get smaller. In this talk, we will present our density functional theory calculation results on the atomic and electronic structure and dynamical behavior of native defects and dopant-defect complexes in disordered/strained Si and oxide systems, such as i) clean and absorbent-modified Si(100) surface and subsurface layers, ii) amorphous-crystalline Si interfaces and iii) amorphous SiO2/Si interfaces. The fundamental understanding and data is essential in developing a comprehensive kinetic model for junction formation, which would contribute greatly in improving current process technologies.

Gurtin-Murdoch surface elasticity theory revisit: An orbital-free density functional theory perspective

NASA Astrophysics Data System (ADS)

Zhu, Yichao; Wei, Yihai; Guo, Xu

2017-12-01

In the present paper, the well-established Gurtin-Murdoch theory of surface elasticity (Gurtin and Murdoch, 1975, 1978) is revisited from an orbital-free density functional theory (OFDFT) perspective by taking the boundary layer into consideration. Our analysis indicates that firstly, the quantities introduced in the Gurtin-Murdoch theory of surface elasticity can all find their explicit expressions in the derived OFDFT-based theoretical model. Secondly, the derived expression for surface energy density captures a competition between the surface normal derivatives of the electron density and the electrostatic potential, which well rationalises the onset of signed elastic constants that are observed both experimentally and computationally. Thirdly, the established model naturally yields an inversely linear relationship between the materials surface stiffness and its size, which conforms to relevant findings in literature. Since the proposed OFDFT-based model is established under arbitrarily imposed boundary condition of electron density, electrostatic potential and external load, it also has the potential of being used to investigate the electro-mechanical behaviour of nanoscale materials manifesting surface effect.

Viscous drop collisions on surfaces of varying wettability

NASA Astrophysics Data System (ADS)

Bolleddula, Daniel; Berchielli, Al; Aliseda, Alberto

2010-11-01

We present an experimental study of increasingly viscous acetone rich and Newtonian equivalent liquid drops colliding on surfaces of varying wettability. This class of liquids applies directly to spray coating processes in pharmaceutical industries. The results from this study will elucidate the physics in a regime where resisting viscous forces and the restoring forces of capillarity are balanced, Oh˜ 1. Early spreading dynamics τ=Ut/D 1 indicate negligible dependence on contact angles while longer times demonstrate deviations from Tanner's law, D˜t^1/10. We will compare our results with recent theory to demonstrate the feasibility of modelling complex rheology spreading characteristics over short and long time scales. Preliminary results indicate an intermediate spreading regime following the inertial phase where the diameter, D˜t^n with 1/7 < n < 1/5.

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

Mishra, P.; Purdue University, West Lafayette, Indiana 47907; Verma, K.

Borazine is isoelectronic with benzene and is popularly referred to as inorganic benzene. The study of non-covalent interactions with borazine and comparison with its organic counterpart promises to show interesting similarities and differences. The motivation of the present study of the borazine-water interaction, for the first time, stems from such interesting possibilities. Hydrogen-bonded complexes of borazine and water were studied using matrix isolation infrared spectroscopy and quantum chemical calculations. Computations were performed at M06-2X and MP2 levels of theory using 6-311++G(d,p) and aug-cc-pVDZ basis sets. At both the levels of theory, the complex involving an N–H⋯O interaction, where the N–Hmore » of borazine serves as the proton donor to the oxygen of water was found to be the global minimum, in contrast to the benzene-water system, which showed an H–π interaction. The experimentally observed infrared spectra of the complexes corroborated well with our computations for the complex corresponding to the global minimum. In addition to the global minimum, our computations also located two local minima on the borazine-water potential energy surface. Of the two local minima, one corresponded to a structure where the water was the proton donor to the nitrogen of borazine, approaching the borazine ring from above the plane of the ring; a structure that resembled the global minimum in the benzene-water H–π complex. The second local minimum corresponded to an interaction of the oxygen of water with the boron of borazine, which can be termed as the boron bond. Clearly the borazine-water system presents a richer landscape than the benzene-water system.« less

Leadership as an Emergent Feature in Social Organizations: Insights from A Laboratory Simulation Experiment.

PubMed

Curral, Luis; Marques-Quinteiro, Pedro; Gomes, Catarina; Lind, Pedro G

2016-01-01

Recent theoretical contributions have suggested a theory of leadership that is grounded in complexity theory, hence regarding leadership as a complex process (i.e., nonlinear; emergent). This article tests if complexity leadership theory promotes efficiency in work groups. 40 groups of five participants each had to complete four decision making tasks using the city simulation game SimCity4. Before engaging in the four decision making tasks, participants received information regarding what sort of leadership behaviors were more adequate to help them perform better. Results suggest that if complexity leadership theory is applied, groups can achieve higher efficiency over time, when compared with other groups where complexity leadership is not applied. This study goes beyond traditional views of leadership as a centralized form of control, and presents new evidence suggesting that leadership is a collective and emergent phenomenon, anchored in simple rules of behavior.

Leadership as an Emergent Feature in Social Organizations: Insights from A Laboratory Simulation Experiment

PubMed Central

Marques-Quinteiro, Pedro; Gomes, Catarina; Lind, Pedro G.

2016-01-01

Recent theoretical contributions have suggested a theory of leadership that is grounded in complexity theory, hence regarding leadership as a complex process (i.e., nonlinear; emergent). This article tests if complexity leadership theory promotes efficiency in work groups. 40 groups of five participants each had to complete four decision making tasks using the city simulation game SimCity4. Before engaging in the four decision making tasks, participants received information regarding what sort of leadership behaviors were more adequate to help them perform better. Results suggest that if complexity leadership theory is applied, groups can achieve higher efficiency over time, when compared with other groups where complexity leadership is not applied. This study goes beyond traditional views of leadership as a centralized form of control, and presents new evidence suggesting that leadership is a collective and emergent phenomenon, anchored in simple rules of behavior. PMID:27973596

The Development of the Ducted Fan Noise Propagation and Radiation Code CDUCT-LaRC

NASA Technical Reports Server (NTRS)

Nark, Douglas M.; Farassat, F.; Pope, D. Stuart; Vatsa, Veer

2003-01-01

The development of the ducted fan noise propagation and radiation code CDUCT-LaRC at NASA Langley Research Center is described. This code calculates the propagation and radiation of given acoustic modes ahead of the fan face or aft of the exhaust guide vanes in the inlet or exhaust ducts, respectively. This paper gives a description of the modules comprising CDUCT-LaRC. The grid generation module provides automatic creation of numerical grids for complex (non-axisymmetric) geometries that include single or multiple pylons. Files for performing automatic inviscid mean flow calculations are also generated within this module. The duct propagation is based on the parabolic approximation theory of R. P. Dougherty. This theory allows the handling of complex internal geometries and the ability to study the effect of non-uniform (i.e. circumferentially and axially segmented) liners. Finally, the duct radiation module is based on the Ffowcs Williams-Hawkings (FW-H) equation with a penetrable data surface. Refraction of sound through the shear layer between the external flow and bypass duct flow is included. Results for benchmark annular ducts, as well as other geometries with pylons, are presented and compared with available analytical data.

Interacting complex systems: Theory and application to real-world situations

NASA Astrophysics Data System (ADS)

Piccinini, Nicola

The interest in complex systems has increased exponentially during the past years because it was found helpful in addressing many of today's challenges. The study of the brain, biology, earthquakes, markets and social sciences are only a few examples of the fields that have benefited from the investigation of complex systems. Internet, the increased mobility of people and the raising energy demand are among the factors that brought in contact complex systems that were isolated till a few years ago. A theory for the interaction between complex systems is becoming more and more urgent to help mankind in this transition. The present work builds upon the most recent results in this field by solving a theoretical problem that prevented previous work to be applied to important complex systems, like the brain. It also shows preliminary laboratory results of perturbation of in vitro neural networks that were done to test the theory. Finally, it gives a preview of the studies that are being done to create a theory that is even closer to the interaction between real complex systems.

Structure and Dynamics of Individual Diastereomeric Complexes on Platinum: Surface Studies Related to Heterogeneous Enantioselective Catalysis.

PubMed

Dong, Yi; Goubert, Guillaume; Groves, Michael N; Lemay, Jean-Christian; Hammer, Bjørk; McBreen, Peter H

2017-05-16

The modification of heterogeneous catalysts through the chemisorption of chiral molecules is a method to create catalytic sites for enantioselective surface reactions. The chiral molecule is called a chiral modifier by analogy to the terms chiral auxiliary or chiral ligand used in homogeneous asymmetric catalysis. While there has been progress in understanding how chirality transfer occurs, the intrinsic difficulties in determining enantioselective reaction mechanisms are compounded by the multisite nature of heterogeneous catalysts and by the challenges facing stereospecific surface analysis. However, molecular descriptions have now emerged that are sufficiently detailed to herald rapid advances in the area. The driving force for the development of heterogeneous enantioselective catalysts stems, at the minimum, from the practical advantages they might offer over their homogeneous counterparts in terms of process scalability and catalyst reusability. The broader rewards from their study lie in the insights gained on factors controlling selectivity in heterogeneous catalysis. Reactions on surfaces to produce a desired enantiomer in high excess are particularly challenging since at room temperature, barrier differences as low as ∼2 kcal/mol between pathways to R and S products are sufficient to yield an enantiomeric ratio (er) of 90:10. Such small energy differences are comparable to weak interadsorbate interaction energies and are much smaller than chemisorption or even most physisorption energies. In this Account, we describe combined experimental and theoretical surface studies of individual diastereomeric complexes formed between chiral modifiers and prochiral reactants on the Pt(111) surface. Our work is inspired by the catalysis literature on the enantioselective hydrogenation of activated ketones on cinchona-modified Pt catalysts. Using scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations, we probe the structures and relative abundances of non-covalently bonded complexes formed between three representative prochiral molecules and (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA). All three prochiral molecules, 2,2,2-trifluoroacetophenone (TFAP), ketopantolactone (KPL), and methyl 3,3,3-trifluoropyruvate (MTFP), are found to form multiple complexation configurations around the ethylamine group of chemisorbed (R)-NEA. The principal intermolecular interaction is NH···O H-bonding. In each case, submolecularly resolved STM images permit the determination of the prochiral ratio (pr), pro-R to pro-S, proper to specific locations around the ethylamine group. The overall pr observed in experiments on large ensembles of KPL-(R)-NEA complexes is close to the er reported in the literature for the hydrogenation of KPL to pantolactone on (R)-NEA-modified Pt catalysts at 1 bar H 2 . The results of independent DFT and STM studies are merged to determine the geometries of the most abundant complexation configurations. The structures reveal the hierarchy of chemisorption and sometimes multiple H-bonding interactions operating in complexes. In particular, privileged complexes formed by KPL and MTFP reveal the participation of secondary CH···O interactions in stereocontrol. State-specific STM measurements on individual TFAP-(R)-NEA complexes show that complexation states interconvert through processes including prochiral inversion. The state-specific information on structure, prochirality, dynamics, and energy barriers delivered by the combination of DFT and STM provides insight on how to design better chiral modifiers.

Advanced Thermionic Technology Program

NASA Technical Reports Server (NTRS)

1977-01-01

Topics include surface studies (surface theory, basic surface experiments, and activation chamber experiments); plasma studies (converter theory and enhanced mode conversion experiments); and component development (low temperature conversion experiments, high efficiency conversion experiments, and hot shell development).

"Synergistic selection": a Darwinian frame for the evolution of complexity.

PubMed

Corning, Peter A; Szathmáry, Eörs

2015-04-21

Non-Darwinian theories about the emergence and evolution of complexity date back at least to Lamarck, and include those of Herbert Spencer and the "emergent evolution" theorists of the later nineteenth and early twentieth centuries. In recent decades, this approach has mostly been espoused by various practitioners in biophysics and complexity theory. However, there is a Darwinian alternative - in essence, an economic theory of complexity - proposing that synergistic effects of various kinds have played an important causal role in the evolution of complexity, especially in the "major transitions". This theory is called the "synergism hypothesis". We posit that otherwise unattainable functional advantages arising from various cooperative phenomena have been favored over time in a dynamic that the late John Maynard Smith characterized and modeled as "synergistic selection". The term highlights the fact that synergistic "wholes" may become interdependent "units" of selection. We provide some historical perspective on this issue, as well as a brief explication of the underlying theory and the concept of synergistic selection, and we describe two relevant models. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reliability analysis in interdependent smart grid systems

NASA Astrophysics Data System (ADS)

Peng, Hao; Kan, Zhe; Zhao, Dandan; Han, Jianmin; Lu, Jianfeng; Hu, Zhaolong

2018-06-01

Complex network theory is a useful way to study many real complex systems. In this paper, a reliability analysis model based on complex network theory is introduced in interdependent smart grid systems. In this paper, we focus on understanding the structure of smart grid systems and studying the underlying network model, their interactions, and relationships and how cascading failures occur in the interdependent smart grid systems. We propose a practical model for interdependent smart grid systems using complex theory. Besides, based on percolation theory, we also study the effect of cascading failures effect and reveal detailed mathematical analysis of failure propagation in such systems. We analyze the reliability of our proposed model caused by random attacks or failures by calculating the size of giant functioning components in interdependent smart grid systems. Our simulation results also show that there exists a threshold for the proportion of faulty nodes, beyond which the smart grid systems collapse. Also we determine the critical values for different system parameters. In this way, the reliability analysis model based on complex network theory can be effectively utilized for anti-attack and protection purposes in interdependent smart grid systems.

Multivariate Tensor-based Morphometry on Surfaces: Application to Mapping Ventricular Abnormalities in HIV/AIDS

PubMed Central

Wang, Yalin; Zhang, Jie; Gutman, Boris; Chan, Tony F.; Becker, James T.; Aizenstein, Howard J.; Lopez, Oscar L.; Tamburo, Robert J.; Toga, Arthur W.; Thompson, Paul M.

2010-01-01

Here we developed a new method, called multivariate tensor-based surface morphometry (TBM), and applied it to study lateral ventricular surface differences associated with HIV/AIDS. Using concepts from differential geometry and the theory of differential forms, we created mathematical structures known as holomorphic one-forms, to obtain an efficient and accurate conformal parameterization of the lateral ventricular surfaces in the brain. The new meshing approach also provides a natural way to register anatomical surfaces across subjects, and improves on prior methods as it handles surfaces that branch and join at complex 3D junctions. To analyze anatomical differences, we computed new statistics from the Riemannian surface metrics - these retain multivariate information on local surface geometry. We applied this framework to analyze lateral ventricular surface morphometry in 3D MRI data from 11 subjects with HIV/AIDS and 8 healthy controls. Our method detected a 3D profile of surface abnormalities even in this small sample. Multivariate statistics on the local tensors gave better effect sizes for detecting group differences, relative to other TBM-based methods including analysis of the Jacobian determinant, the largest and smallest eigenvalues of the surface metric, and the pair of eigenvalues of the Jacobian matrix. The resulting analysis pipeline may improve the power of surface-based morphometry studies of the brain. PMID:19900560

Oxidovanadium(IV) complexes involving dehydroacetic acid and β-diketones of bioinorganic and medicinal relevance: Their synthesis, characterization, thermal behavior and DFT aspects

NASA Astrophysics Data System (ADS)

Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.

2015-03-01

Six new mixed-ligand complexes of oxidovanadium(IV) of the general composition [VO(dha)(L)(H2O)], where dhaH = dehydroacetic acid, LH = β-diketones, viz., acetoacetanilide (aaaH), o-acetoacetotoluidide (o-aatdH), o-acetoacetanisidide (o-aansH), acetylacetone (acacH), methyl acetoacetate (macacH) or ethyl acetoacetate (eacacH) have been synthesized by the reaction of VOSO4ṡ5H2O and the ligands given above in aqueous-ethanol medium. The resulting complexes have been characterized on the basis of elemental analyses, vanadium determination, molar conductance and magnetic measurements, mass spectrometry, thermogravimetric analysis, infrared and electron spin resonance spectral studies. The thermal decomposition processes of two representative complexes are discussed and the order of reaction (n) and the activation energy (Ea) for the particular decomposition steps have been calculated from thermogravimetric (TG) curve. Geometry optimizations were performed with the Gaussian 09 software package by using density functional theory (DFT) methods with Becke-3-Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional and the standard LANL2 MB basis set for dhaH and its complex [VO(dha)(acac)(H2O)]. Molecular surface electrostatic potentials (MSEP), vibrational frequency calculations, bond lengths, bond angles, dihedral angles, natural population analysis and calculations of molecular energies, HOMO and LUMO were made. No imaginary frequency was found in the optimized model compounds and hence ensures that the molecule is in the lowest point of the potential energy surface, that is, a energy minimum. Finally calculated results were applied to simulated Infrared spectra of the title compound which show good agreement with observed spectra. Based on experimental and theoretical data, suitable trans-octahedral structures have been proposed for these complexes.

Nonlinear functional for solvation in Density Functional Theory

NASA Astrophysics Data System (ADS)

Gunceler, Deniz; Sundararaman, Ravishankar; Schwarz, Kathleen; Letchworth-Weaver, Kendra; Arias, T. A.

2013-03-01

Density functional calculations of molecules and surfaces in a liquid can accelerate the development of many technologies ranging from solar energy harvesting to lithium batteries. Such studies require the development of robust functionals describing the liquid. Polarizable continuum models (PCM's) have been applied to some solvated systems; but they do not sufficiently capture solvation effects to describe highly polar systems like surfaces of ionic solids. In this work, we present a nonlinear fluid functional within the framework of Joint Density Functional Theory. The fluid is treated not as a linear dielectric, but as a distribution of dipoles that responds to the solute, which we describe starting from the exact free energy functional for point dipoles. We also show PCM's can be recovered as the linear limit of our functional. Our description is of similar computational cost to PCM's, and captures complex solvation effects like dielectric saturation without requiring new fit parameters. For polar and nonpolar molecules, it achieves millihartree level agreement with experimental solvation energies. Furthermore, our functional now makes it possible to investigate chemistry on the surface of lithium battery materials, which PCM's predict to be unstable. Supported as part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001086

The complex and quaternionic quantum bit from relativity of simultaneity on an interferometer

NASA Astrophysics Data System (ADS)

Garner, Andrew J. P.; Müller, Markus P.; Dahlsten, Oscar C. O.

2017-12-01

The patterns of fringes produced by an interferometer have long been important testbeds for our best contemporary theories of physics. Historically, interference has been used to contrast quantum mechanics with classical physics, but recently experiments have been performed that test quantum theory against even more exotic alternatives. A physically motivated family of theories are those where the state space of a two-level system is given by a sphere of arbitrary dimension. This includes classical bits, and real, complex and quaternionic quantum theory. In this paper, we consider relativity of simultaneity (i.e. that observers may disagree about the order of events at different locations) as applied to a two-armed interferometer, and show that this forbids most interference phenomena more complicated than those of complex quantum theory. If interference must depend on some relational property of the setting (such as path difference), then relativity of simultaneity will limit state spaces to standard complex quantum theory, or a subspace thereof. If this relational assumption is relaxed, we find one additional theory compatible with relativity of simultaneity: quaternionic quantum theory. Our results have consequences for current laboratory interference experiments: they have to be designed carefully to avoid rendering beyond-quantum effects invisible by relativity of simultaneity.

The complex and quaternionic quantum bit from relativity of simultaneity on an interferometer.

PubMed

Garner, Andrew J P; Müller, Markus P; Dahlsten, Oscar C O

2017-12-01

The patterns of fringes produced by an interferometer have long been important testbeds for our best contemporary theories of physics. Historically, interference has been used to contrast quantum mechanics with classical physics, but recently experiments have been performed that test quantum theory against even more exotic alternatives. A physically motivated family of theories are those where the state space of a two-level system is given by a sphere of arbitrary dimension. This includes classical bits, and real, complex and quaternionic quantum theory. In this paper, we consider relativity of simultaneity (i.e. that observers may disagree about the order of events at different locations) as applied to a two-armed interferometer, and show that this forbids most interference phenomena more complicated than those of complex quantum theory. If interference must depend on some relational property of the setting (such as path difference), then relativity of simultaneity will limit state spaces to standard complex quantum theory, or a subspace thereof. If this relational assumption is relaxed, we find one additional theory compatible with relativity of simultaneity: quaternionic quantum theory. Our results have consequences for current laboratory interference experiments: they have to be designed carefully to avoid rendering beyond-quantum effects invisible by relativity of simultaneity.

Comparison of the GHSSmooth and the Rayleigh-Rice surface scatter theories

NASA Astrophysics Data System (ADS)

Harvey, James E.; Pfisterer, Richard N.

2016-09-01

The scalar-based GHSSmooth surface scatter theory results in an expression for the BRDF in terms of the surface PSD that is very similar to that provided by the rigorous Rayleigh-Rice (RR) vector perturbation theory. However it contains correction factors for two extreme situations not shared by the RR theory: (i) large incident or scattered angles that result in some portion of the scattered radiance distribution falling outside of the unit circle in direction cosine space, and (ii) the situation where the relevant rms surface roughness, σrel, is less than the total intrinsic rms roughness of the scattering surface. Also, the RR obliquity factor has been discovered to be an approximation of the more general GHSSmooth obliquity factor due to a little-known (or long-forgotten) implicit assumption in the RR theory that the surface autocovariance length is longer than the wavelength of the scattered radiation. This assumption allowed retaining only quadratic terms and lower in the series expansion for the cosine function, and results in reducing the validity of RR predictions for scattering angles greater than 60°. This inaccurate obliquity factor in the RR theory is also the cause of a complementary unrealistic "hook" at the high spatial frequency end of the predicted surface PSD when performing the inverse scattering problem. Furthermore, if we empirically substitute the polarization reflectance, Q, from the RR expression for the scalar reflectance, R, in the GHSSmooth expression, it inherits all of the polarization capabilities of the rigorous RR vector perturbation theory.

MEPSA: minimum energy pathway analysis for energy landscapes.

PubMed

Marcos-Alcalde, Iñigo; Setoain, Javier; Mendieta-Moreno, Jesús I; Mendieta, Jesús; Gómez-Puertas, Paulino

2015-12-01

From conformational studies to atomistic descriptions of enzymatic reactions, potential and free energy landscapes can be used to describe biomolecular systems in detail. However, extracting the relevant data of complex 3D energy surfaces can sometimes be laborious. In this article, we present MEPSA (Minimum Energy Path Surface Analysis), a cross-platform user friendly tool for the analysis of energy landscapes from a transition state theory perspective. Some of its most relevant features are: identification of all the barriers and minima of the landscape at once, description of maxima edge profiles, detection of the lowest energy path connecting two minima and generation of transition state theory diagrams along these paths. In addition to a built-in plotting system, MEPSA can save most of the generated data into easily parseable text files, allowing more versatile uses of MEPSA's output such as the generation of molecular dynamics restraints from a calculated path. MEPSA is freely available (under GPLv3 license) at: http://bioweb.cbm.uam.es/software/MEPSA/ CONTACT: pagomez@cbm.csic.es. Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Theoretical study of the adsorption of DNA bases on the acidic external surface of montmorillonite.

PubMed

Mignon, Pierre; Sodupe, Mariona

2012-01-14

In the present study, DFT periodic plane wave calculations, at the PBE-D level of theory, were carried out to investigate the interaction of DNA nucleobases with acidic montmorillonite. The surface model was considered in its octahedral (Osub) and tetrahedral (Tsub) substituted forms, known to have different acidic properties. The adsorption of adenine, guanine and cytosine was considered in both orthogonal and coplanar orientations with the surface, interacting with the proton via a given heteroatom. In almost all considered cases, adsorption involved the spontaneous proton transfer to the nucleobase, with a more pronounced character in the Osub structures. The binding energy is about 10 kcal mol(-1) larger for Osub than for Tsub complexes mainly due to the larger acidity in Osub surfaces and due to the better stabilization by H-bond contacts between the negatively charged surface and the protonated base. The binding energy of coplanar orientations of the base is observed to be as large as the orthogonal ones due to a balance between electrostatic and dispersion contributions. Finally the binding of guanine and adenine on the acidic surface amounts to 50 kcal mol(-1) while that of cytosine rises to 44 kcal mol(-1).

Evolution of complexity following a quantum quench in free field theory

NASA Astrophysics Data System (ADS)

Alves, Daniel W. F.; Camilo, Giancarlo

2018-06-01

Using a recent proposal of circuit complexity in quantum field theories introduced by Jefferson and Myers, we compute the time evolution of the complexity following a smooth mass quench characterized by a time scale δ t in a free scalar field theory. We show that the dynamics has two distinct phases, namely an early regime of approximately linear evolution followed by a saturation phase characterized by oscillations around a mean value. The behavior is similar to previous conjectures for the complexity growth in chaotic and holographic systems, although here we have found that the complexity may grow or decrease depending on whether the quench increases or decreases the mass, and also that the time scale for saturation of the complexity is of order δ t (not parametrically larger).

The Conceptual Mechanism for Viable Organizational Learning Based on Complex System Theory and the Viable System Model

ERIC Educational Resources Information Center

Sung, Dia; You, Yeongmahn; Song, Ji Hoon

2008-01-01

The purpose of this research is to explore the possibility of viable learning organizations based on identifying viable organizational learning mechanisms. Two theoretical foundations, complex system theory and viable system theory, have been integrated to provide the rationale for building the sustainable organizational learning mechanism. The…

Teaching the Dynamics of Framing Competitions

ERIC Educational Resources Information Center

Rinke, Eike Mark

2012-01-01

Framing theory is one of the most thriving and complex fields of communication theory, and as such it has grown to be an integral part of many political communication, public opinion, and communication theory courses. Part of the complexity stems from scholars' efforts to develop accounts of framing processes that are closer to the "real world" of…

Applying Chaos Theory to Lesson Planning and Delivery

ERIC Educational Resources Information Center

Cvetek, Slavko

2008-01-01

In this article, some of the ways in which thinking about chaos theory can help teachers and student-teachers to accept uncertainty and randomness as natural conditions in the classroom are considered. Building on some key features of complex systems commonly attributed to chaos theory (e.g. complexity, nonlinearity, sensitivity to initial…

The Complexity of Language Learning

ERIC Educational Resources Information Center

Nelson, Charles

2011-01-01

This paper takes a complexity theory approach to looking at language learning, an approach that investigates how language learners adapt to and interact with people and their environment. Based on interviews with four graduate students, it shows how complexity theory can help us understand both the situatedness of language learning and also…

Ecosystemic Complexity Theory of Conflict: Understanding the Fog of Conflict

ERIC Educational Resources Information Center

Brack, Greg; Lassiter, Pamela S.; Hill, Michele B.; Moore, Sarah A.

2011-01-01

Counselors often engage in conflict mediation in professional practice. A model for understanding the complex and subtle nature of conflict resolution is presented. The ecosystemic complexity theory of conflict is offered to assist practitioners in navigating the fog of conflict. Theoretical assumptions are discussed with implications for clinical…

Modelling of Surfaces. Part 1: Monatomic Metallic Surfaces Using Equivalent Crystal Theory

NASA Technical Reports Server (NTRS)

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

1994-01-01

We present a detailed description of equivalent crystal theory focusing on its application to the study of surface structure. While the emphasis is in the structure of the algorithm and its computational aspects, we also present a comprehensive discussion on the calculation of surface energies of metallic systems with equivalent crystal theory and other approaches. Our results are compared to experiment and other semiempirical as well as first-principles calculations for a variety of fcc and bcc metals.

Systems and complexity thinking in the general practice literature: an integrative, historical narrative review.

PubMed

Sturmberg, Joachim P; Martin, Carmel M; Katerndahl, David A

2014-01-01

Over the past 7 decades, theories in the systems and complexity sciences have had a major influence on academic thinking and research. We assessed the impact of complexity science on general practice/family medicine. We performed a historical integrative review using the following systematic search strategy: medical subject heading [humans] combined in turn with the terms complex adaptive systems, nonlinear dynamics, systems biology, and systems theory, limited to general practice/family medicine and published before December 2010. A total of 16,242 articles were retrieved, of which 49 were published in general practice/family medicine journals. Hand searches and snowballing retrieved another 35. After a full-text review, we included 56 articles dealing specifically with systems sciences and general/family practice. General practice/family medicine engaged with the emerging systems and complexity theories in 4 stages. Before 1995, articles tended to explore common phenomenologic general practice/family medicine experiences. Between 1995 and 2000, articles described the complex adaptive nature of this discipline. Those published between 2000 and 2005 focused on describing the system dynamics of medical practice. After 2005, articles increasingly applied the breadth of complex science theories to health care, health care reform, and the future of medicine. This historical review describes the development of general practice/family medicine in relation to complex adaptive systems theories, and shows how systems sciences more accurately reflect the discipline's philosophy and identity. Analysis suggests that general practice/family medicine first embraced systems theories through conscious reorganization of its boundaries and scope, before applying empirical tools. Future research should concentrate on applying nonlinear dynamics and empirical modeling to patient care, and to organizing and developing local practices, engaging in community development, and influencing health care reform.

Systems and Complexity Thinking in the General Practice Literature: An Integrative, Historical Narrative Review

PubMed Central

Sturmberg, Joachim P.; Martin, Carmel M.; Katerndahl, David A.

2014-01-01

PURPOSE Over the past 7 decades, theories in the systems and complexity sciences have had a major influence on academic thinking and research. We assessed the impact of complexity science on general practice/family medicine. METHODS We performed a historical integrative review using the following systematic search strategy: medical subject heading [humans] combined in turn with the terms complex adaptive systems, nonlinear dynamics, systems biology, and systems theory, limited to general practice/family medicine and published before December 2010. A total of 16,242 articles were retrieved, of which 49 were published in general practice/family medicine journals. Hand searches and snowballing retrieved another 35. After a full-text review, we included 56 articles dealing specifically with systems sciences and general/family practice. RESULTS General practice/family medicine engaged with the emerging systems and complexity theories in 4 stages. Before 1995, articles tended to explore common phenomenologic general practice/family medicine experiences. Between 1995 and 2000, articles described the complex adaptive nature of this discipline. Those published between 2000 and 2005 focused on describing the system dynamics of medical practice. After 2005, articles increasingly applied the breadth of complex science theories to health care, health care reform, and the future of medicine. CONCLUSIONS This historical review describes the development of general practice/family medicine in relation to complex adaptive systems theories, and shows how systems sciences more accurately reflect the discipline’s philosophy and identity. Analysis suggests that general practice/family medicine first embraced systems theories through conscious reorganization of its boundaries and scope, before applying empirical tools. Future research should concentrate on applying nonlinear dynamics and empirical modeling to patient care, and to organizing and developing local practices, engaging in community development, and influencing health care reform. PMID:24445105

Surface transport processes in charged porous media

DOE PAGES

Gabitto, Jorge; Tsouris, Costas

2017-03-03

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Surface transport processes in charged porous media

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

Gabitto, Jorge; Tsouris, Costas

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Uni-directional liquid spreading on asymmetric nanostructured surfaces

NASA Astrophysics Data System (ADS)

Chu, Kuang-Han; Xiao, Rong; Wang, Evelyn N.

2010-05-01

Controlling surface wettability and liquid spreading on patterned surfaces is of significant interest for a broad range of applications, including DNA microarrays, digital lab-on-a-chip, anti-fogging and fog-harvesting, inkjet printing and thin-film lubrication. Advancements in surface engineering, with the fabrication of various micro/nanoscale topographic features, and selective chemical patterning on surfaces, have enhanced surface wettability and enabled control of the liquid film thickness and final wetted shape. In addition, groove geometries and patterned surface chemistries have produced anisotropic wetting, where contact-angle variations in different directions resulted in elongated droplet shapes. In all of these studies, however, the wetting behaviour preserves left-right symmetry. Here, we demonstrate that we can harness the design of asymmetric nanostructured surfaces to achieve uni-directional liquid spreading, where the liquid propagates in a single preferred direction and pins in all others. Through experiments and modelling, we determined that the spreading characteristic is dependent on the degree of nanostructure asymmetry, the height-to-spacing ratio of the nanostructures and the intrinsic contact angle. The theory, based on an energy argument, provides excellent agreement with experimental data. The insights gained from this work offer new opportunities to tailor advanced nanostructures to achieve active control of complex flow patterns and wetting on demand.

Adsorption of benzene on low index surfaces of platinum in the presence of van der Waals interactions

NASA Astrophysics Data System (ADS)

K, Ayishabi P.; Chatanathodi, Raghu

2017-10-01

We have studied the adsorption of benzene on three low index surfaces of platinum using plane-wave Density Functional Theory (DFT) calculations, taking into consideration van der Waals (vdW) interaction. Experimentally, it is known that benzene adsorbs at the bridge site on the (111) surface, but in case of (110) and (100), this is not known yet. Our calculations show that benzene preferably adsorbs on bridge position on Pt(111) surface, whereas on Pt(110) and Pt(100) surfaces, the hollow position is energetically more favoured. The structural and electronic modifications of molecule and the surfaces are also examined. In all cases, adsorption-induced distortions of adsorbate-substrate complex are found to be modest in character, but relatively maximum in case of the (110) facet. The molecule is bound most strongly to the (110) surface. Importantly, we find that adsorption at bridge and atop positions are energetically feasible on the (110) surface, with the canting of benzene ring at a small angle from the metal plane. We study changes in electronic structure and the net charge transfer upon adsorption of benzene on all three low index planes. Inclusion of vdW interactions is important for obtaining realistic adsorption strengths for benzene on various Pt facets.

On a theory of surface waves in a smoothly inhomogeneous plasma in an external magnetic field

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

Kuzelev, M. V., E-mail: kuzelev@mail.ru; Orlikovskaya, N. G.

2016-12-15

A theory of surface waves in a magnetoactive plasma with smooth boundaries has been developed. A dispersion equation for surface waves has been derived for a linear law of density change at the plasma boundary. The frequencies of surface waves and their collisionless damping rates have been determined. A generalization to an arbitrary density profile at the plasma boundary is given. The collisions have been taken into account, and the application of the Landau rule in the theory of surface wave damping in a spatially inhomogeneous magnetoactive collisional plasma has been clarified.

Calculation of the distributed loads on the blades of individual multiblade propellers in axial flow using linear and nonlinear lifting surface theories

NASA Technical Reports Server (NTRS)

Pesetskaya, N. N.; Timofeev, I. YA.; Shipilov, S. D.

1988-01-01

In recent years much attention has been given to the development of methods and programs for the calculation of the aerodynamic characteristics of multiblade, saber-shaped air propellers. Most existing methods are based on the theory of lifting lines. Elsewhere, the theory of a lifting surface is used to calculate screw and lifting propellers. In this work, methods of discrete eddies are described for the calculation of the aerodynamic characteristics of propellers using the linear and nonlinear theories of lifting surfaces.

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

PubMed

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Efficient Destruction of Pollutants in Water by a Dual-Reaction-Center Fenton-like Process over Carbon Nitride Compounds-Complexed Cu(II)-CuAlO2.

PubMed

Lyu, Lai; Yan, Dengbiao; Yu, Guangfei; Cao, Wenrui; Hu, Chun

2018-04-03

Carbon nitride compounds (CN) complexed with the in-situ-produced Cu(II) on the surface of CuAlO 2 substrate (CN-Cu(II)-CuAlO 2 ) is prepared via a surface growth process for the first time and exhibits exceptionally high activity and efficiency for the degradation of the refractory pollutants in water through a Fenton-like process in a wide pH range. The reaction rate for bisphenol A removal is ∼25 times higher than that of the CuAlO 2 . According to the characterization, Cu(II) generation on the surface of CuAlO 2 during the surface growth process results in the marked decrease of the surface oxygen vacancies and the formation of the C-O-Cu bridges between CN and Cu(II)-CuAlO 2 in the catalyst. The electron paramagnetic resonance (EPR) analysis and density functional theory (DFT) calculations demonstrate that the dual reaction centers are produced around the Cu and C sites due to the cation-π interactions through the C-O-Cu bridges in CN-Cu(II)-CuAlO 2 . During the Fenton-like reactions, the electron-rich center around Cu is responsible for the efficient reduction of H 2 O 2 to • OH, and the electron-poor center around C captures electrons from H 2 O 2 or pollutants and diverts them to the electron-rich area via the C-O-Cu bridge. Thus, the catalyst exhibits excellent catalytic performance for the refractory pollutant degradation. This study can deepen our understanding on the enhanced Fenton reactivity for water purification through functionalizing with organic solid-phase ligands on the catalyst surface.

Marcus-Hush-Chidsey theory of electron transfer to and from species bound at a non-uniform electrode surface: Theory and experiment

NASA Astrophysics Data System (ADS)

Henstridge, Martin C.; Batchelor-McAuley, Christopher; Gusmão, Rui; Compton, Richard G.

2011-11-01

Two simple models of electrode surface inhomogeneity based on Marcus-Hush theory are considered; a distribution in formal potentials and a distribution in electron tunnelling distances. Cyclic voltammetry simulated using these models is compared with that simulated using Marcus-Hush theory for a flat, uniform and homogeneous electrode surface, with the two models of surface inhomogeneity yielding broadened peaks with decreased peak-currents. An edge-plane pyrolytic graphite electrode is covalently modified with ferrocene via 'click' chemistry and the resulting voltammetry compared with each of the three previously considered models. The distribution of formal potentials is seen to fit the experimental data most closely.

Symmetrical group theory for mathematical complexity reduction of digital holograms

NASA Astrophysics Data System (ADS)

Perez-Ramirez, A.; Guerrero-Juk, J.; Sanchez-Lara, R.; Perez-Ramirez, M.; Rodriguez-Blanco, M. A.; May-Alarcon, M.

2017-10-01

This work presents the use of mathematical group theory through an algorithm to reduce the multiplicative computational complexity in the process of creating digital holograms. An object is considered as a set of point sources using mathematical symmetry properties of both the core in the Fresnel integral and the image, where the image is modeled using group theory. This algorithm has multiplicative complexity equal to zero and an additive complexity ( k - 1) × N for the case of sparse matrices and binary images, where k is the number of pixels other than zero and N is the total points in the image.

Detecting the chaotic nature in a transitional boundary layer using symbolic information-theory quantifiers.

PubMed

Zhang, Wen; Liu, Peiqing; Guo, Hao; Wang, Jinjun

2017-11-01

The permutation entropy and the statistical complexity are employed to study the boundary-layer transition induced by the surface roughness. The velocity signals measured in the transition process are analyzed with these symbolic quantifiers, as well as the complexity-entropy causality plane, and the chaotic nature of the instability fluctuations is identified. The frequency of the dominant fluctuations has been found according to the time scales corresponding to the extreme values of the symbolic quantifiers. The laminar-turbulent transition process is accompanied by the evolution in the degree of organization of the complex eddy motions, which is also characterized with the growing smaller and flatter circles in the complexity-entropy causality plane. With the help of the permutation entropy and the statistical complexity, the differences between the chaotic fluctuations detected in the experiments and the classical Tollmien-Schlichting wave are shown and discussed. It is also found that the chaotic features of the instability fluctuations can be approximated with a number of regular sine waves superimposed on the fluctuations of the undisturbed laminar boundary layer. This result is related to the physical mechanism in the generation of the instability fluctuations, which is the noise-induced chaos.

Detecting the chaotic nature in a transitional boundary layer using symbolic information-theory quantifiers

NASA Astrophysics Data System (ADS)

Zhang, Wen; Liu, Peiqing; Guo, Hao; Wang, Jinjun

2017-11-01

The permutation entropy and the statistical complexity are employed to study the boundary-layer transition induced by the surface roughness. The velocity signals measured in the transition process are analyzed with these symbolic quantifiers, as well as the complexity-entropy causality plane, and the chaotic nature of the instability fluctuations is identified. The frequency of the dominant fluctuations has been found according to the time scales corresponding to the extreme values of the symbolic quantifiers. The laminar-turbulent transition process is accompanied by the evolution in the degree of organization of the complex eddy motions, which is also characterized with the growing smaller and flatter circles in the complexity-entropy causality plane. With the help of the permutation entropy and the statistical complexity, the differences between the chaotic fluctuations detected in the experiments and the classical Tollmien-Schlichting wave are shown and discussed. It is also found that the chaotic features of the instability fluctuations can be approximated with a number of regular sine waves superimposed on the fluctuations of the undisturbed laminar boundary layer. This result is related to the physical mechanism in the generation of the instability fluctuations, which is the noise-induced chaos.

Sample entropy and regularity dimension in complexity analysis of cortical surface structure in early Alzheimer's disease and aging.

PubMed

Chen, Ying; Pham, Tuan D

2013-05-15

We apply for the first time the sample entropy (SampEn) and regularity dimension model for measuring signal complexity to quantify the structural complexity of the brain on MRI. The concept of the regularity dimension is based on the theory of chaos for studying nonlinear dynamical systems, where power laws and entropy measure are adopted to develop the regularity dimension for modeling a mathematical relationship between the frequencies with which information about signal regularity changes in various scales. The sample entropy and regularity dimension of MRI-based brain structural complexity are computed for early Alzheimer's disease (AD) elder adults and age and gender-matched non-demented controls, as well as for a wide range of ages from young people to elder adults. A significantly higher global cortical structure complexity is detected in AD individuals (p<0.001). The increase of SampEn and the regularity dimension are also found to be accompanied with aging which might indicate an age-related exacerbation of cortical structural irregularity. The provided model can be potentially used as an imaging bio-marker for early prediction of AD and age-related cognitive decline. Copyright © 2013 Elsevier B.V. All rights reserved.

On the buckling of elastic rings by external confinement.

PubMed

Hazel, Andrew L; Mullin, Tom

2017-05-13

We report the results of an experimental and numerical investigation into the buckling of thin elastic rings confined within containers of circular or regular polygonal cross section. The rings float on the surface of water held in the container and controlled removal of the fluid increases the confinement of the ring. The increased compressive forces can cause the ring to buckle into a variety of shapes. For the circular container, finite perturbations are required to induce buckling, whereas in polygonal containers the buckling occurs through a linear instability that is closely related to the canonical Euler column buckling. A model based on Kirchhoff-Love beam theory is developed and solved numerically, showing good agreement with the experiments and revealing that in polygons increasing the number of sides means that buckling occurs at reduced levels of confinement.This article is part of the themed issue 'Patterning through instabilities in complex media: theory and applications.' © 2017 The Author(s).

Theory of high-resolution tunneling spin transport on a magnetic skyrmion

NASA Astrophysics Data System (ADS)

Palotás, Krisztián; Rózsa, Levente; Szunyogh, László

2018-05-01

Tunneling spin transport characteristics of a magnetic skyrmion are described theoretically in magnetic scanning tunneling microscopy (STM). The spin-polarized charge current in STM (SP-STM) and tunneling spin transport vector quantities, the longitudinal spin current and the spin transfer torque, are calculated in high spatial resolution within the same theoretical framework. A connection between the conventional charge current SP-STM image contrasts and the magnitudes of the spin transport vectors is demonstrated that enables the estimation of tunneling spin transport properties based on experimentally measured SP-STM images. A considerable tunability of the spin transport vectors by the involved spin polarizations is also highlighted. These possibilities and the combined theory of tunneling charge and vector spin transport pave the way for gaining deep insight into electric-current-induced tunneling spin transport properties in SP-STM and to the related dynamics of complex magnetic textures at surfaces.

Radiative transfer modelling inside thermal protection system using hybrid homogenization method for a backward Monte Carlo method coupled with Mie theory

NASA Astrophysics Data System (ADS)

Le Foll, S.; André, F.; Delmas, A.; Bouilly, J. M.; Aspa, Y.

2012-06-01

A backward Monte Carlo method for modelling the spectral directional emittance of fibrous media has been developed. It uses Mie theory to calculate the radiative properties of single fibres, modelled as infinite cylinders, and the complex refractive index is computed by a Drude-Lorenz model for the dielectric function. The absorption and scattering coefficient are homogenised over several fibres, but the scattering phase function of a single one is used to determine the scattering direction of energy inside the medium. Sensitivity analysis based on several Monte Carlo results has been performed to estimate coefficients for a Multi-Linear Model (MLM) specifically developed for inverse analysis of experimental data. This model concurs with the Monte Carlo method and is highly computationally efficient. In contrast, the surface emissivity model, which assumes an opaque medium, shows poor agreement with the reference Monte Carlo calculations.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

NASA Astrophysics Data System (ADS)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

On the buckling of elastic rings by external confinement

PubMed Central

Hazel, Andrew L.

2017-01-01

We report the results of an experimental and numerical investigation into the buckling of thin elastic rings confined within containers of circular or regular polygonal cross section. The rings float on the surface of water held in the container and controlled removal of the fluid increases the confinement of the ring. The increased compressive forces can cause the ring to buckle into a variety of shapes. For the circular container, finite perturbations are required to induce buckling, whereas in polygonal containers the buckling occurs through a linear instability that is closely related to the canonical Euler column buckling. A model based on Kirchhoff–Love beam theory is developed and solved numerically, showing good agreement with the experiments and revealing that in polygons increasing the number of sides means that buckling occurs at reduced levels of confinement. This article is part of the themed issue ‘Patterning through instabilities in complex media: theory and applications.’ PMID:28373386

A two-fluid study of oblique tearing modes in a force-free current sheet

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

Akçay, Cihan, E-mail: akcay@lanl.gov; Daughton, William; Lukin, Vyacheslav S.

2016-01-15

Kinetic simulations have demonstrated that three-dimensional reconnection in collisionless regimes proceeds through the formation and interaction of magnetic flux ropes, which are generated due to the growth of tearing instabilities at multiple resonance surfaces. Since kinetic simulations are intrinsically expensive, it is desirable to explore the feasibility of reduced two-fluid models to capture this complex evolution, particularly, in the strong guide field regime, where two-fluid models are better justified. With this goal in mind, this paper compares the evolution of the collisionless tearing instability in a force-free current sheet with a two-fluid model and fully kinetic simulations. Our results indicatemore » that the most unstable modes are oblique for guide fields larger than the reconnecting field, in agreement with the kinetic results. The standard two-fluid tearing theory is extended to address the tearing instability at oblique angles. The resulting theory yields a flat oblique spectrum and underestimates the growth of oblique modes in a similar manner to kinetic theory relative to kinetic simulations.« less

Monolithic ceramic analysis using the SCARE program

NASA Technical Reports Server (NTRS)

Manderscheid, Jane M.

1988-01-01

The Structural Ceramics Analysis and Reliability Evaluation (SCARE) computer program calculates the fast fracture reliability of monolithic ceramic components. The code is a post-processor to the MSC/NASTRAN general purpose finite element program. The SCARE program automatically accepts the MSC/NASTRAN output necessary to compute reliability. This includes element stresses, temperatures, volumes, and areas. The SCARE program computes two-parameter Weibull strength distributions from input fracture data for both volume and surface flaws. The distributions can then be used to calculate the reliability of geometrically complex components subjected to multiaxial stress states. Several fracture criteria and flaw types are available for selection by the user, including out-of-plane crack extension theories. The theoretical basis for the reliability calculations was proposed by Batdorf. These models combine linear elastic fracture mechanics (LEFM) with Weibull statistics to provide a mechanistic failure criterion. Other fracture theories included in SCARE are the normal stress averaging technique and the principle of independent action. The objective of this presentation is to summarize these theories, including their limitations and advantages, and to provide a general description of the SCARE program, along with example problems.

A two-fluid study of oblique tearing modes in a force-free current sheet

DOE PAGES

Akçay, Cihan; Daughton, William; Lukin, Vyacheslav S.; ...

2016-01-01

Kinetic simulations have demonstrated that three-dimensional reconnection in collisionless regimes proceeds through the formation and interaction of magnetic flux ropes, which are generated due to the growth of tearing instabilities at multiple resonance surfaces. Because kinetic simulations are intrinsically expensive, it is desirable to explore the feasibility of reduced two-fluid models to capture this complex evolution, particularly, in the strong guide field regime, where two-fluid models are better justified. With this goal in mind, this paper compares the evolution of the collisionless tearing instability in a force-free current sheet with a two-fluid model and fully kinetic simulations. Our results indicatemore » that the most unstable modes are oblique for guide fields larger than the reconnecting field, in agreement with the kinetic results. The standard two-fluid tearing theory is extended to address the tearing instability at oblique angles. As a results this theory yields a flat oblique spectrum and underestimates the growth of oblique modes in a similar manner to kinetic theory relative to kinetic simulations.« less

Complexity Theory, School Leadership and Management: Questions for Theory and Practice

ERIC Educational Resources Information Center

Morrison, Keith

2010-01-01

Complexity theory (CT) has had a meteoric rise in management literature and the social sciences. Its fledgling importation into school leadership and management raises several questions and concerns. This article takes one view of CT and argues that, though its key elements have much to offer school leadership and management, caution has to be…

Thickened boundary layer theory for air film drag reduction on a van body surface

NASA Astrophysics Data System (ADS)

Xie, Xiaopeng; Cao, Lifeng; Huang, Heng

2018-05-01

To elucidate drag reduction mechanism on a van body surface under air film condition, a thickened boundary layer theory was proposed and a frictional resistance calculation model of the van body surface was established. The frictional resistance on the van body surface was calculated with different parameters of air film thickness. In addition, the frictional resistance of the van body surface under the air film condition was analyzed by computational fluid dynamics (CFD) simulation and different air film states that influenced the friction resistance on the van body surface were discussed. As supported by the CFD simulation results, the thickened boundary layer theory may provide reference for practical application of air film drag reduction on a van body surface.

Assessment and Computerized Modeling of the Environmental Deposition of Military Smokes. Characterization of the Atmospheric Boundary Layer in Complex Terrain and Results from the Amadeus Smoke Dispersion Experiments

DTIC Science & Technology

1991-12-01

profiles may De seriously distorted in the presence 3 of large roughness elements or hills. Regardless of surface characteristics, similarity theory may...scaling parameters described in Section 2.2.1 These profiles may be written in the following form 24 du u. ( - 4m() (2.15) de e. 4 (2.16) where $m and 4h...temperature sensor on Station A103 "exhibited a very slow response time as compared with the other sur- face-station sensors . These stations ran continuously

Theoretical predictions of vibration-rotation-tunneling dynamics of the weakly bound trimer (H 2O) 2HCl

NASA Astrophysics Data System (ADS)

Struniewicz, Cezary; Korona, Tatiana; Moszynski, Robert; Milet, Anne

2001-08-01

In this Letter we report a theoretical study of the vibration-rotation-tunneling (VRT) states of the (H 2O) 2HCl trimer. Five degrees of freedom are considered: two angles corresponding to the torsional (flipping) motions of the free, non-hydrogen-bonded, hydrogen atoms in the complex, and three angles describing the overall rotation of the trimer in the space. A two-dimensional potential energy surface is generated ab initio by symmetry-adapted perturbation theory (SAPT). Tunneling splittings, frequencies of the intermolecular vibrations, and vibrational line strengths of spectroscopic transitions are predicted.

What Is Complexity Theory and What Are Its Implications for Educational Change?

ERIC Educational Resources Information Center

Mason, Mark

2008-01-01

HistoryThis paper considers questions of continuity and change in education from the perspective of complexity theory, introducing the field to educationists who might not be familiar with it. Given a significant degree of complexity in a particular environment (or "dynamical system"), new properties and behaviours, which are not necessarily…

A shallow water model for the propagation of tsunami via Lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Zergani, Sara; Aziz, Z. A.; Viswanathan, K. K.

2015-01-01

An efficient implementation of the lattice Boltzmann method (LBM) for the numerical simulation of the propagation of long ocean waves (e.g. tsunami), based on the nonlinear shallow water (NSW) wave equation is presented. The LBM is an alternative numerical procedure for the description of incompressible hydrodynamics and has the potential to serve as an efficient solver for incompressible flows in complex geometries. This work proposes the NSW equations for the irrotational surface waves in the case of complex bottom elevation. In recent time, equation involving shallow water is the current norm in modelling tsunami operations which include the propagation zone estimation. Several test-cases are presented to verify our model. Some implications to tsunami wave modelling are also discussed. Numerical results are found to be in excellent agreement with theory.

Thermodynamic holography.

PubMed

Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

2015-10-19

The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics.

Theory of Change: a theory-driven approach to enhance the Medical Research Council's framework for complex interventions

PubMed Central

2014-01-01

Background The Medical Research Councils’ framework for complex interventions has been criticized for not including theory-driven approaches to evaluation. Although the framework does include broad guidance on the use of theory, it contains little practical guidance for implementers and there have been calls to develop a more comprehensive approach. A prospective, theory-driven process of intervention design and evaluation is required to develop complex healthcare interventions which are more likely to be effective, sustainable and scalable. Methods We propose a theory-driven approach to the design and evaluation of complex interventions by adapting and integrating a programmatic design and evaluation tool, Theory of Change (ToC), into the MRC framework for complex interventions. We provide a guide to what ToC is, how to construct one, and how to integrate its use into research projects seeking to design, implement and evaluate complex interventions using the MRC framework. We test this approach by using ToC within two randomized controlled trials and one non-randomized evaluation of complex interventions. Results Our application of ToC in three research projects has shown that ToC can strengthen key stages of the MRC framework. It can aid the development of interventions by providing a framework for enhanced stakeholder engagement and by explicitly designing an intervention that is embedded in the local context. For the feasibility and piloting stage, ToC enables the systematic identification of knowledge gaps to generate research questions that strengthen intervention design. ToC may improve the evaluation of interventions by providing a comprehensive set of indicators to evaluate all stages of the causal pathway through which an intervention achieves impact, combining evaluations of intervention effectiveness with detailed process evaluations into one theoretical framework. Conclusions Incorporating a ToC approach into the MRC framework holds promise for improving the design and evaluation of complex interventions, thereby increasing the likelihood that the intervention will be ultimately effective, sustainable and scalable. We urge researchers developing and evaluating complex interventions to consider using this approach, to evaluate its usefulness and to build an evidence base to further refine the methodology. Trial registration Clinical trials.gov: NCT02160249 PMID:24996765

Theory of Change: a theory-driven approach to enhance the Medical Research Council's framework for complex interventions.

PubMed

De Silva, Mary J; Breuer, Erica; Lee, Lucy; Asher, Laura; Chowdhary, Neerja; Lund, Crick; Patel, Vikram

2014-07-05

The Medical Research Councils' framework for complex interventions has been criticized for not including theory-driven approaches to evaluation. Although the framework does include broad guidance on the use of theory, it contains little practical guidance for implementers and there have been calls to develop a more comprehensive approach. A prospective, theory-driven process of intervention design and evaluation is required to develop complex healthcare interventions which are more likely to be effective, sustainable and scalable. We propose a theory-driven approach to the design and evaluation of complex interventions by adapting and integrating a programmatic design and evaluation tool, Theory of Change (ToC), into the MRC framework for complex interventions. We provide a guide to what ToC is, how to construct one, and how to integrate its use into research projects seeking to design, implement and evaluate complex interventions using the MRC framework. We test this approach by using ToC within two randomized controlled trials and one non-randomized evaluation of complex interventions. Our application of ToC in three research projects has shown that ToC can strengthen key stages of the MRC framework. It can aid the development of interventions by providing a framework for enhanced stakeholder engagement and by explicitly designing an intervention that is embedded in the local context. For the feasibility and piloting stage, ToC enables the systematic identification of knowledge gaps to generate research questions that strengthen intervention design. ToC may improve the evaluation of interventions by providing a comprehensive set of indicators to evaluate all stages of the causal pathway through which an intervention achieves impact, combining evaluations of intervention effectiveness with detailed process evaluations into one theoretical framework. Incorporating a ToC approach into the MRC framework holds promise for improving the design and evaluation of complex interventions, thereby increasing the likelihood that the intervention will be ultimately effective, sustainable and scalable. We urge researchers developing and evaluating complex interventions to consider using this approach, to evaluate its usefulness and to build an evidence base to further refine the methodology. Clinical trials.gov: NCT02160249.

Ion beam texturing of surfaces

NASA Technical Reports Server (NTRS)

Kaufman, H. R.; Robinson, R. S.

1979-01-01

Textured surfaces, typically with conical structures, have been produced previously by simultaneously etching a surface and seeding that surface with another material. A theory based on surface diffusion predicts a variation in cone spacing with surface temperature, as well as a critical temperature below which cones will not form. Substantial agreement with theory has been found for several combinations of seed and surface materials, including one with a high sputter yield seed on a low sputter yield surface (gold on aluminum). Coning with this last combination was predicted by the theory for a sufficiently mobile seed material. The existence of a minimum temperature for the formation of cones should also be important to those interested in ion-beam machining smooth surfaces. Elements contained in the environmental contaminants or in the sputtered alloys or compounds may serve as seed material.

Analysis of surface segregation in polymer mixtures: A combination of mean field and statistical associated fluid theories

NASA Astrophysics Data System (ADS)

Krawczyk, Jaroslaw; Croce, Salvatore; Chakrabarti, Buddhapriya; Tasche, Jos

The surface segregation in polymer mixtures remains a challenging problem for both academic exploration as well as industrial applications. Despite its ubiquity and several theoretical attempts a good agreement between computed and experimentally observed profiles has not yet been achieved. A simple theoretical model proposed in this context by Schmidt and Binder combines Flory-Huggins free energy of mixing with the square gradient theory of wetting of a wall by fluid. While the theory gives us a qualitative understanding of the surface induced segregation and the surface enrichment it lacks the quantitative comparison with the experiment. The statistical associating fluid theory (SAFT) allows us to calculate accurate free energy for a real polymeric materials. In an earlier work we had shown that increasing the bulk modulus of a polymer matrix through which small molecules migrate to the free surface causes reduction in the surface migrant fraction using Schmidt-Binder and self-consistent field theories. In this work we validate this idea by combining mean field theories and SAFT to identify parameter ranges where such an effect should be observable. Department of Molecular Physics, Łódź University of Technology, Żeromskiego 116, 90-924 Łódź, Poland.

Nonperturbative theory of atom-surface interaction: corrections at short separations

NASA Astrophysics Data System (ADS)

Bordag, M.; Klimchitskaya, G. L.; Mostepanenko, V. M.

2018-02-01

The nonperturbative expressions for the free energy and force of interaction between a ground-state atom and a real-material surface at any temperature are presented. The transition to the Matsubara representation is performed, whereupon the comparison is made with the commonly used perturbative results based on the standard Lifshitz theory. It is shown that the Lifshitz formulas for the free energy and force of an atom-surface interaction follow from the nonperturbative ones in the lowest order of the small parameter. Numerical computations of the free energy and force for the atoms of He{\\hspace{0pt}}\\ast and Na interacting with a surface of an Au plate have been performed using the frequency-dependent dielectric permittivity of Au and highly accurate dynamic atomic polarizabilities in the framework of both the nonperturbative and perturbative theories. According to our results, the maximum deviations between the two theories are reached at the shortest atom-surface separations of about 1 nm. Simple analytic expressions for the atom-surface free energy are derived in the classical limit and for an ideal-metal plane. In the lowest order of the small parameter, they are found in agreement with the perturbative ones following from the standard Lifshitz theory. Possible applications of the obtained results in the theory of van der Waals adsorption are discussed.

Embedded correlated wavefunction schemes: theory and applications.

PubMed

Libisch, Florian; Huang, Chen; Carter, Emily A

2014-09-16

Conspectus Ab initio modeling of matter has become a pillar of chemical research: with ever-increasing computational power, simulations can be used to accurately predict, for example, chemical reaction rates, electronic and mechanical properties of materials, and dynamical properties of liquids. Many competing quantum mechanical methods have been developed over the years that vary in computational cost, accuracy, and scalability: density functional theory (DFT), the workhorse of solid-state electronic structure calculations, features a good compromise between accuracy and speed. However, approximate exchange-correlation functionals limit DFT's ability to treat certain phenomena or states of matter, such as charge-transfer processes or strongly correlated materials. Furthermore, conventional DFT is purely a ground-state theory: electronic excitations are beyond its scope. Excitations in molecules are routinely calculated using time-dependent DFT linear response; however applications to condensed matter are still limited. By contrast, many-electron wavefunction methods aim for a very accurate treatment of electronic exchange and correlation. Unfortunately, the associated computational cost renders treatment of more than a handful of heavy atoms challenging. On the other side of the accuracy spectrum, parametrized approaches like tight-binding can treat millions of atoms. In view of the different (dis-)advantages of each method, the simulation of complex systems seems to force a compromise: one is limited to the most accurate method that can still handle the problem size. For many interesting problems, however, compromise proves insufficient. A possible solution is to break up the system into manageable subsystems that may be treated by different computational methods. The interaction between subsystems may be handled by an embedding formalism. In this Account, we review embedded correlated wavefunction (CW) approaches and some applications. We first discuss our density functional embedding theory, which is formally exact. We show how to determine the embedding potential, which replaces the interaction between subsystems, at the DFT level. CW calculations are performed using a fixed embedding potential, that is, a non-self-consistent embedding scheme. We demonstrate this embedding theory for two challenging electron transfer phenomena: (1) initial oxidation of an aluminum surface and (2) hot-electron-mediated dissociation of hydrogen molecules on a gold surface. In both cases, the interaction between gas molecules and metal surfaces were treated by sophisticated CW techniques, with the remainder of the extended metal surface being treated by DFT. Our embedding approach overcomes the limitations of conventional Kohn-Sham DFT in describing charge transfer, multiconfigurational character, and excited states. From these embedding simulations, we gained important insights into fundamental processes that are crucial aspects of fuel cell catalysis (i.e., O2 reduction at metal surfaces) and plasmon-mediated photocatalysis by metal nanoparticles. Moreover, our findings agree very well with experimental observations, while offering new views into the chemistry. We finally discuss our recently formulated potential-functional embedding theory that provides a seamless, first-principles way to include back-action onto the environment from the embedded region.

Wall-crossing in coupled 2d-4d systems

NASA Astrophysics Data System (ADS)

Gaiotto, Davide; Moore, Gregory W.; Neitzke, Andrew

2012-12-01

We introduce a new wall-crossing formula which combines and generalizes the Cecotti-Vafa and Kontsevich-Soibelman formulas for supersymmetric 2d and 4d systems respectively. This 2d-4d wall-crossing formula governs the wall-crossing of BPS states in an {N}=2 supersymmetric 4d gauge theory coupled to a supersymmetric surface defect. When the theory and defect are compactified on a circle, we get a 3d theory with a supersymmetric line operator, corresponding to a hyperholomorphic connection on a vector bundle over a hyperkähler space. The 2d-4d wall-crossing formula can be interpreted as a smoothness condition for this hyperholomorphic connection. We explain how the 2d-4d BPS spectrum can be determined for 4d theories of class {S} , that is, for those theories obtained by compactifying the six-dimensional (0, 2) theory with a partial topological twist on a punctured Riemann surface C. For such theories there are canonical surface defects. We illustrate with several examples in the case of A 1 theories of class {S} . Finally, we indicate how our results can be used to produce solutions to the A 1 Hitchin equations on the Riemann surface C.

Electronic properties of semiconductor-water interfaces: Predictions from ab-initio molecular dynamics and many-body perturbation theory

NASA Astrophysics Data System (ADS)

Pham, Tuan Anh

2015-03-01

Photoelectrochemical cells offer a promising avenue for hydrogen production from water and sunlight. The efficiency of these devices depends on the electronic structure of the interface between the photoelectrode and liquid water, including the alignment between the semiconductor band edges and the water redox potential. In this talk, we will present the results of first principles calculations of semiconductor-water interfaces that are obtained with a combination of density functional theory (DFT)-based molecular dynamics simulations and many-body perturbation theory (MBPT). First, we will discuss the development of an MBPT approach that is aimed at improving the efficiency and accuracy of existing methodologies while still being applicable to complex heterogeneous interfaces consisting of hundreds of atoms. We will then present studies of the electronic structure of liquid water and aqueous solutions using MBPT, which represent an essential step in establishing a quantitative framework for computing the energy alignment at semiconductor-water interfaces. Finally, using a combination of DFT-based molecular dynamics simulations and MBPT, we will describe the relationship between interfacial structure, electronic properties of semiconductors and their reactivity in aqueous solutions through a number of examples, including functionalized Si surfaces and GaP/InP surfaces in contact with liquid water. T.A.P was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and by the Lawrence Fellowship Program.

Mechanics of active surfaces

NASA Astrophysics Data System (ADS)

Salbreux, Guillaume; Jülicher, Frank

2017-09-01

We derive a fully covariant theory of the mechanics of active surfaces. This theory provides a framework for the study of active biological or chemical processes at surfaces, such as the cell cortex, the mechanics of epithelial tissues, or reconstituted active systems on surfaces. We introduce forces and torques acting on a surface, and derive the associated force balance conditions. We show that surfaces with in-plane rotational symmetry can have broken up-down, chiral, or planar-chiral symmetry. We discuss the rate of entropy production in the surface and write linear constitutive relations that satisfy the Onsager relations. We show that the bending modulus, the spontaneous curvature, and the surface tension of a passive surface are renormalized by active terms. Finally, we identify active terms which are not found in a passive theory and discuss examples of shape instabilities that are related to active processes in the surface.

[A complexity analysis of Chinese herbal property theory: the multiple formations of herbal property].

PubMed

Jin, Rui; Zhang, Bing

2012-11-01

Chinese herbal property theory (CHPT) is the fundamental characteristic of Chinese materia medica different from modern medicines. It reflects the herbal properties associated with efficacy and formed the early framework of four properties and five flavors in Shennong's Classic of Materia Medica. After the supplement and improvement of CHPT in the past thousands of years, it has developed a theory system including four properties, five flavors, meridian entry, direction of medicinal actions (ascending, descending, floating and sinking) and toxicity. However, because of the influence of philosophy about yin-yang theory and five-phase theory and the difference of cognitive approach and historical background at different times, CHPT became complex. One of the complexity features was the multiple methods for determining herbal property, which might include the inference from herbal efficacy, the thought of Chinese Taoist School and witchcraft, the classification thinking according to manifestations, etc. Another complexity feature was the multiselection associations between herbal property and efficacy, which indicated that the same property could be inferred from different kinds of efficacy. This paper analyzed these complexity features and provided the importance of cognitive approaches and efficacy attributes corresponding to certain herbal property in the study of CHPT.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Advances in the Surface Renewal Flux Measurement Method

NASA Astrophysics Data System (ADS)

Shapland, T. M.; McElrone, A.; Paw U, K. T.; Snyder, R. L.

2011-12-01

The measurement of ecosystem-scale energy and mass fluxes between the planetary surface and the atmosphere is crucial for understanding geophysical processes. Surface renewal is a flux measurement technique based on analyzing the turbulent coherent structures that interact with the surface. It is a less expensive technique because it does not require fast-response velocity measurements, but only a fast-response scalar measurement. It is therefore also a useful tool for the study of the global cycling of trace gases. Currently, surface renewal requires calibration against another flux measurement technique, such as eddy covariance, to account for the linear bias of its measurements. We present two advances in the surface renewal theory and methodology that bring the technique closer to becoming a fully independent flux measurement method. The first advance develops the theory of turbulent coherent structure transport associated with the different scales of coherent structures. A novel method was developed for identifying the scalar change rate within structures at different scales. Our results suggest that for canopies less than one meter in height, the second smallest coherent structure scale dominates the energy and mass flux process. Using the method for resolving the scalar exchange rate of the second smallest coherent structure scale, calibration is unnecessary for surface renewal measurements over short canopies. This study forms the foundation for analysis over more complex surfaces. The second advance is a sensor frequency response correction for measuring the sensible heat flux via surface renewal. Inexpensive fine-wire thermocouples are frequently used to record high frequency temperature data in the surface renewal technique. The sensible heat flux is used in conjunction with net radiation and ground heat flux measurements to determine the latent heat flux as the energy balance residual. The robust thermocouples commonly used in field experiments underestimate the sensible heat flux, yielding results that are less than 50% of the sensible heat flux measured with finer sensors. We present the methodology for correcting the thermocouple signal to avoid underestimating the heat flux at both the smallest and the second smallest coherent structure scale.

Out-of-Plane Designed Soft Metasurface for Tunable Surface Plasmon Polariton.

PubMed

Liu, Xin; Huang, Zhao; Zhu, Chengkai; Wang, Li; Zang, Jianfeng

2018-02-14

Reliable and repeatable tunability gives functional diversity for reconfigurable plasmonics devices, while reversible and large mechanical deformation enabled by soft materials provides a new way for the global or partial regulation of metadevices. Here, we demonstrate a soft metasurface with an out-of-plane design for tuning the energy of surface plasmon polaritons (SPPs) bloch wave using theory, simulation, and experiments. Our metasurface is composed of two-layered gold nanoribbon arrays (2GNRs) on a soft substrate. The out-of-plane coupling mechanism is systematically analyzed in terms of separation height effect. Moreover, by harnessing mechanical deformation, continuously tunable plasmonic resonance has been achieved in the visible and near-infrared ranges. We further studied the angle-dependent reflection spectra of our metastructure. Compared with its planar counterpart, our soft and two-layered metastructure exhibits diverse tunability and significant field enhancement by out-of-plane interactions. Our approach in designing soft metasurface with out-of-plane structures can be extended to more-complex photonic devices and finds prominent applications such as biosensing, high-density plasmonic circuits, surface-enhanced luminescence, and surface-enhanced Raman scattering.

Elasticity dominated surface segregation of small molecules in polymer mixtures

NASA Astrophysics Data System (ADS)

Croce, Salvatore; Krawczyk, Jaroslaw; McLeish, Tom; Chakrabarti, Buddhapriya

When a binary polymer mixture with mobile components is left to equilibrate, the low molecular weight component migrates to the free surface. A balance between loss of translational entropy and gain in surface energy dictates the equilibrium partitioning ratio and the migrant fraction. Despite its ubiquity and several theoretical and experimental investigations, the phenomenon is not fully understood. Further, methods by which migration can be controlled are in its nascent stage of development. We propose a new phenomenological free energy functional that incorporates the elasticity of bulk polymer mixtures (reticulated networks and gels) and show (using mean field and self-consistent field theories) that the migrant fraction decreases with increasing the bulk modulus of the system. Further, a wetting transition observed otherwise for large values of miscibility parameter and polymerization index can be avoided by increasing the elastic modulus of the system. Estimated values of moduli (for the effect to be observable) are akin to those of rubbery polymers. Our work paves the way for controlling surface migration in complex industrial formulations with polymeric ingredients where this effect leads to decreased product stability and performance.

Identifying and tracing potential energy surfaces of electronic excitations with specific character via their transition origins: application to oxirane.

PubMed

Li, Jian-Hao; Zuehlsdorff, T J; Payne, M C; Hine, N D M

2015-05-14

We show that the transition origins of electronic excitations identified by quantified natural transition orbital (QNTO) analysis can be employed to connect potential energy surfaces (PESs) according to their character across a wide range of molecular geometries. This is achieved by locating the switching of transition origins of adiabatic potential surfaces as the geometry changes. The transition vectors for analysing transition origins are provided by linear response time-dependent density functional theory (TDDFT) calculations under the Tamm-Dancoff approximation. We study the photochemical CO ring opening of oxirane as an example and show that the results corroborate the traditional Gomer-Noyes mechanism derived experimentally. The knowledge of specific states for the reaction also agrees well with that given by previous theoretical work using TDDFT surface-hopping dynamics that was validated by high-quality quantum Monte Carlo calculations. We also show that QNTO can be useful for considerably larger and more complex systems: by projecting the excitations to those of a reference oxirane molecule, the approach is able to identify and analyse specific excitations of a trans-2,3-diphenyloxirane molecule.

Heats of Segregation of BCC Metals Using Ab Initio and Quantum Approximate Methods

NASA Technical Reports Server (NTRS)

Good, Brian; Chaka, Anne; Bozzolo, Guillermo

2003-01-01

Many multicomponent alloys exhibit surface segregation, in which the composition at or near a surface may be substantially different from that of the bulk. A number of phenomenological explanations for this tendency have been suggested, involving, among other things, differences among the components' surface energies, molar volumes, and heats of solution. From a theoretical standpoint, the complexity of the problem has precluded a simple, unified explanation, thus preventing the development of computational tools that would enable the identification of the driving mechanisms for segregation. In that context, we investigate the problem of surface segregation in a variety of bcc metal alloys by computing dilute-limit heats of segregation using both the quantum-approximate energy method of Bozzolo, Ferrante and Smith (BFS), and all-electron density functional theory. In addition, the composition dependence of the heats of segregation is investigated using a BFS-based Monte Carlo procedure, and, for selected cases of interest, density functional calculations. Results are discussed in the context of a simple picture that describes segregation behavior as the result of a competition between size mismatch and alloying effects

Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation.

PubMed

Shukla, Manoj K; Poda, Aimee

2016-06-01

This manuscript reports results of an integrated theoretical and experimental investigation of adsorption of two emerging contaminants (DNAN and FOX-7) and legacy compound TNT on cellulose surface. Cellulose was modeled as trimeric form of the linear chain of 1 → 4 linked of β-D-glucopyranos in (4)C1 chair conformation. Geometries of modeled cellulose, munitions compounds and their complexes were optimized at the M06-2X functional level of Density Functional Theory using the 6-31G(d,p) basis set in gas phase and in water solution. The effect of water solution was modeled using the CPCM approach. Nature of potential energy surfaces was ascertained through harmonic vibrational frequency analysis. Interaction energies were corrected for basis set superposition error and the 6-311G(d,p) basis set was used. Molecular electrostatic potential mapping was performed to understand the reactivity of the investigated systems. It was predicted that adsorbates will be weakly adsorbed on the cellulose surface in water solution than in the gas phase.

CH stretching vibration of N-methylformamide as a sensitive probe of its complexation: infrared matrix isolation and computational study.

PubMed

Sałdyka, M; Mielke, Z; Mierzwicki, K; Coussan, S; Roubin, P

2011-08-21

The complexes between trans-N-methylformamide (t-NMF) and Ar, N(2), CO, H(2)O have been studied by infrared matrix isolation spectroscopy and/or ab initio calculations. The infrared spectra of NMF/Ne, NMF/Ar and NMF/N(2)(CO,H(2)O)/Ar matrices have been measured and the effect of the complexation on the perturbation of t-NMF frequencies was analyzed. The geometries of the complexes formed between t-NMF and Ar, N(2), CO and H(2)O were optimized in two steps at the MP2/6-311++G(2d,2p) level of theory. The four structures, found for every system at this level, were reoptimized on the CP-corrected potential energy surface; both normal and CP corrected harmonic frequencies and intensities were calculated. For every optimized structure the interaction energy was partitioned according to the SAPT scheme and the topological distribution of the charge density (AIM theory) was performed. The analysis of the experimental and theoretical results indicates that the t-NMF-N(2) and CO complexes present in the matrices are stabilized by very weak N-H···N and N-H···C hydrogen bonds in which the N-H group of t-NMF serves as a proton donor. In turn, the t-NMF-H(2)O complex present in the matrix is stabilized by O-H···O(C) hydrogen bonding in which the carbonyl group of t-NMF acts as a proton acceptor. Both, the theoretical and experimental results indicate that involvement of the NH group of t-NMF in formation of very weak hydrogen bonds with the N(2) or CO molecules leads to a clearly noticeable red shift of the CH stretching wavenumber whereas engagement of the CO group as a proton acceptor triggers a blue shift of this wavenumber.

Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

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

García-Melchor, Max; Vilella, Laia; López, Núria

2016-04-29

An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO 2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity.more » Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.« less

Recent modelling advances for ultrasonic TOFD inspections

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

Darmon, Michel; Ferrand, Adrien; Dorval, Vincent

The ultrasonic TOFD (Time of Flight Diffraction) Technique is commonly used to detect and characterize disoriented cracks using their edge diffraction echoes. An overview of the models integrated in the CIVA software platform and devoted to TOFD simulation is presented. CIVA allows to predict diffraction echoes from complex 3D flaws using a PTD (Physical Theory of Diffraction) based model. Other dedicated developments have been added to simulate lateral waves in 3D on planar entry surfaces and in 2D on irregular surfaces by a ray approach. Calibration echoes from Side Drilled Holes (SDHs), specimen echoes and shadowing effects from flaws canmore » also been modelled. Some examples of theoretical validation of the models are presented. In addition, experimental validations have been performed both on planar blocks containing calibration holes and various notches and also on a specimen with an irregular entry surface and allow to draw conclusions on the validity of all the developed models.« less

In-cell thermodynamics and a new role for protein surfaces.

PubMed

Smith, Austin E; Zhou, Larry Z; Gorensek, Annelise H; Senske, Michael; Pielak, Gary J

2016-02-16

There is abundant, physiologically relevant knowledge about protein cores; they are hydrophobic, exquisitely well packed, and nearly all hydrogen bonds are satisfied. An equivalent understanding of protein surfaces has remained elusive because proteins are almost exclusively studied in vitro in simple aqueous solutions. Here, we establish the essential physiological roles played by protein surfaces by measuring the equilibrium thermodynamics and kinetics of protein folding in the complex environment of living Escherichia coli cells, and under physiologically relevant in vitro conditions. Fluorine NMR data on the 7-kDa globular N-terminal SH3 domain of Drosophila signal transduction protein drk (SH3) show that charge-charge interactions are fundamental to protein stability and folding kinetics in cells. Our results contradict predictions from accepted theories of macromolecular crowding and show that cosolutes commonly used to mimic the cellular interior do not yield physiologically relevant information. As such, we provide the foundation for a complete picture of protein chemistry in cells.

Harnessing catalytic pumps for directional delivery of microparticles in microchambers

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

Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia

The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less

Harnessing catalytic pumps for directional delivery of microparticles in microchambers

DOE PAGES

Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia; ...

2017-02-17

The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less

Could gastropods crawl using Newtonian mucus?

NASA Astrophysics Data System (ADS)

Lai, Janice; Vazquez-Torres, Maria; Del Alamo, Juan C.; Rodriguez-Rodriguez, Javier; Lasheras, Juan C.

2010-11-01

The locomotion of terrestrial gastropods is driven by a train of periodic muscle contractions (pedal waves) and relaxations (interwaves) that propagate from their tail to their head (direct waves). We study the locomotion of these animals on smooth flat surfaces by measuring the three-dimensional displacements of the ventral foot surface induced by the passage of the waves. A simple model based on lubrication theory is proposed in accordance with the experimental observations. This model uncovers a new mode of locomotion that works even when the lubricant between the foot and the animal is Newtonian. The model can also be adapted to situations where the animal's foot is in contact with the ground only at discrete points, as is the case when it crawls on a wire mesh or on rough soil surfaces. Furthermore, comparison between the stress exerted by the animal on the substrate and the model predictions allows us to clarify the role of the complex rheology observed in the mucus of terrestrial gastropods.

Carbon dioxide hydrogenation on Ni(110).

PubMed

Vesselli, Erik; De Rogatis, Loredana; Ding, Xunlei; Baraldi, Alessandro; Savio, Letizia; Vattuone, Luca; Rocca, Mario; Fornasiero, Paolo; Peressi, Maria; Baldereschi, Alfonso; Rosei, Renzo; Comelli, Giovanni

2008-08-27

We demonstrate that the key step for the reaction of CO 2 with hydrogen on Ni(110) is a change of the activated molecule coordination to the metal surface. At 90 K, CO 2 is negatively charged and chemically bonded via the carbon atom. When the temperature is increased and H approaches, the H-CO 2 complex flips and binds to the surface through the two oxygen atoms, while H binds to the carbon atom, thus yielding formate. We provide the atomic-level description of this process by means of conventional ultrahigh vacuum surface science techniques combined with density functional theory calculations and corroborated by high pressure reactivity tests. Knowledge about the details of the mechanisms involved in this reaction can yield a deeper comprehension of heterogeneous catalytic organic synthesis processes involving carbon dioxide as a reactant. We show why on Ni the CO 2 hydrogenation barrier is remarkably smaller than that on the common Cu metal-based catalyst. Our results provide a possible interpretation of the observed high catalytic activity of NiCu alloys.

Tetrel bond-σ-hole bond as a preliminary stage of the SN2 reaction.

PubMed

Grabowski, Sławomir J

2014-02-07

MP2/aug-cc-pVTZ calculations were carried out on complexes of ZH4, ZFH3 and ZF4 (Z = C, Si and Ge) molecules with HCN, LiCN and Cl(-) species acting as Lewis bases through nitrogen centre or chlorine ion. Z-Atoms in these complexes usually act as Lewis acid centres forming σ-hole bonds with Lewis bases. Such noncovalent interactions may adopt a name of tetrel bonds since they concern the elements of the group IV. There are exceptions for complexes of CH4 and CF4, as well as for the F4SiNCH complex where the tetrel bond is not formed. The energetic and geometrical parameters of the complexes were analyzed and numerous correlations between them were found. The Quantum Theory of 'Atoms in Molecules' and Natural Bonds Orbital (NBO) method used here should deepen the understanding of the nature of the tetrel bond. An analysis of the electrostatic potential surfaces of the interacting species is performed. The electron charge redistribution, being the result of the tetrel bond formation, is the same as that of the SN2 reaction. The energetic and geometrical parameters of the complexes analyzed here correspond to different stages of the SN2 process.

Landau-de Gennes theory of surface-enhanced ordering in smectic films.

PubMed

Shalaginov, A N; Sullivan, D E

2001-03-01

A Landau theory for surface-enhanced ordering in smectic-A free-standing films is described, based on a generalization of de Gennes' model for a "presmectic" fluid confined between two walls. According to the theory, smectic ordering in free-standing films heated above the bulk smectic melting temperature is due to an intrinsic surface contribution rather than an external field. The theory yields a persistent finite-size effect, in that the film melting temperatures do not tend to the bulk transition temperature in the limit of infinite film thickness. It also predicts that a continuous transition from (N+1)- to N-layer films is impossible without an external field. The theory closely fits existing experimental data on layer-thinning transitions in compounds which exhibit a bulk smectic-A to nematic phase transition. Possible origins of the intrinsic surface contribution are discussed.

Envisioning a New Foundation for Gifted Education: Evolving Complexity Theory (ECT) of Talent Development

ERIC Educational Resources Information Center

Dai, David Yun

2017-01-01

This article presents a new theory of talent development, evolving complexity theory (ECT), in the context of the changing theoretical directions as well as the landscape of gifted education. I argue that gifted education needs a new foundation that provides a broad psychosocial basis than what the notion of giftedness can afford. A focus on…

Influence of the large-small split effect on strategy choice in complex subtraction.

PubMed

Xiang, Yan Hui; Wu, Hao; Shang, Rui Hong; Chao, Xiaomei; Ren, Ting Ting; Zheng, Li Ling; Mo, Lei

2018-04-01

Two main theories have been used to explain the arithmetic split effect: decision-making process theory and strategy choice theory. Using the inequality paradigm, previous studies have confirmed that individuals tend to adopt a plausibility-checking strategy and a whole-calculation strategy to solve large and small split problems in complex addition arithmetic, respectively. This supports strategy choice theory, but it is unknown whether this theory also explains performance in solving different split problems in complex subtraction arithmetic. This study used small, intermediate and large split sizes, with each split condition being further divided into problems requiring and not requiring borrowing. The reaction times (RTs) for large and intermediate splits were significantly shorter than those for small splits, while accuracy was significantly higher for large and middle splits than for small splits, reflecting no speed-accuracy trade-off. Further, RTs and accuracy differed significantly between the borrow and no-borrow conditions only for small splits. This study indicates that strategy choice theory is suitable to explain the split effect in complex subtraction arithmetic. That is, individuals tend to choose the plausibility-checking strategy or the whole-calculation strategy according to the split size. © 2016 International Union of Psychological Science.

Contact activation of blood-plasma coagulation

NASA Astrophysics Data System (ADS)

Golas, Avantika

Surface engineering of biomaterials with improved hemocompatibility is an imperative, given the widespread global need for cardiovascular devices. Research summarized in this dissertation focuses on contact activation of FXII in buffer and blood plasma frequently referred to as autoactivation. The extant theory of contact activation imparts FXII autoactivation ability to negatively charged, hydrophilic surfaces. According to this theory, contact activation of plasma involves assembly of proteins comprising an "activation complex" on activating surfaces mediated by specific chemical interactions between complex proteins and the surface. This work has made key discoveries that significantly improve our core understanding of contact activation and unravel the existing paradigm of plasma coagulation. It is shown herein that contact activation of blood factor XII (FXII, Hageman factor) in neat-buffer solution exhibits a parabolic profile when scaled as a function of silanized-glass-particle activator surface energy (measured as advancing water adhesion tension t°a=g° Iv costheta in dyne/cm, where g°Iv is water interfacial tension in dyne/cm and theta is the advancing contact angle). Nearly equal activation is observed at the extremes of activator water-wetting properties --36 < t°a < 72 dyne/cm (O° ≤ theta < 120°), falling sharply through a broad minimum within the 20 < t°a < 40 dyne/cm (55° < theta < 75°). Furthermore, contact activation of FXII in buffer solution produces an ensemble of protein fragments exhibiting either procoagulant properties in plasma (proteolysis of blood factor XI or prekallikrein), amidolytic properties (cleavage of s-2302 chromogen), or the ability to suppress autoactivation through currently unknown biochemistry. The relative proportions of these fragments depend on activator surface chemistry/energy. We have also discovered that contact activation is moderated by adsorption of plasma proteins unrelated to coagulation through an "adsorption-dilution" effect that blocks FXII contact with hydrophobic activator surfaces. The adsorption-dilution effect explains the apparent specificity for hydrophilic activators pursued by earlier investigators. Finally a comparison of FXII autoactivation in buffer, serum, protein cocktail, and plasma solutions is shown herein. Activation of blood plasma coagulation in vitro by contact with material surfaces is demonstrably dependent on plasma-volume-to-activator-surface-area ratio. However, activation of factor XII dissolved in buffer, protein cocktail, heat-denatured serum, and FXI deficient plasma does not exhibit activator surface-area dependence. Instead, a highly-variable burst of procoagulant-enzyme yield is measured that exhibits no measurable kinetics, sensitivity to mixing, or solution-temperature dependence. Thus, FXII activation in both buffer and protein-containing solutions does not exhibit characteristics of a biochemical reaction but rather appears to be a "mechanochemical" reaction induced by FXII molecule interactions with hydrophilic activator particles that do not formally adsorb blood proteins from solution. Results strongly suggest that activator surface-area dependence observed in contact activation of plasma coagulation does not solely arise at the FXII activation step of the intrinsic pathway.

Understanding Teacher Collaboration Processes from a Complexity Theory Perspective: A Case Study of a Chinese Secondary School

ERIC Educational Resources Information Center

Yuan, Rui; Zhang, Jia; Yu, Shulin

2018-01-01

Although research on teacher collaboration has proliferated in the last few decades, scant attention has been paid to the development of teacher collaboration in school contexts. Informed by the perspective of complexity theory, this study investigates the complex process of teacher collaboration through qualitative interviews in an English…

A Call for a Multifaceted Approach to Language Learning Motivation Research: Combining Complexity, Humanistic, and Critical Perspectives

ERIC Educational Resources Information Center

Pigott, Julian

2012-01-01

In this paper I give an overview of recent developments in the L2 motivation field, in particular the movement away from quantitative, questionnaire-based methodologies toward smaller-scale qualitative studies incorporating concepts from complexity theory. While complexity theory provides useful concepts for exploring motivation in new ways, it…

Particle size segregation in granular avalanches: A brief review of recent progress

NASA Astrophysics Data System (ADS)

Gray, J. M. N. T.

2010-05-01

Hazardous natural flows such as snow avalanches, debris-flows, lahars and pyroclastic flows are part of a much wider class of granular avalanches, that frequently occur in industrial processes and in our kitchens! Granular avalanches are very efficient at sorting particles by size, with the smaller ones percolating down towards the base and squeezing the larger grains up towards the free-surface, to create inversely-graded layers. This paper provides a short introduction and review of recent theoretical advances in describing segregation and remixing with relatively simple hyperbolic and parabolic models. The derivation from two phase mixture theory is briefly summarized and links are drawn to earlier models of Savage & Lun and Dolgunin & Ukolov. The more complex parabolic version of the theory has a diffusive force that competes against segregation and yields S-shaped steady-state concentration profiles through the avalanche depth, that are able to reproduce results obtained from particle dynamics simulations. Time-dependent exact solutions can be constructed by using the Cole-Hopf transformation to linearize the segregation-remixing equation and the nonlinear surface and basal boundary conditions. In the limit of no diffusion, the theory is hyperbolic and the grains tend to separate out into completely segregated inversely graded layers. A series of elementary problems are used to demonstrate how concentration shocks, expansion fans, breaking waves and the large and small particles paths can be computed exactly using the model. The theory is able to capture the key features of the size distribution observed in stratification experiments, and explains how a large particle rich front is connected to an inversely graded avalanche in the interior. The theory is simple enough to couple it to the bulk flow field to investigate segregation-mobility feedback effects that spontaneously generate self-channelizing leveed avalanches, which can significantly enhance the total run-out distance of geophysical mass flows.

Theoretical Study of Infrared and Raman Spectra of Hydrated Magnesium Sulfate Salts

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Huo, Winifred M.; Lee, Timothy J.; Kwak, Dochan (Technical Monitor)

2002-01-01

Harmonic and anharmonic vibrational frequencies, as well as infrared and Raman intensities, are calculated for MgSO4.nH20 (n=1-3). Electronic structure theory at the second order Moller-Plesset perturbation theory (MP2) level with a triple-zeta + polarization (TZP) basis set is used to determine the geometry, properties, and vibrational spectra of pure and hydrated MgSO4 salts. The direct vibrational self-consistent field (VSCF) method and its correlation corrected (CC-VSCF) extension are used to determine anharmonic corrections to vibrational frequencies and intensities for the pure MgSO4 and its complex with one water molecule. Very significant differences are found between vibrational of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies are shifted to the red very significantly (by up to 1500-2000/cm) upon complexation with magnesium sulfate. They should be observed between 1700 and 3000/cm in a region very different from the corresponding O-H stretch frequency region of pure water (3700-3800/cm). In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. They can serve as unique identifiers for the presence of sulfate salts. The predicted infrared and Raman spectra should be of valuable help in the design of future missions and analysis of observed data from the ice surface of Jupiter's moon Europa that possibly contains hydrated MgSO4 salts.

Growth, structure, Hirshfeld surface and spectroscopic properties of 2-amino-4-hydroxy-6-methylpyrimidinium-2,3-pyrazinedicorboxylate single crystal

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Alam, Mohammad Jane; Afroz, Ziya; Rodrigues, Vítor Hugo Nunes; Ahmad, Shabbir

2018-03-01

The present work is focused on the crystal structure, vibrational spectroscopy and DFT calculations of hydrogen bonded 2,3-pyrazinedicorboxylic acid and 2-amino-4-hydroxy-6-methylpyrimidine (PDCA-.AHMP+) crystal. The crystal structure has been determined using single crystal X-ray diffraction analysis which shows that the crystal belongs to monoclinic space group P21/n. The PDCA-.AHMP+ crystal has been characterized by FTIR, FT-Raman and FT-NMR spectroscopic techniques. The FTIR and FT-Raman spectra of the complex have unique spectroscopic feature as compared with those of the starting material to confirm salt formation. The theoretical vibrational studies have been performed to understand the modes of the vibrations of asymmetric unit of the complex by DFT methods. Hirschfeld surface and 2D fingerprint plots analyses were carried out to investigate the intermolecular interactions and its contribution in the building of PDCA-.AHMP+ crystal. The experimental and simulated 13C and 1H NMR studies have assisted in structural analysis of PDCA-.AHMP+ crystal. The electronic spectroscopic properties of the complex were explored by the experimental as well as theoretical electronic spectra simulated using TD-DFT/IEF-PCM method at B3LYP/6-311++G (d,p) level of theory. In addition, frontier molecular orbitals, molecular electrostatic potential map (MEP) and nonlinear optical (NLO) properties using DFT method have been also presented.

A Study of Theory U and Its Application to a Complex Japanese Maritime Self-Defense Force Problem

DTIC Science & Technology

2014-06-01

NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA THESIS Approved for public release; distribution is unlimited A STUDY OF “ THEORY ...AND DATES COVERED Master’s Thesis 4. TITLE AND SUBTITLE A STUDY OF “ THEORY U” AND ITS APPLICATION TO A COMPLEX JAPANESE MARITIME SELF-DEFENSE...and a new approach to this way of thinking, called “ Theory U.” This thesis describes the types of problems that require managers to change their

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

NASA Astrophysics Data System (ADS)

Ryu, S.; Zhou, H.; Paudel, T. R.; Irwin, J.; Podkaminer, J. P.; Bark, C. W.; Lee, D.; Kim, T. H.; Fong, D. D.; Rzchowski, M. S.; Tsymbal, E. Y.; Eom, C. B.

2017-10-01

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internal structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.

Electric field theory based approach to search-direction line definition in image segmentation: application to optimal femur-tibia cartilage segmentation in knee-joint 3-D MR

NASA Astrophysics Data System (ADS)

Yin, Y.; Sonka, M.

2010-03-01

A novel method is presented for definition of search lines in a variety of surface segmentation approaches. The method is inspired by properties of electric field direction lines and is applicable to general-purpose n-D shapebased image segmentation tasks. Its utility is demonstrated in graph construction and optimal segmentation of multiple mutually interacting objects. The properties of the electric field-based graph construction guarantee that inter-object graph connecting lines are non-intersecting and inherently covering the entire object-interaction space. When applied to inter-object cross-surface mapping, our approach generates one-to-one and all-to-all vertex correspondent pairs between the regions of mutual interaction. We demonstrate the benefits of the electric field approach in several examples ranging from relatively simple single-surface segmentation to complex multiobject multi-surface segmentation of femur-tibia cartilage. The performance of our approach is demonstrated in 60 MR images from the Osteoarthritis Initiative (OAI), in which our approach achieved a very good performance as judged by surface positioning errors (average of 0.29 and 0.59 mm for signed and unsigned cartilage positioning errors, respectively).

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li xMn 2O 4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from Li xMn 2O 4 (100) surfaces

DOE PAGES

Leung, Kevin

2012-04-13

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; andmore » chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

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

Ryu, S.; Zhou, H.; Paudel, T. R.

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internalmore » structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.« less

Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density Functional Theory

DTIC Science & Technology

2013-08-20

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--13-9479 Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using ...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density...structure associated with Fe, Mn, and Mg water complexes using time-dependent density functional theory (TD-DFT). Calculation of excited state resonance

Utilizing a Sense of Community Theory in Order to Optimize Interagency Response to Complex Contingencies

DTIC Science & Technology

2010-06-01

of Not at all Somewhat Mostly Completely membership such as clothes , signs, art, architecture, logos , landmarks, and flags that people can...on a ?whole of nation? approach to solving complex problems. Psychological sense of community (PSOC) theory provides the link that explains how an...States during complex contingency operations depends on a “whole of nation” approach to solving complex problems. Psychological sense of community

Toward a Definition of Complexity for Quantum Field Theory States.

PubMed

Chapman, Shira; Heller, Michal P; Marrochio, Hugo; Pastawski, Fernando

2018-03-23

We investigate notions of complexity of states in continuous many-body quantum systems. We focus on Gaussian states which include ground states of free quantum field theories and their approximations encountered in the context of the continuous version of the multiscale entanglement renormalization ansatz. Our proposal for quantifying state complexity is based on the Fubini-Study metric. It leads to counting the number of applications of each gate (infinitesimal generator) in the transformation, subject to a state-dependent metric. We minimize the defined complexity with respect to momentum-preserving quadratic generators which form su(1,1) algebras. On the manifold of Gaussian states generated by these operations, the Fubini-Study metric factorizes into hyperbolic planes with minimal complexity circuits reducing to known geodesics. Despite working with quantum field theories far outside the regime where Einstein gravity duals exist, we find striking similarities between our results and those of holographic complexity proposals.

Toward a Definition of Complexity for Quantum Field Theory States

NASA Astrophysics Data System (ADS)

Chapman, Shira; Heller, Michal P.; Marrochio, Hugo; Pastawski, Fernando

2018-03-01

We investigate notions of complexity of states in continuous many-body quantum systems. We focus on Gaussian states which include ground states of free quantum field theories and their approximations encountered in the context of the continuous version of the multiscale entanglement renormalization ansatz. Our proposal for quantifying state complexity is based on the Fubini-Study metric. It leads to counting the number of applications of each gate (infinitesimal generator) in the transformation, subject to a state-dependent metric. We minimize the defined complexity with respect to momentum-preserving quadratic generators which form s u (1 ,1 ) algebras. On the manifold of Gaussian states generated by these operations, the Fubini-Study metric factorizes into hyperbolic planes with minimal complexity circuits reducing to known geodesics. Despite working with quantum field theories far outside the regime where Einstein gravity duals exist, we find striking similarities between our results and those of holographic complexity proposals.

Choosing the Optimal Number of B-spline Control Points (Part 1: Methodology and Approximation of Curves)

NASA Astrophysics Data System (ADS)

Harmening, Corinna; Neuner, Hans

2016-09-01

Due to the establishment of terrestrial laser scanner, the analysis strategies in engineering geodesy change from pointwise approaches to areal ones. These areal analysis strategies are commonly built on the modelling of the acquired point clouds. Freeform curves and surfaces like B-spline curves/surfaces are one possible approach to obtain space continuous information. A variety of parameters determines the B-spline's appearance; the B-spline's complexity is mostly determined by the number of control points. Usually, this number of control points is chosen quite arbitrarily by intuitive trial-and-error-procedures. In this paper, the Akaike Information Criterion and the Bayesian Information Criterion are investigated with regard to a justified and reproducible choice of the optimal number of control points of B-spline curves. Additionally, we develop a method which is based on the structural risk minimization of the statistical learning theory. Unlike the Akaike and the Bayesian Information Criteria this method doesn't use the number of parameters as complexity measure of the approximating functions but their Vapnik-Chervonenkis-dimension. Furthermore, it is also valid for non-linear models. Thus, the three methods differ in their target function to be minimized and consequently in their definition of optimality. The present paper will be continued by a second paper dealing with the choice of the optimal number of control points of B-spline surfaces.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

4D and 2D superconformal index with surface operator

NASA Astrophysics Data System (ADS)

Nakayama, Yu

2011-08-01

We study the superconformal index of the mathcal{N} = 4 super-Yang-Milles theory on S 3 × S 1 with the half BPS superconformal surface operator (defect) inserted at the great circle of S 3. The half BPS superconformal surface operators preserve the same supersymmetry as well as the symmetry of the chemical potential used in the definition of the superconformal index, so the structure and the parameterization of the superconformal index remain unaffected by the presence of the surface operator. On the surface defect, a two-dimensional (4, 4) superconformal field theory resides, and the four-dimensional super-conformal index may be regarded as a superconformal index of the two-dimensional (4, 4) superconformal field theory coupled with the four-dimensional bulk system. We construct the matrix model that computes the superconformal index with the surface operator when it couples with the bulk mathcal{N} = 4 super-Yang-Milles theory through the defect hypermultiplets on it.

Intersecting surface defects and two-dimensional CFT

NASA Astrophysics Data System (ADS)

Gomis, Jaume; Le Floch, Bruno; Pan, Yiwen; Peelaers, Wolfger

2017-08-01

We initiate the study of intersecting surface operators/defects in 4D quantum field theories (QFTs). We characterize these defects by coupled 4D/2D/0D theories constructed by coupling the degrees of freedom localized at a point and on intersecting surfaces in spacetime to each other and to the 4D QFT. We construct supersymmetric intersecting surface defects preserving just two supercharges in N =2 gauge theories. These defects are amenable to exact analysis by localization of the partition function of the underlying 4D/2D/0D QFT. We identify the 4D/2D/0D QFTs that describe intersecting surface operators in N =2 gauge theories realized by intersecting M2 branes ending on N M5 branes wrapping a Riemann surface. We conjecture and provide evidence for an explicit equivalence between the squashed four-sphere partition function of these intersecting defects and correlation functions in Liouville/Toda CFT with the insertion of arbitrary degenerate vertex operators, which are labeled by two representations of S U (N ).

Acoustic emission source location in composite structure by Voronoi construction using geodesic curve evolution.

PubMed

Gangadharan, R; Prasanna, G; Bhat, M R; Murthy, C R L; Gopalakrishnan, S

2009-11-01

Conventional analytical/numerical methods employing triangulation technique are suitable for locating acoustic emission (AE) source in a planar structure without structural discontinuities. But these methods cannot be extended to structures with complicated geometry, and, also, the problem gets compounded if the material of the structure is anisotropic warranting complex analytical velocity models. A geodesic approach using Voronoi construction is proposed in this work to locate the AE source in a composite structure. The approach is based on the fact that the wave takes minimum energy path to travel from the source to any other point in the connected domain. The geodesics are computed on the meshed surface of the structure using graph theory based on Dijkstra's algorithm. By propagating the waves in reverse virtually from these sensors along the geodesic path and by locating the first intersection point of these waves, one can get the AE source location. In this work, the geodesic approach is shown more suitable for a practicable source location solution in a composite structure with arbitrary surface containing finite discontinuities. Experiments have been conducted on composite plate specimens of simple and complex geometry to validate this method.

Discriminating Sea Spikes in Incoherent Radar Measurements of Sea Clutter

DTIC Science & Technology

2008-03-01

het detecteren echter niet te verwachten dat bet gebruik van sea spikes te onderzoeken. Een van deze modellen zal leiden tot een Auteur (s) dergelijk...report I TNO-DV 2008 A067 6/33 Abbreviations CFAR Constant False-Alarm Rate CST Composite Surface Theory FFT Fast Fourier Transform PDF Probability Density...described by the composite surface theory (CST). This theory describes the sea surface as small Bragg-resonant capillary waves riding on top of

Nonlinear dynamical systems for theory and research in ergonomics.

PubMed

Guastello, Stephen J

2017-02-01

Nonlinear dynamical systems (NDS) theory offers new constructs, methods and explanations for phenomena that have in turn produced new paradigms of thinking within several disciplines of the behavioural sciences. This article explores the recent developments of NDS as a paradigm in ergonomics. The exposition includes its basic axioms, the primary constructs from elementary dynamics and so-called complexity theory, an overview of its methods, and growing areas of application within ergonomics. The applications considered here include: psychophysics, iconic displays, control theory, cognitive workload and fatigue, occupational accidents, resilience of systems, team coordination and synchronisation in systems. Although these applications make use of different subsets of NDS constructs, several of them share the general principles of the complex adaptive system. Practitioner Summary: Nonlinear dynamical systems theory reframes problems in ergonomics that involve complex systems as they change over time. The leading applications to date include psychophysics, control theory, cognitive workload and fatigue, biomechanics, occupational accidents, resilience of systems, team coordination and synchronisation of system components.

Application of Percolation Theory to Complex Interconnected Networks in Advanced Functional Composites

NASA Astrophysics Data System (ADS)

Hing, P.

2011-11-01

Percolation theory deals with the behaviour of connected clusters in a system. Originally developed for studying the flow of liquid in a porous body, the percolation theory has been extended to quantum computation and communication, entanglement percolation in quantum networks, cosmology, chaotic situations, properties of disordered solids, pandemics, petroleum industry, finance, control of traffic and so on. In this paper, the application of various models of the percolation theory to predict and explain the properties of a specially developed family of dense sintered and highly refractory Al2O3-W composites for potential application in high intensity discharge light sources such as high pressure sodium lamps and ceramic metal halide lamps are presented and discussed. The low cost, core-shell concept can be extended to develop functional composite materials with unusual dielectric, electrical, magnetic, superconducting, and piezoelectric properties starting from a classical insulator. The core shell concept can also be applied to develop catalysts with high specific surface areas with minimal amount of expensive platinium, palladium or rare earth nano structured materials for light harvesting, replicating natural photosynthesis, in synthetic zeolite composites for the cracking and separation of crude oil. There is also possibility of developing micron and nanosize Faraday cages for quantum devices, nano electronics and spintronics. The possibilities are limitless.

Linearization instability for generic gravity in AdS spacetime

NASA Astrophysics Data System (ADS)

Altas, Emel; Tekin, Bayram

2018-01-01

In general relativity, perturbation theory about a background solution fails if the background spacetime has a Killing symmetry and a compact spacelike Cauchy surface. This failure, dubbed as linearization instability, shows itself as non-integrability of the perturbative infinitesimal deformation to a finite deformation of the background. Namely, the linearized field equations have spurious solutions which cannot be obtained from the linearization of exact solutions. In practice, one can show the failure of the linear perturbation theory by showing that a certain quadratic (integral) constraint on the linearized solutions is not satisfied. For non-compact Cauchy surfaces, the situation is different and for example, Minkowski space having a non-compact Cauchy surface, is linearization stable. Here we study, the linearization instability in generic metric theories of gravity where Einstein's theory is modified with additional curvature terms. We show that, unlike the case of general relativity, for modified theories even in the non-compact Cauchy surface cases, there are some theories which show linearization instability about their anti-de Sitter backgrounds. Recent D dimensional critical and three dimensional chiral gravity theories are two such examples. This observation sheds light on the paradoxical behavior of vanishing conserved charges (mass, angular momenta) for non-vacuum solutions, such as black holes, in these theories.

Surface defects and chiral algebras

NASA Astrophysics Data System (ADS)

Córdova, Clay; Gaiotto, Davide; Shao, Shu-Heng

2017-05-01

We investigate superconformal surface defects in four-dimensional N=2 superconformal theories. Each such defect gives rise to a module of the associated chiral algebra and the surface defect Schur index is the character of this module. Various natural chiral algebra operations such as Drinfeld-Sokolov reduction and spectral flow can be interpreted as constructions involving four-dimensional surface defects. We compute the index of these defects in the free hypermultiplet theory and Argyres-Douglas theories, using both infrared techniques involving BPS states, as well as renormalization group flows onto Higgs branches. In each case we find perfect agreement with the predicted characters.

Chaos, complexity and complicatedness: lessons from rocket science.

PubMed

Norman, Geoff

2011-06-01

Recently several authors have drawn parallels between educational research and some theories of natural science, in particular complexity theory and chaos theory. The central claim is that both the natural science theories are useful metaphors for education research in that they deal with phenomena that involve many variables interacting in complex, non-linear and unstable ways, and leading to effects that are neither reproducible nor comprehensible. This paper presents a counter-argument. I begin by carefully examining the concepts of uncertainty, complexity and chaos, as described in physical science. I distinguish carefully between systems that are, respectively, complex, chaotic and complicated. I demonstrate that complex and chaotic systems have highly specific characteristics that are unlikely to be present in education systems. I then suggest that, in fact, there is ample evidence that human learning can be understood adequately with conventional linear models. The implications of these opposing world views are substantial. If education science has the properties of complex or chaotic systems, we should abandon any attempt at control or understanding. However, as I point out, to do so would ignore a number of recent developments in our understanding of learning that hold promise to yield substantial improvements in effectiveness and efficiency of learning. © Blackwell Publishing Ltd 2011.

Changing the Known; Knowing the Changing: General Systems Theory Paradigms as Ways to Study Complex Change and Complex Thoughts.

ERIC Educational Resources Information Center

Sinnott, Jan D.

This paper discusses the utility of a general systems theory paradigm for psychology. The paradigm can be used for conceptualizing such complex phenomena as change over time in living systems, person-society interactions, and the epistemology of multiply determined changes. Consideration is also given to applications of the approach to…

Calculations of the surface tensions of liquid metals

NASA Technical Reports Server (NTRS)

Stroud, D. G.

1981-01-01

The understanding of the surface tension of liquid metals and alloys from as close to first principles as possible is discussed. The two ingredients which are combined in these calculations are: the electron theory of metals, and the classical theory of liquids, as worked out within the framework of statistical mechanics. The results are a new theory of surface tensions and surface density profiles from knowledge purely of the bulk properties of the coexisting liquid and vapor phases. It is found that the method works well for the pure liquid metals on which it was tested; work is extended to mixtures of liquid metals, interfaces between immiscible liquid metals, and to the temperature derivative of the surface tension.

Introducing Evidence Through Research "Push": Using Theory and Qualitative Methods.

PubMed

Morden, Andrew; Ong, Bie Nio; Brooks, Lauren; Jinks, Clare; Porcheret, Mark; Edwards, John J; Dziedzic, Krysia S

2015-11-01

A multitude of factors can influence the uptake and implementation of complex interventions in health care. A plethora of theories and frameworks recognize the need to establish relationships, understand organizational dynamics, address context and contingency, and engage key decision makers. Less attention is paid to how theories that emphasize relational contexts can actually be deployed to guide the implementation of an intervention. The purpose of the article is to demonstrate the potential role of qualitative research aligned with theory to inform complex interventions. We detail a study underpinned by theory and qualitative research that (a) ensured key actors made sense of the complex intervention at the earliest stage of adoption and (b) aided initial engagement with the intervention. We conclude that using theoretical approaches aligned with qualitative research can provide insights into the context and dynamics of health care settings that in turn can be used to aid intervention implementation. © The Author(s) 2015.

Disorder in Complex Human System

NASA Astrophysics Data System (ADS)

Akdeniz, K. Gediz

2011-11-01

Since the world of human and whose life becomes more and more complex every day because of the digital technology and under the storm of knowledge (media, internet, governmental and non-governmental organizations, etc...) the simulation is rapidly growing in the social systems and in human behaviors. The formation of the body and mutual interactions are left to digital technological, communication mechanisms and coding the techno genetics of the body. Deconstruction begins everywhere. The linear simulation mechanism with modern realities are replaced by the disorder simulation of human behaviors with awareness realities. In this paper I would like to introduce simulation theory of "Disorder Sensitive Human Behaviors". I recently proposed this theory to critique the role of disorder human behaviors in social systems. In this theory the principle of realty is the chaotic awareness of the complexity of human systems inside of principle of modern thinking in Baudrillard's simulation theory. Proper examples will be also considered to investigate the theory.

Radiometry rocks

NASA Astrophysics Data System (ADS)

Harvey, James E.

2012-10-01

Professor Bill Wolfe was an exceptional mentor for his graduate students, and he made a major contribution to the field of optical engineering by teaching the (largely ignored) principles of radiometry for over forty years. This paper describes an extension of Bill's work on surface scatter behavior and the application of the BRDF to practical optical engineering problems. Most currently-available image analysis codes require the BRDF data as input in order to calculate the image degradation from residual optical fabrication errors. This BRDF data is difficult to measure and rarely available for short EUV wavelengths of interest. Due to a smooth-surface approximation, the classical Rayleigh-Rice surface scatter theory cannot be used to calculate BRDFs from surface metrology data for even slightly rough surfaces. The classical Beckmann-Kirchhoff theory has a paraxial limitation and only provides a closed-form solution for Gaussian surfaces. Recognizing that surface scatter is a diffraction process, and by utilizing sound radiometric principles, we first developed a linear systems theory of non-paraxial scalar diffraction in which diffracted radiance is shift-invariant in direction cosine space. Since random rough surfaces are merely a superposition of sinusoidal phase gratings, it was a straightforward extension of this non-paraxial scalar diffraction theory to develop a unified surface scatter theory that is valid for moderately rough surfaces at arbitrary incident and scattered angles. Finally, the above two steps are combined to yield a linear systems approach to modeling image quality for systems suffering from a variety of image degradation mechanisms. A comparison of image quality predictions with experimental results taken from on-orbit Solar X-ray Imager (SXI) data is presented.

A unified perturbation expansion for surface scattering

NASA Technical Reports Server (NTRS)

Rodriguez, Ernesto; Kim, Yunjin

1992-01-01

Starting with the extinction theorem, a perturbation expansion which, to first and second orders, converges over a wider domain than the small perturbation expansion and the momentum transfer expansion is presented. It is shown that, in the appropriate limits, both of these theories, as well as the two-scale expansion, are recovered. There is no adjustable parameter, such as a spectral split, in the theory. This theory is applied to random rough surfaces and derive analytic expressions for the coherent field and the bistatic cross section. Finally, a numerical test of the theory against method of moments results for Gaussian random rough surfaces with a power law spectrum is given. These results show that the expansion is ramarkably accurate over a large range of surface heights and slopes for both horizontal and vertical polarization.

Surface operators in 5d gauge theories and duality relations

NASA Astrophysics Data System (ADS)

Ashok, S. K.; Billò, M.; Dell'Aquila, E.; Frau, M.; Gupta, V.; John, R. R.; Lerda, A.

2018-05-01

We study half-BPS surface operators in 5d N = 1 gauge theories compactified on a circle. Using localization methods and the twisted chiral ring relations of coupled 3d/5d quiver gauge theories, we calculate the twisted chiral superpotential that governs the infrared properties of these surface operators. We make a detailed analysis of the localization integrand, and by comparing with the results from the twisted chiral ring equations, we obtain constraints on the 3d and 5d Chern-Simons levels so that the instanton partition function does not depend on the choice of integration contour. For these values of the Chern-Simons couplings, we comment on how the distinct quiver theories that realize the same surface operator are related to each other by Aharony-Seiberg dualities.

Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

DOE R&D Accomplishments Database

Marcus, R. A.

1964-01-01

In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

Modelling realistic TiO2 nanospheres: A benchmark study of SCC-DFTB against hybrid DFT

NASA Astrophysics Data System (ADS)

Selli, Daniele; Fazio, Gianluca; Di Valentin, Cristiana

2017-10-01

TiO2 nanoparticles (NPs) are nowadays considered fundamental building blocks for many technological applications. Morphology is found to play a key role with spherical NPs presenting higher binding properties and chemical activity. From the experimental point of view, the characterization of these nano-objects is extremely complex, opening a large room for computational investigations. In this work, TiO2 spherical NPs of different sizes (from 300 to 4000 atoms) have been studied with a two-scale computational approach. Global optimization to obtain stable and equilibrated nanospheres was performed with a self-consistent charge density functional tight-binding (SCC-DFTB) simulated annealing process, causing a considerable atomic rearrangement within the nanospheres. Those SCC-DFTB relaxed structures have been then optimized at the DFT(B3LYP) level of theory. We present a systematic and comparative SCC-DFTB vs DFT(B3LYP) study of the structural properties, with particular emphasis on the surface-to-bulk sites ratio, coordination distribution of surface sites, and surface energy. From the electronic point of view, we compare HOMO-LUMO and Kohn-Sham gaps, total and projected density of states. Overall, the comparisons between DFTB and hybrid density functional theory show that DFTB provides a rather accurate geometrical and electronic description of these nanospheres of realistic size (up to a diameter of 4.4 nm) at an extremely reduced computational cost. This opens for new challenges in simulations of very large systems and more extended molecular dynamics.

Differential continuum damage mechanics models for creep and fatigue of unidirectional metal matrix composites

NASA Technical Reports Server (NTRS)

Arnold, S. M.; Kruch, S.

1991-01-01

Three multiaxial isothermal continuum damage mechanics models for creep, fatigue, and creep/fatigue interaction of a unidirectional metal matrix composite volume element are presented, only one of which will be discussed in depth. Each model is phenomenological and stress based, with varying degrees of complexity to accurately predict the initiation and propagation of intergranular and transgranular defects over a wide range of loading conditions. The development of these models is founded on the definition of an initially transversely isotropic fatigue limit surface, static fracture surface, normalized stress amplitude function and isochronous creep damage failure surface, from which both fatigue and creep damage evolutionary laws can be obtained. The anisotropy of each model is defined through physically meaningful invariants reflecting the local stress and material orientation. All three transversely isotropic models have been shown, when taken to their isotropic limit, to directly simplify to previously developed and validated creep and fatigue continuum damage theories. Results of a nondimensional parametric study illustrate (1) the flexibility of the present formulation when attempting to characterize a large class of composite materials, and (2) its ability to predict anticipated qualitative trends in the fatigue behavior of unidirectional metal matrix composites. Additionally, the potential for the inclusion of various micromechanical effects (e.g., fiber/matrix bond strength, fiber volume fraction, etc.), into the phenomenological anisotropic parameters is noted, as well as a detailed discussion regarding the necessary exploratory and characterization experiments needed to utilize the featured damage theories.

On relativistic spin network vertices

NASA Astrophysics Data System (ADS)

Reisenberger, Michael P.

1999-04-01

Barrett and Crane have proposed a model of simplicial Euclidean quantum gravity in which a central role is played by a class of Spin(4) spin networks called "relativistic spin networks" which satisfy a series of physically motivated constraints. Here a proof is presented that demonstrates that the intertwiner of a vertex of such a spin network is uniquely determined, up to normalization, by the representations on the incident edges and the constraints. Moreover, the constraints, which were formulated for four valent spin networks only, are extended to networks of arbitrary valence, and the generalized relativistic spin networks proposed by Yetter are shown to form the entire solution set (mod normalization) of the extended constraints. Finally, using the extended constraints, the Barrett-Crane model is generalized to arbitrary polyhedral complexes (instead of just simplicial complexes) representing space-time. It is explained how this model, like the Barret-Crane model can be derived from BF theory, a simple topological field theory [G. Horowitz, Commun. Math. Phys. 125, 417 (1989)], by restricting the sum over histories to ones in which the left-handed and right-handed areas of any 2-surface are equal. It is known that the solutions of classical Euclidean general relativity form a branch of the stationary points of the BF action with respect to variations preserving this condition.

Kinetics of Hydrogen Abstraction and Addition Reactions of 3-Hexene by ȮH Radicals.

PubMed

Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Zhang, Yingjia; Tang, Chenglong; Huang, Zuohua

2017-03-09

Rate coefficients of H atom abstraction and H atom addition reactions of 3-hexene by the hydroxyl radicals were determined using both conventional transition-state theory and canonical variational transition-state theory, with the potential energy surface (PES) evaluated at the CCSD(T)/CBS//BHandHLYP/6-311G(d,p) level and quantum mechanical effect corrected by the compounded methods including one-dimensional Wigner method, multidimensional zero-curvature tunneling method, and small-curvature tunneling method. Results reveal that accounting for approximate 70% of the overall H atom abstractions occur in the allylic site via both direct and indirect channels. The indirect channel containing two van der Waals prereactive complexes exhibits two times larger rate coefficient relative to the direct one. The OH addition reaction also contains two van der Waals complexes, and its submerged barrier results in a negative temperature coefficient behavior at low temperatures. In contrast, The OH addition pathway dominates only at temperatures below 450 K whereas the H atom abstraction reactions dominate overwhelmingly at temperature over 1000 K. All of the rate coefficients calculated with an uncertainty of a factor of 5 were fitted in a quasi-Arrhenius formula. Analyses on the PES, minimum reaction path and activation free Gibbs energy were also performed in this study.

Quasiparticle Level Alignment for Photocatalytic Interfaces.

PubMed

Migani, Annapaoala; Mowbray, Duncan J; Zhao, Jin; Petek, Hrvoje; Rubio, Angel

2014-05-13

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO2(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and G0W0, scQPGW1, scQPGW0, and scQPGW QP calculations. Our results demonstrate that G0W0, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.

Application of signal detection theory to optics. [image evaluation and restoration

NASA Technical Reports Server (NTRS)

Helstrom, C. W.

1973-01-01

Basic quantum detection and estimation theory, applications to optics, photon counting, and filtering theory are studied. Recent work on the restoration of degraded optical images received at photoelectrically emissive surfaces is also reported, the data used by the method are the numbers of electrons ejected from various parts of the surface.

What Can Quantum Optics Say about Computational Complexity Theory?

NASA Astrophysics Data System (ADS)

Rahimi-Keshari, Saleh; Lund, Austin P.; Ralph, Timothy C.

2015-02-01

Considering the problem of sampling from the output photon-counting probability distribution of a linear-optical network for input Gaussian states, we obtain results that are of interest from both quantum theory and the computational complexity theory point of view. We derive a general formula for calculating the output probabilities, and by considering input thermal states, we show that the output probabilities are proportional to permanents of positive-semidefinite Hermitian matrices. It is believed that approximating permanents of complex matrices in general is a #P-hard problem. However, we show that these permanents can be approximated with an algorithm in the BPPNP complexity class, as there exists an efficient classical algorithm for sampling from the output probability distribution. We further consider input squeezed-vacuum states and discuss the complexity of sampling from the probability distribution at the output.

CASE STUDY RESEARCH: THE VIEW FROM COMPLEXITY SCIENCE

PubMed Central

Anderson, Ruth; Crabtree, Benjamin F.; Steele, David J.; McDaniel, Reuben R.

2005-01-01

Many wonder why there has been so little change in care quality, despite substantial quality improvement efforts. Questioning why current approaches are not making true changes draws attention to the organization as a source of answers. We bring together the case study method and complexity science to suggest new ways to study health care organizations. The case study provides a method for studying systems. Complexity theory suggests that keys to understanding the system are contained in patterns of relationships and interactions among the system’s agents. We propose some of the “objects” of study that are implicated by complexity theory and discuss how studying these using case methods may provide useful maps of the system. We offer complexity theory, partnered with case study method, as a place to begin the daunting task of studying a system as an integrated whole. PMID:15802542

Information Theory Applied to Dolphin Whistle Vocalizations with Possible Application to SETI Signals

NASA Astrophysics Data System (ADS)

Doyle, Laurance R.; McCowan, Brenda; Hanser, Sean F.

2002-01-01

Information theory allows a quantification of the complexity of a given signaling system. We are applying information theory to dolphin whistle vocalizations, humpback whale songs, squirrel monkey chuck calls, and several other animal communication systems' in order to develop a quantitative and objective way to compare inter species communication systems' complexity. Once signaling units have been correctly classified the communication system must obey certain statistical distributions in order to contain complexity whether it is human languages, dolphin whistle vocalizations, or even a system of communication signals received from an extraterrestrial source.

A study of the spreading scheme for viral marketing based on a complex network model

NASA Astrophysics Data System (ADS)

Yang, Jianmei; Yao, Canzhong; Ma, Weicheng; Chen, Guanrong

2010-02-01

Buzzword-based viral marketing, known also as digital word-of-mouth marketing, is a marketing mode attached to some carriers on the Internet, which can rapidly copy marketing information at a low cost. Viral marketing actually uses a pre-existing social network where, however, the scale of the pre-existing network is believed to be so large and so random, so that its theoretical analysis is intractable and unmanageable. There are very few reports in the literature on how to design a spreading scheme for viral marketing on real social networks according to the traditional marketing theory or the relatively new network marketing theory. Complex network theory provides a new model for the study of large-scale complex systems, using the latest developments of graph theory and computing techniques. From this perspective, the present paper extends the complex network theory and modeling into the research of general viral marketing and develops a specific spreading scheme for viral marking and an approach to design the scheme based on a real complex network on the QQ instant messaging system. This approach is shown to be rather universal and can be further extended to the design of various spreading schemes for viral marketing based on different instant messaging systems.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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.

F-theory models on K3 surfaces with various Mordell-Weil ranks — constructions that use quadratic base change of rational elliptic surfaces

NASA Astrophysics Data System (ADS)

Kimura, Yusuke

2018-05-01

We constructed several families of elliptic K3 surfaces with Mordell-Weil groups of ranks from 1 to 4. We studied F-theory compactifications on these elliptic K3 surfaces times a K3 surface. Gluing pairs of identical rational elliptic surfaces with nonzero Mordell-Weil ranks yields elliptic K3 surfaces, the Mordell-Weil groups of which have nonzero ranks. The sum of the ranks of the singularity type and the Mordell-Weil group of any rational elliptic surface with a global section is 8. By utilizing this property, families of rational elliptic surfaces with various nonzero Mordell-Weil ranks can be obtained by choosing appropriate singularity types. Gluing pairs of these rational elliptic surfaces yields families of elliptic K3 surfaces with various nonzero Mordell-Weil ranks. We also determined the global structures of the gauge groups that arise in F-theory compactifications on the resulting K3 surfaces times a K3 surface. U(1) gauge fields arise in these compactifications.

Comparison of two fractal interpolation methods

NASA Astrophysics Data System (ADS)

Fu, Yang; Zheng, Zeyu; Xiao, Rui; Shi, Haibo

2017-03-01

As a tool for studying complex shapes and structures in nature, fractal theory plays a critical role in revealing the organizational structure of the complex phenomenon. Numerous fractal interpolation methods have been proposed over the past few decades, but they differ substantially in the form features and statistical properties. In this study, we simulated one- and two-dimensional fractal surfaces by using the midpoint displacement method and the Weierstrass-Mandelbrot fractal function method, and observed great differences between the two methods in the statistical characteristics and autocorrelation features. From the aspect of form features, the simulations of the midpoint displacement method showed a relatively flat surface which appears to have peaks with different height as the fractal dimension increases. While the simulations of the Weierstrass-Mandelbrot fractal function method showed a rough surface which appears to have dense and highly similar peaks as the fractal dimension increases. From the aspect of statistical properties, the peak heights from the Weierstrass-Mandelbrot simulations are greater than those of the middle point displacement method with the same fractal dimension, and the variances are approximately two times larger. When the fractal dimension equals to 1.2, 1.4, 1.6, and 1.8, the skewness is positive with the midpoint displacement method and the peaks are all convex, but for the Weierstrass-Mandelbrot fractal function method the skewness is both positive and negative with values fluctuating in the vicinity of zero. The kurtosis is less than one with the midpoint displacement method, and generally less than that of the Weierstrass-Mandelbrot fractal function method. The autocorrelation analysis indicated that the simulation of the midpoint displacement method is not periodic with prominent randomness, which is suitable for simulating aperiodic surface. While the simulation of the Weierstrass-Mandelbrot fractal function method has strong periodicity, which is suitable for simulating periodic surface.

Stern Layer Structure and Energetics at Mica-Water Interfaces

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

Bourg, Ian C.; Lee, Sang Soo; Fenter, Paul

2017-04-11

The screening of surface charge by dissolved ions at solid liquid interfaces in the region of interfacial fluid known as the electrical double layer (EDL)-plays a recurrent role in surface science, from ion adsorption to colloidal mechanics to the transport properties of nanoporous media. A persistent unknown in theories of EDL-related phenomena is the structure of the Stern layer, the near-surface portion of the EDL where water molecules and adsorbed ions form specific short-range interactions with surface atoms. Here, we describe a set of synchrotron X-ray reflectivity (XRR) experiments and molecular dynamics (MD) simulations carried out under identical conditions formore » a range of 0.1 M alkali chloride (Li-, Na-, K-, Rb-, or CsCl) solutions on the basal surface of muscovite mica, a mineral isostructural to phyllosilicate clay minerals and one of the most widely studied reference surfaces in interfacial science. Our XRR and MD simulation results provide a remarkably consistent view of the structure and energetics of the Stern layer, with some discrepancy on the fraction of the minor outer-sphere component of Rb and on the adsorption energetics of Li. The results of both techniques, along with surface complexation model calculations, provide insight into the sensitivity of water structure and ion adsorption to surface topography and the type of adsorbed counterion.« less

Polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent counterions: A Monte Carlo simulation study

NASA Astrophysics Data System (ADS)

Luque-Caballero, Germán; Martín-Molina, Alberto; Quesada-Pérez, Manuel

2014-05-01

Both experiments and theory have evidenced that multivalent cations can mediate the interaction between negatively charged polyelectrolytes and like-charged objects, such as anionic lipoplexes (DNA-cation-anionic liposome complexes). In this paper, we use Monte Carlo simulations to study the electrostatic interaction responsible for the trivalent-counterion-mediated adsorption of polyelectrolytes onto a like-charged planar surface. The evaluation of the Helmholtz free energy allows us to characterize both the magnitude and the range of the interaction as a function of the polyelectrolyte charge, surface charge density, [3:1] electrolyte concentration, and cation size. Both polyelectrolyte and surface charge favor the adsorption. It should be stressed, however, that the adsorption will be negligible if the surface charge density does not exceed a threshold value. The effect of the [3:1] electrolyte concentration has also been analyzed. In certain range of concentrations, the counterion-mediated attraction seems to be independent of this parameter, whereas very high concentrations of salt weaken the adsorption. If the trivalent cation diameter is doubled the adsorption moderates due to the excluded volume effects. The analysis of the integrated charge density and ionic distributions suggests that a delicate balance between charge inversion and screening effects governs the polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent cations.

Sensual Surfaces and Stylistic Excess: The Pleasure and Politics of "Miami Vice."

ERIC Educational Resources Information Center

Schwichtenberg, Cathy

Using Jean Baudrillard's postmodernist theories, this paper analyzes how the television program, "Miami Vice," operationalizes his theory through its attention to surfaces and style. The paper notes that Baudrillard proposes life as a surface comprised of animated models indistinguishable from the reality these models represent and…

Design tools for complex dynamic security systems.

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

Byrne, Raymond Harry; Rigdon, James Brian; Rohrer, Brandon Robinson

2007-01-01

The development of tools for complex dynamic security systems is not a straight forward engineering task but, rather, a scientific task where discovery of new scientific principles and math is necessary. For years, scientists have observed complex behavior but have had difficulty understanding it. Prominent examples include: insect colony organization, the stock market, molecular interactions, fractals, and emergent behavior. Engineering such systems will be an even greater challenge. This report explores four tools for engineered complex dynamic security systems: Partially Observable Markov Decision Process, Percolation Theory, Graph Theory, and Exergy/Entropy Theory. Additionally, enabling hardware technology for next generation security systemsmore » are described: a 100 node wireless sensor network, unmanned ground vehicle and unmanned aerial vehicle.« less

The design of dual-mode complex signal processors based on quadratic modular number codes

NASA Astrophysics Data System (ADS)

Jenkins, W. K.; Krogmeier, J. V.

1987-04-01

It has been known for a long time that quadratic modular number codes admit an unusual representation of complex numbers which leads to complete decoupling of the real and imaginary channels, thereby simplifying complex multiplication and providing error isolation between the real and imaginary channels. This paper first presents a tutorial review of the theory behind the different types of complex modular rings (fields) that result from particular parameter selections, and then presents a theory for a 'dual-mode' complex signal processor based on the choice of augmented power-of-2 moduli. It is shown how a diminished-1 binary code, used by previous designers for the realization of Fermat number transforms, also leads to efficient realizations for dual-mode complex arithmetic for certain augmented power-of-2 moduli. Then a design is presented for a recursive complex filter based on a ROM/ACCUMULATOR architecture and realized in an augmented power-of-2 quadratic code, and a computer-generated example of a complex recursive filter is shown to illustrate the principles of the theory.

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios.

PubMed

Nazmutdinov, Renat R; Zinkicheva, Tamara T; Vassiliev, Sergey Yu; Glukhov, Dmitri V; Tsirlina, Galina A; Probst, Michael

2010-04-01

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms ("dimers") was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition. Copyright 2010. Published by Elsevier B.V.

Machine Learning Estimates of Natural Product Conformational Energies

PubMed Central

Rupp, Matthias; Bauer, Matthias R.; Wilcken, Rainer; Lange, Andreas; Reutlinger, Michael; Boeckler, Frank M.; Schneider, Gisbert

2014-01-01

Machine learning has been used for estimation of potential energy surfaces to speed up molecular dynamics simulations of small systems. We demonstrate that this approach is feasible for significantly larger, structurally complex molecules, taking the natural product Archazolid A, a potent inhibitor of vacuolar-type ATPase, from the myxobacterium Archangium gephyra as an example. Our model estimates energies of new conformations by exploiting information from previous calculations via Gaussian process regression. Predictive variance is used to assess whether a conformation is in the interpolation region, allowing a controlled trade-off between prediction accuracy and computational speed-up. For energies of relaxed conformations at the density functional level of theory (implicit solvent, DFT/BLYP-disp3/def2-TZVP), mean absolute errors of less than 1 kcal/mol were achieved. The study demonstrates that predictive machine learning models can be developed for structurally complex, pharmaceutically relevant compounds, potentially enabling considerable speed-ups in simulations of larger molecular structures. PMID:24453952

On multiscale moving contact line theory.

PubMed

Li, Shaofan; Fan, Houfu

2015-07-08

In this paper, a multiscale moving contact line (MMCL) theory is presented and employed to simulate liquid droplet spreading and capillary motion. The proposed MMCL theory combines a coarse-grained adhesive contact model with a fluid interface membrane theory, so that it can couple molecular scale adhesive interaction and surface tension with hydrodynamics of microscale flow. By doing so, the intermolecular force, the van der Waals or double layer force, separates and levitates the liquid droplet from the supporting solid substrate, which avoids the shear stress singularity caused by the no-slip condition in conventional hydrodynamics theory of moving contact line. Thus, the MMCL allows the difference of the surface energies and surface stresses to drive droplet spreading naturally. To validate the proposed MMCL theory, we have employed it to simulate droplet spreading over various elastic substrates. The numerical simulation results obtained by using MMCL are in good agreement with the molecular dynamics results reported in the literature.

Theory of back-surface-field solar cells

NASA Technical Reports Server (NTRS)

Vonroos, O.

1979-01-01

Report describes simple concise theory of back-surface-field (BSF) solar cells (npp + junctions) based on Shockley's depletion-layer approximation and cites superiority of two-junction devices over conventional unijunction cells.

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

PubMed Central

Gao, Xiaodong; Root, Robert A.; Farrell, James; Ela, Wendell; Chorover, Jon

2014-01-01

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 – 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92–2.94 and 3.41–3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms. PMID:25382933

The Importance of Why: An Intelligence Approach for a Multi-Polar World

DTIC Science & Technology

2016-04-04

December 27, 2015). 12. 2 Jupiter Scientific, “Definitions of Important Terms in Chaos Theory ,” Jupiter Scientific website, http...Important Terms in Chaos Theory .” Linearizing a system is approximating a nonlinear system through the application of linear system model. 25...Complexity Theory to Anticipate Strategic Surprise,” 24. 16 M. Mitchell Waldrop, Complexity: The Emerging Science at the Edge of Order and Chaos (New

Long-Range Superexchange in Electron Transport Proteins

NASA Astrophysics Data System (ADS)

Gruschus, James Michael

A new Hamiltonian model for the calculation of long-range electronic couplings in complex molecular systems is presented. These couplings make possible the electron transfers occurring at several critical steps in photosynthesis and respiration. The couplings studied are demonstrated to arise from a mechanism known as superexchange, where the electrons of the insulating medium are intimately involved in the delocalization of the donor wavefunction tail, allowing significant interaction with the acceptor at much greater separations than could be achieved were the medium absent. Superexchange phenomena in molecules of moderate complexity are first compared to couplings calculated with the model Hamiltonian, with very encouraging results. The method is then applied to several cytochrome c proteins where electron transfer has been measured between a zinc-substituted porphyrin and a ruthenium complex ligated to several sites at the protein surface. The calculated couplings are in unprecedented agreement with experiment. Novel, analytical derivatives of the superexchange coupling with respect to the orbital energies and interactions are then carried out on these proteins yielding the general, chemically relevant result that the entire three-dimensional zone between redox sites is important in mediating the superexchange coupling, in contrast to the prevailing assumption that the coupling can be characterized by a one-dimensional pathway consisting primarily of chains of bonded atoms. In addition, the derivatives provide the most comprehensive ever, atom-by -atom visualization of the superexchange process. Using AMBER molecular dynamics trajectories of the cytochrome c proteins, the effect of structural fluctuations on superexchange is examined. The calculated couplings show a substantial variability, a result contrary to the constant coupling implicit in most present-day transfer rate theory. Couplings are also calculated on surfaces enveloping several variants of cytochrome c, as well as plastocyanin, cytochrome b _5, and cytochrome c peroxidase. The surfaces reveal important clues as to which conformations of the electron transport protein complexes actually give rise to electron transfer, a subject of broad biological interest.

Oxides Surfaces and Novel Electronic Properties

NASA Astrophysics Data System (ADS)

Koirala, Pratik

The scope of this thesis extends to the study of surface structures and electronic properties in a number of complex oxides. The c(6x2) surface reconstruction on SrTiO3 (001) was solved using a combination of plan view transmission electron microscopy imaging, atomic resolution secondary electron imaging, and density functional theory calculations. This work provided fundamental insights on the effects of dielectric screening in secondary electron generation. A thorough analysis on the limitation and functionality of transmission plan view imaging showed that the kinematical approximations used in the separation of top and bottom surfaces is only valid in thin samples (˜5 nm or less for SrTiO3). The presence of an inversion center in the surface structure also made separation of the top and bottom surfaces more robust. Surface studies of two other oxides, KTaO3 and NdGaO3, provided understanding on the mechanism of surface heterogeneity and segregation. In the case of KTaO3, selective ion sputtering and the loss of K resulted in large stoichiometric variations at the surface. Annealing of such samples led to the formation of a potassium deficient tetragonal phase (K 6Ta10.8O30) on the surface. A similar phenomenon was also observed in NdGaO3. Exploratory surface studies of the rare earth scandates (ReScO3 , Re = Gd, Tb, Dy) led to the observation of large flexoelectric bending inside an electron microscope. Thin rods of these scandates bent by up to 90 degree under a focused electron beam; the bending was fully reversible. Ex-situ measurements of flexoelectric coe cient performed by an- other graduate student, Christopher Mizzi, confirmed that the scandates have a large flexocoupling voltage (˜42 V). Electronic structure of the lanthanide scandates was studied using temperature depen- dent X-ray photoelectron spectroscopy and hybrid density functional theory calculations. The amount of charging under X-ray illumination was greatly reduced with increasing temperature owing to the presence of oxygen vacancies and surface band gap reduction. These results also indicated that the 4f-electrons are active components of the valence band electronic structure. We believe that the lanthanide scandates are a rich playground of material properties and have potential for applications in electronic and nano-mechanical devices.

Broadening conceptions of learning in medical education: the message from teamworking.

PubMed

Bleakley, Alan

2006-02-01

There is a mismatch between the broad range of learning theories offered in the wider education literature and a relatively narrow range of theories privileged in the medical education literature. The latter are usually described under the heading of 'adult learning theory'. This paper critically addresses the limitations of the current dominant learning theories informing medical education. An argument is made that such theories, which address how an individual learns, fail to explain how learning occurs in dynamic, complex and unstable systems such as fluid clinical teams. Models of learning that take into account distributed knowing, learning through time as well as space, and the complexity of a learning environment including relationships between persons and artefacts, are more powerful in explaining and predicting how learning occurs in clinical teams. Learning theories may be privileged for ideological reasons, such as medicine's concern with autonomy. Where an increasing amount of medical education occurs in workplace contexts, sociocultural learning theories offer a best-fit exploration and explanation of such learning. We need to continue to develop testable models of learning that inform safe work practice. One type of learning theory will not inform all practice contexts and we need to think about a range of fit-for-purpose theories that are testable in practice. Exciting current developments include dynamicist models of learning drawing on complexity theory.

Structure and Reactivity of Alucone-Coated Films on Si and Li(x)Si(y) Surfaces.

PubMed

Ma, Yuguang; Martinez de la Hoz, Julibeth M; Angarita, Ivette; Berrio-Sanchez, Jose M; Benitez, Laura; Seminario, Jorge M; Son, Seoung-Bum; Lee, Se-Hee; George, Steven M; Ban, Chunmei; Balbuena, Perla B

2015-06-10

Coating silicon particles with a suitable thin film has appeared as a possible solution to accommodate the swelling of silicon upon lithiation and its posterior cracking and pulverization during cycling of Li-ion batteries. In particular, aluminum alkoxide (alucone) films have been recently deposited over Si anodes, and the lithiation and electrochemical behavior of the system have been characterized. However, some questions remain regarding the lithium molecular migration mechanisms through the film and the electronic properties of the alucone film. Here we use density functional theory, ab initio molecular dynamics simulations, and Green's function theory to examine the film formation, lithiation, and reactivity in contact with an electrolyte solution. It is found that the film is composed of Al-O complexes with 3-O or 4-O coordination. During lithiation, Li atoms bind very strongly to the O atoms in the most energetically favorable sites. After the film is irreversibly saturated with Li atoms, it becomes electronically conductive. The ethylene carbonate molecules in liquid phase are found to be reduced at the surface of the Li-saturated alucone film following similar electron transfer mechanisms as found previously for lithiated silicon anodes. The theoretical results are in agreement with those from morphology and electrochemical analyses.

Origin of the Anomalous Color of Egyptian and Han Blue Historical Pigments: Going beyond the Complex Approximation in Ligand Field Theory

ERIC Educational Resources Information Center

García-Fernandez, Pablo; Moreno, Miguel; Aramburu, José Antonio

2016-01-01

The complex approximation is widely used in the framework of the Ligand Field Theory for explaining the optical properties of crystalline coordination compounds. Here, we show that there are essential features of these systems that cannot be understood with the usual approximation that only considers an isolated complex at the correct equilibrium…

VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu2(μ-O2)], [Fe2(μ-O2)] and Fe(IV)-O cores based on DFT potential energy surfaces.

PubMed

Kim, Yongho; Mai, Binh Khanh; Park, Sumin

2017-04-01

High-valent Cu and Fe species, which are generated from dioxygen activation in metalloenzymes, carry out the functionalization of strong C-H bonds. Understanding the atomic details of the catalytic mechanism has long been one of the main objectives of bioinorganic chemistry. Large H/D kinetic isotope effects (KIEs) were observed in the C-H activation by high-valent non-heme Cu or Fe complexes in enzymes and their synthetic models. The H/D KIE depends significantly on the transition state properties, such as structure, energies, frequencies, and shape of the potential energy surface, when the tunneling effect is large. Therefore, theoretical predictions of kinetic parameters such as rate constants and KIEs can provide a reliable link between atomic-level quantum mechanical mechanisms and experiments. The accurate prediction of the tunneling effect is essential to reproduce the kinetic parameters. The rate constants and HD/KIE have been calculated using the variational transition-state theory including multidimensional tunneling based on DFT potential energy surfaces along the reaction coordinate. Excellent agreement was observed between the predicted and experimental results, which assures the validity of the DFT potential energy surfaces and, therefore, the proposed atomic-level mechanisms. The [Cu 2 (μ-O) 2 ], [Fe 2 (μ-O) 2 ], and Fe(IV)-oxo species were employed for C-H activation, and their role as catalysts was discussed at an atomic level.

Location and magnetic relaxation properties of the stable tyrosine radical in photosystem II.

PubMed

Innes, J B; Brudvig, G W

1989-02-07

Dipolar interactions with neighboring metal ions can cause enhanced spin-lattice relaxation of free radicals. We have applied the theory of dipolar relaxation enhancement and shown that the dependence of the enhanced relaxation on the protein structure surrounding the free radical can be used to obtain distances from the free radical to the protein surface. To test the theoretical predictions, we have examined the effect of added Dy3+ complexes on the microwave power saturation of free radicals in two protein complexes of known structure: myoglobin nitroxide and the reaction center from Rhodobacter sphaeroides. Three cases have been considered: (1) metal ions bound to a specific site, (2) metal ions bound randomly over the protein surface, and (3) metal ions distributed randomly in solution. Only case 3, which assumes no specific binding, gave good agreement between the distances obtained by using the two model systems. The effect of added Dy3+ complexes on the microwave power saturation of signal IIslow from photosystem II (PSII) was used to determine the location of the stable tyrosine radical giving rise to signal IIslow. Assuming that the surface of a membrane-bound protein can be approximated as planar, we have obtained distances from the tyrosine radical to the membrane surface in thylakoids, in PSII membranes, and in Tris-washed PSII membranes. The distances we have determined are in good agreement with those predicted on the basis of a structural homology between the D1 and D2 subunits of PSII and the structurally characterized L and M subunits of the reaction center from purple non-sulfur bacteria. We have also examined the temperature dependence of the microwave power at half-saturation (P1/2) of signal IIslow from 4 to 200 K in dark-adapted PSII membranes. Above 70 K, the P1/2 increases as T2.5, which is consistent with a Raman relaxation mechanism.(ABSTRACT TRUNCATED AT 250 WORDS)

Computational Complexity and Human Decision-Making.

PubMed

Bossaerts, Peter; Murawski, Carsten

2017-12-01

The rationality principle postulates that decision-makers always choose the best action available to them. It underlies most modern theories of decision-making. The principle does not take into account the difficulty of finding the best option. Here, we propose that computational complexity theory (CCT) provides a framework for defining and quantifying the difficulty of decisions. We review evidence showing that human decision-making is affected by computational complexity. Building on this evidence, we argue that most models of decision-making, and metacognition, are intractable from a computational perspective. To be plausible, future theories of decision-making will need to take into account both the resources required for implementing the computations implied by the theory, and the resource constraints imposed on the decision-maker by biology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of Immune Complex Structure by Statistical Mechanics and Light Scattering Techniques.

NASA Astrophysics Data System (ADS)

Busch, Nathan Adams

1995-01-01

The size and structure of immune complexes determine their behavior in the immune system. The chemical physics of the complex formation is not well understood; this is due in part to inadequate characterization of the proteins involved, and in part by lack of sufficiently well developed theoretical techniques. Understanding the complex formation will permit rational design of strategies for inhibiting tissue deposition of the complexes. A statistical mechanical model of the proteins based upon the theory of associating fluids was developed. The multipole electrostatic potential for each protein used in this study was characterized for net protein charge, dipole moment magnitude, and dipole moment direction. The binding sites, between the model antigen and antibodies, were characterized for their net surface area, energy, and position relative to the dipole moment of the protein. The equilibrium binding graphs generated with the protein statistical mechanical model compares favorably with experimental data obtained from radioimmunoassay results. The isothermal compressibility predicted by the model agrees with results obtained from dynamic light scattering. The statistical mechanics model was used to investigate association between the model antigen and selected pairs of antibodies. It was found that, in accordance to expectations from thermodynamic arguments, the highest total binding energy yielded complex distributions which were skewed to higher complex size. From examination of the simulated formation of ring structures from linear chain complexes, and from the joint shape probability surfaces, it was found that ring configurations were formed by the "folding" of linear chains until the ends are within binding distance. By comparing the single antigen/two antibody system which differ only in their respective binding site locations, it was found that binding site location influences complex size and shape distributions only when ring formation occurs. The internal potential energy of a ring complex is considerably less than that of the non-associating system; therefore the ring complexes are quite stable and show no evidence of breaking, and collapsing into smaller complexes. The ring formation will occur only in systems where the total free energy of each complex may be minimized. Thus, ring formation will occur even though entropically unfavorable conformations result if the total free energy can be minimized by doing so.

Information and complexity measures in the interface of a metal and a superconductor

NASA Astrophysics Data System (ADS)

Moustakidis, Ch. C.; Panos, C. P.

2018-06-01

Fisher information, Shannon information entropy and Statistical Complexity are calculated for the interface of a normal metal and a superconductor, as a function of the temperature for several materials. The order parameter Ψ (r) derived from the Ginzburg-Landau theory is used as an input together with experimental values of critical transition temperature Tc and the superconducting coherence length ξ0. Analytical expressions are obtained for information and complexity measures. Thus Tc is directly related in a simple way with disorder and complexity. An analytical relation is found of the Fisher Information with the energy profile of superconductivity i.e. the ratio of surface free energy and the bulk free energy. We verify that a simple relation holds between Shannon and Fisher information i.e. a decomposition of a global information quantity (Shannon) in terms of two local ones (Fisher information), previously derived and verified for atoms and molecules by Liu et al. Finally, we find analytical expressions for generalized information measures like the Tsallis entropy and Fisher information. We conclude that the proper value of the non-extensivity parameter q ≃ 1, in agreement with previous work using a different model, where q ≃ 1.005.

Direct quantitative identification of the “surface trans-effect”

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

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Direct quantitative identification of the “surface trans-effect”

DOE PAGES

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin; ...

2016-06-09

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Thermo-Osmotic Flow in Thin Films.

PubMed

Bregulla, Andreas P; Würger, Alois; Günther, Katrin; Mertig, Michael; Cichos, Frank

2016-05-06

We report on the first microscale observation of the velocity field imposed by a nonuniform heat content along the solid-liquid boundary. We determine both radial and vertical velocity components of this thermo-osmotic flow field by tracking single tracer nanoparticles. The measured flow profiles are compared to an approximate analytical theory and to numerical calculations. From the measured slip velocity we deduce the thermo-osmotic coefficient for both bare glass and Pluronic F-127 covered surfaces. The value for Pluronic F-127 agrees well with Soret data for polyethylene glycol, whereas that for glass differs from literature values and indicates the complex boundary layer thermodynamics of glass-water interfaces.

Studies into Equine Electrocardiography and Vectorcardiography

PubMed Central

Holmes, J. R.; Alps, B. J.

1967-01-01

Theoretical consideration has been given in two horses to the properties of the electric field created by the equine heart acting as a simple electric generator. The principles of the vectorial theory have been applied to test the validity of application of the dipole concept. The cardiac electric forces, althrough complex in the immediate region of the heart, appear at the body surface in a similar form to those arising from a relatively immobile, single equivalent dipole. The potential value of the technique of vectorcardiography in cardiological investigations is briefly discussed. ImagesFig. 1.Fig. 3.Fig. 5.Fig. 10.Fig. 12.Fig. 13. PMID:17649586

Viscous drag reduction in boundary layers

NASA Technical Reports Server (NTRS)

Bushnell, Dennis M. (Editor); Hefner, Jerry N. (Editor)

1990-01-01

The present volume discusses the development status of stability theory for laminar flow control design, applied aspects of laminar-flow technology, transition delays using compliant walls, the application of CFD to skin friction drag-reduction, active-wave control of boundary-layer transitions, and such passive turbulent-drag reduction methods as outer-layer manipulators and complex-curvature concepts. Also treated are such active turbulent drag-reduction technique applications as those pertinent to MHD flow drag reduction, as well as drag reduction in liquid boundary layers by gas injection, drag reduction by means of polymers and surfactants, drag reduction by particle addition, viscous drag reduction via surface mass injection, and interactive wall-turbulence control.

ART AND SCIENCE OF IMAGE MAPS.

USGS Publications Warehouse

Kidwell, Richard D.; McSweeney, Joseph A.

1985-01-01

The visual image of reflected light is influenced by the complex interplay of human color discrimination, spatial relationships, surface texture, and the spectral purity of light, dyes, and pigments. Scientific theories of image processing may not always achieve acceptable results as the variety of factors, some psychological, are in part, unpredictable. Tonal relationships that affect digital image processing and the transfer functions used to transform from the continuous-tone source image to a lithographic image, may be interpreted for an insight of where art and science fuse in the production process. The application of art and science in image map production at the U. S. Geological Survey is illustrated and discussed.

Scattering by a boundary with complex structure.

PubMed

Naplekov, D M; Tur, A V; Yanovsky, V V

2013-04-01

The distribution of escape times is usually studied in open billiards theory. In this work, we will concentrate on another important question: The distribution of outgoing rays by exit directions, which we refer to as billiard's indicatrix. It can be obtained analytically and consists of two parts: the symmetric diffuse part and the asymmetric directed part. The criterion for the separation of the indicatrix into these two parts is established. The asymmetry of the directed part of the indicatrix and the influence of the billiard's borders on it is investigated. We also propose a method of the creation of a matte surface model using open billiards with a fully diffuse indicatrix.

Effect of rotating electric field on 3D complex (dusty) plasma

NASA Astrophysics Data System (ADS)

Wörner, L.; Nosenko, V.; Ivlev, A. V.; Zhdanov, S. K.; Thomas, H. M.; Morfill, G. E.; Kroll, M.; Schablinski, J.; Block, D.

2011-06-01

The effect of rotating electric field on 3D particle clusters suspended in rf plasma was studied experimentally. Spheroidal clusters were suspended inside a glass box mounted on the lower horizontal rf electrode, with gravity partially balanced by thermophoretic force. Clusters rotated in the horizontal plane, in response to rotating electric field that was created inside the box using conducting coating on its inner surfaces ("rotating wall" technique). Cluster rotation was always in the direction of applied field and had a shear in the vertical direction. The angular speed of rotation was 104-107 times lower than applied frequency. The experiment is compared to a recent theory.

Surface defects and chiral algebras

DOE PAGES

Córdova, Clay; Gaiotto, Davide; Shao, Shu-Heng

2017-05-26

Here, we investigate superconformal surface defects in four-dimensional N = 2 superconformal theories. Each such defect gives rise to a module of the associated chiral algebra and the surface defect Schur index is the character of this module. Various natural chiral algebra operations such as Drinfield-Sokolov reduction and spectral flow can be interpreted as constructions involving four-dimensional surface defects. We compute the index of these defects in the free hypermultiplet theory and Argyres-Douglas theories, using both infrared techniques involving BPS states, as well as renormalization group flows onto Higgs branches. We find perfect agreement with the predicted characters, in eachmore » case.« less

Surface defects and chiral algebras

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

Córdova, Clay; Gaiotto, Davide; Shao, Shu-Heng

Here, we investigate superconformal surface defects in four-dimensional N = 2 superconformal theories. Each such defect gives rise to a module of the associated chiral algebra and the surface defect Schur index is the character of this module. Various natural chiral algebra operations such as Drinfield-Sokolov reduction and spectral flow can be interpreted as constructions involving four-dimensional surface defects. We compute the index of these defects in the free hypermultiplet theory and Argyres-Douglas theories, using both infrared techniques involving BPS states, as well as renormalization group flows onto Higgs branches. We find perfect agreement with the predicted characters, in eachmore » case.« less