Van der Waals equation of state revisited: importance of the dispersion correction.

PubMed

de Visser, Sam P

2011-04-28

One of the most basic equations of state describing nonideal gases and liquids is the van der Waals equation of state, and as a consequence, it is generally taught in most first year undergraduate chemistry courses. In this work, we show that the constants a and b in the van der Waals equation of state are linearly proportional to the polarizability volume of the molecules in a gas or liquid. Using this information, a new thermodynamic one-parameter equation of state is derived that contains experimentally measurable variables and physics constants only. This is the first equation of state apart from the Ideal Gas Law that contains experimentally measurable variables and physics constants only, and as such, it may be a very useful and practical equation for the description of dilute gases and liquids. The modified van der Waals equation of state describes pV as the sum of repulsive and attractive intermolecular interaction energies that are represented by an exponential repulsion function between the electron clouds of the molecules and a London dispersion component, respectively. The newly derived equation of state is tested against experimental data for several gas and liquid examples, and the agreement is satisfactory. The description of the equation of state as a one-parameter function also has implications on other thermodynamic functions, such as critical parameters, virial coefficients, and isothermal compressibilities. Using our modified van der Waals equation of state, we show that all of these properties are a function of the molecular polarizability volume. Correlations of experimental data confirm the derived proportionalities.

van der Waals forces in density functional theory: a review of the vdW-DF method.

PubMed

Berland, Kristian; Cooper, Valentino R; Lee, Kyuho; Schröder, Elsebeth; Thonhauser, T; Hyldgaard, Per; Lundqvist, Bengt I

2015-06-01

A density functional theory (DFT) that accounts for van der Waals (vdW) interactions in condensed matter, materials physics, chemistry, and biology is reviewed. The insights that led to the construction of the Rutgers-Chalmers van der Waals density functional (vdW-DF) are presented with the aim of giving a historical perspective, while also emphasizing more recent efforts which have sought to improve its accuracy. In addition to technical details, we discuss a range of recent applications that illustrate the necessity of including dispersion interactions in DFT. This review highlights the value of the vdW-DF method as a general-purpose method, not only for dispersion bound systems, but also in densely packed systems where these types of interactions are traditionally thought to be negligible.

Effect of van der Waals forces on thermal conductance at the interface of a single-wall carbon nanotube array and silicon

NASA Astrophysics Data System (ADS)

Feng, Ya; Zhu, Jie; Tang, Dawei

2014-12-01

Molecular dynamics simulations are performed to evaluate the effect of van der Waals forces among single-wall carbon nanotubes (SWNTs) on the interfacial thermal conductance between a SWNT array and silicon substrate. First, samples of SWNTs vertically aligned on silicon substrate are simulated, where both the number and arrangement of SWNTs are varied. Results reveal that the interfacial thermal conductance of a SWNT array/Si with van der Waals forces present is higher than when they are absent. To better understand how van der Waals forces affect heat transfer through the interface between SWNTs and silicon, further constructs of one SWNT surrounded by different numbers of other ones are studied, and the results show that the interfacial thermal conductance of the central SWNT increases with increasing van der Waals forces. Through analysis of the covalent bonds and vibrational density of states at the interface, we find that heat transfer across the interface is enhanced with a greater number of chemical bonds and that improved vibrational coupling of the two sides of the interface results in higher interfacial thermal conductance. Van der Waals forces stimulate heat transfer at the interface.

van der Waals forces in density functional theory: a review of the vdW-DF method

DOE PAGES

Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho; ...

2015-05-15

We review a density functional theory (DFT) that accounts for van der Waals (vdW) interactions in condensed matter, materials physics, chemistry, and biology. The insights that led to the construction of the Rutgers–Chalmers van der Waals density functional (vdW-DF) are presented with the aim of giving a historical perspective, while also emphasizing more recent efforts which have sought to improve its accuracy. In addition to technical details, we discuss a range of recent applications that illustrate the necessity of including dispersion interactions in DFT. This review highlights the value of the vdW-DF method as a general-purpose method, not only formore » dispersion bound systems, but also in densely packed systems where these types of interactions are traditionally thought to be negligible.« less

Effects of van der Waals Force and Thermal Stresses on Pull-in Instability of Clamped Rectangular Microplates

PubMed Central

Batra, Romesh C.; Porfiri, Maurizio; Spinello, Davide

2008-01-01

We study the influence of von Kármán nonlinearity, van der Waals force, and thermal stresses on pull-in instability and small vibrations of electrostatically actuated microplates. We use the Galerkin method to develop a tractable reduced-order model for electrostatically actuated clamped rectangular microplates in the presence of van der Waals forces and thermal stresses. More specifically, we reduce the governing two-dimensional nonlinear transient boundary-value problem to a single nonlinear ordinary differential equation. For the static problem, the pull-in voltage and the pull-in displacement are determined by solving a pair of nonlinear algebraic equations. The fundamental vibration frequency corresponding to a deflected configuration of the microplate is determined by solving a linear algebraic equation. The proposed reduced-order model allows for accurately estimating the combined effects of van der Waals force and thermal stresses on the pull-in voltage and the pull-in deflection profile with an extremely limited computational effort. PMID:27879752

An Introduction to Dispersive Interactions

ERIC Educational Resources Information Center

Taddei, M. M.; Mendes, T. N. C.; Farina, C.

2010-01-01

Dispersive forces are a kind of van der Waals intermolecular force which could only be fully understood with the establishment of quantum mechanics and, in particular, of quantum electrodynamics. In this pedagogical paper, we introduce the subject in a more elementary approach, aiming at students with basic knowledge of quantum mechanics. We…

Direction-specific van der Waals attraction between rutile TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Xin; He, Yang; Sushko, Maria L.; Liu, Jia; Luo, Langli; De Yoreo, James J.; Mao, Scott X.; Wang, Chongmin; Rosso, Kevin M.

2017-04-01

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. We report measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation, the attraction is weak and shows no dependence on azimuthal alignment or surface hydration. At separations of approximately one hydration layer, the attraction is strongly dependent on azimuthal alignment and systematically decreases as intervening water density increases. Measured forces closely agree with predictions from Lifshitz theory and show that dispersion forces can generate a torque between particles interacting in solution and between grains in materials.

Controlling dispersion forces between small particles with artificially created random light fields

PubMed Central

Brügger, Georges; Froufe-Pérez, Luis S.; Scheffold, Frank; José Sáenz, Juan

2015-01-01

Appropriate combinations of laser beams can be used to trap and manipulate small particles with optical tweezers as well as to induce significant optical binding forces between particles. These interaction forces are usually strongly anisotropic depending on the interference landscape of the external fields. This is in contrast with the familiar isotropic, translationally invariant, van der Waals and, in general, Casimir–Lifshitz interactions between neutral bodies arising from random electromagnetic waves generated by equilibrium quantum and thermal fluctuations. Here we show, both theoretically and experimentally, that dispersion forces between small colloidal particles can also be induced and controlled using artificially created fluctuating light fields. Using optical tweezers as a gauge, we present experimental evidence for the predicted isotropic attractive interactions between dielectric microspheres induced by laser-generated, random light fields. These light-induced interactions open a path towards the control of translationally invariant interactions with tuneable strength and range in colloidal systems. PMID:26096622

Influence of van der Waals forces on increasing the strength and toughness in dynamic fracture of nanofibre networks: a peridynamic approach

NASA Astrophysics Data System (ADS)

Bobaru, F.

2007-07-01

The peridynamic method is used here to analyse the effect of van der Waals forces on the mechanical behaviour and strength and toughness properties of three-dimensional nanofibre networks under imposed stretch deformation. The peridynamic formulation allows for a natural inclusion of long-range forces (such as van der Waals forces) by considering all interactions as 'long-range'. We use van der Waals interactions only between different fibres and do not need to model individual atoms. Fracture is introduced at the microstructural (peridynamic bond) level for the microelastic type bonds, while van der Waals bonds can reform at any time. We conduct statistical studies to determine a certain volume element for which the network of randomly oriented fibres becomes quasi-isotropic and insensitive to statistical variations. This qualitative study shows that the presence of van der Waals interactions and of heterogeneities (sacrificial bonds) in the strength of the bonds at the crosslinks between fibres can help in increasing the strength and toughness of the nanofibre network. Two main mechanisms appear to control the deformation of nanofibre networks: fibre reorientation (caused by deformation and breakage) and fibre accretion (due to van der Waals interaction). Similarities to the observed toughness of polymer adhesive in the abalone shell composition are explained. The author would like to dedicate this work to the 60th anniversary of Professor Subrata Mukherjee.

Direction-specific van der Waals attraction between rutile TiO2 nanocrystals.

PubMed

Zhang, Xin; He, Yang; Sushko, Maria L; Liu, Jia; Luo, Langli; De Yoreo, James J; Mao, Scott X; Wang, Chongmin; Rosso, Kevin M

2017-04-28

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. We report measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation, the attraction is weak and shows no dependence on azimuthal alignment or surface hydration. At separations of approximately one hydration layer, the attraction is strongly dependent on azimuthal alignment and systematically decreases as intervening water density increases. Measured forces closely agree with predictions from Lifshitz theory and show that dispersion forces can generate a torque between particles interacting in solution and between grains in materials. Copyright © 2017, American Association for the Advancement of Science.

Direction-specific van der Waals attraction between rutile TiO 2 nanocrystals

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

Zhang, Xin; He, Yang; Sushko, Maria L.

Mutual lattice orientations dictate the types and magnitudes of forces between crystalline particles. When lattice polarizability is anisotropic, the van der Waals dispersion attraction can, in principle, contribute to this direction dependence. Here we report direct measurement of this attraction between rutile nanocrystals, as a function of their mutual orientation and surface hydration extent. At tens of nanometers of separation the attraction is weak and shows no dependence on azimuthal alignment nor surface hydration. At separations of approximately one hydration layer the attraction is strongly dependent on azimuthal alignment, and systematically decreases as intervening water density increases. Measured forces aremore » in close agreement with predictions from Lifshitz theory, and show that dispersion forces are capable of generating a torque between particles interacting in solution and between grains in materials.« less

Effects of van der Waals Force and Thermal Stresses on Pull-in Instability of Clamped Rectangular Microplates.

PubMed

Batra, Romesh C; Porfiri, Maurizio; Spinello, Davide

2008-02-15

We study the influence of von Karman nonlinearity, van der Waals force, and a athermal stresses on pull-in instability and small vibrations of electrostatically actuated mi-croplates. We use the Galerkin method to develop a tractable reduced-order model for elec-trostatically actuated clamped rectangular microplates in the presence of van der Waals forcesand thermal stresses. More specifically, we reduce the governing two-dimensional nonlineartransient boundary-value problem to a single nonlinear ordinary differential equation. For thestatic problem, the pull-in voltage and the pull-in displacement are determined by solving apair of nonlinear algebraic equations. The fundamental vibration frequency corresponding toa deflected configuration of the microplate is determined by solving a linear algebraic equa-tion. The proposed reduced-order model allows for accurately estimating the combined effectsof van der Waals force and thermal stresses on the pull-in voltage and the pull-in deflectionprofile with an extremely limited computational effort.

Combination Rules for Morse-Based van der Waals Force Fields.

PubMed

Yang, Li; Sun, Lei; Deng, Wei-Qiao

2018-02-15

In traditional force fields (FFs), van der Waals interactions have been usually described by the Lennard-Jones potentials. Conventional combination rules for the parameters of van der Waals (VDW) cross-termed interactions were developed for the Lennard-Jones based FFs. Here, we report that the Morse potentials were a better function to describe VDW interactions calculated by highly precise quantum mechanics methods. A new set of combination rules was developed for Morse-based FFs, in which VDW interactions were described by Morse potentials. The new set of combination rules has been verified by comparing the second virial coefficients of 11 noble gas mixtures. For all of the mixed binaries considered in this work, the combination rules work very well and are superior to all three other existing sets of combination rules reported in the literature. We further used the Morse-based FF by using the combination rules to simulate the adsorption isotherms of CH 4 at 298 K in four covalent-organic frameworks (COFs). The overall agreement is great, which supports the further applications of this new set of combination rules in more realistic simulation systems.

Non-additivity of molecule-surface van der Waals potentials from force measurements.

PubMed

Wagner, Christian; Fournier, Norman; Ruiz, Victor G; Li, Chen; Müllen, Klaus; Rohlfing, Michael; Tkatchenko, Alexandre; Temirov, Ruslan; Tautz, F Stefan

2014-11-26

Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction.

Analysis of dispersive interactions at polymer/TiAlN interfaces by means of dynamic force spectroscopy.

PubMed

Wiesing, M; de Los Arcos, T; Gebhard, M; Devi, A; Grundmeier, G

2017-12-20

The structural and electronic origins of the interactions between polycarbonate and sputter deposited TiAlN were analysed using a combined electron and force spectroscopic approach. Interaction forces were measured by means of dynamic force spectroscopy and the surface polarizability was analysed by X-ray photoelectron valence band spectroscopy. It could be shown that the adhesive interactions between polycarbonate and TiAlN are governed by van der Waals forces. Different surface cleansing and oxidizing treatments were investigated and the effect of the surface chemistry on the force interactions was analysed. Intense surface oxidation resulted in a decreased adhesion force by a factor of two due to the formation of a 2 nm thick Ti 0.21 Al 0.45 O surface oxide layer. The origin of the residual adhesion forces caused by the mixed Ti 0.21 Al 0.45 O surface oxide was clarified by considering the non-retarded Hamaker coefficients as calculated by Lifshitz theory, based on optical data from Reflection Electron Energy Loss Spectroscopy. This disclosed increased dispersion forces of Ti 0.21 Al 0.45 O due to the presence of Ti(iv) ions and related Ti 3d band optical transitions.

Optimizing Protein-Protein van der Waals Interactions for the AMBER ff9x/ff12 Force Field.

PubMed

Chapman, Dail E; Steck, Jonathan K; Nerenberg, Paul S

2014-01-14

The quality of molecular dynamics (MD) simulations relies heavily on the accuracy of the underlying force field. In recent years, considerable effort has been put into developing more accurate dihedral angle potentials for MD force fields, but relatively little work has focused on the nonbonded parameters, many of which are two decades old. In this work, we assess the accuracy of protein-protein van der Waals interactions in the AMBER ff9x/ff12 force field. Across a test set of 44 neat organic liquids containing the moieties present in proteins, we find root-mean-square (RMS) errors of 1.26 kcal/mol in enthalpy of vaporization and 0.36 g/cm(3) in liquid densities. We then optimize the van der Waals radii and well depths for all of the relevant atom types using these observables, which lowers the RMS errors in enthalpy of vaporization and liquid density of our validation set to 0.59 kcal/mol (53% reduction) and 0.019 g/cm(3) (46% reduction), respectively. Limitations in our parameter optimization were evident for certain atom types, however, and we discuss the implications of these observations for future force field development.

Hydrogen bonding and interparticle forces in platelet alpha-Al2O3 dispersions: yield stress and zeta potential.

PubMed

Khoo, Kay-Sen; Teh, E-Jen; Leong, Yee-Kwong; Ong, Ban Choon

2009-04-09

Adsorbed phosphate on smooth platelet alpha-Al2O3 particles at saturation surface coverage gives rise to strong interparticle attractive forces in dispersion. The maximum yield stress at the point of zero charge was increased by 2-fold. This was attributed to a high density of intermolecular hydrogen bonding between the adsorbed phosphate layers of the interacting particles. Adsorbed citrate at saturation surface coverage, however, reduced the maximum yield stress by 50%. It adsorbed to form a very effective steric barrier as intramolecular hydrogen bonding between -OH and the free terminal carboxylic group prevented strong interactions with other adsorbed citrate molecules residing on the second interacting particle. This steric barrier kept the interacting platelet particles further apart, thereby weakening the van der Waals attraction. The platelet alpha-Al2O3 dispersions were flocculated at all pH level. These dispersions displayed a maximum yield stress at the point of zero zeta potential at the pH approximately 8.0. They also obeyed the yield stress-DLVO force model as characterized by a linear decrease in the yield stress with the square of the zeta potential.

A Smart Magnetically Active Nanovehicle for on-Demand Targeted Drug Delivery: Where van der Waals Force Balances the Magnetic Interaction.

PubMed

Panja, Sudipta; Maji, Somnath; Maiti, Tapas K; Chattopadhyay, Santanu

2015-11-04

The magnetic field is a promising external stimulus for controlled and targeted delivery of therapeutic agents. Here, we focused on the preparation of a novel magnetically active polymeric micelle (MAPM) for magnetically targeted controlled drug delivery. To accomplish this, a number of superparamagnetic as well as biocompatible hybrid micelles were prepared by grafting four armed pentaerythretol poly(ε-caprolactone) (PE-PCL) onto the surface of Fe3O4 magnetic nanoparticles (MNPs) of two different ranges of size (∼5 nm and ∼15 nm). PE-PCL (four-armed) was synthesized by ring-opening polymerization, and it has been subsequently grafted onto the surface of modified MNP through urethane (-NHCO-) linkage. Polymer-immobilized MNP (5 and 15 nm) showed peculiar dispersion behavior. One displayed uniform dispersion of MNP (5 nm), while the other (15 nm) revealed associated structure. This type of size dependent contradictory dispersion behavior was realized by taking the van der Waals force as well as magnetic dipole-dipole force into consideration. The uniformly dispersed polymer immobilized MNP (5 nm) was used for the preparation of MAPM. The hydrodynamic size and bulk morphology of MAPM were studied by dynamic light scattering and high-resolution transmission electron microscopy. The anticancer drug (DOX) was encapsulated into the MAPM. The magnetic field triggers cell uptake of MAPM micelles preferentially toward targeted cells compare to untargeted ones. The cell viabilities of MAMP, DOX-encapsulated MAPM, and free DOX were studied against HeLa cell by MTT assay. In vitro release profile displayed about 51.5% release of DOX from MAPM (just after 1 h) under the influence of high frequency alternating magnetic field (HFAMF; prepared in-house device). The DOX release rate has also been tailored by on-demand application of HFAMF.

van der Waals torque and force between anisotropic topological insulator slabs

NASA Astrophysics Data System (ADS)

Lu, Bing-Sui

2018-01-01

We investigate the character of the van der Waals (vdW) torque and force between two coplanar and dielectrically anisotropic topological insulator (TI) slabs separated by a vacuum gap in the nonretardation regime, where the optic axes of the slabs are each perpendicular to the normal direction to the slab-gap interface and also generally differently oriented from each other. We find that in addition to the magnetoelectric coupling strength, the anisotropy can also influence the sign of the vdW force, viz., a repulsive vdW force can become attractive if the anisotropy is increased sufficiently. In addition, the vdW force oscillates as a function of the angular difference between the optic axes of the TI slabs, being most repulsive/least attractive (least repulsive/most attractive) for angular differences that are integer (half-integer) multiples of π . Our third finding is that the vdW torque for TI slabs is generally weaker than that for ordinary dielectric slabs. Our work provides an instance in which the vector potential appears in a calculation of the vdW interaction for which the limit is nonretarded or static.

van der Waals three-body force shell model (VTSM) for the lattice dynamical studies of thallous bromide

NASA Astrophysics Data System (ADS)

Tiwari, Sarvesh K.; Pandey, L. K.; Shukla, Lal Ji; Upadhyaya, K. S.

2009-12-01

The van der Waals three-body force shell model (VTSM) has been developed by modifying the three-body force shell model (TSM) for the lattice dynamics of ionic crystals with cesium chloride (CsCl) structure. This new model incorporates van der Waals interactions along with long-range Coulomb interactions, three-body interactions and short-range second neighbour interactions in the framework of a rigid shell model (RSM). In the present paper, VTSM has been used to study the lattice dynamics of thallous bromide (TlBr), from which adequacy of VTSM has been established. A comparative study of the dynamical behaviour of TlBr has also been done between the present model and TSM, the model over which modification has been made to obtain the present model VTSM. Good agreement has been observed between the theoretical and experimental results, which give confidence that it is an appropriate model for the complete description of ionic crystals with CsCl structure.

Particles with nonlinear electric response: Suppressing van der Waals forces by an external field.

PubMed

Soo, Heino; Dean, David S; Krüger, Matthias

2017-01-01

We study the classical thermal component of Casimir, or van der Waals, forces between point particles with highly anharmonic dipole Hamiltonians when they are subjected to an external electric field. Using a model for which the individual dipole moments saturate in a strong field (a model that mimics the charges in a neutral, perfectly conducting sphere), we find that the resulting Casimir force depends strongly on the strength of the field, as demonstrated by analytical results. For a certain angle between the external field and center-to-center axis, the fluctuation force can be tuned and suppressed to arbitrarily small values. We compare the forces between these particles with those between particles with harmonic Hamiltonians and also provide a simple formula for asymptotically large external fields, which we expect to be generally valid for the case of saturating dipole moments.

Application of Diffusion Monte Carlo to Materials Dominated by van der Waals Interactions

DOE PAGES

Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; ...

2014-06-12

Van der Waals forces are notoriously difficult to account for from first principles. We perform extensive calculation to assess the usefulness and validity of diffusion quantum Monte Carlo when applied to van der Waals forces. We present results for noble gas solids and clusters - archetypical van der Waals dominated assemblies, as well as a relevant pi-pi stacking supramolecular complex: DNA + intercalating anti-cancer drug Ellipticine.

Dispersion Forces and the Molecular Origin of Internal Friction in Protein.

PubMed

Sashi, Pulikallu; Ramakrishna, Dasari; Bhuyan, Abani K

2016-08-23

Internal friction in macromolecules is one of the curious phenomena that control conformational changes and reaction rates. It is held here that dispersion interactions and London-van der Waals forces between nonbonded atoms are major contributors to internal friction. To demonstrate this, the flipping motion of aromatic rings of F10 and Y97 amino acid residues of cytochrome c has been studied in glycerol/water mixtures by cross relaxation-suppressed exchange nuclear magnetic resonance spectroscopy. The ring-flip rate is highly overdamped by glycerol, but this is not due to the effect of protein-solvent interactions on the Brownian dynamics of the protein, because glycerol cannot penetrate into the protein to slow the internal collective motions. Sound velocity in the protein under matching solvent conditions shows that glycerol exerts its effect by rather smothering the protein interior to produce reduced molecular compressibility and root-mean-square volume fluctuation (δVRMS), implying an increased number of dispersion interactions of nonbonded atoms. Hence, δVRMS can be used as a proxy for internal friction. By using the ansatz that internal friction is related to nonbonded interactions by the equation f(n) = f0 + f1n + f2n(2) + ..., where the variable n is the extent of nonbonded interactions with fi coefficients, the barrier to aromatic ring rotation is found to be flat. Also interesting is the appearance of a turnover region in the δVRMS dependence of the ring-flip rate, suggesting anomalous internal diffusion. We conclude that cohesive forces among nonbonded atoms are major contributors to the molecular origin of internal friction.

van der Waals torque

NASA Astrophysics Data System (ADS)

Esquivel-Sirvent, Raul; Schatz, George

2014-03-01

The theory of generalized van der Waals forces by Lifshtz when applied to optically anisotropic media predicts the existence of a torque. In this work we present a theoretical calculation of the van der Waals torque for two systems. First we consider two isotropic parallel plates where the anisotropy is induced using an external magnetic field. The anisotropy will in turn induce a torque. As a case study we consider III-IV semiconductors such as InSb that can support magneto plasmons. The calculations of the torque are done in the Voigt configuration, that occurs when the magnetic field is parallel to the surface of the slabs. The change in the dielectric function as the magnetic field increases has the effect of decreasing the van der Waals force and increasing the torque. Thus, the external magnetic field is used to tune both the force and torque. The second example we present is the use of the torque in the non retarded regime to align arrays of nano particle slabs. The torque is calculated within Barash and Ginzburg formalism in the nonretarded limit, and is quantified by the introduction of a Hamaker torque constant. Calculations are conducted between anisotropic slabs of materials including BaTiO3 and arrays of Ag nano particles. Depending on the shape and arrangement of the Ag nano particles the effective dielectric function of the array can be tuned as to make it more or less anisotropic. We show how this torque can be used in self assembly of arrays of nano particles. ref. R. Esquivel-Sirvent, G. C. Schatz, Phys. Chem C, 117, 5492 (2013). partial support from DGAPA-UNAM.

Enhanced Chiral Discriminatory van der Waals Interactions Mediated by Chiral Surfaces

NASA Astrophysics Data System (ADS)

Barcellona, Pablo; Safari, Hassan; Salam, A.; Buhmann, Stefan Yoshi

2017-05-01

We predict a discriminatory interaction between a chiral molecule and an achiral molecule which is mediated by a chiral body. To achieve this, we generalize the van der Waals interaction potential between two ground-state molecules with electric, magnetic, and chiral response to nontrivial environments. The force is evaluated using second-order perturbation theory with an effective Hamiltonian. Chiral media enhance or reduce the free interaction via many-body interactions, making it possible to measure the chiral contributions to the van der Waals force with current technology. The van der Waals interaction is discriminatory with respect to enantiomers of different handedness and could be used to separate enantiomers. We also suggest a specific geometric configuration where the electric contribution to the van der Waals interaction is zero, making the chiral component the dominant effect.

Effect of van der Waals interactions on the stability of SiC polytypes

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

Kawanishi, Sakiko, E-mail: s-kawa@tagen.tohoku.ac.jp; Mizoguchi, Teruyasu

2016-05-07

Density functional theory calculations with a correction of the long-range dispersion force, namely, the van der Waals (vdW) force, are performed for SiC polytypes. The lattice parameters are in good agreement with those obtained from the experiments. Furthermore, the stability of the polytypes in the experiments, which show 3C-SiC as the most stable, is reproduced by the present calculations. The effects of the vdW force on the electronic structure and the stability of polytypes are discussed. We observe that the vdW interaction is more sensitive to the cubic site than the hexagonal site. Thus, the influence of the vdW forcemore » increases with decreasing the hexagonality of the polytype, which results in the confirmation that the most stable polytype is 3C-SiC.« less

Ab-initio adsorption study of chitosan on functionalized graphene: critical role of van der Waals interactions.

PubMed

Rahman, R; Mazumdar, D

2012-03-01

We investigate the adsorption process of an organic biomolecule (chitosan) on epoxy-functionalized graphene using ab-initio density functional methods incorporating van-der-waals (vdW) interactions. The role of London dispersion force on the cohesive energy and conformal preference of the molecule is quantitatively elucidated. Functionalizing graphene with epoxy leads to weak hydrogen-bond interactions with chitosan. Binding energy values increase by over an order of magnitude after including vdW corrections, implying that dispersive interactions dominate the physisorption process. Conformal study show binding upto 30 kcal/mol when the molecule is oriented with the hydroxyl group approaching the functionalized graphene. Our study advances the promise of functionalized graphene for a variety of applications.

Effect of van der Waals interactions on the structural and binding properties of GaSe

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

Sarkisov, Sergey Y., E-mail: sarkisov@mail.tsu.ru; Kosobutsky, Alexey V., E-mail: kosobutsky@kemsu.ru; Kemerovo State University, Krasnaya 6, 650043 Kemerovo

The influence of van der Waals interactions on the lattice parameters, band structure, elastic moduli and binding energy of layered GaSe compound has been studied using projector-augmented wave method within density functional theory. We employed the conventional local/semilocal exchange-correlation functionals and recently developed van der Waals functionals which are able to describe dispersion forces. It is found that application of van der Waals density functionals allows to substantially increase the accuracy of calculations of the lattice constants a and c and interlayer distance in GaSe at ambient conditions and under hydrostatic pressure. The pressure dependences of the a-parameter, Ga–Ga, Ga–Semore » bond lengths and Ga–Ga–Se bond angle are characterized by a relatively low curvature, while c(p) has a distinct downward bowing due to nonlinear shrinking of the interlayer spacing. From the calculated binding energy curves we deduce the interlayer binding energy of GaSe, which is found to be in the range 0.172–0.197 eV/layer (14.2–16.2 meV/Å{sup 2}). - Highlights: • Effects of van der Waals interactions are analyzed using advanced density functionals. • Calculations with vdW-corrected functionals closely agree with experiment. • Interlayer binding energy of GaSe is estimated to be 14.2–16.2 meV/Å{sup 2}.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

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

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong

2017-07-05

Oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type, andmore » electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

DOE PAGES

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong; ...

2017-07-05

Here, oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type,more » and electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

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

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong

Oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type, andmore » electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

Assessing photocatalytic power of g-C3N4 for solar fuel production: A first-principles study involving quasi-particle theory and dispersive forces.

PubMed

Osorio-Guillén, J M; Espinosa-García, W F; Moyses Araujo, C

2015-09-07

First-principles quasi-particle theory has been employed to assess catalytic power of graphitic carbon nitride, g-C3N4, for solar fuel production. A comparative study between g-h-triazine and g-h-heptazine has been carried out taking also into account van der Waals dispersive forces. The band edge potentials have been calculated using a recently developed approach where quasi-particle effects are taken into account through the GW approximation. First, it was found that the description of ground state properties such as cohesive and surface formation energies requires the proper treatment of dispersive interaction. Furthermore, through the analysis of calculated band-edge potentials, it is shown that g-h-triazine has high reductive power reaching the potential to reduce CO2 to formic acid, coplanar g-h-heptazine displays the highest thermodynamics force toward H2O/O2 oxidation reaction, and corrugated g-h-heptazine exhibits a good capacity for both reactions. This rigorous theoretical study shows a route to further improve the catalytic performance of g-C3N4.

A bi-stable nanoelectromechanical non-volatile memory based on van der Waals force

NASA Astrophysics Data System (ADS)

Soon, Bo Woon; Jiaqiang Ng, Eldwin; Qian, You; Singh, Navab; Julius Tsai, Minglin; Lee, Chengkuo

2013-07-01

By using complementary-metal-oxide-semiconductor processes, a silicon based bi-stable nanoelectromechanical non-volatile memory is fabricated and characterized. The main feature of this device is an 80 nm wide and 3 μm high silicon nanofin (SiNF) of a high aspect ratio (1:35). The switching mechanism is realized by electrostatic actuation between two lateral electrodes, i.e., terminals. Bi-stable hysteresis behavior is demonstrated when the SiNF maintains its contact to one of the two terminals by leveraging on van der Waals force even after voltage bias is turned off. The compelling results indicate that this design is promising for realization of high density non-volatile memory application due to its nano-scale footprint and zero on-hold power consumption.

Van der Waals Interactions Involving Proteins

NASA Technical Reports Server (NTRS)

Roth, Charles M.; Neal, Brian L.; Lenhoff, Abraham M.

1996-01-01

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.

Van der Waals interactions and the limits of isolated atom models at interfaces

PubMed Central

Kawai, Shigeki; Foster, Adam S.; Björkman, Torbjörn; Nowakowska, Sylwia; Björk, Jonas; Canova, Filippo Federici; Gade, Lutz H.; Jung, Thomas A.; Meyer, Ernst

2016-01-01

Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar–Xe, Kr–Xe and Xe–Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal–organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems. PMID:27174162

Theory of coherent van der Waals matter.

PubMed

Kulić, Igor M; Kulić, Miodrag L

2014-12-01

We explain in depth the previously proposed theory of the coherent van der Waals (cvdW) interaction, the counterpart of van der Waals (vdW) force, emerging in spatially coherently fluctuating electromagnetic fields. We show that cvdW driven matter is dominated by many-body interactions, which are significantly stronger than those found in standard van der Waals (vdW) systems. Remarkably, the leading two- and three-body interactions are of the same order with respect to the distance (∝R(-6)), in contrast to the usually weak vdW three-body effects (∝R(-9)). From a microscopic theory we show that the anisotropic cvdW many-body interactions drive the formation of low-dimensional structures such as chains, membranes, and vesicles with very unusual, nonlocal properties. In particular, cvdW chains display a logarithmically growing stiffness with the chain length, while cvdW membranes have a bending modulus growing linearly with their size. We argue that the cvdW anisotropic many-body forces cause local cohesion but also a negative effective "surface tension." We conclude by deriving the equation of state for cvdW materials and propose experiments to test the theory, in particular the unusual three-body nature of cvdW.

Theory of coherent van der Waals matter

NASA Astrophysics Data System (ADS)

Kulić, Igor M.; Kulić, Miodrag L.

2014-12-01

We explain in depth the previously proposed theory of the coherent van der Waals (cvdW) interaction, the counterpart of van der Waals (vdW) force, emerging in spatially coherently fluctuating electromagnetic fields. We show that cvdW driven matter is dominated by many-body interactions, which are significantly stronger than those found in standard van der Waals (vdW) systems. Remarkably, the leading two- and three-body interactions are of the same order with respect to the distance (∝R-6) , in contrast to the usually weak vdW three-body effects (∝R-9 ). From a microscopic theory we show that the anisotropic cvdW many-body interactions drive the formation of low-dimensional structures such as chains, membranes, and vesicles with very unusual, nonlocal properties. In particular, cvdW chains display a logarithmically growing stiffness with the chain length, while cvdW membranes have a bending modulus growing linearly with their size. We argue that the cvdW anisotropic many-body forces cause local cohesion but also a negative effective "surface tension." We conclude by deriving the equation of state for cvdW materials and propose experiments to test the theory, in particular the unusual three-body nature of cvdW.

A mean-density model of ionic surfactants for the dispersion of carbon nanotubes in aqueous solutions

NASA Astrophysics Data System (ADS)

Joung, Young Soo

2018-05-01

We propose a new analytical model of ionic surfactants used for the dispersion of carbon nanotubes (CNTs) in aqueous solutions. Although ionic surfactants are commonly used to facilitate the dispersion of CNTs in aqueous solutions, understanding the dispersion process is challenging and time-consuming owing to its complexity and nonlinearity. In this work, we develop a mean-density model of ionic surfactants to simplify the calculation of interaction forces between CNTs stabilized by ionic surfactants. Using this model, we can evaluate various interaction forces between the CNTs and ionic surfactants under different conditions. The dispersion mechanism is investigated by estimating the potential of mean force (PMF) as a function of van der Waals forces, electrostatic forces, interfacial tension, and osmotic pressure. To verify the proposed model, we compare the PMFs derived using our method with those derived from molecular dynamics simulations using comparable CNTs and ionic surfactants. Notably, for stable dispersions, the osmotic pressure and interfacial energy are important for long-range and short-range interactions, respectively, in comparison with the effect of electrostatic forces. Our model effectively prescribes specific surfactants and their concentrations to achieve stable aqueous suspensions of CNTs.

Dynamic forces on agglomerated particles caused by high-intensity ultrasound.

PubMed

Knoop, Claas; Fritsching, Udo

2014-03-01

In this paper the acoustic forces on particles and agglomerates caused by high-intensity ultrasound in gaseous atmosphere are derived by means of computational fluid dynamics (CFD). Sound induced forces cause an oscillating stress scenario where the primary particles of an agglomerate are alternatingly pressed together and torn apart with the frequency of the applied wave. A comparison of the calculated acoustic forces with respect to the inter particle adhesion forces from Van-der-Waals and liquid bridge interactions reveals that the separation forces may reach the same order of magnitude for 80 μm sized SiO2-particles. Hence, with finite probability acoustically agitated gases may de-agglomerate/disperse solid agglomerate structures. This effect is confirmed by dispersion experiments in an acoustic particle levitation setup. Copyright © 2013 Elsevier B.V. All rights reserved.

Effective field theories for van der Waals interactions

NASA Astrophysics Data System (ADS)

Brambilla, Nora; Shtabovenko, Vladyslav; Tarrús Castellà, Jaume; Vairo, Antonio

2017-06-01

Van der Waals interactions between two neutral but polarizable systems at a separation R much larger than the typical size of the systems are at the core of a broad sweep of contemporary problems in settings ranging from atomic, molecular and condensed matter physics to strong interactions and gravity. In this paper, we reexamine the dispersive van der Waals interactions between two hydrogen atoms. The novelty of the analysis resides in the usage of nonrelativistic effective field theories of quantum electrodynamics. In this framework, the van der Waals potential acquires the meaning of a matching coefficient in an effective field theory, dubbed van der Waals effective field theory, suited to describe the low-energy dynamics of an atom pair. It may be computed systematically as a series in R times some typical atomic scale and in the fine-structure constant α . The van der Waals potential gets short-range contributions and radiative corrections, which we compute in dimensional regularization and renormalize here for the first time. Results are given in d space-time dimensions. One can distinguish among different regimes depending on the relative size between 1 /R and the typical atomic bound-state energy, which is of order m α2. Each regime is characterized by a specific hierarchy of scales and a corresponding tower of effective field theories. The short-distance regime is characterized by 1 /R ≫m α2 and the leading-order van der Waals potential is the London potential. We also compute next-to-next-to-next-to-leading-order corrections. In the long-distance regime we have 1 /R ≪m α2. In this regime, the van der Waals potential contains contact terms, which are parametrically larger than the Casimir-Polder potential that describes the potential at large distances. In the effective field theory, the Casimir-Polder potential counts as a next-to-next-to-next-to-leading-order effect. In the intermediate-distance regime, 1 /R ˜m α2, a significantly more complex

Grippers Based on Opposing Van Der Waals Adhesive Pads

NASA Technical Reports Server (NTRS)

Parness, Aaron (Inventor); Kennedy, Brett A. (Inventor); Heverly, Matthew C (Inventor); Cutkosky, Mark R. (Inventor); Hawkes, Elliot Wright (Inventor)

2016-01-01

Novel gripping structures based on van der Waals adhesive forces are disclosed. Pads covered with fibers can be activated in pairs by opposite forces, thereby enabling control of the adhesive force in an ON or OFF state. Pads can be used in groups, each comprising a group of opposite pads. The adhesive structures enable anchoring forces that can resist adverse forces from different directions. The adhesive structures can be used to enable the operation of robots on surfaces of space vehicles.

Thin Film Evaporation Model with Retarded Van Der Waals Interaction (Postprint)

DTIC Science & Technology

2013-11-01

Waals interaction. The retarded van der Waals interaction is derived from Hamaker theory, the summation of retarded pair potentials for all molecules...interaction is derived from Hamaker theory, the summation of retarded pair potentials for all molecules for a given geometry. When combined, the governing...interaction force is the negative derivative with respect to distance of the interaction energy. The method due to Hamaker essentially sums all pair

Tuning group-velocity dispersion by optical force.

PubMed

Jiang, Wei C; Lin, Qiang

2013-07-15

We propose an optomechanical approach for dispersion dynamic tuning and microengineering by taking advantage of the optical force in nano-optomechanical structures. Simulations of a suspended coupled silicon waveguide show that the zero-dispersion wavelength can be tuned by 40 nm by an optical pump power of 3 mW. Our approach exhibits great potential for broad applications in dispersion-sensitive processes, which not only offers a new root toward versatile tunable nonlinear photonics but may also open up a great avenue toward a new regime of nonlinear dynamics coupling between nonlinear optical and optomechanical effects.

EDITORIAL: Van der Waals interactions in advanced materials, in memory of David C Langreth Van der Waals interactions in advanced materials, in memory of David C Langreth

NASA Astrophysics Data System (ADS)

Hyldgaard, Per; Rahman, Talat S.

2012-10-01

The past decade has seen a dramatic rise in interest in exploring the role that van der Waals (vdW) or dispersion forces play in materials and in material behavior. Part of this stems from the obvious fact that vdW interactions (and other weak forces, such as Casimir) underpin molecular recognition, i.e., nature's approach to search for a match between genes and anti-genes and hence enable biological function. Less obvious is the recognition that vdW interactions affect a multitude of properties of a vast variety of materials in general, some of which also have strong technological applications. While for two atom- or orbital-sized material fragments the dispersive contributions to binding are small compared to those from the better known forms (ionic, covalent, metallic), those between sparse materials (spread over extended areas) can be of paramount importance. For example, an understanding of binding in graphite cannot arise solely from a study of the graphene layers individually, but also requires insight from inter-sheet graphene vdW bonding. It is the extended-area vdW bonding that provides sufficient cohesion to make graphite a robust, naturally occurring material. In fact, it is the vdW-bonded graphite, and not the all-covalently bonded diamond, that is the preferred form of pure carbon under ambient conditions. Also important is the understanding that vdW attraction can attain a dramatic relevance even if the material fragments, the building blocks, are not necessarily parallel from the outset or smooth when viewed in isolation (such as a graphene sheet or a carbon nanotube). This can happen if the building blocks have some softness and flexibility and allow an internal relative alignment to emerge. The vdW forces can then cause increasingly larger parts of the interacting fragments to line up at sub-nanometer separations and thus beget more areas with a sizable vdW bonding contribution. The gecko can scale a wall because it can bring its flexible hairs

Assessing photocatalytic power of g-C{sub 3}N{sub 4} for solar fuel production: A first-principles study involving quasi-particle theory and dispersive forces

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

Osorio-Guillén, J. M., E-mail: mario.osorio@udea.edu.co; Espinosa-García, W. F.; Grupo de Investigación en Modelamiento y Simulación Computacional, Facultad de Ingenierías, Universidad de San Buenaventura Seccional Medellín, Carrera 56C No 51-110, Medellín

2015-09-07

First-principles quasi-particle theory has been employed to assess catalytic power of graphitic carbon nitride, g-C{sub 3}N{sub 4}, for solar fuel production. A comparative study between g-h-triazine and g-h-heptazine has been carried out taking also into account van der Waals dispersive forces. The band edge potentials have been calculated using a recently developed approach where quasi-particle effects are taken into account through the GW approximation. First, it was found that the description of ground state properties such as cohesive and surface formation energies requires the proper treatment of dispersive interaction. Furthermore, through the analysis of calculated band-edge potentials, it is shownmore » that g-h-triazine has high reductive power reaching the potential to reduce CO{sub 2} to formic acid, coplanar g-h-heptazine displays the highest thermodynamics force toward H{sub 2}O/O{sub 2} oxidation reaction, and corrugated g-h-heptazine exhibits a good capacity for both reactions. This rigorous theoretical study shows a route to further improve the catalytic performance of g-C{sub 3}N{sub 4}.« less

Evaluating Force-Field London Dispersion Coefficients Using the Exchange-Hole Dipole Moment Model.

PubMed

Mohebifar, Mohamad; Johnson, Erin R; Rowley, Christopher N

2017-12-12

London dispersion interactions play an integral role in materials science and biophysics. Force fields for atomistic molecular simulations typically represent dispersion interactions by the 12-6 Lennard-Jones potential using empirically determined parameters. These parameters are generally underdetermined, and there is no straightforward way to test if they are physically realistic. Alternatively, the exchange-hole dipole moment (XDM) model from density-functional theory predicts atomic and molecular London dispersion coefficients from first principles, providing an innovative strategy to validate the dispersion terms of molecular-mechanical force fields. In this work, the XDM model was used to obtain the London dispersion coefficients of 88 organic molecules relevant to biochemistry and pharmaceutical chemistry and the values compared with those derived from the Lennard-Jones parameters of the CGenFF, GAFF, OPLS, and Drude polarizable force fields. The molecular dispersion coefficients for the CGenFF, GAFF, and OPLS models are systematically higher than the XDM-calculated values by a factor of roughly 1.5, likely due to neglect of higher order dispersion terms and premature truncation of the dispersion-energy summation. The XDM dispersion coefficients span a large range for some molecular-mechanical atom types, suggesting an unrecognized source of error in force-field models, which assume that atoms of the same type have the same dispersion interactions. Agreement with the XDM dispersion coefficients is even poorer for the Drude polarizable force field. Popular water models were also examined, and TIP3P was found to have dispersion coefficients similar to the experimental and XDM references, although other models employ anomalously high values. Finally, XDM-derived dispersion coefficients were used to parametrize molecular-mechanical force fields for five liquids-benzene, toluene, cyclohexane, n-pentane, and n-hexane-which resulted in improved accuracy in the

Investigating the Role of Ferromagnetic Materials on the Casimir Force & Investigation of the Van Der Waals/Casimir Force with Graphene

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

Mohideen, Umar

2015-04-14

Duration of award was from 4/15/10-4/14/15. In this grant period our contributions to the field of VdW/Casimir forces are 24 refereed publications in journals such as Physical Review Letters (4) [1-4], Physical Review B (10) [5-14], Physical Review D (2) [15,16], Applied Physics Letters (1) [17], Review of Scientific Instruments (1) [18] and the International Journal of Modern Physics A (5) [19-23] and B(1) (invited review article [24]). We presented 2 plenary conference talks, 3 lectures at the Pan American School on Frontiers in Casimir Physics, 2 conferences, 1 colloquium and 11 APS talks. If publications are restricted to onlymore » those with direct connection to the aims proposed in the prior grant period, then it will be a total of 12: Physical Review Letters (3) [2-4], Physical Review B (6) [6-8,12,13,25], Review of Scientific Instruments (1) [18], International Journal of Modern Physics A (1) [19] and B(1) [169]. A brief aggregated description of the directly connected accomplishments is below. The following topics are detailed: dispersion force measurements with graphene, dispersion force from ferromagnetic metals, conclusion on role of electrostatic patches, UV radiation induced modification of the Casimir force, low temperature measurement of the Casimir force, and Casimir force from thin fluctuating membranes.« less

The effect of solid interaction forces on pneumatic handling of sorbent powders

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

Lee, R.J.; Fan, L.S.

1993-06-01

This study shows that a comparison of powder characteristics--particle morphologies, particle size distributions, and static dielectric and Hamaker constants--can be used to interpret differences in dispersion and transport behavior between powders. These differences are attributed to the relative values of the solid-solid interaction forces experience by each powder in the process. The static dielectric constants of the powders are used as the material properties related to the relative magnitudes of the electrostatic forces. Similarly, the Hamaker constants are the material properties used to indicate the relative magnitudes of the van der Waals forces. The effects of differences in particle morphologiesmore » and size distributions are used to evaluate the dispersibility and efficiency of transport of four calcium-based powder materials used as sorbents in flue-gas desulfurization.« less

van der Waals-type forces in spontaneously broken supersymmetries

NASA Astrophysics Data System (ADS)

Radescu, E. E.

1983-03-01

In spontaneously broken rigid supersymmetry, Goldstone-fermion pair exchange should lead to a universal interaction between massive bodies uniquely fixed by the existing low-energy theorem. The resulting van der Waals-type potential is shown to be V(r)=-Mmπ-3F-4r-7+O(r-8), where M and m are the masses of the interacting bodies while F is the scale of the breaking. The change in the situation when the supersymmetry is promoted to a local symmetry is briefly discussed.

Signatures of van der Waals binding: A coupling-constant scaling analysis

NASA Astrophysics Data System (ADS)

Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per

2018-02-01

The van der Waals (vdW) density functional (vdW-DF) method [Rep. Prog. Phys. 78, 066501 (2015), 10.1088/0034-4885/78/6/066501] describes dispersion or vdW binding by tracking the effects of an electrodynamic coupling among pairs of electrons and their associated exchange-correlation holes. This is done in a nonlocal-correlation energy term Ecnl, which permits density functional theory calculation in the Kohn-Sham scheme. However, to map the nature of vdW forces in a fully interacting materials system, it is necessary to also account for associated kinetic-correlation energy effects. Here, we present a coupling-constant scaling analysis, which permits us to compute the kinetic-correlation energy Tcnl that is specific to the vdW-DF account of nonlocal correlations. We thus provide a more complete spatially resolved analysis of the electrodynamical-coupling nature of nonlocal-correlation binding, including vdW attraction, in both covalently and noncovalently bonded systems. We find that kinetic-correlation energy effects play a significant role in the account of vdW or dispersion interactions among molecules. Furthermore, our mapping shows that the total nonlocal-correlation binding is concentrated to pockets in the sparse electron distribution located between the material fragments.

Interface bonding in silicon oxide nanocontacts: interaction potentials and force measurements.

PubMed

Wierez-Kien, M; Craciun, A D; Pinon, A V; Roux, S Le; Gallani, J L; Rastei, M V

2018-04-01

The interface bonding between two silicon-oxide nanoscale surfaces has been studied as a function of atomic nature and size of contacting asperities. The binding forces obtained using various interaction potentials are compared with experimental force curves measured in vacuum with an atomic force microscope. In the limit of small nanocontacts (typically <10 3 nm 2 ) measured with sensitive probes the bonding is found to be influenced by thermal-induced fluctuations. Using interface interactions described by Morse, embedded atom model, or Lennard-Jones potential within reaction rate theory, we investigate three bonding types of covalent and van der Waals nature. The comparison of numerical and experimental results reveals that a Lennard-Jones-like potential originating from van der Waals interactions captures the binding characteristics of dry silicon oxide nanocontacts, and likely of other nanoscale materials adsorbed on silicon oxide surfaces. The analyses reveal the importance of the dispersive surface energy and of the effective contact area which is altered by stretching speeds. The mean unbinding force is found to decrease as the contact spends time in the attractive regime. This contact weakening is featured by a negative aging coefficient which broadens and shifts the thermal-induced force distribution at low stretching speeds.

Interface bonding in silicon oxide nanocontacts: interaction potentials and force measurements

NASA Astrophysics Data System (ADS)

Wierez-Kien, M.; Craciun, A. D.; Pinon, A. V.; Le Roux, S.; Gallani, J. L.; Rastei, M. V.

2018-04-01

The interface bonding between two silicon-oxide nanoscale surfaces has been studied as a function of atomic nature and size of contacting asperities. The binding forces obtained using various interaction potentials are compared with experimental force curves measured in vacuum with an atomic force microscope. In the limit of small nanocontacts (typically <103 nm2) measured with sensitive probes the bonding is found to be influenced by thermal-induced fluctuations. Using interface interactions described by Morse, embedded atom model, or Lennard-Jones potential within reaction rate theory, we investigate three bonding types of covalent and van der Waals nature. The comparison of numerical and experimental results reveals that a Lennard-Jones-like potential originating from van der Waals interactions captures the binding characteristics of dry silicon oxide nanocontacts, and likely of other nanoscale materials adsorbed on silicon oxide surfaces. The analyses reveal the importance of the dispersive surface energy and of the effective contact area which is altered by stretching speeds. The mean unbinding force is found to decrease as the contact spends time in the attractive regime. This contact weakening is featured by a negative aging coefficient which broadens and shifts the thermal-induced force distribution at low stretching speeds.

The effects of van der Waals attractions on cloud droplet growth by coalescence

NASA Technical Reports Server (NTRS)

Rogers, Jan R.; Davis, Robert H.

1990-01-01

The inclusion of van der Waals attractions in the interaction between cloud droplets has been recently shown to significantly increase the collision efficiencies of the smaller droplets. In the current work, these larger values for the collision efficiencies are used in a population dynamics model of the droplet size distribution evolution with time, in hopes of at least partially resolving the long-standing paradox in cloud microphysics that predicted rates of the onset of precipitation are generally much lower than those which are observed. Evolutions of several initial cloud droplet spectra have been tracked in time. Size evolutions are compared as predicted from the use of collision efficiencies computed using two different models to allow for droplet-droplet contact: one which considers slip flow effects only, and one which considers the combined effects of van der Waals forces and slip flow. The rate at which the droplet mass density function shifts to larger droplet sizes is increased by typically 20-25 percent, when collision efficiencies which include van der Waals forces are used.

Error estimates for (semi-)empirical dispersion terms and large biomacromolecules.

PubMed

Korth, Martin

2013-10-14

The first-principles modeling of biomaterials has made tremendous advances over the last few years with the ongoing growth of computing power and impressive developments in the application of density functional theory (DFT) codes to large systems. One important step forward was the development of dispersion corrections for DFT methods, which account for the otherwise neglected dispersive van der Waals (vdW) interactions. Approaches at different levels of theory exist, with the most often used (semi-)empirical ones based on pair-wise interatomic C6R(-6) terms. Similar terms are now also used in connection with semiempirical QM (SQM) methods and density functional tight binding methods (SCC-DFTB). Their basic structure equals the attractive term in Lennard-Jones potentials, common to most force field approaches, but they usually use some type of cutoff function to make the mixing of the (long-range) dispersion term with the already existing (short-range) dispersion and exchange-repulsion effects from the electronic structure theory methods possible. All these dispersion approximations were found to perform accurately for smaller systems, but error estimates for larger systems are very rare and completely missing for really large biomolecules. We derive such estimates for the dispersion terms of DFT, SQM and MM methods using error statistics for smaller systems and dispersion contribution estimates for the PDBbind database of protein-ligand interactions. We find that dispersion terms will usually not be a limiting factor for reaching chemical accuracy, though some force fields and large ligand sizes are problematic.

Non-Markovianity in atom-surface dispersion forces

DOE PAGES

Intravaia, F.; Behunin, R. O.; Henkel, C.; ...

2016-10-18

Here, we discuss the failure of the Markov approximation in the description of atom-surface fluctuation-induced interactions, both in equilibrium (Casimir-Polder forces) and out of equilibrium (quantum friction). Using general theoretical arguments, we show that the Markov approximation can lead to erroneous predictions of such phenomena with regard to both strength and functional dependencies on system parameters. Particularly, we show that the long-time power-law tails of two-time dipole correlations and their corresponding low-frequency behavior, neglected in the Markovian limit, affect the prediction of the force. These findings highlight the importance of non-Markovian effects in dispersion interactions.

Non-Markovianity in atom-surface dispersion forces

NASA Astrophysics Data System (ADS)

Intravaia, F.; Behunin, R. O.; Henkel, C.; Busch, K.; Dalvit, D. A. R.

2016-10-01

We discuss the failure of the Markov approximation in the description of atom-surface fluctuation-induced interactions, both in equilibrium (Casimir-Polder forces) and out of equilibrium (quantum friction). Using general theoretical arguments, we show that the Markov approximation can lead to erroneous predictions of such phenomena with regard to both strength and functional dependencies on system parameters. In particular, we show that the long-time power-law tails of two-time dipole correlations and their corresponding low-frequency behavior, neglected in the Markovian limit, affect the prediction of the force. Our findings highlight the importance of non-Markovian effects in dispersion interactions.

Hydrophobic forces in the foam films stabilized by sodium dodecyl sulfate: effect of electrolyte.

PubMed

Wang, Liguang; Yoon, Roe-Hoan

2004-12-21

Further studies of the hydrophobic force in foam films were carried out, including the effect of added inorganic electrolyte. We used a thin film balance of Scheludko-Exerowa type to obtain the disjoining pressure isotherms of the foam films stabilized by 10(-4) M sodium dodecyl sulfate in varying concentrations of sodium chloride. The results were compared with the disjoining pressure isotherms predicted from the extended Derjaguin-Landau-Verwey-Overbeek theory, which considers contributions from hydrophobic force in addition to those from double layer and van der Waals dispersion forces. The double layer forces were calculated from the surface potentials (psi s) obtained using the Gibbs adsorption equation and corrected for the counterion binding effect, while the dispersion forces were calculated using the Hamaker constant (A232) of 3.7 x 10(-20) J. The hydrophobic forces were calculated from the equilibrium film thickness as described previously. The predicted disjoining pressure isotherms were in good agreement with the experimental ones. It was found that the hydrophobic force is dampened substantially by the added electrolyte.

Surface instability of an imperfectly bonded thin elastic film under surface van der Waals forces

NASA Astrophysics Data System (ADS)

Wang, Xu; Jing, Rong

2017-02-01

This paper studies surface instability of a thin elastic film imperfectly bonded to a rigid substrate interacting with a rigid contactor through van der Waals forces under plane strain conditions. The film-substrate interface is modeled as a linear spring with vanishing thickness described in terms of the normal and tangential interface parameters. Depending on the ratio of the two imperfect interface parameters, the critical value of the Poisson's ratio for the occurrence of surface wrinkling in the absence of surface energy can be greater than, equal to, or smaller than 0.25, which is the critical Poisson's ratio for a perfect film-substrate interface. The critical surface energy for the inhibition of the surface wrinkling is also obtained. Finally, we propose a very simple and effective method to study the surface instability of a multilayered elastic film with imperfect interfaces interacting with a rigid contactor or with another multilayered elastic film (or a multilayered simply supported plate) with imperfect interfaces.

Calculation of Hamaker constants in non-aqueous fluid media

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

BELL,NELSON S.; DIMOS,DUANE B.

2000-05-09

Calculations of the Hamaker constants representing the van der Waals interactions between conductor, resistor and dielectric materials are performed using Lifshitz theory. The calculation of the parameters for the Ninham-Parsegian relationship for several non-aqueous liquids has been derived based on literature dielectric data. Discussion of the role of van der Waals forces in the dispersion of particles is given for understanding paste formulation. Experimental measurements of viscosity are presented to show the role of dispersant truncation of attractive van der Waals forces.

Characterizing Students' Mechanistic Reasoning about London Dispersion Forces

ERIC Educational Resources Information Center

Becker, Nicole; Noyes, Keenan; Cooper, Melanie

2016-01-01

Characterizing how students construct causal mechanistic explanations for chemical phenomena can provide us with important insights into the ways that students develop understanding of chemistry concepts. Here, we present two qualitative studies of undergraduate general chemistry students' reasoning about the causes of London dispersion forces in…

Influence of electrical double-layer dispersion forces and size dependency on pull-in instability of clamped microplate immersed in ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Karimipour, I.; Beni, Yaghoub Tadi; Taheri, N.

2017-10-01

Plate-type clamped microplate is of the most common constructive elements for developing in-liquid-operating devices. While the electromechanical behavior of clamped microplate in non-liquid environments has exclusively been addressed in the literature, no theoretical studies have yet been conducted on precise modeling of the clamped microplate in electrolyte liquid. Herein, the electromechanical response and instability of the clamped microplate immersed in ionic electrolyte media are investigated. The electrochemical force field is determined using double layer theory and linearized Poisson-Boltzmann equation. The presence of dispersion forces, i.e., Casimir and van der Waals attractions, are included in the theoretical model considering the correction due to the presence of liquid media between the interacting surfaces (three-layer model). To this end, a kind of microplate has been designed, i.e., a square microplate with all edges clamped supported. The strain gradient elasticity is employed to model the size-dependent structural behavior of the clamped microplate. To solve the nonlinear constitutive equation of the system, Extended Kantorovich Method, is employed and the pull-in parameter of the microplate are extracted. Impacts of the dispersion forces and size effect on the instability characteristics are discussed as well as the effect of ion concentration and potential ratio. It is found that the significant difference between the pull-in instability parameters in the modified strain gradient theory and the classical theory for thin microplates is merely due to the consideration of size effect parameter in the modified strain gradient theory. To confirm the validity of formulations, the numerical values of the results are compared. The results predicted via the aforementioned approach are in excellent agreement with those in the literature. Some new examples are solved to demonstrate the applicability of the procedure.

van der Waals interactions between nanostructures: Some analytic results from series expansions

NASA Astrophysics Data System (ADS)

Stedman, T.; Drosdoff, D.; Woods, L. M.

2014-01-01

The van der Waals force between objects of nontrivial geometries is considered. A technique based on a perturbation series approach is formulated in the dilute limit. We show that the dielectric response and object size can be decoupled and dominant contributions in terms of object separations can be obtained. This is a powerful method, which enables straightforward calculations of the interaction for different geometries. Our results for planar structures, such as thin sheets, infinitely long ribbons, and ribbons with finite dimensions, may be applicable for nanostructured devices where the van der Waals interaction plays an important role.

On the exchange-hole model of London dispersion forces

NASA Astrophysics Data System (ADS)

Ángyán, János G.

2007-07-01

First-principles derivation is given for the heuristic exchange-hole model of London dispersion forces by Becke and Johnson [J. Chem. Phys. 122, 154104 (2005)]. A one-term approximation is used for the dynamic charge density response function, and it is shown that a central nonempirical ingredient of the approximate nonexpanded dispersion energy is the charge density autocorrelation function, a two-particle property, related to the exchange-correlation hole. In the framework of a dipolar approximation of the Coulomb interaction around the molecular origin, one obtains the so-called Salem-Tang-Karplus approximation to the C6 dispersion coefficient. Alternatively, by expanding the Coulomb interaction around the center of charge (centroid) of the exchange-correlation hole associated with each point in the molecular volume, a multicenter expansion is obtained around the centroids of electron localization domains, always in terms of the exchange-correlation hole. In order to get a formula analogous to that of Becke and Johnson, which involves the exchange-hole only, further assumptions are needed, related to the difficulties of obtaining the expectation value of a two-electron operator from a single determinant. Thus a connection could be established between the conventional fluctuating charge density model of London dispersion forces and the notion of the "exchange-hole dipole moment" shedding some light on the true nature of the approximations implicit in the Becke-Johnson model.

Quantum Monte Carlo Simulation of condensed van der Waals Systems

NASA Astrophysics Data System (ADS)

Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; Kim, Jeongnim; Anatole von Lilienfeld, O.

2012-02-01

Van der Waals forces are as ubiquitous as infamous. While post-Hartree-Fock methods enable accurate estimates of these forces in molecules and clusters, they remain elusive for dealing with many-electron condensed phase systems. We present Quantum Monte Carlo [1,2] results for condensed van der Waals systems. Interatomic many-body contributions to cohesive energies and bulk modulus will be discussed. Numerical evidence is presented for crystals of rare gas atoms, and compared to experiments and methods [3]. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DoE's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.[4pt] [1] J. Kim, K. Esler, J. McMinis and D. Ceperley, SciDAC 2010, J. of Physics: Conference series, Chattanooga, Tennessee, July 11 2011 [0pt] [2] QMCPACK simulation suite, http://qmcpack.cmscc.org (unpublished)[0pt] [3] O. A. von Lillienfeld and A. Tkatchenko, J. Chem. Phys. 132 234109 (2010)

Dynamical importance of van der Waals saddle and excited potential surface in C(1D)+D2 complex-forming reaction

PubMed Central

Shen, Zhitao; Ma, Haitao; Zhang, Chunfang; Fu, Mingkai; Wu, Yanan; Bian, Wensheng; Cao, Jianwei

2017-01-01

Encouraged by recent advances in revealing significant effects of van der Waals wells on reaction dynamics, many people assume that van der Waals wells are inevitable in chemical reactions. Here we find that the weak long-range forces cause van der Waals saddles in the prototypical C(1D)+D2 complex-forming reaction that have very different dynamical effects from van der Waals wells at low collision energies. Accurate quantum dynamics calculations on our highly accurate ab initio potential energy surfaces with van der Waals saddles yield cross-sections in close agreement with crossed-beam experiments, whereas the same calculations on an earlier surface with van der Waals wells produce much smaller cross-sections at low energies. Further trajectory calculations reveal that the van der Waals saddle leads to a torsion then sideways insertion reaction mechanism, whereas the well suppresses reactivity. Quantum diffraction oscillations and sharp resonances are also predicted based on our ground- and excited-state potential energy surfaces. PMID:28094253

Large-scale compensation of errors in pairwise-additive empirical force fields: comparison of AMBER intermolecular terms with rigorous DFT-SAPT calculations.

PubMed

Zgarbová, Marie; Otyepka, Michal; Sponer, Jirí; Hobza, Pavel; Jurecka, Petr

2010-09-21

The intermolecular interaction energy components for several molecular complexes were calculated using force fields available in the AMBER suite of programs and compared with Density Functional Theory-Symmetry Adapted Perturbation Theory (DFT-SAPT) values. The extent to which such comparison is meaningful is discussed. The comparability is shown to depend strongly on the intermolecular distance, which means that comparisons made at one distance only are of limited value. At large distances the coulombic and van der Waals 1/r(6) empirical terms correspond fairly well with the DFT-SAPT electrostatics and dispersion terms, respectively. At the onset of electronic overlap the empirical values deviate from the reference values considerably. However, the errors in the force fields tend to cancel out in a systematic manner at equilibrium distances. Thus, the overall performance of the force fields displays errors an order of magnitude smaller than those of the individual interaction energy components. The repulsive 1/r(12) component of the van der Waals expression seems to be responsible for a significant part of the deviation of the force field results from the reference values. We suggest that further improvement of the force fields for intermolecular interactions would require replacement of the nonphysical 1/r(12) term by an exponential function. Dispersion anisotropy and its effects are discussed. Our analysis is intended to show that although comparing the empirical and non-empirical interaction energy components is in general problematic, it might bring insights useful for the construction of new force fields. Our results are relevant to often performed force-field-based interaction energy decompositions.

Understanding the nanoscale local buckling behavior of vertically aligned MWCNT arrays with van der Waals interactions

NASA Astrophysics Data System (ADS)

Li, Yupeng; Kim, Hyung-Ick; Wei, Bingqing; Kang, Junmo; Choi, Jae-Boong; Nam, Jae-Do; Suhr, Jonghwan

2015-08-01

The local buckling behavior of vertically aligned carbon nanotubes (VACNTs) has been investigated and interpreted in the view of a collective nanotube response by taking van der Waals interactions into account. To the best of our knowledge, this is the first report on the case of collective VACNT behavior regarding van der Waals force among nanotubes as a lateral support effect during the buckling process. The local buckling propagation and development of VACNTs were experimentally observed and theoretically analyzed by employing finite element modeling with lateral support from van der Waals interactions among nanotubes. Both experimental and theoretical analyses show that VACNTs buckled in the bottom region with many short waves and almost identical wavelengths, indicating a high mode buckling. Furthermore, the propagation and development mechanism of buckling waves follow the wave damping effect.The local buckling behavior of vertically aligned carbon nanotubes (VACNTs) has been investigated and interpreted in the view of a collective nanotube response by taking van der Waals interactions into account. To the best of our knowledge, this is the first report on the case of collective VACNT behavior regarding van der Waals force among nanotubes as a lateral support effect during the buckling process. The local buckling propagation and development of VACNTs were experimentally observed and theoretically analyzed by employing finite element modeling with lateral support from van der Waals interactions among nanotubes. Both experimental and theoretical analyses show that VACNTs buckled in the bottom region with many short waves and almost identical wavelengths, indicating a high mode buckling. Furthermore, the propagation and development mechanism of buckling waves follow the wave damping effect. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03581c

Defect mediated van der Waals epitaxy of hexagonal boron nitride on graphene

NASA Astrophysics Data System (ADS)

Heilmann, M.; Bashouti, M.; Riechert, H.; Lopes, J. M. J.

2018-04-01

Van der Waals heterostructures comprising of hexagonal boron nitride and graphene are promising building blocks for novel two-dimensional devices such as atomically thin transistors or capacitors. However, demonstrators of those devices have been so far mostly fabricated by mechanical assembly, a non-scalable and time-consuming method, where transfer processes can contaminate the surfaces. Here, we investigate a direct growth process for the fabrication of insulating hexagonal boron nitride on high quality epitaxial graphene using plasma assisted molecular beam epitaxy. Samples were grown at varying temperatures and times and studied using atomic force microscopy, revealing a growth process limited by desorption at high temperatures. Nucleation was mostly commencing from morphological defects in epitaxial graphene, such as step edges or wrinkles. Raman spectroscopy combined with x-ray photoelectron measurements confirm the formation of hexagonal boron nitride and prove the resilience of graphene against the nitrogen plasma used during the growth process. The electrical properties and defects in the heterostructures were studied with high lateral resolution by tunneling current and Kelvin probe force measurements. This correlated approach revealed a nucleation apart from morphological defects in epitaxial graphene, which is mediated by point defects. The presented results help understanding the nucleation and growth behavior during van der Waals epitaxy of 2D materials, and point out a route for a scalable production of van der Waals heterostructures.

Photovoltaic Effect in an Electrically Tunable van der Waals Heterojunction

PubMed Central

2014-01-01

Semiconductor heterostructures form the cornerstone of many electronic and optoelectronic devices and are traditionally fabricated using epitaxial growth techniques. More recently, heterostructures have also been obtained by vertical stacking of two-dimensional crystals, such as graphene and related two-dimensional materials. These layered designer materials are held together by van der Waals forces and contain atomically sharp interfaces. Here, we report on a type-II van der Waals heterojunction made of molybdenum disulfide and tungsten diselenide monolayers. The junction is electrically tunable, and under appropriate gate bias an atomically thin diode is realized. Upon optical illumination, charge transfer occurs across the planar interface and the device exhibits a photovoltaic effect. Advances in large-scale production of two-dimensional crystals could thus lead to a new photovoltaic solar technology. PMID:25057817

Dissecting the structure of surface stabilizer on the dispersion of inorganic nanoparticles in aqueous medium

NASA Astrophysics Data System (ADS)

Ding, Yong; Yu, Zongzhi; Zheng, Junping

2017-03-01

Dispersing inorganic nanoparticles in aqueous solutions is a key requirement for a great variety of products and processes, including carriers in drug delivery or fillers in polymers. To be highly functional in the final product, inorganic particles are required to be finely dispersed in nanoscale. In this study, silica was selected as a representative inorganic particle. Surface stabilizers with different chain length and charged group were designed to reveal the influence of electrostatic and van der Waals forces between silica and stabilizer on the dispersion of silica particles in aqueous medium. Results showed surface stabilizer with longer alkyl chain and charged group exerted best ability to deaggregate silica, leading to a hydrodynamic size of 51.1 nm. Surface stabilizer designing with rational structure is a promising solution for deagglomerating and reducing process time and energy. Giving the designability and adaptability of surface stabilizer, this method is of potential for dispersion of other inorganic nanoparticles.

Improved finite-difference computation of the van der Waals force: One-dimensional case

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

Pinto, Fabrizio

2009-10-15

We present an improved demonstration of the calculation of Casimir forces in one-dimensional systems based on the recently proposed numerical imaginary frequency Green's function computation approach. The dispersion force on two thick lossy dielectric slabs separated by an empty gap and placed within a perfectly conducting cavity is obtained from the Green's function of the modified Helmholtz equation by means of an ordinary finite-difference method. In order to demonstrate the possibility to develop algorithms to explore complex geometries in two and three dimensions to higher order in the mesh spacing, we generalize existing classical electromagnetism algebraic methods to generate themore » difference equations for dielectric boundaries not coinciding with any grid points. Diagnostic tests are presented to monitor the accuracy of our implementation of the method and follow-up applications in higher dimensions are introduced.« less

Molecular adsorption on metal surfaces with van der Waals density functionals

NASA Astrophysics Data System (ADS)

Li, Guo; Tamblyn, Isaac; Cooper, Valentino R.; Gao, Hong-Jun; Neaton, Jeffrey B.

2012-03-01

The adsorption of 1,4-benzenediamine (BDA) on Au(111) and azobenzene on Ag(111) is investigated using density functional theory (DFT) with the nonlocal van der Waals density functional (vdW-DF) and the semilocal Perdew-Burke-Ernzerhof functional. For BDA on Au(111), the inclusion of London dispersion interactions not only dramatically enhances the molecule-substrate binding, resulting in adsorption energies consistent with experimental results, but also significantly alters the BDA binding geometry. For azobenzene on Ag(111), vdW-DFs produce superior adsorption energies compared to those obtained with other dispersion-corrected DFT approaches. These results provide evidence for the applicability of the vdW-DF approach and serve as practical benchmarks for the investigation of molecules adsorbed on noble-metal surfaces.

Efimov states near a Feshbach resonance and the limits of van der Waals universality at finite background scattering length

NASA Astrophysics Data System (ADS)

Langmack, Christian; Schmidt, Richard; Zwerger, Wilhelm

2018-03-01

We calculate the spectrum of three-body Efimov bound states near a Feshbach resonance within a model which accounts both for the finite range of interactions and the presence of background scattering. The latter may be due to direct interactions in an open channel or a second overlapping Feshbach resonance. It is found that background scattering gives rise to substantial changes in the trimer spectrum as a function of the detuning away from a Feshbach resonance, in particular in the regime where the background channel supports Efimov states on its own. Compared to the situation with negligible background scattering, the regime where van der Waals universality applies is shifted to larger values of the resonance strength if the background scattering length is positive. For negative background scattering lengths, in turn, van der Waals universality extends to even small values of the resonance strength parameter, consistent with experimental results on Efimov states in 39K. Within a simple model, we show that short-range three-body forces do not affect van der Waals universality significantly. Repulsive three-body forces may, however, explain the observed variation between around -8 and -10 of the ratio between the scattering length where the first Efimov trimer appears and the van der Waals length.

Alginic Acid-Aided Dispersion of Carbon Nanotubes, Graphene, and Boron Nitride Nanomaterials for Microbial Toxicity Testing

PubMed Central

Chang, Chong Hyun

2018-01-01

Robust evaluation of potential environmental and health risks of carbonaceous and boron nitride nanomaterials (NMs) is imperative. However, significant agglomeration of pristine carbonaceous and boron nitride NMs due to strong van der Waals forces renders them not suitable for direct toxicity testing in aqueous media. Here, the natural polysaccharide alginic acid (AA) was used as a nontoxic, environmentally relevant dispersant with defined composition to disperse seven types of carbonaceous and boron nitride NMs, including multiwall carbon nanotubes, graphene, boron nitride nanotubes, and hexagonal boron nitride flakes, with various physicochemical characteristics. AA’s biocompatibility was confirmed by examining AA effects on viability and growth of two model microorganisms (the protozoan Tetrahymena thermophila and the bacterium Pseudomonas aeruginosa). Using 400 mg·L−1 AA, comparably stable NM (200 mg·L−1) stock dispersions were obtained by 30-min probe ultrasonication. AA non-covalently interacted with NM surfaces and improved the dispersibility of NMs in water. The dispersion stability varied with NM morphology and size rather than chemistry. The optimized dispersion protocol established here can facilitate preparing homogeneous NM dispersions for reliable exposures during microbial toxicity testing, contributing to improved reproducibility of toxicity results. PMID:29385723

Alginic Acid-Aided Dispersion of Carbon Nanotubes, Graphene, and Boron Nitride Nanomaterials for Microbial Toxicity Testing.

PubMed

Wang, Ying; Mortimer, Monika; Chang, Chong Hyun; Holden, Patricia A

2018-01-30

Robust evaluation of potential environmental and health risks of carbonaceous and boron nitride nanomaterials (NMs) is imperative. However, significant agglomeration of pristine carbonaceous and boron nitride NMs due to strong van der Waals forces renders them not suitable for direct toxicity testing in aqueous media. Here, the natural polysaccharide alginic acid (AA) was used as a nontoxic, environmentally relevant dispersant with defined composition to disperse seven types of carbonaceous and boron nitride NMs, including multiwall carbon nanotubes, graphene, boron nitride nanotubes, and hexagonal boron nitride flakes, with various physicochemical characteristics. AA's biocompatibility was confirmed by examining AA effects on viability and growth of two model microorganisms (the protozoan Tetrahymena thermophila and the bacterium Pseudomonas aeruginosa ). Using 400 mg·L -1 AA, comparably stable NM (200 mg·L -1 ) stock dispersions were obtained by 30-min probe ultrasonication. AA non-covalently interacted with NM surfaces and improved the dispersibility of NMs in water. The dispersion stability varied with NM morphology and size rather than chemistry. The optimized dispersion protocol established here can facilitate preparing homogeneous NM dispersions for reliable exposures during microbial toxicity testing, contributing to improved reproducibility of toxicity results.

A Van der Waals-like theory of plasma double layers

NASA Technical Reports Server (NTRS)

Katz, Ira; Davis, V. A.

1989-01-01

A theory describing plasma double layers in terms of multiple roots of the charge density expression is presented. The theory presented uses the fact that equilibrium plasmas shield small potential perturbations linearly; for high potentials, the shielding decreases. The approach is analogous to Van der Waals' theory of simple fluids in which inclusion of approximate expressions for both excluded volume and long range attractive forces sufficiently describes the first-order liquid-gas phase transition.

Van-der-Waals interaction of atoms in dipolar Rydberg states

NASA Astrophysics Data System (ADS)

Kamenski, Aleksandr A.; Mokhnenko, Sergey N.; Ovsiannikov, Vitaly D.

2018-02-01

An asymptotic expression for the van-der-Waals constant C 6( n) ≈ -0.03 n 12 K p ( x) is derived for the long-range interaction between two highly excited hydrogen atoms A and B in their extreme Stark states of equal principal quantum numbers n A = n B = n ≫ 1 and parabolic quantum numbers n 1(2) = n - 1, n 2(1) = m = 0 in the case of collinear orientation of the Stark-state dipolar electric moments and the interatomic axis. The cubic polynomial K 3( x) in powers of reciprocal values of the principal quantum number x = 1/ n and quadratic polynomial K 2( y) in powers of reciprocal values of the principal quantum number squared y = 1/ n 2 were determined on the basis of the standard curve fitting polynomial procedure from the calculated data for C 6( n). The transformation of attractive van-der-Waals force ( C 6 > 0) for low-energy states n < 23 into repulsive force ( C 6 < 0) for all higher-energy states of n ≥ 23, is observed from the results of numerical calculations based on the second-order perturbation theory for the operator of the long-range interaction between neutral atoms. This transformation is taken into account in the asymptotic formulas (in both cases of p = 2, 3) by polynomials K p tending to unity at n → ∞ ( K p (0) = 1). The transformation from low- n attractive van-der-Waals force into high- n repulsive force demonstrates the gradual increase of the negative contribution to C 6( n) from the lower-energy two-atomic states, of the A(B)-atom principal quantum numbers n'A(B) = n-Δ n (where Δ n = 1, 2, … is significantly smaller than n for the terms providing major contribution to the second-order series), which together with the states of n″B(A) = n+Δ n make the joint contribution proportional to n 12. So, the hydrogen-like manifold structure of the energy spectrum is responsible for the transformation of the power-11 asymptotic dependence C 6( n) ∝ n 11of the low-angular-momenta Rydberg states in many-electron atoms into the power

Dispersal of Sediment in the Western Adriatic during Energetic Wintertime Forcing

NASA Astrophysics Data System (ADS)

Harris, C. K.; Sherwood, C. R.; Mullenbach, B. L.; Pullen, J. D.

2003-12-01

EuroSTRATAFORM aims to relate sediment delivery and reworking to seabed morphology and stratigraphy through observations and modeling of water column transport. The Po River dominates buoyancy and sediment input into the Adriatic Sea, but small Apeninne rivers (the Chienti, Pescara, etc.) may produce locally important signals. Sedimentation is influenced by fluvial supply, resuspension by waves and currents, and transport by oceanographic currents forced by winds and buoyancy. Transport is likely highest during times of energetic forcing; including Bora events with northeasterly winds and Sirocco events with southeasterly winds. It is difficult, from field measurements alone, to characterize dispersal and convergence patterns over the relevant spatial scales. We applied a three-dimensional hydrodynamic model that includes fluvial delivery, transport, resuspension, and deposition of sediment to quantify sediment dispersal with a 2-km resolution over the entire Adriatic. Circulation calculations were driven by spatially- and temporally-varying wind fields for the Fall / Winter of 2002 / 2003 and realistic Po and Apennine river discharges. Waves were hindcast with the SWAN model. Dispersion of both resuspended and river-derived sediment was estimated for periods that contained intense Bora and Sirocco winds. Predicted sediment dispersal rates and patterns are sensitive to forcing winds, buoyancy flux, and wave patterns. Higher sediment flux was predicted during Bora conditions than during Sirocco conditions. Sirocco winds weaken the Western Adriatic Coastal Current (WACC), and because they tend to concentrate over the Eastern Adriatic, they often fail to create especially energetic waves in the Western Adriatic. Bora wind conditions, on the other hand, intensify the WACC and can build high wave energies over the northwestern Adriatic. Most of the sediment transport occurs during Bora, with a net southward flux. These predictions will be compared to field observations

Anomalous van der Waals-Casimir interactions on graphene: A concerted effect of temperature, retardation, and non-locality

NASA Astrophysics Data System (ADS)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2018-04-01

Dispersion forces play a major role in graphene, largely influencing adhesion of adsorbate moieties and stabilization of functional multilayered structures. However, the reliable prediction of dispersion interactions on graphene up to the relevant ˜10 nm scale is an extremely challenging task: in fact, electromagnetic retardation effects and the highly non-local character of π electrons can imply sizeable qualitative variations of the interaction with respect to known pairwise approaches. Here we address both issues, determining the finite-temperature van der Waals (vdW)-Casimir interaction for point-like and extended adsorbates on graphene, explicitly accounting for the non-local dielectric permittivity. We find that temperature, retardation, and non-locality play a crucial role in determining the actual vdW scaling laws and the stability of both atomic and larger molecular adsorbates. Our results highlight the importance of these effects for a proper description of systems of current high interest, such as graphene interacting with biomolecules, and self-assembly of complex nanoscale structures. Due to the generality of our approach and the observed non-locality of other 2D materials, our results suggest non-trivial vdW interactions from hexagonal mono-layered materials from group 14 of the periodic table, to transition metal dichalcogenides.

Anomalous van der Waals-Casimir interactions on graphene: A concerted effect of temperature, retardation, and non-locality.

PubMed

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2018-04-07

Dispersion forces play a major role in graphene, largely influencing adhesion of adsorbate moieties and stabilization of functional multilayered structures. However, the reliable prediction of dispersion interactions on graphene up to the relevant ∼10 nm scale is an extremely challenging task: in fact, electromagnetic retardation effects and the highly non-local character of π electrons can imply sizeable qualitative variations of the interaction with respect to known pairwise approaches. Here we address both issues, determining the finite-temperature van der Waals (vdW)-Casimir interaction for point-like and extended adsorbates on graphene, explicitly accounting for the non-local dielectric permittivity. We find that temperature, retardation, and non-locality play a crucial role in determining the actual vdW scaling laws and the stability of both atomic and larger molecular adsorbates. Our results highlight the importance of these effects for a proper description of systems of current high interest, such as graphene interacting with biomolecules, and self-assembly of complex nanoscale structures. Due to the generality of our approach and the observed non-locality of other 2D materials, our results suggest non-trivial vdW interactions from hexagonal mono-layered materials from group 14 of the periodic table, to transition metal dichalcogenides.

van der Waals Interactions on the Mesoscale: Open-Science Implementation, Anisotropy, Retardation, and Solvent Effects.

PubMed

Dryden, Daniel M; Hopkins, Jaime C; Denoyer, Lin K; Poudel, Lokendra; Steinmetz, Nicole F; Ching, Wai-Yim; Podgornik, Rudolf; Parsegian, Adrian; French, Roger H

2015-09-22

The self-assembly of heterogeneous mesoscale systems is mediated by long-range interactions, including van der Waals forces. Diverse mesoscale architectures, built of optically and morphologically anisotropic elements such as DNA, collagen, single-walled carbon nanotubes, and inorganic materials, require a tool to calculate the forces, torques, interaction energies, and Hamaker coefficients that govern assembly in such systems. The mesoscale Lifshitz theory of van der Waals interactions can accurately describe solvent and temperature effects, retardation, and optically and morphologically anisotropic materials for cylindrical and planar interaction geometries. The Gecko Hamaker open-science software implementation of this theory enables new and sophisticated insights into the properties of important organic/inorganic systems: interactions show an extended range of magnitudes and retardation rates, DNA interactions show an imprint of base pair composition, certain SWCNT interactions display retardation-dependent nonmonotonicity, and interactions are mapped across a range of material systems in order to facilitate rational mesoscale design.

Antiferromagnetism in the van der Waals layered spin-lozenge semiconductor CrTe 3

DOE PAGES

McGuire, Michael A.; Garlea, V. Ovidiu; KC, Santosh; ...

2017-04-14

We have investigated the crystallographic, magnetic, and transport properties of the van der Waals bonded, layered compound CrTe 3 on single-crystal and polycrystalline materials. Furthermore, the crystal structure contains layers made up of lozenge-shaped Cr 4 tetramers. Electrical resistivity measurements show the crystals to be semiconducting, with a temperature dependence consistent with a band gap of 0.3 eV. The magnetic susceptibility exhibits a broad maximum near 300 K characteristic of low dimensional magnetic systems. Weak anomalies are observed in the susceptibility and heat capacity near 55 K, and single-crystal neutron diffraction reveals the onset of long-range antiferromagnetic order at thismore » temperature. Strongly dispersive spin waves are observed in the ordered state. Significant magnetoelastic coupling is indicated by the anomalous temperature dependence of the lattice parameters and is evident in structural optimization in van der Waals density functional theory calculations for different magnetic configurations. The cleavability of the compound is apparent from its handling and is confirmed by first-principles calculations, which predict a cleavage energy 0.5 J / m 2 , similar to graphite. Based on our results, CrTe 3 is identified as a promising compound for studies of low dimensional magnetism in bulk crystals as well as magnetic order in monolayer materials and van der Waals heterostructures.« less

Antiferromagnetism in the van der Waals layered spin-lozenge semiconductor CrTe 3

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

McGuire, Michael A.; Garlea, V. Ovidiu; KC, Santosh

We have investigated the crystallographic, magnetic, and transport properties of the van der Waals bonded, layered compound CrTe 3 on single-crystal and polycrystalline materials. Furthermore, the crystal structure contains layers made up of lozenge-shaped Cr 4 tetramers. Electrical resistivity measurements show the crystals to be semiconducting, with a temperature dependence consistent with a band gap of 0.3 eV. The magnetic susceptibility exhibits a broad maximum near 300 K characteristic of low dimensional magnetic systems. Weak anomalies are observed in the susceptibility and heat capacity near 55 K, and single-crystal neutron diffraction reveals the onset of long-range antiferromagnetic order at thismore » temperature. Strongly dispersive spin waves are observed in the ordered state. Significant magnetoelastic coupling is indicated by the anomalous temperature dependence of the lattice parameters and is evident in structural optimization in van der Waals density functional theory calculations for different magnetic configurations. The cleavability of the compound is apparent from its handling and is confirmed by first-principles calculations, which predict a cleavage energy 0.5 J / m 2 , similar to graphite. Based on our results, CrTe 3 is identified as a promising compound for studies of low dimensional magnetism in bulk crystals as well as magnetic order in monolayer materials and van der Waals heterostructures.« less

Drastic reduction in the growth temperature of graphene on copper via enhanced London dispersion force

PubMed Central

Choi, Jin-Ho; Li, Zhancheng; Cui, Ping; Fan, Xiaodong; Zhang, Hui; Zeng, Changgan; Zhang, Zhenyu

2013-01-01

London dispersion force is ubiquitous in nature, and is increasingly recognized to be an important factor in a variety of surface processes. Here we demonstrate unambiguously the decisive role of London dispersion force in non-equilibrium growth of ordered nanostructures on metal substrates using aromatic source molecules. Our first-principles based multi-scale modeling shows that a drastic reduction in the growth temperature, from ~1000°C to ~300°C, can be achieved in graphene growth on Cu(111) when the typical carbon source of methane is replaced by benzene or p-Terphenyl. The London dispersion force enhances their adsorption energies by about (0.5–1.8) eV, thereby preventing their easy desorption, facilitating dehydrogenation, and promoting graphene growth at much lower temperatures. These quantitative predictions are validated in our experimental tests, showing convincing demonstration of monolayer graphene growth using the p-Terphenyl source. The general trends established are also more broadly applicable in molecular synthesis of surface-based nanostructures. PMID:23722566

Forces dictating colloidal interactions between viruses and soil

USGS Publications Warehouse

Chattopadhyay, Sandip; Puls, Robert W.

2000-01-01

The fate and transport of viruses in soil and aquatic environments were studied with respect to the different forces involved in the process of sorption of these viruses on soil particles. In accordance with the classical DLVO theory, we have calculated the repulsive electrostatic forces and the attractive van der Waals forces. Bacteriophages have been used as model sorbates, while different clays have been used as model sorbents. The equations used for the determination of the change in free energy for the process (ΔG) takes into consideration the roughness of the sorbent surfaces. Results indicate that attractive van der Waals forces predominate the process of sorption of the selected bacteriophages on clays.

Van der Waals interaction in uniaxial anisotropic media.

PubMed

Kornilovitch, Pavel E

2013-01-23

Van der Waals interactions between flat surfaces in uniaxial anisotropic media are investigated in the nonretarded limit. The main focus is the effect of nonzero tilt between the optical axis and the surface normal on the strength of the van der Waals attraction. General expressions for the van der Waals free energy are derived using the surface mode method and the transfer-matrix formalism. To facilitate numerical calculations a temperature-dependent three-band parameterization of the dielectric tensor of the liquid crystal 5CB is developed. A solid slab immersed in a liquid crystal experiences a van der Waals torque that aligns the surface normal relative to the optical axis of the medium. The preferred orientation is different for different materials. Two solid slabs in close proximity experience a van der Waals attraction that is strongest for homeotropic alignment of the intervening liquid crystal for all the materials studied. The results have implications for the stability of plate-like colloids in liquid crystal hosts.

Impact of Acoustic Radiation Force Excitation Geometry on Shear Wave Dispersion and Attenuation Estimates.

PubMed

Lipman, Samantha L; Rouze, Ned C; Palmeri, Mark L; Nightingale, Kathryn R

2018-04-01

Shear wave elasticity imaging (SWEI) characterizes the mechanical properties of human tissues to differentiate healthy from diseased tissue. Commercial scanners tend to reconstruct shear wave speeds for a region of interest using time-of-flight methods reporting a single shear wave speed (or elastic modulus) to the end user under the assumptions that tissue is elastic and shear wave speeds are not dependent on the frequency content of the shear waves. Human tissues, however, are known to be viscoelastic, resulting in dispersion and attenuation. Shear wave spectroscopy and spectral methods have been previously reported in the literature to quantify shear wave dispersion and attenuation, commonly making an assumption that the acoustic radiation force excitation acts as a cylindrical source with a known geometric shear wave amplitude decay. This work quantifies the bias in shear dispersion and attenuation estimates associated with making this cylindrical wave assumption when applied to shear wave sources with finite depth extents, as commonly occurs with realistic focal geometries, in elastic and viscoelastic media. Bias is quantified using analytically derived shear wave data and shear wave data generated using finite-element method models. Shear wave dispersion and attenuation bias (up to 15% for dispersion and 41% for attenuation) is greater for more tightly focused acoustic radiation force sources with smaller depths of field relative to their lateral extent (height-to-width ratios <16). Dispersion and attenuation errors associated with assuming a cylindrical geometric shear wave decay in SWEI can be appreciable and should be considered when analyzing the viscoelastic properties of tissues with acoustic radiation force source distributions with limited depths of field. Copyright © 2018 World Federation for Ultrasound in Medicine and Biology. Published by Elsevier Inc. All rights reserved.

Generalized closed form solutions for feasible dimension limit and pull-in characteristics of nanocantilever under the Influences of van der Waals and Casimir forces

NASA Astrophysics Data System (ADS)

Mukherjee, Banibrata; Sen, Siddhartha

2018-04-01

This paper presents generalized closed form expressions for determining the dimension limit for the basic design parameters as well as the pull-in characteristics of a nanocantilever beam under the influences of van der Waals and Casimir forces. The coupled nonlinear electromechanical problem of electrostatic nanocantilever is formulated in nondimensional form with Galerkin’s approximation considering the effects of these intermolecular forces and fringe field. The resulting integrals and higher order polynomials are solved numerically to derive the closed form expressions for maximum permissible detachment length, minimum feasible gap spacing and critical pull-in limit. The derived expressions are compared and validated as well with several reported literature showing reasonable agreement. The major advantages of the proposed closed form expressions are that, they do not contain any complex mathematical term or operation unlike in reported literature and thus they will serve as convenient tools for the NEMS community in successful design of various electrostatically actuated nanosystems.

Van der Waals potential and vibrational energy levels of the ground state radon dimer

NASA Astrophysics Data System (ADS)

Sheng, Xiaowei; Qian, Shifeng; Hu, Fengfei

2017-08-01

In the present paper, the ground state van der Waals potential of the Radon dimer is described by the Tang-Toennies potential model, which requires five essential parameters. Among them, the two dispersion coefficients C6 and C8 are estimated from the well determined dispersion coefficients C6 and C8 of Xe2. C10 is estimated by using the approximation equation that C6C10/C82 has an average value of 1.221 for all the rare gas dimers. With these estimated dispersion coefficients and the well determined well depth De and Re the Born-Mayer parameters A and b are derived. Then the vibrational energy levels of the ground state radon dimer are calculated. 40 vibrational energy levels are observed in the ground state of Rn2 dimer. The last vibrational energy level is bound by only 0.0012 cm-1.

Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films.

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered

Design and damping force characterization of a new magnetorheological damper activated by permanent magnet flux dispersion

NASA Astrophysics Data System (ADS)

Lee, Tae-Hoon; Han, Chulhee; Choi, Seung-Bok

2018-01-01

This work proposes a novel type of tunable magnetorheological (MR) damper operated based solely on the location of a permanent magnet incorporated into the piston. To create a larger damping force variation in comparison with the previous model, a different design configuration of the permanent-magnet-based MR (PMMR) damper is introduced to provide magnetic flux dispersion in two magnetic circuits by utilizing two materials with different magnetic reluctance. After discussing the design configuration and some advantages of the newly designed mechanism, the magnetic dispersion principle is analyzed through both the formulated analytical model of the magnetic circuit and the computer simulation based on the magnetic finite element method. Sequentially, the principal design parameters of the damper are determined and fabricated. Then, experiments are conducted to evaluate the variation in damping force depending on the location of the magnet. It is demonstrated that the new design and magnetic dispersion concept are valid showing higher damping force than the previous model. In addition, a curved structure of the two materials is further fabricated and tested to realize the linearity of the damping force variation.

Ultra-confined surface phonon polaritons in molecular layers of van der Waals dielectrics.

PubMed

Dubrovkin, Alexander M; Qiang, Bo; Krishnamoorthy, Harish N S; Zheludev, Nikolay I; Wang, Qi Jie

2018-05-02

Improvements in device density in photonic circuits can only be achieved with interconnects exploiting highly confined states of light. Recently this has brought interest to highly confined plasmon and phonon polaritons. While plasmonic structures have been extensively studied, the ultimate limits of phonon polariton squeezing, in particular enabling the confinement (the ratio between the excitation and polariton wavelengths) exceeding 10 2 , is yet to be explored. Here, exploiting unique structure of 2D materials, we report for the first time that atomically thin van der Waals dielectrics (e.g., transition-metal dichalcogenides) on silicon carbide substrate demonstrate experimentally record-breaking propagating phonon polaritons confinement resulting in 190-times squeezed surface waves. The strongly dispersive confinement can be potentially tuned to greater than 10 3 near the phonon resonance of the substrate, and it scales with number of van der Waals layers. We argue that our findings are a substantial step towards infrared ultra-compact phonon polaritonic circuits and resonators, and would stimulate further investigations on nanophotonics in non-plasmonic atomically thin interface platforms.

Strain engineering of van der Waals heterostructures.

PubMed

Vermeulen, Paul A; Mulder, Jefta; Momand, Jamo; Kooi, Bart J

2018-01-18

Modifying the strain state of solids allows control over a plethora of functional properties. The weak interlayer bonding in van der Waals (vdWaals) materials such as graphene, hBN, MoS 2 , and Bi 2 Te 3 might seem to exclude strain engineering, since strain would immediately relax at the vdWaals interfaces. Here we present direct observations of the contrary by showing growth of vdWaals heterostructures with persistent in-plane strains up to 5% and we show that strain relaxation follows a not yet reported process distinctly different from strain relaxation in three-dimensionally bonded (3D) materials. For this, 2D bonded Bi 2 Te 3 -Sb 2 Te 3 and 2D/3D bonded Bi 2 Te 3 -GeTe multilayered films are grown using Pulsed Laser Deposition (PLD) and their structure is monitored in situ using Reflective High Energy Electron Diffraction (RHEED) and post situ analysis is performed using Transmission Electron Microscopy (TEM). Strain relaxation is modeled and found to solely depend on the layer being grown and its initial strain. This insight demonstrates that strain engineering of 2D bonded heterostructures obeys different rules than hold for epitaxial 3D materials and opens the door to precise tuning of the strain state of the individual layers to optimize functional performance of vdWaals heterostructures.

A simplified implementation of van der Waals density functionals for first-principles molecular dynamics applications

NASA Astrophysics Data System (ADS)

Wu, Jun; Gygi, François

2012-06-01

We present a simplified implementation of the non-local van der Waals correlation functional introduced by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)] and reformulated by Román-Pérez et al. [Phys. Rev. Lett. 103, 096102 (2009)]. The proposed numerical approach removes the logarithmic singularity of the kernel function. Complete expressions of the self-consistent correlation potential and of the stress tensor are given. Combined with various choices of exchange functionals, five versions of van der Waals density functionals are implemented. Applications to the computation of the interaction energy of the benzene-water complex and to the computation of the equilibrium cell parameters of the benzene crystal are presented. As an example of crystal structure calculation involving a mixture of hydrogen bonding and dispersion interactions, we compute the equilibrium structure of two polymorphs of aspirin (2-acetoxybenzoic acid, C9H8O4) in the P21/c monoclinic structure.

Mixed Dimensional Van der Waals Heterostructures for Opto-Electronics.

NASA Astrophysics Data System (ADS)

Jariwala, Deep

The isolation of a growing number of two-dimensional (2D) materials has inspired worldwide efforts to integrate distinct 2D materials into van der Waals (vdW) heterostructures. While a tremendous amount of research activity has occurred in assembling disparate 2D materials into ``all-2D'' van der Waals heterostructures, this concept is not limited to 2D materials alone. Given that any passivated, dangling bond-free surface will interact with another via vdW forces, the vdW heterostructure concept can be extended to include the integration of 2D materials with non-2D materials that adhere primarily through noncovalent interactions. In the first part of this talk I will present our work on emerging mixed-dimensional (2D + nD, where n is 0, 1 or 3) heterostructure devices performed at Northwestern University. I will present two distinct examples of gate-tunable p-n heterojunctions 1. Single layer n-type MoS2\\ (2D) combined with p-type semiconducting single walled carbon nanotubes (1D) and 2. Single layer MoS2 combined with 0D molecular semiconductor, pentacene. I will present the unique electrical properties, underlying charge transport mechanisms and photocurrent responses in both the above systems using a variety of scanning probe microscopy techniques as well as computational analysis. This work shows that van der Waals interactions are robust across different dimensionalities of materials and can allow fabrication of semiconductor devices with unique geometries and properties unforeseen in bulk semiconductors. Finally, I will briefly discuss our recent work from Caltech on near-unity absorption in atomically-thin photovoltaic devices. This work is supported by the Materials Research Center at Northwestern University, funded by the National Science Foundation (NSF DMR-1121262) and the Resnick Sustainability Institute at Caltech.

Benchmarking Density Functional Theory Based Methods To Model NiOOH Material Properties: Hubbard and van der Waals Corrections vs Hybrid Functionals.

PubMed

Zaffran, Jeremie; Caspary Toroker, Maytal

2016-08-09

NiOOH has recently been used to catalyze water oxidation by way of electrochemical water splitting. Few experimental data are available to rationalize the successful catalytic capability of NiOOH. Thus, theory has a distinctive role for studying its properties. However, the unique layered structure of NiOOH is associated with the presence of essential dispersion forces within the lattice. Hence, the choice of an appropriate exchange-correlation functional within Density Functional Theory (DFT) is not straightforward. In this work, we will show that standard DFT is sufficient to evaluate the geometry, but DFT+U and hybrid functionals are required to calculate the oxidation states. Notably, the benefit of DFT with van der Waals correction is marginal. Furthermore, only hybrid functionals succeed in opening a bandgap, and such methods are necessary to study NiOOH electronic structure. In this work, we expect to give guidelines to theoreticians dealing with this material and to present a rational approach in the choice of the DFT method of calculation.

Infrared hyperbolic metasurface based on nanostructured van der Waals materials

NASA Astrophysics Data System (ADS)

Li, Peining; Dolado, Irene; Alfaro-Mozaz, Francisco Javier; Casanova, Fèlix; Hueso, Luis E.; Liu, Song; Edgar, James H.; Nikitin, Alexey Y.; Vélez, Saül; Hillenbrand, Rainer

2018-02-01

Metasurfaces with strongly anisotropic optical properties can support deep subwavelength-scale confined electromagnetic waves (polaritons), which promise opportunities for controlling light in photonic and optoelectronic applications. We developed a mid-infrared hyperbolic metasurface by nanostructuring a thin layer of hexagonal boron nitride that supports deep subwavelength-scale phonon polaritons that propagate with in-plane hyperbolic dispersion. By applying an infrared nanoimaging technique, we visualize the concave (anomalous) wavefronts of a diverging polariton beam, which represent a landmark feature of hyperbolic polaritons. The results illustrate how near-field microscopy can be applied to reveal the exotic wavefronts of polaritons in anisotropic materials and demonstrate that nanostructured van der Waals materials can form a highly variable and compact platform for hyperbolic infrared metasurface devices and circuits.

Hybrid, Gate-Tunable, van der Waals p–n Heterojunctions from Pentacene and MoS 2

DOE PAGES

Jariwala, Deep; Howell, Sarah L.; Chen, Kan-Sheng; ...

2015-12-18

The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semimetallic graphene and insulating boron nitride, has enabled the fabrication of “all 2D” van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration withmore » 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS2. The resulting p–n heterojunction is gate-tunable and shows asymmetric control over the antiambipolar transfer characteristic. In addition, the pentacene/MoS2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS2 can function as an acceptor in hybrid solar cells.« less

Hybrid, Gate-Tunable, van der Waals p–n Heterojunctions from Pentacene and MoS 2

DOE PAGES

Jariwala, Deep; Howell, Sarah L.; Chen, Kan -Sheng; ...

2015-12-10

Here, the recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semimetallic graphene and insulating boron nitride, has enabled the fabrication of “all 2D” van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integrationmore » with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS 2. The resulting p–n heterojunction is gate-tunable and shows asymmetric control over the antiambipolar transfer characteristic. In addition, the pentacene/MoS 2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS 2 can function as an acceptor in hybrid solar cells.« less

Hybrid, Gate-Tunable, van der Waals p–n Heterojunctions from Pentacene and MoS 2

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

Jariwala, Deep; Howell, Sarah L.; Chen, Kan -Sheng

Here, the recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semimetallic graphene and insulating boron nitride, has enabled the fabrication of “all 2D” van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integrationmore » with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS 2. The resulting p–n heterojunction is gate-tunable and shows asymmetric control over the antiambipolar transfer characteristic. In addition, the pentacene/MoS 2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS 2 can function as an acceptor in hybrid solar cells.« less

Scaling laws for van der Waals interactions in nanostructured materials.

PubMed

Gobre, Vivekanand V; Tkatchenko, Alexandre

2013-01-01

Van der Waals interactions have a fundamental role in biology, physics and chemistry, in particular in the self-assembly and the ensuing function of nanostructured materials. Here we utilize an efficient microscopic method to demonstrate that van der Waals interactions in nanomaterials act at distances greater than typically assumed, and can be characterized by different scaling laws depending on the dimensionality and size of the system. Specifically, we study the behaviour of van der Waals interactions in single-layer and multilayer graphene, fullerenes of varying size, single-wall carbon nanotubes and graphene nanoribbons. As a function of nanostructure size, the van der Waals coefficients follow unusual trends for all of the considered systems, and deviate significantly from the conventionally employed pairwise-additive picture. We propose that the peculiar van der Waals interactions in nanostructured materials could be exploited to control their self-assembly.

Effects of van der Waals density functional corrections on trends in furfural adsorption and hydrogenation on close-packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Liu, Bin; Cheng, Lei; Curtiss, Larry; Greeley, Jeffrey

2014-04-01

The hydrogenation of furfural to furfuryl alcohol on Pd(111), Cu(111) and Pt(111) is studied with both standard Density Functional Theory (DFT)-GGA functionals and with van der Waals-corrected density functionals. VdW-DF functionals, including optPBE, optB88, optB86b, and Grimme's method, are used to optimize the adsorption configurations of furfural, furfuryl alcohol, and related intermediates resulting from hydrogenation of furfural, and the results are compared to corresponding values determined with GGA functionals, including PW91 and PBE. On Pd(111) and Pt(111), the adsorption geometries of the intermediates are not noticeably different between the two classes of functionals, while on Cu(111), modest changes are seen in both the perpendicular distance and the orientation of the aromatic ring with respect to the planar surface. In general, the binding energies increase substantially in magnitude as a result of van der Waals contributions on all metals. In contrast, however, dispersion effects on the kinetics of hydrogenation are relatively small. It is found that activation barriers are not significantly affected by the inclusion of dispersion effects, and a Brønsted-Evans-Polanyi relationship developed solely from PW91 calculations on Pd(111) is capable of describing corresponding results on Cu(111) and Pt(111), even when the dispersion effects are included. Finally, the reaction energies and barriers derived from the dispersion-corrected and pure GGA calculations are used to plot simple potential energy profiles for furfural hydrogenation to furfuryl alcohol on the three considered metals, and an approximately constant downshift of the energetics due to the dispersion corrections is observed.

Assessing implicit models for nonpolar mean solvation forces: The importance of dispersion and volume terms

PubMed Central

Wagoner, Jason A.; Baker, Nathan A.

2006-01-01

Continuum solvation models provide appealing alternatives to explicit solvent methods because of their ability to reproduce solvation effects while alleviating the need for expensive sampling. Our previous work has demonstrated that Poisson-Boltzmann methods are capable of faithfully reproducing polar explicit solvent forces for dilute protein systems; however, the popular solvent-accessible surface area model was shown to be incapable of accurately describing nonpolar solvation forces at atomic-length scales. Therefore, alternate continuum methods are needed to reproduce nonpolar interactions at the atomic scale. In the present work, we address this issue by supplementing the solvent-accessible surface area model with additional volume and dispersion integral terms suggested by scaled particle models and Weeks–Chandler–Andersen theory, respectively. This more complete nonpolar implicit solvent model shows very good agreement with explicit solvent results and suggests that, although often overlooked, the inclusion of appropriate dispersion and volume terms are essential for an accurate implicit solvent description of atomic-scale nonpolar forces. PMID:16709675

Interlayer coupling effects on Schottky barrier in the arsenene-graphene van der Waals heterostructures

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

Xia, Congxin, E-mail: xiacongxin@htu.edu.cn; Xue, Bin; Wang, Tianxing

The electronic characteristics of arsenene-graphene van der Waals (vdW) heterostructures are studied by using first-principles methods. The results show that a linear Dirac-like dispersion relation around the Fermi level can be quite well preserved in the vdW heterostructures. Moreover, the p-type Schottky barrier (0.18 eV) to n-type Schottky barrier (0.31 eV) transition occurs when the interlayer distance increases from 2.8 to 4.5 Å, which indicates that the Schottky barrier can be tuned effectively by the interlayer distance in the vdW heterostructures.

Nonlocal van der Waals functionals: The case of rare-gas dimers and solids

NASA Astrophysics Data System (ADS)

Tran, Fabien; Hutter, Jürg

2013-05-01

Recently, the nonlocal van der Waals (vdW) density functionals [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004), 10.1103/PhysRevLett.92.246401] have attracted considerable attention due to their good performance for systems where weak interactions are important. Since the physics of dispersion is included in these functionals, they are usually more accurate and show less erratic behavior than the semilocal and hybrid methods. In this work, several variants of the vdW functionals have been tested on rare-gas dimers (from He2 to Kr2) and solids (Ne, Ar, and Kr) and their accuracy compared to standard semilocal approximations, supplemented or not by an atom-pairwise dispersion correction [S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010), 10.1063/1.3382344]. An analysis of the results in terms of energy decomposition is also provided.

Mirror force induced wave dispersion in Alfvén waves

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

Damiano, P. A.; Johnson, J. R.

2013-06-15

Recent hybrid MHD-kinetic electron simulations of global scale standing shear Alfvén waves along the Earth's closed dipolar magnetic field lines show that the upward parallel current region within these waves saturates and broadens perpendicular to the ambient magnetic field and that this broadening increases with the electron temperature. Using resistive MHD simulations, with a parallel Ohm's law derived from the linear Knight relation (which expresses the current-voltage relationship along an auroral field line), we explore the nature of this broadening in the context of the increased perpendicular Poynting flux resulting from the increased parallel electric field associated with mirror forcemore » effects. This increased Poynting flux facilitates wave energy dispersion across field lines which in-turn allows for electron acceleration to carry the field aligned current on adjacent field lines. This mirror force driven dispersion can dominate over that associated with electron inertial effects for global scale waves.« less

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

NASA Astrophysics Data System (ADS)

Miceli, Giacomo; de Gironcoli, Stefano; Pasquarello, Alfredo

2015-01-01

We investigate the structural properties of liquid water at near ambient conditions using first-principles molecular dynamics simulations based on a semilocal density functional augmented with nonlocal van der Waals interactions. The adopted scheme offers the advantage of simulating liquid water at essentially the same computational cost of standard semilocal functionals. Applied to the water dimer and to ice Ih, we find that the hydrogen-bond energy is only slightly enhanced compared to a standard semilocal functional. We simulate liquid water through molecular dynamics in the NpH statistical ensemble allowing for fluctuations of the system density. The structure of the liquid departs from that found with a semilocal functional leading to more compact structural arrangements. This indicates that the directionality of the hydrogen-bond interaction has a diminished role as compared to the overall attractions, as expected when dispersion interactions are accounted for. This is substantiated through a detailed analysis comprising the study of the partial radial distribution functions, various local order indices, the hydrogen-bond network, and the selfdiffusion coefficient. The explicit treatment of the van der Waals interactions leads to an overall improved description of liquid water.

Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.

PubMed

Pramanik, Chandrani; Gissinger, Jacob R; Kumar, Satish; Heinz, Hendrik

2017-12-26

Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m 2 in the pure solvents, + 20 to +40 mJ/m 2 in PAN solutions, and +20 to +60 mJ/m 2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Measuring the thermal boundary resistance of van der Waals contacts using an individual carbon nanotube.

PubMed

Hirotani, Jun; Ikuta, Tatsuya; Nishiyama, Takashi; Takahashi, Koji

2013-01-16

Interfacial thermal transport via van der Waals interaction is quantitatively evaluated using an individual multi-walled carbon nanotube bonded on a platinum hot-film sensor. The thermal boundary resistance per unit contact area was obtained at the interface between the closed end or sidewall of the nanotube and platinum, gold, or a silicon dioxide surface. When taking into consideration the surface roughness, the thermal boundary resistance at the sidewall is found to coincide with that at the closed end. A new finding is that the thermal boundary resistance between a carbon nanotube and a solid surface is independent of the materials within the experimental errors, which is inconsistent with a traditional phonon mismatch model, which shows a clear material dependence of the thermal boundary resistance. Our data indicate the inapplicability of existing phonon models when weak van der Waals forces are dominant at the interfaces.

van der Waals criticality in AdS black holes: A phenomenological study

NASA Astrophysics Data System (ADS)

Bhattacharya, Krishnakanta; Majhi, Bibhas Ranjan; Samanta, Saurav

2017-10-01

Anti-de Sitter black holes exhibit van der Waals-type phase transition. In the extended phase-space formalism, the critical exponents for any spacetime metric are identical to the standard ones. Motivated by this fact, we give a general expression for the Helmholtz free energy near the critical point, which correctly reproduces these exponents. The idea is similar to the Landau model, which gives a phenomenological description of the usual second-order phase transition. Here, two main inputs are taken into account for the analysis: (a) black holes should have van der Waals-like isotherms, and (b) free energy can be expressed solely as a function of thermodynamic volume and horizon temperature. Resulting analysis shows that the form of Helmholtz free energy correctly encapsulates the features of the Landau function. We also discuss the isolated critical point accompanied by nonstandard values of critical exponents. The whole formalism is then extended to two other criticalities, namely, Y -X and T -S (based on the standard; i.e., nonextended phase space), where X and Y are generalized force and displacement, whereas T and S are the horizon temperature and entropy. We observe that in the former case Gibbs free energy plays the role of Landau function, whereas in the later case, that role is played by the internal energy (here, it is the black hole mass). Our analysis shows that, although the existence of a van der Waals phase transition depends on the explicit form of the black hole metric, the values of the critical exponents are universal in nature.

Effect of dispersion forces on squeezing with Rydberg atoms

NASA Technical Reports Server (NTRS)

Ng, S. K.; Muhamad, M. R.; Wahiddin, M. R. B.

1994-01-01

We report exact results concerning the effect of dipole-dipole interaction (dispersion forces) on dynamic and steady-state characteristics of squeezing in the emitted fluorescent field from two identical coherently driven two-level atoms. The atomic system is subjected to three different damping baths in particular the normal vacuum, a broad band thermal field and a broad band squeezed vacuum. The atomic model is the Dicke model, hence possible experiments are most likely to agree with theory when performed on systems of Rydberg atoms making microwave transitions. The presence of dipole-dipole interaction can enhance squeezing for realizable values of the various parameters involved.

Modified Van der Waals equation and law of corresponding states

NASA Astrophysics Data System (ADS)

Zhong, Wei; Xiao, Changming; Zhu, Yongkai

2017-04-01

It is well known that the Van der Waals equation is a modification of the ideal gas law, yet it can be used to describe both gas and liquid, and some important messages can be obtained from this state equation. However, the Van der Waals equation is not a precise state equation, and it does not give a good description of the law of corresponding states. In this paper, we expand the Van der Waals equation into its Taylor's series form, and then modify the fourth order expansion by changing the constant Virial coefficients into their analogous ones. Via this way, a more precise result about the law of corresponding states has been obtained, and the law of corresponding states can then be expressed as: in terms of the reduced variables, all fluids should obey the same equation with the analogous Virial coefficients. In addition, the system of 3 He with quantum effects has also been taken into consideration with our modified Van der Waals equation, and it is found that, for a normal system without quantum effect, the modification on ideal gas law from the Van der Waals equation is more significant than the real case, however, for a system with quantum effect, this modification is less significant than the real case, thus a factor is introduced in this paper to weaken or strengthen the modification of the Van der Waals equation, respectively.

van der Waals epitaxy of Ge films on mica

NASA Astrophysics Data System (ADS)

Littlejohn, A. J.; Xiang, Y.; Rauch, E.; Lu, T.-M.; Wang, G.-C.

2017-11-01

To date, many materials have been successfully grown on substrates through van der Waals epitaxy without adhering to the constraint of lattice matching as is required for traditional chemical epitaxy. However, for elemental semiconductors such as Ge, this has been challenging and therefore it has not been achieved thus far. In this paper, we report the observation of Ge epitaxially grown on mica at a narrow substrate temperature range around 425 °C. Despite the large lattice mismatch (23%) and the lack of high in-plane symmetry in the mica surface, an epitaxial Ge film with [111] out-of-plane orientation is observed. Crystallinity and electrical properties degrade upon deviation from the ideal growth temperature, as shown by Raman spectroscopy, X-ray diffraction, and Hall effect measurements. X-ray pole figure analysis reveals that there exist multiple rotational domains in the epitaxial Ge film with dominant in-plane orientations between Ge [" separators="|1 ¯10 ] and mica[100] of (20 n )°, where n = 0, 1, 2, 3, 4, 5. A superlattice area mismatch model was used to account for the likelihood of the in-plane orientation formation and was found to be qualitatively consistent with the observed dominant orientations. Our observation of Ge epitaxy with one out-of-plane growth direction through van der Waals forces is a step toward the growth of single crystal Ge films without the constraint in the lattice and symmetry matches with the substrates.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

NASA Astrophysics Data System (ADS)

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N.; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-01

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10-21 J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

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

Elzbieciak-Wodka, Magdalena; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10{sup −21} J at a separation distance of about 10 nm. Thismore » value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.« less

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory.

PubMed

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N; Montes Ruiz-Cabello, F Javier; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10(-21) J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Density-Dependent Formulation of Dispersion-Repulsion Interactions in Hybrid Multiscale Quantum/Molecular Mechanics (QM/MM) Models.

PubMed

Curutchet, Carles; Cupellini, Lorenzo; Kongsted, Jacob; Corni, Stefano; Frediani, Luca; Steindal, Arnfinn Hykkerud; Guido, Ciro A; Scalmani, Giovanni; Mennucci, Benedetta

2018-03-13

Mixed multiscale quantum/molecular mechanics (QM/MM) models are widely used to explore the structure, reactivity, and electronic properties of complex chemical systems. Whereas such models typically include electrostatics and potentially polarization in so-called electrostatic and polarizable embedding approaches, respectively, nonelectrostatic dispersion and repulsion interactions are instead commonly described through classical potentials despite their quantum mechanical origin. Here we present an extension of the Tkatchenko-Scheffler semiempirical van der Waals (vdW TS ) scheme aimed at describing dispersion and repulsion interactions between quantum and classical regions within a QM/MM polarizable embedding framework. Starting from the vdW TS expression, we define a dispersion and a repulsion term, both of them density-dependent and consistently based on a Lennard-Jones-like potential. We explore transferable atom type-based parametrization strategies for the MM parameters, based on either vdW TS calculations performed on isolated fragments or on a direct estimation of the parameters from atomic polarizabilities taken from a polarizable force field. We investigate the performance of the implementation by computing self-consistent interaction energies for the S22 benchmark set, designed to represent typical noncovalent interactions in biological systems, in both equilibrium and out-of-equilibrium geometries. Overall, our results suggest that the present implementation is a promising strategy to include dispersion and repulsion in multiscale QM/MM models incorporating their explicit dependence on the electronic density.

Rapid estimation of the electron correlation energy for van der Waals complexes RgX (Rg = Kr, Xe, X = Br, I)

NASA Astrophysics Data System (ADS)

Xinying, Li; Yongfang, Zhao; Xiaogong, Jing; Fengli, Liu; Fengyou, Hao

2006-01-01

We present the rules of electron correlation energies for RgX (Rg = Kr, Xe, X = Br, I) van der Waals (vdW) complex systems at CCSD(T) theoretical level with SDB-cc-pVQZ basis set by the Gaussian 98 program. A new method to derive the dispersion coefficient C6 by fitting the intermonomer electron correlation energies to C6R-6 function is introduced. The present C6 values are compared with the corresponding theoretical ones.

Uncertainties in forces extracted from non-contact atomic force microscopy measurements by fitting of long-range background forces.

PubMed

Sweetman, Adam; Stannard, Andrew

2014-01-01

In principle, non-contact atomic force microscopy (NC-AFM) now readily allows for the measurement of forces with sub-nanonewton precision on the atomic scale. In practice, however, the extraction of the often desired 'short-range' force from the experimental observable (frequency shift) is often far from trivial. In most cases there is a significant contribution to the total tip-sample force due to non-site-specific van der Waals and electrostatic forces. Typically, the contribution from these forces must be removed before the results of the experiment can be successfully interpreted, often by comparison to density functional theory calculations. In this paper we compare the 'on-minus-off' method for extracting site-specific forces to a commonly used extrapolation method modelling the long-range forces using a simple power law. By examining the behaviour of the fitting method in the case of two radically different interaction potentials we show that significant uncertainties in the final extracted forces may result from use of the extrapolation method.

Colossal terahertz nonlinearity of tunneling van der Waals gap (Conference Presentation)

NASA Astrophysics Data System (ADS)

Bahk, Young-Mi; Kang, Bong Joo; Kim, Yong Seung; Kim, Joon-Yeon; Kim, Won Tae; Kim, Tae Yun; Kang, Taehee; Rhie, Ji Yeah; Han, Sanghoon; Park, Cheol-Hwan; Rotermund, Fabian; Kim, Dai-Sik

2016-09-01

We manufactured an array of three angstrom-wide, five millimeter-long van der Waals gaps of copper-graphene-copper composite, in which unprecedented nonlinearity was observed. To probe and manipulate van der Waals gaps with long wavelength electromagnetic waves such as terahertz waves, one is required to fabricate vertically oriented van der Waals gaps sandwiched between two metal planes with an infinite length in the sense of being much larger than any of the wavelengths used. By comparison with the simple vertical stacking of metal-graphene-metal structure, in our structure, background signals are completely blocked enabling all the light to squeeze through the gap without any strays. When the angstrom-sized van der Waals gaps are irradiated with intense terahertz pulses, the transient voltage across the gap reaches up to 5 V with saturation, sufficiently strong to deform the quantum barrier of angstrom gaps. The large transient potential difference across the gap facilitates electron tunneling through the quantum barrier, blocking terahertz waves completely. This negative feedback of electron tunneling leads to colossal nonlinear optical response, a 97% decrease in the normalized transmittance. Our technology for infinitely long van der Waals gaps can be utilized for other atomically thin materials than single layer graphene, enabling linear and nonlinear angstrom optics in a broad spectral range.

Ergodicity of Truncated Stochastic Navier Stokes with Deterministic Forcing and Dispersion

NASA Astrophysics Data System (ADS)

Majda, Andrew J.; Tong, Xin T.

2016-10-01

Turbulence in idealized geophysical flows is a very rich and important topic. The anisotropic effects of explicit deterministic forcing, dispersive effects from rotation due to the β -plane and F-plane, and topography together with random forcing all combine to produce a remarkable number of realistic phenomena. These effects have been studied through careful numerical experiments in the truncated geophysical models. These important results include transitions between coherent jets and vortices, and direct and inverse turbulence cascades as parameters are varied, and it is a contemporary challenge to explain these diverse statistical predictions. Here we contribute to these issues by proving with full mathematical rigor that for any values of the deterministic forcing, the β - and F-plane effects and topography, with minimal stochastic forcing, there is geometric ergodicity for any finite Galerkin truncation. This means that there is a unique smooth invariant measure which attracts all statistical initial data at an exponential rate. In particular, this rigorous statistical theory guarantees that there are no bifurcations to multiple stable and unstable statistical steady states as geophysical parameters are varied in contrast to claims in the applied literature. The proof utilizes a new statistical Lyapunov function to account for enstrophy exchanges between the statistical mean and the variance fluctuations due to the deterministic forcing. It also requires careful proofs of hypoellipticity with geophysical effects and uses geometric control theory to establish reachability. To illustrate the necessity of these conditions, a two-dimensional example is developed which has the square of the Euclidean norm as the Lyapunov function and is hypoelliptic with nonzero noise forcing, yet fails to be reachable or ergodic.

Cosmological models constructed by van der Waals fluid approximation and volumetric expansion

NASA Astrophysics Data System (ADS)

Samanta, G. C.; Myrzakulov, R.

The universe modeled with van der Waals fluid approximation, where the van der Waals fluid equation of state contains a single parameter ωv. Analytical solutions to the Einstein’s field equations are obtained by assuming the mean scale factor of the metric follows volumetric exponential and power-law expansions. The model describes a rapid expansion where the acceleration grows in an exponential way and the van der Waals fluid behaves like an inflation for an initial epoch of the universe. Also, the model describes that when time goes away the acceleration is positive, but it decreases to zero and the van der Waals fluid approximation behaves like a present accelerated phase of the universe. Finally, it is observed that the model contains a type-III future singularity for volumetric power-law expansion.

Statistical Physics of Colloidal Dispersions.

NASA Astrophysics Data System (ADS)

Canessa, E.

Available from UMI in association with The British Library. Requires signed TDF. This thesis is concerned with the equilibrium statistical mechanics of colloidal dispersions which represent useful model systems for the study of condensed matter physics; namely, charge stabilized colloidal dispersions and polymer stabilized colloidal dispersions. A one-component macroparticle approach is adopted in order to treat the macroscopic and microscopic properties of these systems in a simple and comprehensive manner. The thesis opens with the description of the nature of the colloidal state before reviewing some basic definitions and theory in Chapter II. In Chapter III a variational theory of phase equilibria based on the Gibbs-Bogolyobov inequality is applied to sterically stabilized colloidal dispersions. Hard spheres are chosen as the reference system for the disordered phases while an Einstein model is used for the ordered phases. The new choice of pair potential, taken for mathematical convenience, is a superposition of two Yukawa functions. By matching a double Yukawa potential to the van der Waals attractive potential at different temperatures and introducing a purely temperature dependent coefficient to the repulsive part, a rich variety of observed phase separation phenomena is qualitatively described. The behaviour of the potential is found to be consistent with a small decrease of the polymer layer thickness with increasing temperature. Using the same concept of a collapse transition the non-monotonic second virial coefficient is also explained and quantified. It is shown that a reduction of the effective macroparticle diameter with increasing temperature can only be partially examined from the point of view of a (binary-) polymer solution theory. This chapter concludes with the description of the observed, reversible, depletion flocculation behaviour. This is accomplished by using the variational formalism and by invoking the double Yukawa potential to allow

Scanning Probe Microscopy and Electrical Transport Studies of Ferroelectric Thin Films and 2D van der Waals Materials

NASA Astrophysics Data System (ADS)

Xiao, Zhiyong

In this dissertation, I present the scanning microscopy and electrical transport studies of ferroelectric thin films and ferroic/2D van der Waals heterostructures. Based on the conducting probe atomic force microscopy and piezo-response force microscopy (PFM) studies of the static and dynamic behavior of ferroelectric domain walls (DW), we found that the ferroelectric polymer poly(vinylidene-fluoride-trifluorethylene) P(VDF-TrFE) is composed of two-dimensional (2D) ferroelectric monolayers (MLs) that are weakly coupled to each other. We also observed polarization asymmetry in epitaxial thin films of ferroelectric Pb(Zr,Ti)O3, which is attributed to the screening properties of the underlying conducting oxide. PFM studies also reveal ferroelectric relaxor-type behavior in ultrathin Sr(Zr,Ti)O3 films epitaxially deposited on Ge. We exploited scanning-probe-controlled domain patterning in a P(VDF-TrFE) top layer to induce nonvolatile modulation of the conduction characteristic of ML molybdenum disulfide (MoS2) between a transistor and a junction state. In the presence of a DW, MoS2 exhibits rectified Ids-Vds (IV) characteristics that are well described by the thermionic emission model. This approach can be applied to a wide range of van der Waals materials to design various functional homojunctions and nanostructures. We also studied the interfacial charge transfer effect between graphene and magnetoelectric Cr2O3 via electrostatic force microscopy and Kelvin probe force microscopy, which reveal p-type doping with up to 150 meV shift of the Fermi level. The graphene/Cr2O3 heterostructure is promising for developing magnetoelectric graphene transistors for spintronic applications.

Assessing the attractive/repulsive force balance in axial cyclohexane C-Hax ···Yax contacts: A combined computational analysis in monosubstituted cyclohexanes.

PubMed

Silva Lopez, Carlos; Nieto Faza, Olalla; De Proft, Frank; Kolocouris, Antonios

2016-11-15

The interactions of axial substituents in monosubstituted cyclohexane rings are studied in this work using an array of different computational techniques. Additionally, the anomalous axial preference for some bulky substituents is related to stabilizing dispersion interactions. We find that the C-H ax ···Y ax contacts for various substituents with distances ranging from 2 to ∼5 Å may include attractive dispersion forces that can affect the conformational equilibrium; these forces co-exist with Pauli repulsive forces effected by Y ax group due to van der Waals sphere penetration. At distances between 2 and 3 Å stabilizing electron transfer interactions were calculated and the combination of natural bond orbital and QTAIM analysis showed that, in certain cases, Y ax  =  t Bu, C ax -O or C ax  = O or S ax  = O or C ax  = S this interaction can be characterized as an improper H-bond. DFT-D3 and non-covalent interactions calculations (NCIs) in cyclohexane derivatives with Y ax  = SiOR 3 including H Yax ···H cy surfaces at distances ranging between 4 and 6 Å suggest that dispersion has a clear effect on the experimentally observed stabilization of the axial conformer. NCIs computed from the reduced density gradient help to visually identify and analyze these interactions. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Single-particle dispersion in compressible turbulence

NASA Astrophysics Data System (ADS)

Zhang, Qingqing; Xiao, Zuoli

2018-04-01

Single-particle dispersion statistics in compressible box turbulence are studied using direct numerical simulation. Focus is placed on the detailed discussion of effects of the particle Stokes number and turbulent Mach number, as well as the forcing type. When solenoidal forcing is adopted, it is found that the single-particle dispersion undergoes a transition from the ballistic regime at short times to the diffusive regime at long times, in agreement with Taylor's particle dispersion argument. The strongest dispersion of heavy particles is announced when the Stokes number is of order 1, which is similar to the scenario in incompressible turbulence. The dispersion tends to be suppressed as the Mach number increases. When hybrid solenoidal and compressive forcing at a ratio of 1/2 is employed, the flow field shows apparent anisotropic property, characterized by the appearance of large shock wave structures. Accordingly, the single-particle dispersion shows extremely different behavior from the solenoidal forcing case.

Two- and three-body interatomic dispersion energy contributions to binding in molecules and solids

NASA Astrophysics Data System (ADS)

Anatole von Lilienfeld, O.; Tkatchenko, Alexandre

2010-06-01

We present numerical estimates of the leading two- and three-body dispersion energy terms in van der Waals interactions for a broad variety of molecules and solids. The calculations are based on London and Axilrod-Teller-Muto expressions where the required interatomic dispersion energy coefficients, C6 and C9, are computed "on the fly" from the electron density. Inter- and intramolecular energy contributions are obtained using the Tang-Toennies (TT) damping function for short interatomic distances. The TT range parameters are equally extracted on the fly from the electron density using their linear relationship to van der Waals radii. This relationship is empiricially determined for all the combinations of He-Xe rare gas dimers, as well as for the He and Ar trimers. The investigated systems include the S22 database of noncovalent interactions, Ar, benzene and ice crystals, bilayer graphene, C60 dimer, a peptide (Ala10), an intercalated drug-DNA model [ellipticine-d(CG)2], 42 DNA base pairs, a protein (DHFR, 2616 atoms), double stranded DNA (1905 atoms), and 12 molecular crystal polymorphs from crystal structure prediction blind test studies. The two- and three-body interatomic dispersion energies are found to contribute significantly to binding and cohesive energies, for bilayer graphene the latter reaches 50% of experimentally derived binding energy. These results suggest that interatomic three-body dispersion potentials should be accounted for in atomistic simulations when modeling bulky molecules or condensed phase systems.

Excitons in one-dimensional van der Waals materials: Sb2S3 nanoribbons

NASA Astrophysics Data System (ADS)

Caruso, Fabio; Filip, Marina R.; Giustino, Feliciano

2015-09-01

Antimony sulphide Sb2S3 has emerged as a promising material for a variety of energy applications ranging from solar cells to thermoelectrics and solid-state batteries. The most distinctive feature of Sb2S3 is its crystal structure, which consists of parallel 1-nm-wide ribbons held together by weak van der Waals forces. This structure clearly suggests that it should be possible to isolate individual Sb2S3 ribbons using micromechanical or liquid-phase exfoliation techniques. However, it is not clear yet how to identify the ribbons postexfoliation using standard optical probes. Using state-of-the-art first-principles calculations based on many-body perturbation theory, here we show that individual ribbons of Sb2S3 carry optical signatures clearly distinct from those of bulk Sb2S3 . In particular, we find a large blueshift of the optical absorption edge (from 1.38 to 2.30 eV) resulting from the interplay between a reduced screening and the formation of bound excitons. In addition, we observe a transition from an indirect band gap to a direct gap, suggesting an enhanced photoluminescence in the green. These unique fingerprints will enable extending the research on van der Waals materials to the case of one-dimensional chalchogenides.

Quantum state atomic force microscopy

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

Passian, Ali; Siopsis, George

New classical modalities of atomic force microscopy continue to emerge to achieve higher spatial, spectral, and temporal resolution for nanometrology of materials. Here, we introduce the concept of a quantum mechanical modality that capitalizes on squeezed states of probe displacement. We show that such squeezing is enabled nanomechanically when the probe enters the van der Waals regime of interaction with a sample. The effect is studied in the non-contact mode, where we consider the parameter domains characterizing the attractive regime of the probe-sample interaction force.

Quantum state atomic force microscopy

DOE PAGES

Passian, Ali; Siopsis, George

2017-04-10

New classical modalities of atomic force microscopy continue to emerge to achieve higher spatial, spectral, and temporal resolution for nanometrology of materials. Here, we introduce the concept of a quantum mechanical modality that capitalizes on squeezed states of probe displacement. We show that such squeezing is enabled nanomechanically when the probe enters the van der Waals regime of interaction with a sample. The effect is studied in the non-contact mode, where we consider the parameter domains characterizing the attractive regime of the probe-sample interaction force.

On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures.

PubMed

Santra, Biswajit; Klimes, Jirí; Tkatchenko, Alexandre; Alfè, Dario; Slater, Ben; Michaelides, Angelos; Car, Roberto; Scheffler, Matthias

2013-10-21

Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [B. Santra, J. Klimeš, D. Alfè, A. Tkatchenko, B. Slater, A. Michaelides, R. Car, and M. Scheffler, Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.

Dynamical screening of the van der Waals interaction between graphene layers.

PubMed

Dappe, Y J; Bolcatto, P G; Ortega, J; Flores, F

2012-10-24

The interaction between graphene layers is analyzed combining local orbital DFT and second order perturbation theory. For this purpose we use the linear combination of atomic orbitals-orbital occupancy (LCAO-OO) formalism, that allows us to separate the interaction energy as the sum of a weak chemical interaction between graphene layers plus the van der Waals interaction (Dappe et al 2006 Phys. Rev. B 74 205434). In this work, the weak chemical interaction is calculated by means of corrected-LDA calculations using an atomic-like sp(3)d(5) basis set. The van der Waals interaction is calculated by means of second order perturbation theory using an atom-atom interaction approximation and the atomic-like-orbital occupancies. We also analyze the effect of dynamical screening in the van der Waals interaction using a simple model. We find that this dynamical screening reduces by 40% the van der Waals interaction. Taking this effect into account, we obtain a graphene-graphene interaction energy of 70 ± 5 meV/atom in reasonable agreement with the experimental evidence.

Localized overlap algorithm for unexpanded dispersion energies

NASA Astrophysics Data System (ADS)

Rob, Fazle; Misquitta, Alston J.; Podeszwa, Rafał; Szalewicz, Krzysztof

2014-03-01

First-principles-based, linearly scaling algorithm has been developed for calculations of dispersion energies from frequency-dependent density susceptibility (FDDS) functions with account of charge-overlap effects. The transition densities in FDDSs are fitted by a set of auxiliary atom-centered functions. The terms in the dispersion energy expression involving products of such functions are computed using either the unexpanded (exact) formula or from inexpensive asymptotic expansions, depending on the location of these functions relative to the dimer configuration. This approach leads to significant savings of computational resources. In particular, for a dimer consisting of two elongated monomers with 81 atoms each in a head-to-head configuration, the most favorable case for our algorithm, a 43-fold speedup has been achieved while the approximate dispersion energy differs by less than 1% from that computed using the standard unexpanded approach. In contrast, the dispersion energy computed from the distributed asymptotic expansion differs by dozens of percent in the van der Waals minimum region. A further increase of the size of each monomer would result in only small increased costs since all the additional terms would be computed from the asymptotic expansion.

A crossover in anisotropic nanomechanochemistry of van der Waals crystals

NASA Astrophysics Data System (ADS)

Shimamura, Kohei; Misawa, Masaaki; Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Shimojo, Fuyuki; Vashishta, Priya

2015-12-01

In nanoscale mechanochemistry, mechanical forces selectively break covalent bonds to essentially control chemical reactions. An archetype is anisotropic detonation of layered energetic molecular crystals bonded by van der Waals (vdW) interactions. Here, quantum molecular dynamics simulations reveal a crossover of anisotropic nanomechanochemistry of vdW crystal. Within 10-13 s from the passage of shock front, lateral collision produces NO2 via twisting and bending of nitro-groups and the resulting inverse Jahn-Teller effect, which is mediated by strong intra-layer hydrogen bonds. Subsequently, as we transition from heterogeneous to homogeneous mechanochemical regimes around 10-12 s, shock normal to multilayers becomes more reactive, producing H2O assisted by inter-layer N-N bond formation. These time-resolved results provide much needed atomistic understanding of nanomechanochemistry that underlies a wider range of technologies.

A variation-perturbation method for atomic and molecular interactions. I - Theory. II - The interaction potential and van der Waals molecule for Ne-HF

NASA Astrophysics Data System (ADS)

Gallup, G. A.; Gerratt, J.

1985-09-01

The van der Waals energy between the two parts of a system is a very small fraction of the total electronic energy. In such cases, calculations have been based on perturbation theory. However, such an approach involves certain difficulties. For this reason, van der Waals energies have also been directly calculated from total energies. But such a method has definite limitations as to the size of systems which can be treated, and recently ab initio calculations have been combined with damped semiempirical long-range dispersion potentials to treat larger systems. In this procedure, large basis set superposition errors occur, which must be removed by the counterpoise method. The present investigation is concerned with an approach which is intermediate between the previously considered procedures. The first step in the new approach involves a variational calculation based upon valence bond functions. The procedure includes also the optimization of excited orbitals, and an approximation of atomic integrals and Hamiltonian matrix elements.

Hydrogen bonding and pi-stacking: how reliable are force fields? A critical evaluation of force field descriptions of nonbonded interactions.

PubMed

Paton, Robert S; Goodman, Jonathan M

2009-04-01

We have evaluated the performance of a set of widely used force fields by calculating the geometries and stabilization energies for a large collection of intermolecular complexes. These complexes are representative of a range of chemical and biological systems for which hydrogen bonding, electrostatic, and van der Waals interactions play important roles. Benchmark energies are taken from the high-level ab initio values in the JSCH-2005 and S22 data sets. All of the force fields underestimate stabilization resulting from hydrogen bonding, but the energetics of electrostatic and van der Waals interactions are described more accurately. OPLSAA gave a mean unsigned error of 2 kcal mol(-1) for all 165 complexes studied, and outperforms DFT calculations employing very large basis sets for the S22 complexes. The magnitude of hydrogen bonding interactions are severely underestimated by all of the force fields tested, which contributes significantly to the overall mean error; if complexes which are predominantly bound by hydrogen bonding interactions are discounted, the mean unsigned error of OPLSAA is reduced to 1 kcal mol(-1). For added clarity, web-based interactive displays of the results have been developed which allow comparisons of force field and ab initio geometries to be performed and the structures viewed and rotated in three dimensions.

An exact solution of the van der Waals interaction between two ground-state hydrogen atoms

NASA Astrophysics Data System (ADS)

Koga, Toshikatsu; Matsumoto, Shinya

1985-06-01

A momentum space treatment shows that perturbation equations for the H(1s)-H(1s) van der Waals interaction can be exactly solved in their Schrödinger forms without invoking any variational methods. Using the Fock transformation, which projects the momentum vector of an electron from the three-dimensional hyperplane onto the four-dimensional hypersphere, we solve the third order integral-type perturbation equation with respect to the reciprocal of the internuclear distance R. An exact third order wave function is found as a linear combination of infinite number of four-dimensional spherical harmonics. The result allows us to evaluate the exact dispersion energy E6R-6, which is completely determined by the first three coefficients of the above linear combination.

Dispersal forcing of a southern California river plumes, based on field and remote sensing observations

USGS Publications Warehouse

Warrick, Jonathan A.; Mertes, Leal A.K.; Washburn, Libe; Siegel, David A.

2004-01-01

River plumes are important pathways of terrestrial materials entering the sea. In southern California, rivers are known to be the dominant source of littoral, shelf and basin sediment and coastal pollution, although a basic understanding of the dynamics of these river inputs does not exist. Here we evaluate forcing parameters of a southern California river plume using ship-based hydrographic surveys and satellite remote sensing measurements to provide the first insights of river dispersal dynamics in southern California. Our results suggest that plumes of the Santa Clara River are strongly influenced by river inertia, producing jet-like structures ~10 km offshore during annual recurrence (~two-year) flood events and ~30 km during exceptional (~10-year recurrence) floods. Upwelling-favorable winds may be strong following stormwater events and can alter dispersal pathways of thse plumes. Due to similar runoff relationships and other reported satellite observations, we hypothesize that interia-dominated dispersal may be an important characteristic of the small, mountainous rivers throughout southern California.

Establishing conditions for simulating hydrophobic solutes in electric fields by molecular dynamics: effects of the long-range van der Waals treatment on the apparent particle mobility.

PubMed

Miličević, Zoran; Marrink, Siewert J; Smith, Ana-Sunčana; Smith, David M

2014-08-01

Despite considerable effort over the last decade, the interactions between solutes and solvents in the presence of electric fields have not yet been fully understood. A very useful manner in which to study these systems is through the application of molecular dynamics (MD) simulations. However, a number of MD studies have shown a tremendous sensitivity of the migration rate of a hydrophobic solute to the treatment of the long range part of the van der Waals interactions. While the origin of this sensitivity was never explained, the mobility is currently regarded as an artifact of an improper simulation setup. We explain the spread in observed mobilites by performing extensive molecular dynamics simulations using the GROMACS software package on a system consisting of a model hydrophobic object (Lennard-Jones particle) immersed in water both in the presence and absence of a static electric field. We retrieve a unidirectional field-induced mobility of the hydrophobic object when the forces are simply truncated. Careful analysis of the data shows that, only in the specific case of truncated forces, a non-zero van der Waals force acts, on average, on the Lennard-Jones particle. Using the Stokes law we demonstrate that this force yields quantitative agreement with the field-induced mobility found within this setup. In contrast, when the treatment of forces is continuous, no net force is observed. In this manner, we provide a simple explanation for the previously controversial reports.

Many-body van der Waals interactions in molecules and condensed matter.

PubMed

DiStasio, Robert A; Gobre, Vivekanand V; Tkatchenko, Alexandre

2014-05-28

This work reviews the increasing evidence that many-body van der Waals (vdW) or dispersion interactions play a crucial role in the structure, stability and function of a wide variety of systems in biology, chemistry and physics. Starting with the exact expression for the electron correlation energy provided by the adiabatic connection fluctuation-dissipation theorem, we derive both pairwise and many-body interatomic methods for computing the long-range dispersion energy by considering a model system of coupled quantum harmonic oscillators within the random-phase approximation. By coupling this approach to density functional theory, the resulting many-body dispersion (MBD) method provides an accurate and efficient scheme for computing the frequency-dependent polarizability and many-body vdW energy in molecules and materials with a finite electronic gap. A select collection of applications are presented that ascertain the fundamental importance of these non-bonded interactions across the spectrum of intermolecular (the S22 and S66 benchmark databases), intramolecular (conformational energies of alanine tetrapeptide) and supramolecular (binding energy of the 'buckyball catcher') complexes, as well as molecular crystals (cohesive energies in oligoacenes). These applications demonstrate that electrodynamic response screening and beyond-pairwise many-body vdW interactions--both captured at the MBD level of theory--play a quantitative, and sometimes even qualitative, role in describing the properties considered herein. This work is then concluded with an in-depth discussion of the challenges that remain in the future development of reliable (accurate and efficient) methods for treating many-body vdW interactions in complex materials and provides a roadmap for navigating many of the research avenues that are yet to be explored.

Empathy's purity, sympathy's complexities; De Waal, Darwin and Adam Smith.

PubMed

van der Weele, Cor

2011-07-01

Frans de Waal's view that empathy is at the basis of morality directly seems to build on Darwin, who considered sympathy as the crucial instinct. Yet when we look closer, their understanding of the central social instinct differs considerably. De Waal sees our deeply ingrained tendency to sympathize (or rather: empathize) with others as the good side of our morally dualistic nature. For Darwin, sympathizing was not the whole story of the "workings of sympathy"; the (selfish) need to receive sympathy played just as central a role in the complex roads from sympathy to morality. Darwin's understanding of sympathy stems from Adam Smith, who argued that the presence of morally impure motives should not be a reason for cynicism about morality. I suggest that De Waal's approach could benefit from a more thorough alignment with the analysis of the workings of sympathy in the work of Darwin and Adam Smith.

Effect of dispersion forces on the capillary-wave fluctuations of liquid surfaces.

PubMed

Chacón, Enrique; Fernández, Eva M; Tarazona, Pedro

2014-04-01

We present molecular dynamics evidence for the nonanalytic effects of the long-range dispersion forces on the capillary waves fluctuations of a Lennard-Jones liquid surface. The results of the intrinsic sampling method, for the analysis of the instantaneous interfacial shape, are obtained in large systems for several cut-off distances of the potential tail, and they show good agreement with the theoretical prediction by Napiórkowski and Dietrich, based on a density functional analysis. The enhancement of the capillary waves is quantified to be within 1% for a simple liquid near its triple point.

Atomically thin p-n junctions with van der Waals heterointerfaces.

PubMed

Lee, Chul-Ho; Lee, Gwan-Hyoung; van der Zande, Arend M; Chen, Wenchao; Li, Yilei; Han, Minyong; Cui, Xu; Arefe, Ghidewon; Nuckolls, Colin; Heinz, Tony F; Guo, Jing; Hone, James; Kim, Philip

2014-09-01

Semiconductor p-n junctions are essential building blocks for electronic and optoelectronic devices. In conventional p-n junctions, regions depleted of free charge carriers form on either side of the junction, generating built-in potentials associated with uncompensated dopant atoms. Carrier transport across the junction occurs by diffusion and drift processes influenced by the spatial extent of this depletion region. With the advent of atomically thin van der Waals materials and their heterostructures, it is now possible to realize a p-n junction at the ultimate thickness limit. Van der Waals junctions composed of p- and n-type semiconductors--each just one unit cell thick--are predicted to exhibit completely different charge transport characteristics than bulk heterojunctions. Here, we report the characterization of the electronic and optoelectronic properties of atomically thin p-n heterojunctions fabricated using van der Waals assembly of transition-metal dichalcogenides. We observe gate-tunable diode-like current rectification and a photovoltaic response across the p-n interface. We find that the tunnelling-assisted interlayer recombination of the majority carriers is responsible for the tunability of the electronic and optoelectronic processes. Sandwiching an atomic p-n junction between graphene layers enhances the collection of the photoexcited carriers. The atomically scaled van der Waals p-n heterostructures presented here constitute the ultimate functional unit for nanoscale electronic and optoelectronic devices.

Two and three-body interatomic dispersion energy contributions to binding in molecules and solids.

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

von Lilienfeld-Toal, Otto Anatole; Tkatchenko, Alexandre

We present numerical estimates of the leading two- and three-body dispersion energy terms in van der Waals interactions for a broad variety of molecules and solids. The calculations are based on London and Axilrod-Teller-Muto expressions where the required interatomic dispersion energy coefficients, C{sub 6} and C{sub 9}, are computed 'on the fly' from the electron density. Inter- and intramolecular energy contributions are obtained using the Tang-Toennies (TT) damping function for short interatomic distances. The TT range parameters are equally extracted on the fly from the electron density using their linear relationship to van der Waals radii. This relationship is empiriciallymore » determined for all the combinations of He-Xe rare gas dimers, as well as for the He and Ar trimers. The investigated systems include the S22 database of noncovalent interactions, Ar, benzene and ice crystals, bilayer graphene, C{sub 60} dimer, a peptide (Ala{sub 10}), an intercalated drug-DNA model [ellipticine-d(CG){sub 2}], 42 DNA base pairs, a protein (DHFR, 2616 atoms), double stranded DNA (1905 atoms), and 12 molecular crystal polymorphs from crystal structure prediction blind test studies. The two- and three-body interatomic dispersion energies are found to contribute significantly to binding and cohesive energies, for bilayer graphene the latter reaches 50% of experimentally derived binding energy. These results suggest that interatomic three-body dispersion potentials should be accounted for in atomistic simulations when modeling bulky molecules or condensed phase systems.« less

Surface and interface of epitaxial CdTe film on CdS buffered van der Waals mica substrate

NASA Astrophysics Data System (ADS)

Yang, Y.-B.; Seewald, L.; Mohanty, Dibyajyoti; Wang, Y.; Zhang, L. H.; Kisslinger, K.; Xie, Weiyu; Shi, J.; Bhat, I.; Zhang, Shengbai; Lu, T.-M.; Wang, G.-C.

2017-08-01

Single crystal CdTe films are desirable for optoelectronic device applications. An important strategy of creating films with high crystallinity is through epitaxial growth on a proper single crystal substrate. We report the metalorganic chemical vapor deposition of epitaxial CdTe films on the CdS/mica substrate. The epitaxial CdS film was grown on a mica surface by thermal evaporation. Due to the weak van der Waals forces, epitaxy is achieved despite the very large interface lattice mismatch between CdS and mica (∼21-55%). The surface morphology of mica, CdS and CdTe were quantified by atomic force microscopy. The near surface structures, orientations and texture of CdTe and CdS films were characterized by the unique reflection high-energy electron diffraction surface pole figure technique. The interfaces of CdTe and CdS films and mica were characterized by X-ray pole figure technique and transmission electron microscopy. The out-of-plane and in-plane epitaxy of the heteroepitaxial films stack are determined to be CdTe(111)//CdS(0001)//mica(001) and [1 bar2 1 bar]CdTe//[ 1 bar100]CdS//[010]mica, respectively. The measured photoluminescence (PL), time resolved PL, photoresponse, and Hall mobility of the CdTe/CdS/mica indicate quality films. The use of van der Waals surface to grow epitaxial CdTe/CdS films offers an alternative strategy towards infrared imaging and solar cell applications.

Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions.

PubMed

Blood-Forsythe, Martin A; Markovich, Thomas; DiStasio, Robert A; Car, Roberto; Aspuru-Guzik, Alán

2016-03-01

An accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most accurate models for including dispersion into density functional theory (DFT) is the range-separated many-body dispersion (MBD) method [A. Ambrosetti et al. , J. Chem. Phys. , 2014, 140 , 18A508], in which the correlation energy is modeled at short-range by a semi-local density functional and at long-range by a model system of coupled quantum harmonic oscillators. In this work, we develop analytical gradients of the MBD energy with respect to nuclear coordinates, including all implicit coordinate dependencies arising from the partitioning of the charge density into Hirshfeld effective volumes. To demonstrate the efficiency and accuracy of these MBD gradients for geometry optimizations of systems with intermolecular and intramolecular interactions, we optimized conformers of the benzene dimer and isolated small peptides with aromatic side-chains. We find excellent agreement with the wavefunction theory reference geometries of these systems (at a fraction of the computational cost) and find that MBD consistently outperforms the popular TS and D3(BJ) dispersion corrections. To demonstrate the performance of the MBD model on a larger system with supramolecular interactions, we optimized the C 60 @C 60 H 28 buckyball catcher host-guest complex. In our analysis, we also find that neglecting the implicit nuclear coordinate dependence arising from the charge density partitioning, as has been done in prior numerical treatments, leads to an unacceptable error in the MBD forces, with relative errors of ∼20% (on average) that can extend well beyond 100%.

Equations of state for crystalline zirconium iodide: The role of dispersion

NASA Astrophysics Data System (ADS)

Rossi, Matthew L.; Taylor, Christopher D.

2013-02-01

We present the first-principle equations of state of several zirconium iodides, ZrI2, ZrI3, and ZrI4, computed using density functional theory methods that apply various methods for introducing the dispersion correction. Iodides formed due to reaction of molecular or atomic iodine with zirconium and zircaloys are of particular interest due to their application to the cladding material used in the fabrication of nuclear fuel rods. Stress corrosion cracking (SCC), associated with fission product chemistry with the clad material, is a major concern in the life cycle of nuclear fuels, as many of the observed rod failures have occurred due to pellet-cladding chemical interactions (PCCI) [A. Atrens, G. Dannhäuser, G. Bäro, Stress-corrosion-cracking of zircaloy-4 cladding tubes, Journal of Nuclear Materials 126 (1984) 91-102; P. Rudling, R. Adamson, B. Cox, F. Garzarolli, A. Strasser, High burn-up fuel issues, Nuclear Engineering and Technology 40 (2008) 1-8]. A proper understanding of the physical properties of the corrosion products is, therefore, required for the development of a comprehensive SCC model. In this particular work, we emphasize that, while existing modeling techniques include methods to compute crystal structures and associated properties, it is important to capture intermolecular forces not traditionally included, such as van der Waals (dispersion) correction. Furthermore, crystal structures with stoichiometries favoring a high I:Zr ratio are found to be particularly sensitive, such that traditional density functional theory approaches that do not incorporate dispersion incorrectly predict significantly larger volumes of the lattice. This latter point is related to the diffuse nature of the iodide electron cloud.

Non-perturbative theory of dispersion interactions

NASA Astrophysics Data System (ADS)

Boström, M.; Thiyam, P.; Persson, C.; Parsons, D. F.; Buhmann, S. Y.; Brevik, I.; Sernelius, Bo E.

2015-03-01

Some open questions exist with fluctuation-induced forces between extended dipoles. Conventional intuition derives from large-separation perturbative approximations to dispersion force theory. Here, we present a full non-perturbative theory. In addition, we discuss how one can take into account finite dipole size corrections. It is of fundamental value to investigate the limits of validity of the perturbative dispersion force theory.

Controlling the electronic properties of van der Waals heterostructures by applying electrostatic design

NASA Astrophysics Data System (ADS)

Winkler, Christian; Harivyasi, Shashank S.; Zojer, Egbert

2018-07-01

Van der Waals heterostructures based on the heteroassembly of 2D materials represent a recently developed class of materials with promising properties especially for optoelectronic applications. The alignment of electronic energy bands between consecutive layers of these heterostructures crucially determines their functionality. In the present paper, relying on dispersion-corrected density-functional theory calculations, we present electrostatic design as a promising tool for manipulating this band alignment. The latter is achieved by inserting a layer of aligned polar molecules between consecutive transition-metal dichalcogenide (TMD) sheets. As a consequence, collective electrostatic effects induce a shift of as much as 0.3 eV in the band edges of successive TMD layers. Building on that, the proposed approach can be used to design electronically more complex systems, like quantum cascades or quantum wells, or to change the type of band lineup between type II and type I.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions.

PubMed

Wu, Bing; Zhao, Yinghe; Nan, Haiyan; Yang, Ziyi; Zhang, Yuhan; Zhao, Huijuan; He, Daowei; Jiang, Zonglin; Liu, Xiaolong; Li, Yun; Shi, Yi; Ni, Zhenhua; Wang, Jinlan; Xu, Jian-Bin; Wang, Xinran

2016-06-08

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces

PubMed Central

2014-01-01

van der Waals (vdW) forces play a fundamental role in the structure and behavior of diverse systems. Because of development of functionals that include nonlocal correlation, it is possible to study the effects of vdW interactions in systems of industrial and tribological interest. Here we simulated within the framework of density functional theory (DFT) the adsorption of isooctane (2,2,4-trimethylpentane) and ethanol on an Fe(100) surface, employing various exchange–correlation functionals to take vdW forces into account. In particular, this paper discusses the effect of vdW forces on the magnitude of adsorption energies, equilibrium geometries, and their role in the binding mechanism. According to our calculations, vdW interactions increase the adsorption energies and reduce the equilibrium distances. Nevertheless, they do not influence the spatial configuration of the adsorbed molecules. Their effect on the electronic density is a nonisotropic, delocalized accumulation of charge between the molecule and the slab. In conclusion, vdW forces are essential for the adsorption of isooctane and ethanol on a bcc Fe(100) surface. PMID:25126156

Closed-form solution for static pull-in voltage of electrostatically actuated clamped-clamped micro/nano beams under the effect of fringing field and van der Waals force

NASA Astrophysics Data System (ADS)

Bhojawala, V. M.; Vakharia, D. P.

2017-12-01

This investigation provides an accurate prediction of static pull-in voltage for clamped-clamped micro/nano beams based on distributed model. The Euler-Bernoulli beam theory is used adapting geometric non-linearity of beam, internal (residual) stress, van der Waals force, distributed electrostatic force and fringing field effects for deriving governing differential equation. The Galerkin discretisation method is used to make reduced-order model of the governing differential equation. A regime plot is presented in the current work for determining the number of modes required in reduced-order model to obtain completely converged pull-in voltage for micro/nano beams. A closed-form relation is developed based on the relationship obtained from curve fitting of pull-in instability plots and subsequent non-linear regression for the proposed relation. The output of regression analysis provides Chi-square (χ 2) tolerance value equals to 1  ×  10-9, adjusted R-square value equals to 0.999 29 and P-value equals to zero, these statistical parameters indicate the convergence of non-linear fit, accuracy of fitted data and significance of the proposed model respectively. The closed-form equation is validated using available data of experimental and numerical results. The relative maximum error of 4.08% in comparison to several available experimental and numerical data proves the reliability of the proposed closed-form equation.

Resolving dispersion and induction components for polarisable molecular simulations of ionic liquids

NASA Astrophysics Data System (ADS)

Pádua, Agílio A. H.

2017-05-01

One important development in interaction potential models, or atomistic force fields, for molecular simulation is the inclusion of explicit polarisation, which represents the induction effects of charged or polar molecules on polarisable electron clouds. Polarisation can be included through fluctuating charges, induced multipoles, or Drude dipoles. This work uses Drude dipoles and is focused on room-temperature ionic liquids, for which fixed-charge models predict too slow dynamics. The aim of this study is to devise a strategy to adapt existing non-polarisable force fields upon addition of polarisation, because induction was already contained to an extent, implicitly, due to parametrisation against empirical data. Therefore, a fraction of the van der Waals interaction energy should be subtracted so that the Lennard-Jones terms only account for dispersion and the Drude dipoles for induction. Symmetry-adapted perturbation theory is used to resolve the dispersion and induction terms in dimers and to calculate scaling factors to reduce the Lennard-Jones terms from the non-polarisable model. Simply adding Drude dipoles to an existing fixed-charge model already improves the prediction of transport properties, increasing diffusion coefficients, and lowering the viscosity. Scaling down the Lennard-Jones terms leads to still faster dynamics and densities that match experiment extremely well. The concept developed here improves the overall prediction of density and transport properties and can be adapted to other models and systems. In terms of microscopic structure of the ionic liquids, the inclusion of polarisation and the down-scaling of Lennard-Jones terms affect only slightly the ordering of the first shell of counterions, leading to small decreases in coordination numbers. Remarkably, the effect of polarisation is major beyond first neighbours, significantly weakening spatial correlations, a structural effect that is certainly related to the faster dynamics of

Surface and interface of epitaxial CdTe film on CdS buffered van der Waals mica substrate

DOE PAGES

Yang, Y. -B.; Seewald, L.; Mohanty, Dibyajyoti; ...

2017-03-31

We report single crystal CdTe films are desirable for optoelectronic device applications. An important strategy of creating films with high crystallinity is through epitaxial growth on a proper single crystal substrate. We report the metalorganic chemical vapor deposition of epitaxial CdTe films on the CdS/mica substrate. The epitaxial CdS film was grown on a mica surface by thermal evaporation. Due to the weak van der Waals forces, epitaxy is achieved despite the very large interface lattice mismatch between CdS and mica (~21–55%). The surface morphology of mica, CdS and CdTe were quantified by atomic force microscopy. The near surface structures, orientations and texture of CdTe and CdS films were characterized by the unique reflection high-energy electron diffraction surface pole figure technique. The interfaces of CdTe and CdS films and mica were characterized by X-ray pole figure technique and transmission electron microscopy. The out-of-plane and in-plane epitaxy of the heteroepitaxial films stack are determined to be CdTe(111)//CdS(0001)//mica(001) and [more » $$\\overline{1}2\\overline{1}$$] CdTe//[$$\\overline{1}100$$] CdS//[010] mica, respectively. The measured photoluminescence (PL), time resolved PL, photoresponse, and Hall mobility of the CdTe/CdS/mica indicate quality films. Finally, the use of van der Waals surface to grow epitaxial CdTe/CdS films offers an alternative strategy towards infrared imaging and solar cell applications.« less

Surface and interface of epitaxial CdTe film on CdS buffered van der Waals mica substrate

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

Yang, Y. -B.; Seewald, L.; Mohanty, Dibyajyoti

We report single crystal CdTe films are desirable for optoelectronic device applications. An important strategy of creating films with high crystallinity is through epitaxial growth on a proper single crystal substrate. We report the metalorganic chemical vapor deposition of epitaxial CdTe films on the CdS/mica substrate. The epitaxial CdS film was grown on a mica surface by thermal evaporation. Due to the weak van der Waals forces, epitaxy is achieved despite the very large interface lattice mismatch between CdS and mica (~21–55%). The surface morphology of mica, CdS and CdTe were quantified by atomic force microscopy. The near surface structures, orientations and texture of CdTe and CdS films were characterized by the unique reflection high-energy electron diffraction surface pole figure technique. The interfaces of CdTe and CdS films and mica were characterized by X-ray pole figure technique and transmission electron microscopy. The out-of-plane and in-plane epitaxy of the heteroepitaxial films stack are determined to be CdTe(111)//CdS(0001)//mica(001) and [more » $$\\overline{1}2\\overline{1}$$] CdTe//[$$\\overline{1}100$$] CdS//[010] mica, respectively. The measured photoluminescence (PL), time resolved PL, photoresponse, and Hall mobility of the CdTe/CdS/mica indicate quality films. Finally, the use of van der Waals surface to grow epitaxial CdTe/CdS films offers an alternative strategy towards infrared imaging and solar cell applications.« less

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag{sub 2}/graphene

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

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Mitrushchenkov, Alexander O.; Stoll, Hermann

2015-09-14

A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141, 151102 (2014)], is applied to describe the van der Waals dominated Ag{sub 2}/graphene interaction. It extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster model (coronene), andmore » ending with the periodic model of the extended system, modern ab initio methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected density functional-based approaches are put together both to assess the accuracy of the composite scheme and to better characterize the Ag{sub 2}/graphene interaction. The present work illustrates how the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab initio-based schemes in extended systems for surface science applications.« less

Probing interlayer interactions in WS2 -graphene van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Chung, Ting Fung; Yuan, Long; Huang, Libai; Chen, Yong P.

Two-dimensional crystals based van der Waals coupled heterostructures are of interest owing to their potential applications for flexible and transparent electronics and optoelectronics. The interaction between the 2D layered crystals at the interfaces of these heterostructures is crucial in determining the overall performance and is strongly affected by contamination and interfacial strain. We have fabricated heterostructures consisting of atomically thin exfoliated WS2 and chemical-vapor-deposited (CVD) graphene, and studied the interaction and coupling between the WS2 and graphene using atomic force microscopy (AFM), Raman spectroscopy and femtosecond transient absorption measurement (TAM). Information from Raman-active phonon modes allows us to estimate charge doping in graphene and interfacial strain on the crystals. Spatial imaging probed by TAM can be correlated to the heterostructure surface morphology measured by AFM and Raman maps of graphene and WS2, showing how the interlayer coupling alters exciton decay dynamics quantitatively.

Effect of sonication on particle dispersion, administered dose and metal release of non-functionalized, non-inert metal nanoparticles.

PubMed

Pradhan, Sulena; Hedberg, Jonas; Blomberg, Eva; Wold, Susanna; Odnevall Wallinder, Inger

2016-01-01

In this study, we elucidate the effect of different sonication techniques to efficiently prepare particle dispersions from selected non-functionalized NPs (Cu, Al, Mn, ZnO), and corresponding consequences on the particle dose, surface charge and release of metals. Probe sonication was shown to be the preferred method for dispersing non-inert, non-functionalized metal NPs (Cu, Mn, Al). However, rapid sedimentation during sonication resulted in differences between the real and the administered doses in the order of 30-80 % when sonicating in 1 and 2.56 g/L NP stock solutions. After sonication, extensive agglomeration of the metal NPs resulted in rapid sedimentation of all particles. DLVO calculations supported these findings, showing the strong van der Waals forces of the metal NPs to result in significant NP agglomeration. Metal release from the metal NPs was slightly increased by increased sonication. The addition of a stabilizing agent (bovine serum albumin) had an accelerating effect on the release of metals in sonicated solutions. For Cu and Mn NPs, the extent of particle dissolution increased from <1.6 to ~5 % after sonication for 15 min. A prolonged sonication time (3-15 min) had negligible effects on the zeta potential of the studied NPs. In all, it is shown that it is of utmost importance to carefully investigate how sonication influences the physico-chemical properties of dispersed metal NPs. This should be considered in nanotoxicology investigations of metal NPs.

Near-Unity Absorption in van der Waals Semiconductors for Ultrathin Optoelectronics.

PubMed

Jariwala, Deep; Davoyan, Artur R; Tagliabue, Giulia; Sherrott, Michelle C; Wong, Joeson; Atwater, Harry A

2016-09-14

We demonstrate near-unity, broadband absorbing optoelectronic devices using sub-15 nm thick transition metal dichalcogenides (TMDCs) of molybdenum and tungsten as van der Waals semiconductor active layers. Specifically, we report that near-unity light absorption is possible in extremely thin (<15 nm) van der Waals semiconductor structures by coupling to strongly damped optical modes of semiconductor/metal heterostructures. We further fabricate Schottky junction devices using these highly absorbing heterostructures and characterize their optoelectronic performance. Our work addresses one of the key criteria to enable TMDCs as potential candidates to achieve high optoelectronic efficiency.

Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

USGS Publications Warehouse

Lee, M.W.; Meuwly, M.

2013-01-01

The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

Self-Aligned van der Waals Heterojunction Diodes and Transistors.

PubMed

Sangwan, Vinod K; Beck, Megan E; Henning, Alex; Luo, Jiajia; Bergeron, Hadallia; Kang, Junmo; Balla, Itamar; Inbar, Hadass; Lauhon, Lincoln J; Hersam, Mark C

2018-02-14

A general self-aligned fabrication scheme is reported here for a diverse class of electronic devices based on van der Waals materials and heterojunctions. In particular, self-alignment enables the fabrication of source-gated transistors in monolayer MoS 2 with near-ideal current saturation characteristics and channel lengths down to 135 nm. Furthermore, self-alignment of van der Waals p-n heterojunction diodes achieves complete electrostatic control of both the p-type and n-type constituent semiconductors in a dual-gated geometry, resulting in gate-tunable mean and variance of antiambipolar Gaussian characteristics. Through finite-element device simulations, the operating principles of source-gated transistors and dual-gated antiambipolar devices are elucidated, thus providing design rules for additional devices that employ self-aligned geometries. For example, the versatility of this scheme is demonstrated via contact-doped MoS 2 homojunction diodes and mixed-dimensional heterojunctions based on organic semiconductors. The scalability of this approach is also shown by fabricating self-aligned short-channel transistors with subdiffraction channel lengths in the range of 150-800 nm using photolithography on large-area MoS 2 films grown by chemical vapor deposition. Overall, this self-aligned fabrication method represents an important step toward the scalable integration of van der Waals heterojunction devices into more sophisticated circuits and systems.

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy.

PubMed

Kumar, Bharat; Crittenden, Scott R

2013-11-01

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson-Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length.

A notable difference between ideal gas and infinite molar volume limit of van der Waals gas

NASA Astrophysics Data System (ADS)

Liu, Q. H.; Shen, Y.; Bai, R. L.; Wang, X.

2010-05-01

The van der Waals equation of state does not sufficiently represent a gas unless a thermodynamic potential with two proper and independent variables is simultaneously determined. The limiting procedures under which the behaviour of the van der Waals gas approaches that of an ideal gas are letting two van der Waals coefficients be zero rather than letting the molar volume become infinitely large; otherwise, the partial derivative of internal energy with respect to pressure at a fixed temperature does not vanish.

Isotope engineering of van der Waals interactions in hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Vuong, T. Q. P.; Liu, S.; van der Lee, A.; Cuscó, R.; Artús, L.; Michel, T.; Valvin, P.; Edgar, J. H.; Cassabois, G.; Gil, B.

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes (10B and 11B) compared to those with the natural distribution of boron (20 at% 10B and 80 at% 11B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10BN than in 11BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Isotope engineering of van der Waals interactions in hexagonal boron nitride.

PubMed

Vuong, T Q P; Liu, S; Van der Lee, A; Cuscó, R; Artús, L; Michel, T; Valvin, P; Edgar, J H; Cassabois, G; Gil, B

2018-02-01

Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes ( 10 B and 11 B) compared to those with the natural distribution of boron (20 at% 10 B and 80 at% 11 B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10 BN than in 11 BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.

Inflationary universe in terms of a van der Waals viscous fluid

NASA Astrophysics Data System (ADS)

Brevik, I.; Elizalde, E.; Odintsov, S. D.; Timoshkin, A. V.

The inflationary expansion of our early-time universe is considered in terms of the van der Waals equation, as equation of state for the cosmic fluid, where a bulk viscosity contribution is assumed to be present. The corresponding gravitational equations for the energy density in a homogeneous and isotropic Friedmann-Lemaître-Robertson-Walker universe are solved, and an analytic expression for the scale factor is obtained. Attention is paid, specifically, to the role of the viscosity term in the accelerated expansion; the values of the slow-roll parameters, the spectral index, and the tensor-to-scalar ratio for the van der Waals model are calculated and compared with the most recent astronomical data from the Planck satellite. By imposing reasonable restrictions on the parameters of the van der Waals equation, in the presence of viscosity, it is shown to be possible for this model to comply quite precisely with the observational data. One can therefore conclude that the inclusion of viscosity in the theory of the inflationary epoch may definitely improve the cosmological models.

Imaginary-frequency polarizability and van der Waals force constants of two-electron atoms, with rigorous bounds

NASA Technical Reports Server (NTRS)

Glover, R. M.; Weinhold, F.

1977-01-01

Variational functionals of Braunn and Rebane (1972) for the imagery-frequency polarizability (IFP) have been generalized by the method of Gramian inequalities to give rigorous upper and lower bounds, valid even when the true (but unknown) unperturbed wavefunction must be represented by a variational approximation. Using these formulas in conjunction with flexible variational trial functions, tight error bounds are computed for the IFP and the associated two- and three-body van der Waals interaction constants of the ground 1(1S) and metastable 2(1,3S) states of He and Li(+). These bounds generally establish the ground-state properties to within a fraction of a per cent and metastable properties to within a few per cent, permitting a comparative assessment of competing theoretical methods at this level of accuracy. Unlike previous 'error bounds' for these properties, the present results have a completely a priori theoretical character, with no empirical input data.

Van der Waals interactions between planar substrate and tubular lipid membranes undergoing pearling instability

NASA Astrophysics Data System (ADS)

Valchev, G. S.; Djondjorov, P. A.; Vassilev, V. M.; Dantchev, D. M.

2017-10-01

In the current article we study the behavior of the van der Waals force between a planar substrate and an axisymmetric bilayer lipid membrane undergoing pearling instability, caused by uniform hydrostatic pressure difference. To do so, the recently suggested "surface integration approach" is used, which can be considered a generalization of the well known and widely used Derjaguin approximation. The static equilibrium shape after the occurrence of the instability is described in the framework of Helfrich's spontaneous curvature model. Some specific classes of exact analytical solutions to the corresponding shape equation are considered, and the components of the respective position vectors given in terms of elliptic integrals and Jacobi elliptic functions. The mutual orientation between the interacting objects is chosen such that the axis of revolution of the distorted cylinder be parallel to the plane bounding the substrate. Based on the discussed models and approaches we made some estimations for the studied force in real experimentally realizable systems, thus showing the possibility of pearling as an useful technique for reduction of the adhesion in variety of industrial processes using lipid membranes as carriers.

Is dispersal neutral?

PubMed

Lowe, Winsor H; McPeek, Mark A

2014-08-01

Dispersal is difficult to quantify and often treated as purely stochastic and extrinsically controlled. Consequently, there remains uncertainty about how individual traits mediate dispersal and its ecological effects. Addressing this uncertainty is crucial for distinguishing neutral versus non-neutral drivers of community assembly. Neutral theory assumes that dispersal is stochastic and equivalent among species. This assumption can be rejected on principle, but common research approaches tacitly support the 'neutral dispersal' assumption. Theory and empirical evidence that dispersal traits are under selection should be broadly integrated in community-level research, stimulating greater scrutiny of this assumption. A tighter empirical connection between the ecological and evolutionary forces that shape dispersal will enable richer understanding of this fundamental process and its role in community assembly. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of adding Te to layered GaSe crystals to increase the van der Waals bonding force

NASA Astrophysics Data System (ADS)

Tanabe, Tadao; Zhao, Shu; Sato, Yohei; Oyama, Yutaka

2017-10-01

The interplanar binding strength of layered GaSe1-xTex crystals was directly measured using a tensile testing machine. The GaSe1-xTex crystals were grown by a low temperature liquid phase solution method under a controlled Se vapor pressure. The stoichiometry-controlled GaSe1-xTex crystal has the ɛ-polytype structure of GaSe, where the Te atoms are substituted for some of the Se atoms in the GaSe crystal. The effect of adding Te on the bonding strength between the GaSe layers was determined from direct measurements of the van der Waals bonding energy. The bonding energy was increased from 0.023 × 106 N/m2 for GaSe to 0.16 × 106 N/m2 for GaSe1-xTex (x = 0.106).

Fundamental aspects of electric double layer force-distance measurements at liquid-solid interfaces using atomic force microscopy

PubMed Central

Black, Jennifer M.; Zhu, Mengyang; Zhang, Pengfei; Unocic, Raymond R.; Guo, Daqiang; Okatan, M. Baris; Dai, Sheng; Cummings, Peter T.; Kalinin, Sergei V.; Feng, Guang; Balke, Nina

2016-01-01

Atomic force microscopy (AFM) force-distance measurements are used to investigate the layered ion structure of Ionic Liquids (ILs) at the mica surface. The effects of various tip properties on the measured force profiles are examined and reveal that the measured ion position is independent of tip properties, while the tip radius affects the forces required to break through the ion layers as well as the adhesion force. Force data is collected for different ILs and directly compared with interfacial ion density profiles predicted by molecular dynamics. Through this comparison it is concluded that AFM force measurements are sensitive to the position of the ion with the larger volume and mass, suggesting that ion selectivity in force-distance measurements are related to excluded volume effects and not to electrostatic or chemical interactions between ions and AFM tip. The comparison also revealed that at distances greater than 1 nm the system maintains overall electroneutrality between the AFM tip and sample, while at smaller distances other forces (e.g., van der waals interactions) dominate and electroneutrality is no longer maintained. PMID:27587276

Van der Waals interaction mediated by an optically uniaxial layer

NASA Astrophysics Data System (ADS)

Šarlah, A.; Žumer, S.

2001-11-01

We study the van der Waals interaction between macroscopic bodies separated by a thin anisotropic film with a uniaxial permittivity tensor. We describe the effect of anisotropy of the media on the magnitude and sign of the interaction. The resulting differences in the van der Waals interaction are especially important for the stability of strongly confined liquid crystals, and nanostructures characterized by highly uniaxial macroscopic molecular arrangement, such as in self-assemblies of long organic molecules forming films, membranes, colloids, etc. We introduce an improved expression for the Hamaker constant which takes into account the uniaxial symmetry of a medium. In special cases neglecting the optical anisotropy even leads to an incorrect sign of the interaction.

Phase-Defined van der Waals Schottky Junctions with Significantly Enhanced Thermoelectric Properties.

PubMed

Wang, Qiaoming; Yang, Liangliang; Zhou, Shengwen; Ye, Xianjun; Wang, Zhe; Zhu, Wenguang; McCluskey, Matthew D; Gu, Yi

2017-07-06

We demonstrate a van der Waals Schottky junction defined by crystalline phases of multilayer In 2 Se 3 . Besides ideal diode behaviors and the gate-tunable current rectification, the thermoelectric power is significantly enhanced in these junctions by more than three orders of magnitude compared with single-phase multilayer In 2 Se 3 , with the thermoelectric figure-of-merit approaching ∼1 at room temperature. Our results suggest that these significantly improved thermoelectric properties are not due to the 2D quantum confinement effects but instead are a consequence of the Schottky barrier at the junction interface, which leads to hot carrier transport and shifts the balance between thermally and field-driven currents. This "bulk" effect extends the advantages of van der Waals materials beyond the few-layer limit. Adopting such an approach of using energy barriers between van der Waals materials, where the interface states are minimal, is expected to enhance the thermoelectric performance in other 2D materials as well.

Can nonadditive dispersion forces explain chain formation of nanoparticles?

NASA Astrophysics Data System (ADS)

Kwaadgras, Bas W.; Verdult, Maarten W. J.; Dijkstra, Marjolein; van Roij, René

2013-03-01

We study to what extent dielectric nanoparticles prefer to self-assemble into linear chains or into more compact structures. To calculate the Van der Waals (VdW) attraction between the clusters we use the Coupled Dipole Method (CDM), which treats each atom in the nanoparticle as an inducible oscillating point dipole. The VdW attraction then results from the full many-body interactions between the dipoles. For non-capped nanoparticles, we calculate in which configuration the VdW attraction is maximal. We find that in virtually all cases we studied, many-body effects only result in local potential minima at the linear configuration, as opposed to global ones, and that these metastable minima are in most cases rather shallow compared to the thermal energy. In this work, we also compare the CDM results with those from Hamaker-de Boer and Axilrod-Teller theory to investigate the influence of the many-body effects and the accuracy of these two approximate methods.

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy.

PubMed

Jobst, Johannes; van der Torren, Alexander J H; Krasovskii, Eugene E; Balgley, Jesse; Dean, Cory R; Tromp, Rudolf M; van der Molen, Sense Jan

2016-11-29

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the 'chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of.

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

Dalvit, Diego; Messina, Riccardo; Maia Neto, Paulo

We develop the scattering approach for the dispersive force on a ground state atom on top of a corrugated surface. We present explicit results to first order in the corrugation amplitude. A variety of analytical results are derived in different limiting cases, including the van der Waals and Casimir-Polder regimes. We compute numerically the exact first-order dispersive potential for arbitrary separation distances and corrugation wavelengths, for a Rubidium atom on top of a silicon or gold corrugated surface. We consider in detail the correction to the proximity force approximation, and present a very simple approximation algorithm for computing the potential.

Geometrothermodynamics of Van der Waals black hole

NASA Astrophysics Data System (ADS)

Hu, Yumin; Chen, Juhua; Wang, Yongjiu

2017-12-01

We study the geometrothermodynamics of a special asymptotically AdS black hole, i.e. Van der Waals ( VdW) black hole, in the extended phase space where the negative cosmological constant Λ can be regarded as thermodynamic pressure. Analysing some special conditions of this black hole with geometrothermodynamical method, we find a good correlation with ordinary cases according to the state equation.

Reparametrization of Protein Force Field Nonbonded Interactions Guided by Osmotic Coefficient Measurements from Molecular Dynamics Simulations.

PubMed

Miller, Mark S; Lay, Wesley K; Li, Shuxiang; Hacker, William C; An, Jiadi; Ren, Jianlan; Elcock, Adrian H

2017-04-11

There is a small, but growing, body of literature describing the use of osmotic coefficient measurements to validate and reparametrize simulation force fields. Here we have investigated the ability of five very commonly used force field and water model combinations to reproduce the osmotic coefficients of seven neutral amino acids and five small molecules. The force fields tested include AMBER ff99SB-ILDN, CHARMM36, GROMOS54a7, and OPLS-AA, with the first of these tested in conjunction with the TIP3P and TIP4P-Ew water models. In general, for both the amino acids and the small molecules, the tested force fields produce computed osmotic coefficients that are lower than experiment; this is indicative of excessively favorable solute-solute interactions. The sole exception to this general trend is provided by GROMOS54a7 when applied to amino acids: in this case, the computed osmotic coefficients are consistently too high. Importantly, we show that all of the force fields tested can be made to accurately reproduce the experimental osmotic coefficients of the amino acids when minor modifications-some previously reported by others and some that are new to this study-are made to the van der Waals interactions of the charged terminal groups. Special care is required, however, when simulating Proline with a number of the force fields, and a hydroxyl-group specific modification is required in order to correct Serine and Threonine when simulated with AMBER ff99SB-ILDN. Interestingly, an alternative parametrization of the van der Waals interactions in the latter force field, proposed by the Nerenberg and Head-Gordon groups, is shown to immediately produce osmotic coefficients that are in excellent agreement with experiment. Overall, this study reinforces the idea that osmotic coefficient measurements can be used to identify general shortcomings in commonly used force fields' descriptions of solute-solute interactions and further demonstrates that modifications to van der Waals

Reparameterization of Protein Force Field Nonbonded Interactions Guided by Osmotic Coefficient Measurements from Molecular Dynamics Simulations

PubMed Central

Miller, Mark S.; Lay, Wesley K.; Li, Shuxiang; Hacker, William C.; An, Jiadi; Ren, Jianlan; Elcock, Adrian H.

2017-01-01

There is a small, but growing, body of literature describing the use of osmotic coefficient measurements to validate and reparameterize simulation force fields. Here we have investigated the ability of five very commonly used force field and water model combinations to reproduce the osmotic coefficients of seven neutral amino acids and five small molecules. The force fields tested include AMBER ff99SB-ILDN, CHARMM36, GROMOS54a7, and OPLS-AA, with the first of these tested in conjunction with the TIP3P and TIP4P-Ew water models. In general, for both the amino acids and the small molecules, the tested force fields produce computed osmotic coefficients that are lower than experiment; this is indicative of excessively favorable solute-solute interactions. The sole exception to this general trend is provided by GROMOS54a7 when applied to amino acids: in this case, the computed osmotic coefficients are consistently too high. Importantly, we show that all of the force fields tested can be made to accurately reproduce the experimental osmotic coefficients of the amino acids when minor modifications – some previously reported by others and some that are new to this study – are made to the van der Waals interactions of the charged terminal groups. Special care is required, however, when simulating Proline with a number of the force fields, and a hydroxyl-group specific modification is required in order to correct Serine and Threonine when simulated with AMBER ff99SB-ILDN. Interestingly, an alternative parameterization of the van der Waals interactions in the latter force field, proposed by the Nerenberg and Head-Gordon groups, is shown to immediately produce osmotic coefficients that are in excellent agreement with experiment. Overall, this study reinforces the idea that osmotic coefficient measurements can be used to identify general shortcomings in commonly used force fields’ descriptions of solute-solute interactions, and further demonstrates that modifications to

A high-pressure van der Waals compound in solid nitrogen-helium mixtures

NASA Technical Reports Server (NTRS)

Vos, W. L.; Finger, L. W.; Hemley, R. J.; Hu, J. Z.; Mao, H. K.; Schouten, J. A.

1992-01-01

A detailed diamond anvil-cell study using synchrotron X-ray diffraction, Raman scattering, and optical microscopy has been conducted for the He-N system, with a view to the weakly-bound van der Waals molecule interactions that can be formed in the gas phase. High pressure is found to stabilize the formation of a stoichiometric, solid van der Waals compound of He(N2)11 composition which may exemplify a novel class of compounds found at high pressures in the interiors of the outer planets and their satellites.

Measured long-range repulsive Casimir-Lifshitz forces.

PubMed

Munday, J N; Capasso, Federico; Parsegian, V Adrian

2009-01-08

Quantum fluctuations create intermolecular forces that pervade macroscopic bodies. At molecular separations of a few nanometres or less, these interactions are the familiar van der Waals forces. However, as recognized in the theories of Casimir, Polder and Lifshitz, at larger distances and between macroscopic condensed media they reveal retardation effects associated with the finite speed of light. Although these long-range forces exist within all matter, only attractive interactions have so far been measured between material bodies. Here we show experimentally that, in accord with theoretical prediction, the sign of the force can be changed from attractive to repulsive by suitable choice of interacting materials immersed in a fluid. The measured repulsive interaction is found to be weaker than the attractive. However, in both cases the magnitude of the force increases with decreasing surface separation. Repulsive Casimir-Lifshitz forces could allow quantum levitation of objects in a fluid and lead to a new class of switchable nanoscale devices with ultra-low static friction.

EMAT enhanced dispersion of particles in liquid

DOEpatents

Kisner, Roger A.; Rios, Orlando; Melin, Alexander M.; Ludtka, Gerard Michael; Ludtka, Gail Mackiewicz; Wilgen, John B.

2016-11-29

Particulate matter is dispersed in a fluid material. A sample including a first material in a fluid state and second material comprising particulate matter are placed into a chamber. The second material is spatially dispersed in the first material utilizing EMAT force. The dispersion process continues until spatial distribution of the second material enables the sample to meet a specified criterion. The chamber and/or the sample is electrically conductive. The EMAT force is generated by placing the chamber coaxially within an induction coil driven by an applied alternating current and placing the chamber and induction coil coaxially within a high field magnetic. The EMAT force is coupled to the sample without physical contact to the sample or to the chamber, by another physical object. Batch and continuous processing are utilized. The chamber may be folded within the bore of the magnet. Acoustic force frequency and/or temperature may be controlled.

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy

PubMed Central

Jobst, Johannes; van der Torren, Alexander J. H.; Krasovskii, Eugene E.; Balgley, Jesse; Dean, Cory R.; Tromp, Rudolf M.; van der Molen, Sense Jan

2016-01-01

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the ‘chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of. PMID:27897180

Asymmetric van der Waals Forces Drive Orientation of Compositionally Anisotropic Nanocylinders within Smectic Arrays: Experiment and Simulation

PubMed Central

Smith, Benjamin D.; Fichthorn, Kristen A.; Kirby, David J.; Quimby, Lisa M.; Triplett, Derek A.; González, Pedro; Hernández, Darimar; Keating, Christine D.

2014-01-01

Understanding how micro- and nanoparticles interact is important for achieving bottom-up assembly of desired structures. Here, we examine the self-assembly of two-component, compositionally asymmetric nanocylinders that sediment from solution onto a solid surface. These particles spontaneously formed smectic arrays. Within the rows of an array, nanocylinders tended to assemble such that neighboring particles had the same orientation of their segments. As a probe of interparticle interactions, we classified nanocylinder alignments by measuring the segment orientations of many sets of neighboring particles. Monte Carlo simulations incorporating an exact expression for the van der Waals (vdW) energy indicate that differences in the vdW interactions, even when small, are the key factor in producing observed segment alignment. These results point to asymmetrical vdW interactions as a potentially powerful means of controlling orientation in multicomponent cylinder arrays, and suggest that designing for these interactions could yield new ways to control self-assembly. PMID:24308771

Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope.

PubMed

Govyadinov, Alexander A; Konečná, Andrea; Chuvilin, Andrey; Vélez, Saül; Dolado, Irene; Nikitin, Alexey Y; Lopatin, Sergei; Casanova, Fèlix; Hueso, Luis E; Aizpurua, Javier; Hillenbrand, Rainer

2017-07-21

Van der Waals materials exhibit intriguing structural, electronic, and photonic properties. Electron energy loss spectroscopy within scanning transmission electron microscopy allows for nanoscale mapping of such properties. However, its detection is typically limited to energy losses in the eV range-too large for probing low-energy excitations such as phonons or mid-infrared plasmons. Here, we adapt a conventional instrument to probe energy loss down to 100 meV, and map phononic states in hexagonal boron nitride, a representative van der Waals material. The boron nitride spectra depend on the flake thickness and on the distance of the electron beam to the flake edges. To explain these observations, we developed a classical response theory that describes the interaction of fast electrons with (anisotropic) van der Waals slabs, revealing that the electron energy loss is dominated by excitation of hyperbolic phonon polaritons, and not of bulk phonons as often reported. Thus, our work is of fundamental importance for interpreting future low-energy loss spectra of van der Waals materials.Here the authors adapt a STEM-EELS system to probe energy loss down to 100 meV, and apply it to map phononic states in hexagonal boron nitride, revealing that the electron loss is dominated by hyperbolic phonon polaritons.

Fundamental aspects of electric double layer force-distance measurements at liquid-solid interfaces using atomic force microscopy

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

Black, Jennifer M.; Zhu, Mengyang; Zhang, Pengfei

In this paper, atomic force microscopy (AFM) force-distance measurements are used to investigate the layered ion structure of Ionic Liquids (ILs) at the mica surface. The effects of various tip properties on the measured force profiles are examined and reveal that the measured ion position is independent of tip properties, while the tip radius affects the forces required to break through the ion layers as well as the adhesion force. Force data is collected for different ILs and directly compared with interfacial ion density profiles predicted by molecular dynamics. Through this comparison it is concluded that AFM force measurements aremore » sensitive to the position of the ion with the larger volume and mass, suggesting that ion selectivity in force-distance measurements are related to excluded volume effects and not to electrostatic or chemical interactions between ions and AFM tip. Finally, the comparison also revealed that at distances greater than 1 nm the system maintains overall electroneutrality between the AFM tip and sample, while at smaller distances other forces (e.g., van der waals interactions) dominate and electroneutrality is no longer maintained.« less

Fundamental aspects of electric double layer force-distance measurements at liquid-solid interfaces using atomic force microscopy

DOE PAGES

Black, Jennifer M.; Zhu, Mengyang; Zhang, Pengfei; ...

2016-09-02

In this paper, atomic force microscopy (AFM) force-distance measurements are used to investigate the layered ion structure of Ionic Liquids (ILs) at the mica surface. The effects of various tip properties on the measured force profiles are examined and reveal that the measured ion position is independent of tip properties, while the tip radius affects the forces required to break through the ion layers as well as the adhesion force. Force data is collected for different ILs and directly compared with interfacial ion density profiles predicted by molecular dynamics. Through this comparison it is concluded that AFM force measurements aremore » sensitive to the position of the ion with the larger volume and mass, suggesting that ion selectivity in force-distance measurements are related to excluded volume effects and not to electrostatic or chemical interactions between ions and AFM tip. Finally, the comparison also revealed that at distances greater than 1 nm the system maintains overall electroneutrality between the AFM tip and sample, while at smaller distances other forces (e.g., van der waals interactions) dominate and electroneutrality is no longer maintained.« less

Impact of self-assembled surfactant structures on rheology of concentrated nanoparticle dispersions.

PubMed

Zaman, A A; Singh, P; Moudgil, B M

2002-07-15

Rheological behavior of surfactant-stabilized colloidal dispersions of silica particles under extreme conditions (low pH, high ionic strength) has been investigated in relation to interparticle forces and stability of the dispersion. The surfactant used as the dispersing agent was C(12)TAB, a cationic surfactant. Stability analysis through turbidity measurements indicated that there is a sharp increase in the stability of the dispersion when the surfactant concentration is in the range of 8 to 10 mM in the system. The state of the dispersion changes from an unstable regime to a stable regime above a critical concentration of C(12)TAB in the system. In the case of interaction forces measured between the silica substrate and AFM tip, no repulsive force was observed up to a surfactant concentration of 8 mM and a transition from no repulsive forces to steric repulsive forces occurred between 8 and 10 mM. Rheological measurements as a function of C(12)TAB concentration indicated a significant decrease in the viscosity and linear viscoelastic functions of the dispersion over the same range of surfactant concentration (8 to 10 mM C(12)TAB), showing a strong correlation between the viscosity behavior, interparticle forces, and structure development in the dispersion.

Assessing many-body contributions to intermolecular interactions of the AMOEBA force field using energy decomposition analysis of electronic structure calculations.

PubMed

Demerdash, Omar; Mao, Yuezhi; Liu, Tianyi; Head-Gordon, Martin; Head-Gordon, Teresa

2017-10-28

In this work, we evaluate the accuracy of the classical AMOEBA model for representing many-body interactions, such as polarization, charge transfer, and Pauli repulsion and dispersion, through comparison against an energy decomposition method based on absolutely localized molecular orbitals (ALMO-EDA) for the water trimer and a variety of ion-water systems. When the 2- and 3-body contributions according to the many-body expansion are analyzed for the ion-water trimer systems examined here, the 3-body contributions to Pauli repulsion and dispersion are found to be negligible under ALMO-EDA, thereby supporting the validity of the pairwise-additive approximation in AMOEBA's 14-7 van der Waals term. However AMOEBA shows imperfect cancellation of errors for the missing effects of charge transfer and incorrectness in the distance dependence for polarization when compared with the corresponding ALMO-EDA terms. We trace the larger 2-body followed by 3-body polarization errors to the Thole damping scheme used in AMOEBA, and although the width parameter in Thole damping can be changed to improve agreement with the ALMO-EDA polarization for points about equilibrium, the correct profile of polarization as a function of intermolecular distance cannot be reproduced. The results suggest that there is a need for re-examining the damping and polarization model used in the AMOEBA force field and provide further insights into the formulations of polarizable force fields in general.

Assessing many-body contributions to intermolecular interactions of the AMOEBA force field using energy decomposition analysis of electronic structure calculations

NASA Astrophysics Data System (ADS)

Demerdash, Omar; Mao, Yuezhi; Liu, Tianyi; Head-Gordon, Martin; Head-Gordon, Teresa

2017-10-01

In this work, we evaluate the accuracy of the classical AMOEBA model for representing many-body interactions, such as polarization, charge transfer, and Pauli repulsion and dispersion, through comparison against an energy decomposition method based on absolutely localized molecular orbitals (ALMO-EDA) for the water trimer and a variety of ion-water systems. When the 2- and 3-body contributions according to the many-body expansion are analyzed for the ion-water trimer systems examined here, the 3-body contributions to Pauli repulsion and dispersion are found to be negligible under ALMO-EDA, thereby supporting the validity of the pairwise-additive approximation in AMOEBA's 14-7 van der Waals term. However AMOEBA shows imperfect cancellation of errors for the missing effects of charge transfer and incorrectness in the distance dependence for polarization when compared with the corresponding ALMO-EDA terms. We trace the larger 2-body followed by 3-body polarization errors to the Thole damping scheme used in AMOEBA, and although the width parameter in Thole damping can be changed to improve agreement with the ALMO-EDA polarization for points about equilibrium, the correct profile of polarization as a function of intermolecular distance cannot be reproduced. The results suggest that there is a need for re-examining the damping and polarization model used in the AMOEBA force field and provide further insights into the formulations of polarizable force fields in general.

Direct Determination of the Base-Pair Force Constant of DNA from the Acoustic Phonon Dispersion of the Double Helix

NASA Astrophysics Data System (ADS)

van Eijck, L.; Merzel, F.; Rols, S.; Ollivier, J.; Forsyth, V. T.; Johnson, M. R.

2011-08-01

Quantifying the molecular elasticity of DNA is fundamental to our understanding of its biological functions. Recently different groups, through experiments on tailored DNA samples and numerical models, have reported a range of stretching force constants (0.3 to 3N/m). However, the most direct, microscopic measurement of DNA stiffness is obtained from the dispersion of its vibrations. A new neutron scattering spectrometer and aligned, wet spun samples have enabled such measurements, which provide the first data of collective excitations of DNA and yield a force constant of 83N/m. Structural and dynamic order persists unchanged to within 15 K of the melting point of the sample, precluding the formation of bubbles. These findings are supported by large scale phonon and molecular dynamics calculations, which reconcile hard and soft force constants.

Li intercalation in graphite: A van der Waals density-functional study

NASA Astrophysics Data System (ADS)

Hazrati, E.; de Wijs, G. A.; Brocks, G.

2014-10-01

Modeling layered intercalation compounds from first principles poses a problem, as many of their properties are determined by a subtle balance between van der Waals interactions and chemical or Madelung terms, and a good description of van der Waals interactions is often lacking. Using van der Waals density functionals we study the structures, phonons and energetics of the archetype layered intercalation compound Li-graphite. Intercalation of Li in graphite leads to stable systems with calculated intercalation energies of -0.2 to -0.3 eV/Li atom, (referred to bulk graphite and Li metal). The fully loaded stage 1 and stage 2 compounds LiC6 and Li1 /2C6 are stable, corresponding to two-dimensional √{3 }×√{3 } lattices of Li atoms intercalated between two graphene planes. Stage N >2 structures are unstable compared to dilute stage 2 compounds with the same concentration. At elevated temperatures dilute stage 2 compounds easily become disordered, but the structure of Li3 /16C6 is relatively stable, corresponding to a √{7 }×√{7 } in-plane packing of Li atoms. First-principles calculations, along with a Bethe-Peierls model of finite temperature effects, allow for a microscopic description of the observed voltage profiles.

Accurate van der Waals coefficients from density functional theory

PubMed Central

Tao, Jianmin; Perdew, John P.; Ruzsinszky, Adrienn

2012-01-01

The van der Waals interaction is a weak, long-range correlation, arising from quantum electronic charge fluctuations. This interaction affects many properties of materials. A simple and yet accurate estimate of this effect will facilitate computer simulation of complex molecular materials and drug design. Here we develop a fast approach for accurate evaluation of dynamic multipole polarizabilities and van der Waals (vdW) coefficients of all orders from the electron density and static multipole polarizabilities of each atom or other spherical object, without empirical fitting. Our dynamic polarizabilities (dipole, quadrupole, octupole, etc.) are exact in the zero- and high-frequency limits, and exact at all frequencies for a metallic sphere of uniform density. Our theory predicts dynamic multipole polarizabilities in excellent agreement with more expensive many-body methods, and yields therefrom vdW coefficients C6, C8, C10 for atom pairs with a mean absolute relative error of only 3%. PMID:22205765

Franckeite as a naturally occurring van der Waals heterostructure

PubMed Central

Molina-Mendoza, Aday J.; Giovanelli, Emerson; Paz, Wendel S.; Niño, Miguel Angel; Island, Joshua O.; Evangeli, Charalambos; Aballe, Lucía; Foerster, Michael; van der Zant, Herre S. J.; Rubio-Bollinger, Gabino; Agraït, Nicolás; Palacios, J. J.; Pérez, Emilio M.; Castellanos-Gomez, Andres

2017-01-01

The fabrication of van der Waals heterostructures, artificial materials assembled by individual stacking of 2D layers, is among the most promising directions in 2D materials research. Until now, the most widespread approach to stack 2D layers relies on deterministic placement methods, which are cumbersome and tend to suffer from poor control over the lattice orientations and the presence of unwanted interlayer adsorbates. Here, we present a different approach to fabricate ultrathin heterostructures by exfoliation of bulk franckeite which is a naturally occurring and air stable van der Waals heterostructure (composed of alternating SnS2-like and PbS-like layers stacked on top of each other). Presenting both an attractive narrow bandgap (<0.7 eV) and p-type doping, we find that the material can be exfoliated both mechanically and chemically down to few-layer thicknesses. We present extensive theoretical and experimental characterizations of the material's electronic properties and crystal structure, and explore applications for near-infrared photodetectors. PMID:28194037

Giant vacuum forces via transmission lines

PubMed Central

Shahmoon, Ephraim; Mazets, Igor; Kurizki, Gershon

2014-01-01

Quantum electromagnetic fluctuations induce forces between neutral particles, known as the van der Waals and Casimir interactions. These fundamental forces, mediated by virtual photons from the vacuum, play an important role in basic physics and chemistry and in emerging technologies involving, e.g., microelectromechanical systems or quantum information processing. Here we show that these interactions can be enhanced by many orders of magnitude upon changing the character of the mediating vacuum modes. By considering two polarizable particles in the vicinity of any standard electric transmission line, along which photons can propagate in one dimension, we find a much stronger and longer-range interaction than in free space. This enhancement may have profound implications on many-particle and bulk systems and impact the quantum technologies mentioned above. The predicted giant vacuum force is estimated to be measurable in a coplanar waveguide line. PMID:25002503

Spectral asymmetry of atoms in the van der Waals potential of an optical nanofiber

NASA Astrophysics Data System (ADS)

Patterson, B. D.; Solano, P.; Julienne, P. S.; Orozco, L. A.; Rolston, S. L.

2018-03-01

We measure the modification of the transmission spectra of cold 87Rb atoms in the proximity of an optical nanofiber (ONF). Van der Waals interactions between the atoms an the ONF surface decrease the resonance frequency of atoms closer to the surface. An asymmetric spectra of the atoms holds information of their spatial distribution around the ONF. We use a far-detuned laser beam coupled to the ONF to thermally excite atoms at the ONF surface. We study the change of transmission spectrum of these atoms as a function of heating laser power. A semiclassical phenomenological model for the thermal excitation of atoms in the atom-surface van der Waals bound states is in good agreement with the measurements. This result suggests that van der Waals potentials could be used to trap and probe atoms at few nanometers from a dielectric surface, a key tool for hybrid photonic-atomic quantum systems.

Attractive non-DLVO forces induced by adsorption of monovalent organic ions.

PubMed

Smith, Alexander M; Maroni, Plinio; Borkovec, Michal

2017-12-20

Direct force measurements between negatively charged colloidal particles were carried out using an atomic force microscope (AFM) in aqueous solutions containing monovalent organic cations, namely tetraphenylarsonium (Ph 4 As + ), 1-hexyl-3-methylimidazolium (HMIM + ), and 1-octyl-3-methylimidazolium (OMIM + ). These ions adsorb to the particle surface, and induce a charge reversal. The forces become attractive at the charge neutralization point, but they are stronger than van der Waals forces. This additional and unexpected attraction decays exponentially with a decay length of a few nanometers, and is strikingly similar to the one previously observed in the presence of multivalent ions. This attractive force probably originates from coupled spontaneous charge fluctuations on the respective surfaces as initially suggested by Kirkwood and Shumaker.

Sedimentation field-flow fractionation for characterization of citric acid-modified Hβ zeolite particles: Effect of particle dispersion and carrier composition.

PubMed

Dou, Haiyang; Bai, Guoyi; Ding, Liang; Li, Yueqiu; Lee, Seungho

2015-11-27

In this study, sedimentation field-flow fractionation (SdFFF) was, for the first time, applied for determination of size distribution of Hβ zeolite particles modified by citric acid (CA-Hβ). Effects of the particle dispersion and the carrier liquid composition (type of dispersing reagent (surfactant) and salt added in the carrier liquid, ionic strength, and pH) on SdFFF elution behavior of CA-Hβ zeolite particles were systematically investigated. Also the SdFFF separation efficiency of the particles was discussed in terms of the forces such as van der Waals, hydrophobic, and induced-dipole interactions. Results reveal that the type of salt and pH of the carrier liquid significantly affect the SdFFF separation efficiency of the zeolite particles. It was found that addition of a salt (NaN3) into the carrier liquid affects the characteristic of the SdFFF channel surface. It was found that the use of an acidic medium (pH 3.2) leads to a particle-channel interaction, while the use of a basic medium (pH 10.6) promotes an inter-particle hydrophobic interaction. Result from SdFFF was compared with those from scanning electron microscopy (SEM) and dynamic light scattering (DLS). It seems that, once the experimental conditions are optimized, SdFFF becomes a valuable tool for size characterization of the zeolite particles. Copyright © 2015 Elsevier B.V. All rights reserved.

Reliable and accurate extraction of Hamaker constants from surface force measurements.

PubMed

Miklavcic, S J

2018-08-15

A simple and accurate closed-form expression for the Hamaker constant that best represents experimental surface force data is presented. Numerical comparisons are made with the current standard least squares approach, which falsely assumes error-free separation measurements, and a nonlinear version assuming independent measurements of force and separation are subject to error. The comparisons demonstrate that not only is the proposed formula easily implemented it is also considerably more accurate. This option is appropriate for any value of Hamaker constant, high or low, and certainly for any interacting system exhibiting an inverse square distance dependent van der Waals force. Copyright © 2018 Elsevier Inc. All rights reserved.

US Air Force 1989 Research Initiation Program. Volume 2.

DTIC Science & Technology

1992-06-25

University of Minnesota-Duluth Specialtv: Inorganic Chemistry Specialty: Mechanics Dr. Satish Chandra Mr. Asad Yousuf Kansas State University Savannah...the Study Van der Waals forces in capillary tubes have previously been calculated by Philip (1977b]. His study was based on the Hamaker theory, which...important in condensed media, are not taken into account by the Hamaker theory. Calculations using on the Hamaker theory are often based on an unrealistic

Liquid film drag out in the presence of molecular forces

NASA Astrophysics Data System (ADS)

Schmidhalter, I.; Cerro, R. L.; Giavedoni, M. D.; Saita, F. A.

2013-03-01

From a practical as well as a conceptual point of view, one of the most interesting problems of physicochemical hydrodynamics is the drag out of a liquid film by a moving solid out of a pool of liquid. The basic problem, sometimes denoted the Landau-Levich problem [L. Landau and B. Levich, "Dragging of a liquid by a moving plate," Acta Physicochim. USSR 17, 42-54 (1942)], involves an interesting blend of capillary and viscous forces plus a matching of the static solution for capillary rise with a numerical solution of the film evolution equation, neglecting gravity, on the downstream region of the flow field. The original solution describes experimental data for a wide range of Capillary numbers but fails to match results for large and very small Capillary numbers. Molecular level forces are introduced to create an augmented version of the film evolution equation to show the effect of van der Waals forces at the lower range of Capillary numbers. A closed form solution for static capillary rise, including molecular forces, was matched with a numerical solution of the augmented film evolution equation in the dynamic meniscus region. Molecular forces do not sensibly modify the static capillary rise region, since film thicknesses are larger than the range of influence of van der Waals forces, but are determinant in shaping the downstream dynamic meniscus of the very thin liquid films. As expected, a quantitatively different level of disjoining pressure for different values of molecular constants remains in the very thin liquid film far downstream. Computational results for a wide range of Capillary numbers and Hamaker constants show a clear transition towards a region where the film thickness becomes independent of the coating speed.

Hydrophobic forces in thin water films stabilized by dodecylammonium chloride

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

Yoon, R.H.; Aksoy, B.S.

1999-03-01

A thin film balance of Scheludko-Exerowa type was used to determine equilibrium film thicknesses of dodecylammonium chloride (RNH{sub 3}Cl) solutions. The data were analyzed in view of the extended DLVO theory, which considers electrostatic, van der Waals. and hydrophobic forces. The hydrophobic force was represented as a power law which is of the same form as for the van der Waals force, so that its constant K{sub 232} can be directly compared with the Hamaker constant, A{sub 232}. The results showed that at low surfactant concentrations, K{sub 232} is positive and decreases with increasing surfactant concentration, suggesting that hydrophobic forcemore » plays an important role in thin films. When the K{sub 232} versus concentration plot was extrapolated to very dilute solutions, K{sub 232} approaches 10{sup {minus}17} J, which is approximately 270 times larger than A{sub 232}. When the surfactant concentration was increased above 2 {times} 10{sup {minus}3} M, however, K{sub 232} becomes negative, indicating that hydration force appears at high surfactant concentrations. These results suggest that air bubbles are hydrophobic and the hydrophobicity decreases with increasing surfactant concentration. A TFB was used to obtain a disjoining pressure isotherm at 10{sup {minus}3} M RNH{sub 3}Cl in the presence of 10{sup {minus}4} M NaCl. The results can be fitted to the extended DLVO theory with K{sub 232} = 6 {times} 10{sup {minus}19} J. Consideration of hydrophobic force predicted a rupture thickness larger than predicted using the DLVO theory, but is substantially smaller than the experimental result. This discrepancy may be ascribed to the hydrodynamic force operating in the film thinning process.« less

Comparisons of Hamaker constants for ceramic systems with intervening vacuum or water: From force laws and physical properties

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

Ackler, H.D.; Chiang, Y.M.; French, R.H.

1996-05-10

Van der Waals dispersive forces produce attractive interactions between bodies, playing an important role in many material systems influencing colloidal and emulsion stability, wetting behavior, and intergranular forces in glass-ceramic systems. It is of technological importance to accurately quantify these interactions, conveniently represented by the Hamaker constant, A. To set the current level of accuracy for determining A, they were calculated from Lifshitz theory using full spectral data for muscovite mica, Al{sub 2}O{sub 3}, SiO{sub 2}, Si{sub 3}N{sub 4}, and rutile TiO{sub 2}, separated by vacuum or water. These were compared to Hamaker constants calculated from physical properties using themore » Tabor-Winterton approximation, a single oscillator model, a multiple oscillator model, and A`s calculated using force vs separation data from surface force apparatus and atomic force microscope studies. For materials with refractive indices between 1.4 and 1.8 separated by vacuum, all methods produce similar values, but for indices larger than 1.8 separated by vacuum, and any of these materials separated by water, results span a broader range. The present level of accuracy for the determination of Hamaker constants, here taken to be represented by the level of agreement between various methods, ranges from about 10% for the case of SiO{sub 2}/vacuum/SiO{sub 2} and TiO{sub 2}/water/TiO{sub 2} to a factor of approximately 7 for mica/water/mica.« less

Measured long-range repulsive Casimir–Lifshitz forces

PubMed Central

Munday, J. N.; Capasso, Federico; Parsegian, V. Adrian

2014-01-01

Quantum fluctuations create intermolecular forces that pervade macroscopic bodies1–3. At molecular separations of a few nanometres or less, these interactions are the familiar van der Waals forces4. However, as recognized in the theories of Casimir, Polder and Lifshitz5–7, at larger distances and between macroscopic condensed media they reveal retardation effects associated with the finite speed of light. Although these long-range forces exist within all matter, only attractive interactions have so far been measured between material bodies8–11. Here we show experimentally that, in accord with theoretical prediction12, the sign of the force can be changed from attractive to repulsive by suitable choice of interacting materials immersed in a fluid. The measured repulsive interaction is found to be weaker than the attractive. However, in both cases the magnitude of the force increases with decreasing surface separation. Repulsive Casimir–Lifshitz forces could allow quantum levitation of objects in a fluid and lead to a new class of switchable nanoscale devices with ultra-low static friction13–15. PMID:19129843

Aqueous gating of van der Waals materials on bilayer nanopaper.

PubMed

Bao, Wenzhong; Fang, Zhiqiang; Wan, Jiayu; Dai, Jiaqi; Zhu, Hongli; Han, Xiaogang; Yang, Xiaofeng; Preston, Colin; Hu, Liangbing

2014-10-28

In this work, we report transistors made of van der Waals materials on a mesoporous paper with a smooth nanoscale surface. The aqueous transistor has a novel planar structure with source, drain, and gate electrodes on the same surface of the paper, while the mesoporous paper is used as an electrolyte reservoir. These transistors are enabled by an all-cellulose paper with nanofibrillated cellulose (NFC) on the top surface that leads to an excellent surface smoothness, while the rest of the microsized cellulose fibers can absorb electrolyte effectively. Based on two-dimensional van der Waals materials, including MoS2 and graphene, we demonstrate high-performance transistors with a large on-off ratio and low subthreshold swing. Such planar transistors with absorbed electrolyte gating can be used as sensors integrated with other components to form paper microfluidic systems. This study is significant for future paper-based electronics and biosensors.

Cosmology with an interacting van der Waals fluid

NASA Astrophysics Data System (ADS)

Elizalde, E.; Khurshudyan, M.

A model for the late-time accelerated expansion of the Universe is considered where a van der Waals fluid interacting with matter plays the role of dark energy. The transition towards this phase in the cosmic evolution history is discussed in detail and, moreover, a complete classification of the future finite-time singularities is obtained for six different possible forms of the nongravitational interaction between dark energy (the van der Waals fluid) and dark matter. This study shows, in particular, that a Universe with a noninteracting three-parameter van der Waals fluid can evolve into a Universe characterized by a type IV (generalized sudden) singularity. On the other hand, for certain values of the parameters, exit from the accelerated expanding phase is possible in the near future, what means that the expansion of the Universe in the future could become decelerated - to our knowledge, this interesting situation is not commonplace in the literature. On the other hand, our study shows that space can be divided into different regions. For some of them, in particular, the nongravitational interactions Q = 3Hbρde, Q = 3Hbρdm and Q = 3Hb(ρde + ρde) may completely suppress future finite-time singularity formation, for sufficiently high values of b. On the other hand, for some other regions of the parameter space, the mentioned interactions would not affect the singularity type, namely the type IV singularity generated in the case of the noninteracting model would be preserved. A similar conclusion has been archived for the cases of Q = 3bHρdeρdm/(ρde + ρdm), Q = 3bHρdm2/(ρ de + ρdm) and Q = 3bHρde2/(ρ de + ρdm) nongravitational interactions, with only one difference: the Q = 3bHρdm2/(ρ de + ρdm) interaction will change the type IV singularity of the noninteracting model into a type II (the sudden) singularity.

Graphene Substrate for van der Waals Epitaxy of Layer-Structured Bismuth Antimony Telluride Thermoelectric Film.

PubMed

Kim, Eun Sung; Hwang, Jae-Yeol; Lee, Kyu Hyoung; Ohta, Hiromichi; Lee, Young Hee; Kim, Sung Wng

2017-02-01

Graphene as a substrate for the van der Waals epitaxy of 2D layered materials is utilized for the epitaxial growth of a layer-structured thermoelectric film. Van der Waals epitaxial Bi 0.5 Sb 1.5 Te 3 film on graphene synthesized via a simple and scalable fabrication method exhibits good crystallinity and high thermoelectric transport properties comparable to single crystals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

van der Waals interaction between a moving nano-cylinder and a liquid thin film.

PubMed

Ledesma-Alonso, René; Raphaël, Elie; Salez, Thomas; Tordjeman, Philippe; Legendre, Dominique

2017-05-24

We study the static and dynamic interaction between a horizontal cylindrical nano-probe and a thin liquid film. The effects of the physical and geometrical parameters, with a special focus on the film thickness, the probe speed, and the distance between the probe and the free surface are analyzed. Deformation profiles have been computed numerically from a Reynolds lubrication equation, coupled to a modified Young-Laplace equation, which takes into account the probe/liquid and the liquid/substrate non-retarded van der Waals interactions. We have found that the film thickness and the probe speed have a significant effect on the threshold separation distance below which the jump-to-contact instability is triggered. These results encourage the use of horizontal cylindrical nano-probes to scan thin liquid films, in order to determine either the physical or geometrical properties of the latter, through the measurement of interaction forces.

High quality NMR structures: a new force field with implicit water and membrane solvation for Xplor-NIH.

PubMed

Tian, Ye; Schwieters, Charles D; Opella, Stanley J; Marassi, Francesca M

2017-01-01

Structure determination of proteins by NMR is unique in its ability to measure restraints, very accurately, in environments and under conditions that closely mimic those encountered in vivo. For example, advances in solid-state NMR methods enable structure determination of membrane proteins in detergent-free lipid bilayers, and of large soluble proteins prepared by sedimentation, while parallel advances in solution NMR methods and optimization of detergent-free lipid nanodiscs are rapidly pushing the envelope of the size limit for both soluble and membrane proteins. These experimental advantages, however, are partially squandered during structure calculation, because the commonly used force fields are purely repulsive and neglect solvation, Van der Waals forces and electrostatic energy. Here we describe a new force field, and updated energy functions, for protein structure calculations with EEFx implicit solvation, electrostatics, and Van der Waals Lennard-Jones forces, in the widely used program Xplor-NIH. The new force field is based primarily on CHARMM22, facilitating calculations with a wider range of biomolecules. The new EEFx energy function has been rewritten to enable OpenMP parallelism, and optimized to enhance computation efficiency. It implements solvation, electrostatics, and Van der Waals energy terms together, thus ensuring more consistent and efficient computation of the complete nonbonded energy lists. Updates in the related python module allow detailed analysis of the interaction energies and associated parameters. The new force field and energy function work with both soluble proteins and membrane proteins, including those with cofactors or engineered tags, and are very effective in situations where there are sparse experimental restraints. Results obtained for NMR-restrained calculations with a set of five soluble proteins and five membrane proteins show that structures calculated with EEFx have significant improvements in accuracy, precision

Determination of Hamaker constants of polymeric nanoparticles in organic solvents by asymmetrical flow field-flow fractionation.

PubMed

Noskov, Sergey; Scherer, Christian; Maskos, Michael

2013-01-25

Interaction forces between all objects are either of repulsive or attractive nature. Concerning attractive interactions, the determination of dispersion forces are of special interest since they appear in all colloidal systems and have a crucial influence on the properties and processes in these systems. One possibility to link theory and experiment is the description of the London-Van der Waals forces in terms of the Hamaker constant, which leads to the challenging problem of calculating the van der Waals interaction energies between colloidal particles. Hence, the determination of a Hamaker constant for a given material is needed when interfacial phenomena such as adhesion are discussed in terms of the total potential energy between particles and substrates. In this work, the asymmetrical flow field-flow fractionation (AF-FFF) in combination with a Newton algorithm based iteration process was used for the determination of Hamaker constants of different nanoparticles in toluene. Copyright © 2012 Elsevier B.V. All rights reserved.

The waaL gene mutation compromised the inhabitation of Enterobacter sp. Ag1 in the mosquito gut environment.

PubMed

Pei, Dong; Jiang, Jinjin; Yu, Wanqin; Kukutla, Phanidhar; Uentillie, Alejandro; Xu, Jiannong

2015-08-27

The mosquito gut harbors a variety of bacteria that are dynamically associated with mosquitoes in various contexts. However, little is known about bacterial factors that affect bacterial inhabitation in the gut microbial community. Enterobacter sp. Ag1 is a predominant Gram negative bacterium in the mosquito midgut. In a mutant library that was generated using transposon Tn5-mediated mutagenesis, a mutant was identified, in which the gene waaL was disrupted by the Tn5 insertion. The waaL encodes O antigen ligase, which is required for the attachment of O antigen to the outer core oligosaccharide of the lipopolysaccharide (LPS). The waaL(-) mutation caused the O antigen repeat missing in the LPS. The normal LPS structure was restored when the mutant was complemented with a plasmid containing waaL gene. The waaL(-) mutation did not affect bacterial proliferation in LB culture, the mutant cells grew at a rate the same as the wildtype (wt) cells. However, when waaL(-) strain were co-cultured with the wt strain or complemented strain, the mutant cells proliferated with a slower rate, indicating that the mutants were less competitive than wt cells in a community setting. Similarly, in a co-feeding assay, when fluorescently tagged wt strain and waaL(-) strain were orally co-introduced into the gut of Anopheles stephensi mosquitoes, the mutant cells were less prevalent in both sugar-fed and blood-fed guts. The data suggest that the mutation compromised the bacterial inhabitation in the gut community. Besides, the mutant was more sensitive to oxidative stress, demonstrated by lower survival rate upon exposure to 20 mM H₂O₂. Lack of the O antigen structure in LPS of Enterobacter compromised the effective growth in co-culture and co-feeding assays. In addition, O-antigen was involved in protection against oxidative stress. The findings suggest that intact LPS is crucial for the bacteria to steadily stay in the gut microbial community.

Holographic Van der Waals phase transition of the higher-dimensional electrically charged hairy black hole

NASA Astrophysics Data System (ADS)

Li, Hui-Ling; Feng, Zhong-Wen; Zu, Xiao-Tao

2018-01-01

With motivation by holography, employing black hole entropy, two-point connection function and entanglement entropy, we show that, for the higher-dimensional Anti-de Sitter charged hairy black hole in the fixed charged ensemble, a Van der Waals-like phase transition can be observed. Furthermore, based on the Maxwell equal-area construction, we check numerically the equal-area law for a first order phase transition in order to further characterize the Van der Waals-like phase transition.

Loss tangent and complex modulus estimated by acoustic radiation force creep and shear wave dispersion

PubMed Central

Amador, Carolina; Urban, Matthew W; Chen, Shigao; Greenleaf, James F

2012-01-01

Elasticity imaging methods have been used to study tissue mechanical properties and have demonstrated that tissue elasticity changes with disease state. In current shear wave elasticity imaging methods typically only shear wave speed is measured and rheological models, e.g., Kelvin-Voigt, Maxwell and Standard Linear Solid, are used to solve for tissue mechanical properties such as the shear viscoelastic complex modulus. This paper presents a method to quantify viscoelastic material properties in a model-independent way by estimating the complex shear elastic modulus over a wide frequency range using time-dependent creep response induced by acoustic radiation force. This radiation force induced creep (RFIC) method uses a conversion formula that is the analytic solution of a constitutive equation. The proposed method in combination with Shearwave Dispersion Ultrasound Vibrometry (SDUV) is used to measure the complex modulus so that knowledge of the applied radiation force magnitude is not necessary. The conversion formula is shown to be sensitive to sampling frequency and the first reliable measure in time according to numerical simulations using the Kelvin-Voigt model creep strain and compliance. Representative model-free shear complex moduli from homogeneous tissue mimicking phantoms and one excised swine kidney were obtained. This work proposes a novel model-free ultrasound-based elasticity method that does not require a rheological model with associated fitting requirements. PMID:22345425

Loss tangent and complex modulus estimated by acoustic radiation force creep and shear wave dispersion.

PubMed

Amador, Carolina; Urban, Matthew W; Chen, Shigao; Greenleaf, James F

2012-03-07

Elasticity imaging methods have been used to study tissue mechanical properties and have demonstrated that tissue elasticity changes with disease state. In current shear wave elasticity imaging methods typically only shear wave speed is measured and rheological models, e.g. Kelvin-Voigt, Maxwell and Standard Linear Solid, are used to solve for tissue mechanical properties such as the shear viscoelastic complex modulus. This paper presents a method to quantify viscoelastic material properties in a model-independent way by estimating the complex shear elastic modulus over a wide frequency range using time-dependent creep response induced by acoustic radiation force. This radiation force induced creep method uses a conversion formula that is the analytic solution of a constitutive equation. The proposed method in combination with shearwave dispersion ultrasound vibrometry is used to measure the complex modulus so that knowledge of the applied radiation force magnitude is not necessary. The conversion formula is shown to be sensitive to sampling frequency and the first reliable measure in time according to numerical simulations using the Kelvin-Voigt model creep strain and compliance. Representative model-free shear complex moduli from homogeneous tissue mimicking phantoms and one excised swine kidney were obtained. This work proposes a novel model-free ultrasound-based elasticity method that does not require a rheological model with associated fitting requirements.

Spatial dispersion in atom-surface quantum friction

DOE PAGES

Reiche, D.; Dalvit, D. A. R.; Busch, K.; ...

2017-04-15

We investigate the influence of spatial dispersion on atom-surface quantum friction. We show that for atom-surface separations shorter than the carrier's mean free path within the material, the frictional force can be several orders of magnitude larger than that predicted by local optics. In addition, when taking into account spatial dispersion effects, we show that the commonly used local thermal equilibrium approximation underestimates by approximately 95% the drag force, obtained by employing the recently reported nonequilibrium fluctuation-dissipation relation for quantum friction. Unlike the treatment based on local optics, spatial dispersion in conjunction with corrections to local thermal equilibrium change notmore » only the magnitude but also the distance scaling of quantum friction.« less

Launching Phonon Polaritons by Natural Boron Nitride Wrinkles with Modifiable Dispersion by Dielectric Environments.

PubMed

Duan, Jiahua; Chen, Runkun; Li, Jingcheng; Jin, Kuijuan; Sun, Zhigang; Chen, Jianing

2017-10-01

Interference-free hyperbolic phonon polaritons (HPPs) excited by natural wrinkles in a hexagonal boron nitride (hBN) microcrystal are reported both experimentally and theoretically. Although their geometries are off-resonant with the excitation wavelength, the wrinkles compensate for the large momentum mismatch between photon and phonon polariton, and launch the HPPs without interference. The spatial feature of wrinkles is about 200 nm, which is an order of magnitude smaller than resonant metal antennas at the same excitation wavelength. Compared with phonon polaritons launched by an atomic force microscopy tip, the phonon polaritons launched by wrinkles are interference-free, independent of the launcher geometry, and exhibit a smaller damping rate (γ ≈ 0.028). On the same hBN microcrystal, in situ nanoinfrared imaging of HPPs launched by different mechanisms is performed. In addition, the dispersion of HPPs is modified by changing the dielectric environments of hBN crystals. The wavelength of HPPs is compressed twofold when the substrate is changed from SiO 2 to gold. The findings provide insights into the intrinsic properties of hBN-HPPs and demonstrate a new way to launch and control polaritons in van der Waals materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Van der Waals model for phase transitions in thermoresponsive surface films.

PubMed

McCoy, John D; Curro, John G

2009-05-21

Phase transitions in polymeric surface films are studied with a simple model based on the van der Waals equation of state. Each chain is modeled by a single bead attached to the surface by an entropic-Hooke's law spring. The surface coverage is controlled by adjusting the chemical potential, and the equilibrium density profile is calculated with density functional theory. The interesting feature of this model is the multivalued nature of the density profile seen at low temperature. This van der Waals loop behavior is resolved with a Maxwell construction between a high-density phase near the wall and a low-density phase in a "vertical" phase transition. Signatures of the phase transition in experimentally measurable quantities are then found. Numerical calculations are presented for isotherms of surface pressure, for the Poisson ratio, and for the swelling ratio.

Compressible liquid flow in nano- or micro-sized circular tubes considering wall-liquid Lifshitz-van der Waals interaction

NASA Astrophysics Data System (ADS)

Zhang, Xueling; Zhu, Weiyao; Cai, Qiang; Shi, Yutao; Wu, Xuehong; Jin, Tingxiang; Yang, Lianzhi; Song, Hongqing

2018-06-01

Although nano- and micro-scale phenomena for fluid flows are ubiquitous in tight oil reservoirs or in nano- or micro-sized channels, the mechanisms behind them remain unclear. In this study, we consider the wall-liquid interaction to investigate the flow mechanisms behind a compressible liquid flow in nano- or micro-sized circular tubes. We assume that the liquid is attracted by the wall surface primarily by the Lifshitz-van der Waals (LW) force, whereas electrostatic forces are negligible. The long-range LW force is thus introduced into the Navier-Stokes equations. The nonlinear equations of motion are decoupled by using the hydrodynamic vorticity-stream functions, from which an approximate analytical perturbation solution is obtained. The proposed model considers the LW force and liquid compressibility to obtain the velocity and pressure fields, which are consistent with experimentally observed micro-size effects. A smaller tube radius implies smaller dimensionless velocity, and when the tube radius decreases to a certain radius Rm, a fluid no longer flows, where Rm is the lower limit of the movable-fluid radius. The radius Rm is calculated, and the results are consistent with previous experimental results. These results reveal that micro-size effects are caused by liquid compressibility and wall-liquid interactions, such as the LW force, for a liquid flowing in nano- or micro-sized channels or pores. The attractive LW force enhances the flow's radial resistance, and the liquid compressibility transmits the radial resistance to the streaming direction via volume deformation, thereby decreasing the streaming velocity.

Lateral-drag propulsion forces induced by anisotropy.

PubMed

Nefedov, Igor S; Rubi, J Miguel

2017-07-21

We predict the existence of lateral drag forces near the flat surface of an absorbing slab made of an anisotropic material. The forces originate from the fluctuations of the electromagnetic field, when the anisotropy axis of the material forms a certain angle with the surface. In this situation, the spatial spectra of the fluctuating electromagnetic fields becomes asymmetric, different for positive and negative transverse wave vectors components. Differently from the case of van der Waals interactions in which the forward-backward symmetry is broken due to the particle movement, in our case the lateral motion results merely from the anisotropy of the slab. This new effect, of particular significance in hyperbolic materials, could be used for the manipulation of nanoparticles.

Attractive particle interaction forces and packing density of fine glass powders

PubMed Central

Parteli, Eric J. R.; Schmidt, Jochen; Blümel, Christina; Wirth, Karl-Ernst; Peukert, Wolfgang; Pöschel, Thorsten

2014-01-01

We study the packing of fine glass powders of mean particle diameter in the range (4–52) μm both experimentally and by numerical DEM simulations. We obtain quantitative agreement between the experimental and numerical results, if both types of attractive forces of particle interaction, adhesion and non-bonded van der Waals forces are taken into account. Our results suggest that considering only viscoelastic and adhesive forces in DEM simulations may lead to incorrect numerical predictions of the behavior of fine powders. Based on the results from simulations and experiments, we propose a mathematical expression to estimate the packing fraction of fine polydisperse powders as a function of the average particle size. PMID:25178812

van der Waals epitaxial ZnTe thin film on single-crystalline graphene

NASA Astrophysics Data System (ADS)

Sun, Xin; Chen, Zhizhong; Wang, Yiping; Lu, Zonghuan; Shi, Jian; Washington, Morris; Lu, Toh-Ming

2018-01-01

Graphene template has long been promoted as a promising host to support van der Waals flexible electronics. However, van der Waals epitaxial growth of conventional semiconductors in planar thin film form on transferred graphene sheets is challenging because the nucleation rate of film species on graphene is significantly low due to the passive surface of graphene. In this work, we demonstrate the epitaxy of zinc-blende ZnTe thin film on single-crystalline graphene supported by an amorphous glass substrate. Given the amorphous nature and no obvious remote epitaxy effect of the glass substrate, this study clearly proves the van der Waals epitaxy of a 3D semiconductor thin film on graphene. X-ray pole figure analysis reveals the existence of two ZnTe epitaxial orientational domains on graphene, a strong X-ray intensity observed from the ZnTe [ 1 ¯ 1 ¯ 2] ǁ graphene [10] orientation domain, and a weaker intensity from the ZnTe [ 1 ¯ 1 ¯ 2] ǁ graphene [11] orientation domain. Furthermore, this study systematically investigates the optoelectronic properties of this epitaxial ZnTe film on graphene using temperature-dependent Raman spectroscopy, steady-state and time-resolved photoluminescence spectroscopy, and fabrication and characterization of a ZnTe-graphene photodetector. The research suggests an effective approach towards graphene-templated flexible electronics.

Temperature-Dependent and Gate-Tunable Rectification in a Black Phosphorus/WS2 van der Waals Heterojunction Diode.

PubMed

Dastgeer, Ghulam; Khan, Muhammad Farooq; Nazir, Ghazanfar; Afzal, Amir Muhammad; Aftab, Sikandar; Naqvi, Bilal Abbas; Cha, Janghwan; Min, Kyung-Ah; Jamil, Yasir; Jung, Jongwan; Hong, Suklyun; Eom, Jonghwa

2018-04-18

Heterostructures comprising two-dimensional (2D) semiconductors fabricated by individual stacking exhibit interesting characteristics owing to their 2D nature and atomically sharp interface. As an emerging 2D material, black phosphorus (BP) nanosheets have drawn much attention because of their small band gap semiconductor characteristics along with high mobility. Stacking structures composed of p-type BP and n-type transition metal dichalcogenides can produce an atomically sharp interface with van der Waals interaction which leads to p-n diode functionality. In this study, for the first time, we fabricated a heterojunction p-n diode composed of BP and WS 2 . The rectification effects are examined for monolayer, bilayer, trilayer, and multilayer WS 2 flakes in our BP/WS 2 van der Waals heterojunction diodes and also verified by density function theory calculations. We report superior functionalities as compared to other van der Waals heterojunction, such as efficient gate-dependent static rectification of 2.6 × 10 4 , temperature dependence, thickness dependence of rectification, and ideality factor of the device. The temperature dependence of Zener breakdown voltage and avalanche breakdown voltage were analyzed in the same device. Additionally, superior optoelectronic characteristics such as photoresponsivity of 500 mA/W and external quantum efficiency of 103% are achieved in the BP/WS 2 van der Waals p-n diode, which is unprecedented for BP/transition metal dichalcogenides heterostructures. The BP/WS 2 van der Waals p-n diodes have a profound potential to fabricate rectifiers, solar cells, and photovoltaic diodes in 2D semiconductor electronics and optoelectronics.

Effect of dispersion on surface interactions of cobalt(II) octaethylporphyrin monolayer on Au(111) and HOPG(0001) substrates: a comparative first principles study.

PubMed

Chilukuri, Bhaskar; Mazur, Ursula; Hipps, K W

2014-07-21

A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff-Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin-substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

Interlayer excitons in a bulk van der Waals semiconductor.

PubMed

Arora, Ashish; Drüppel, Matthias; Schmidt, Robert; Deilmann, Thorsten; Schneider, Robert; Molas, Maciej R; Marauhn, Philipp; Michaelis de Vasconcellos, Steffen; Potemski, Marek; Rohlfing, Michael; Bratschitsch, Rudolf

2017-09-21

Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments and ab initio calculations for 2H-MoTe 2 , we explain their salient features: the positive sign of the g-factor and the large diamagnetic shift. Our investigations solve the long-standing puzzle of positive g-factors in transition metal dichalcogenides, and pave the way for studying collective phenomena in these materials at elevated temperatures.Excitons, quasi-particles of bound electron-hole pairs, are at the core of the optoelectronic properties of layered transition metal dichalcogenides. Here, the authors unveil the presence of interlayer excitons in bulk van der Waals semiconductors, arising from strong localization and spin-valley coupling of charge carriers.

Van der Waals Epitaxy of Functional Oxide Heterostructures

NASA Astrophysics Data System (ADS)

Chu, Ying-Hao

In the diligent pursuit of low-power consumption, multifunctional, and environmentally friendly electronics, more sophisticated requirements on functional materials are on demand. Recently, the discovery of 2D layered materials has created a revolution to this field. Pioneered by graphene, these new 2D materials exhibit abundant unusual physical phenomena that is undiscovered in bulk forms. These materials are characterized with their layer form and almost pure 2D electronic behavior. The confinement of charge and heat transport at such ultrathin planes offers possibilities to overcome the bottleneck of present device development in thickness limitation, and thus push the technologies into next generation. Van der Waals epitaxy, an epitaxial growth method to combine 2D and 3D materials, is one of current reliable manufacturing processes to fabricate 2D materials by growing these 2D materials epitaxially on 3D materials. Then, transferring the 2D materials to the substrates for practical applications. In the mean time, van der Waals epitaxy has also been used to create free-standing 3D materials by growing 3D materials on 2D materials and then removing them from 2D materials since the interfacial boding between 2D and 3D materials should be weak van der Waals bonds. In this study, we intend to take the same concept, but to integrate a family of functional materials in order to open new avenue to flexible electronics. Due to the interplay of lattice, charge, orbital, and spin degrees of freedom, correlated electrons in oxides generate a rich spectrum of competing phases and physical properties. Recently, lots of studies have suggested that oxide heterostructures provide a powerful route to create and manipulate the degrees of freedom and offer new possibilities for next generation devices, thus create a new playground for researchers to investigate novel physics and the emergence of fascinating states of condensed matter. In this talk, we use a 2D layered material as

Control of excitons in multi-layer van der Waals heterostructures

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

Calman, E. V., E-mail: ecalman@gmail.com; Dorow, C. J.; Fogler, M. M.

2016-03-07

We report an experimental study of excitons in a double quantum well van der Waals heterostructure made of atomically thin layers of MoS{sub 2} and hexagonal boron nitride. The emission of neutral and charged excitons is controlled by gate voltage, temperature, and both the helicity and the power of optical excitation.

Contact Forces between Single Metal Oxide Nanoparticles in Gas-Phase Applications and Processes.

PubMed

Salameh, Samir; van der Veen, Monique A; Kappl, Michael; van Ommen, J Ruud

2017-03-14

In this work we present a comprehensive experimental study to determine the contact forces between individual metal oxide nanoparticles in the gas-phase using atomic force microscopy. In addition, we determined the amount of physisorbed water for each type of particle surface. By comparing our results with mathematical models of the interaction forces, we could demonstrate that classical continuum models of van der Waals and capillary forces alone cannot sufficiently describe the experimental findings. Rather, the discrete nature of the molecules has to be considered, which leads to ordering at the interface and the occurrence of solvation forces. We demonstrate that inclusion of solvation forces in the model leads to quantitative agreement with experimental data and that tuning of the molecular order by addition of isopropanol vapor allows us to control the interaction forces between the nanoparticles.

Contact Forces between Single Metal Oxide Nanoparticles in Gas-Phase Applications and Processes

PubMed Central

2017-01-01

In this work we present a comprehensive experimental study to determine the contact forces between individual metal oxide nanoparticles in the gas-phase using atomic force microscopy. In addition, we determined the amount of physisorbed water for each type of particle surface. By comparing our results with mathematical models of the interaction forces, we could demonstrate that classical continuum models of van der Waals and capillary forces alone cannot sufficiently describe the experimental findings. Rather, the discrete nature of the molecules has to be considered, which leads to ordering at the interface and the occurrence of solvation forces. We demonstrate that inclusion of solvation forces in the model leads to quantitative agreement with experimental data and that tuning of the molecular order by addition of isopropanol vapor allows us to control the interaction forces between the nanoparticles. PMID:28186771

FDTD simulations of forces on particles during holographic assembly.

PubMed

Benito, David C; Simpson, Stephen H; Hanna, Simon

2008-03-03

We present finite-difference time-domain (FDTD) calculations of the forces and torques on dielectric particles of various shapes, held in one or many Gaussian optical traps, as part of a study of the physical limitations involved in the construction of micro- and nanostructures using a dynamic holographic assembler (DHA). We employ a full 3-dimensional FDTD implementation, which includes a complete treatment of optical anisotropy. The Gaussian beams are sourced using a multipole expansion of a fifth order Davis beam. Force and torques are calculated for pairs of silica spheres in adjacent traps, for silica cylinders trapped by multiple beams and for oblate silica spheroids and calcite spheres in both linearly and circularly polarized beams. Comparisons are drawn between the magnitudes of the optical forces and the Van der Waals forces acting on the systems. The paper also considers the limitations of the FDTD approach when applied to optical trapping.

Influence of Casimir-Lifshitz forces on actuation dynamics of MEMS

NASA Astrophysics Data System (ADS)

Broer, Wijnand; Palasantzas, George; Knoester, Jasper; Svetovoy, Vitaly

2013-03-01

Electromagnetic fluctuations generate forces between neutral bodies known as Casimir-Lifshitz forces, of which van der Waals forces are special cases, and which can become important in micromechanical systems (MEMS). For surface areas big enough but gaps small enough, the Casimir force can possibly draw and lock MEMS components together, an effect called stiction, causing device malfunction. Alternatively, stiction can also be exploited to add new functionalities to MEMS architecture. Here, using as inputs the measured frequency dependent dielectric response and surface roughness statistics from Atomic Force Microscopy (AFM) images, we perform the first realistic calculation of MEMS actuation. For our analysis the Casimir force is combined with the electrostatic force between rough surfaces to counterbalance the elastic restoring force. It is found that, even though surface roughness has an adverse effect on the availability of (stable) equilibria, it ensures that those stable equilibria can be reached more easily than in the case of flat surfaces. Hence our results can have significant implications on how to design MEM surfaces. The author would like this abstract to appear in a Casimir related session.

Constraints on stable equilibria with fluctuation-induced (Casimir) forces.

PubMed

Rahi, Sahand Jamal; Kardar, Mehran; Emig, Thorsten

2010-08-13

We examine whether fluctuation-induced forces can lead to stable levitation. First, we analyze a collection of classical objects at finite temperature that contain fixed and mobile charges and show that any arrangement in space is unstable to small perturbations in position. This extends Earnshaw's theorem for electrostatics by including thermal fluctuations of internal charges. Quantum fluctuations of the electromagnetic field are responsible for Casimir or van der Waals interactions. Neglecting permeabilities, we find that any equilibrium position of items subject to such forces is also unstable if the permittivities of all objects are higher or lower than that of the enveloping medium, the former being the generic case for ordinary materials in vacuum.

Communication: Determining the structure of the N{sub 2}Ar van der Waals complex with laser-based channel-selected Coulomb explosion

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

Wu, Chengyin, E-mail: cywu@pku.edu.cn; Liu, Yunquan; Gong, Qihuang

2014-04-14

We experimentally reconstructed the structure of the N{sub 2}Ar van der Waals complex with the technique of laser-based channel-selected Coulomb explosion imaging. The internuclear distance between the N{sub 2} center of mass and the Ar atom, i.e., the length of the van der Waals bond, was determined to be 3.88 Å from the two-body explosion channels. The angle between the van der Waals bond and the N{sub 2} principal axis was determined to be 90° from the three-body explosion channels. The reconstructed structure was contrasted with our high level ab initio calculations. The agreement demonstrated the potential application of laser-basedmore » Coulomb explosion in imaging transient molecular structure, particularly for floppy van der Waals complexes, whose structures remain difficult to be determined by conventional spectroscopic methods.« less

Nucleobases-decorated boron nitride nanoribbons for electrochemical biosensing: a dispersion-corrected DFT study.

PubMed

Dabhi, Shweta D; Roondhe, Basant; Jha, Prafulla K

2018-03-28

Understanding the interactions between biomolecules and boron nitride nanostructures is key for their use in nanobiotechnology and medical engineering. In this study, we investigated the adsorption of nucleobases adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) over armchair and zigzag boron nitride nanoribbons (BNNR) using density functional theory to define the applicability of BNNR for the sensing of nucleobases and DNA sequencing. To appropriately account for dispersion, the van der Waals forces (DFT-D2)-type method developed by Grimme was also included in the calculations. The calculated adsorption energy suggests the following order of adsorption for A-BNNR and Z-BNNR with the nucleobases: G > T > A > U > C and G > C > A > T > U, respectively. The origin of the binding of the different nucleobases with BNNR was analysed and π-π stacking was found to be responsible. In addition, the electronic properties, density of states and work function significantly vary after adsorption. These analyses indicate different binding natures for different nucleobases and BNNRs. Thus, this study demonstrates that BNNR can be applied as biosensors for the detection of nucleobases, which are constituents of DNA and RNA. Furthermore, analysis of electronic properties and adsorption energies will play a key role in targeted drug delivery, enzyme activities and genome sequencing. Our results indicate that BNNRs have better adsorption capacity than graphene and boron nitride nanotubes.

Charge-induced fluctuation forces in graphitic nanostructures

DOE PAGES

Drosdoff, D.; Bondarev, Igor V.; Widom, Allan; ...

2016-01-21

Charge fluctuations in nanocircuits with capacitor components are shown to give rise to a novel type of long-ranged interaction, which coexist with the regular Casimir–van derWaals force. The developed theory distinguishes between thermal and quantum mechanical effects, and it is applied to capacitors involving graphene nanostructures. The charge fluctuations mechanism is captured via the capacitance of the system with geometrical and quantum mechanical components. The dependence on the distance separation, temperature, size, and response properties of the system shows that this type of force can have a comparable and even dominant effect to the Casimir interaction. Lastly, our results stronglymore » indicate that fluctuation-induced interactions due to various thermodynamic quantities can have important thermal and quantum mechanical contributions at the microscale and the nanoscale.« less

Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

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

Ganesh, P.; Kim, Jeongnim; Park, Changwon

2014-11-03

In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based onmore » point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.« less

Two dimensional graphene nanogenerator by coulomb dragging: Moving van der Waals heterostructure

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

Zhong, Huikai; Li, Xiaoqiang; Wu, Zhiqian

2015-06-15

Harvesting energy from environment is the current focus of scientific community. Here, we demonstrate a graphene nanogenerator, which is based on moving van der Waals heterostructure formed between graphene and two dimensional (2D) graphene oxide (GO). This nanogenerator can convert mechanical energy into electricity with a voltage output of around 10 mV. Systematic experiments reveal the generated electricity originates from the coulomb interaction induced momentum transfer between 2D GO and holes in graphene. 2D boron nitride was also demonstrated to be effective in the framework of moving van der Waals heterostructure nanogenerator. This investigation of nanogenerator based on the interaction betweenmore » 2D macromolecule materials will be important to understand the origin of the flow-induced potential in nanomaterials and may have great potential in practical applications.« less

The power laws of nanoscale forces in ambient conditions

NASA Astrophysics Data System (ADS)

Chiesa, Matteo; Santos, Sergio; Lai, Chia-Yun

Power laws are ubiquitous in the physical sciences and indispensable to qualitatively and quantitatively describe physical phenomena. A nanoscale force law that accurately describes the phenomena observed in ambient conditions at several nm or fractions of a nm above a surface however is still lacking. Here we report a power law derived from experimental data and describing the interaction between an atomic force microscope AFM tip modelled as a sphere and a surface in ambient conditions. By employing a graphite surface as a model system the resulting effective power is found to be a function of the tip radius and the distance. The data suggest a nano to mesoscale transition in the power law that results in relative agreement with the distance-dependencies predicted by the Hamaker and Lifshitz theories for van der Waals forces for the larger tip radii only

Metapopulation extinction risk: dispersal's duplicity.

PubMed

Higgins, Kevin

2009-09-01

Metapopulation extinction risk is the probability that all local populations are simultaneously extinct during a fixed time frame. Dispersal may reduce a metapopulation's extinction risk by raising its average per-capita growth rate. By contrast, dispersal may raise a metapopulation's extinction risk by reducing its average population density. Which effect prevails is controlled by habitat fragmentation. Dispersal in mildly fragmented habitat reduces a metapopulation's extinction risk by raising its average per-capita growth rate without causing any appreciable drop in its average population density. By contrast, dispersal in severely fragmented habitat raises a metapopulation's extinction risk because the rise in its average per-capita growth rate is more than offset by the decline in its average population density. The metapopulation model used here shows several other interesting phenomena. Dispersal in sufficiently fragmented habitat reduces a metapopulation's extinction risk to that of a constant environment. Dispersal between habitat fragments reduces a metapopulation's extinction risk insofar as local environments are asynchronous. Grouped dispersal raises the effective habitat fragmentation level. Dispersal search barriers raise metapopulation extinction risk. Nonuniform dispersal may reduce the effective fraction of suitable habitat fragments below the extinction threshold. Nonuniform dispersal may make demographic stochasticity a more potent metapopulation extinction force than environmental stochasticity.

van der Waals-Tonks-type equations of state for hard-hypersphere fluids in four and five dimensions

NASA Astrophysics Data System (ADS)

Wang, Xian-Zhi

2004-04-01

Recently, we developed accurate van der Waals-Tonks-type equations of state for hard-disk and hard-sphere fluids by using the known virial coefficients. In this paper, we derive the van der Waals-Tonks-type equations of state. We further apply these equations of state to hard-hypersphere fluids in four and five dimensions. In the low-density fluid regime, these equations of state are in good agreement with the simulation results and existing equations of state.

Larval Dispersal Modeling of Pearl Oyster Pinctada margaritifera following Realistic Environmental and Biological Forcing in Ahe Atoll Lagoon

PubMed Central

Thomas, Yoann; Dumas, Franck; Andréfouët, Serge

2014-01-01

Studying the larval dispersal of bottom-dwelling species is necessary to understand their population dynamics and optimize their management. The black-lip pearl oyster (Pinctada margaritifera) is cultured extensively to produce black pearls, especially in French Polynesia's atoll lagoons. This aquaculture relies on spat collection, a process that can be optimized by understanding which factors influence larval dispersal. Here, we investigate the sensitivity of P. margaritifera larval dispersal kernel to both physical and biological factors in the lagoon of Ahe atoll. Specifically, using a validated 3D larval dispersal model, the variability of lagoon-scale connectivity is investigated against wind forcing, depth and location of larval release, destination location, vertical swimming behavior and pelagic larval duration (PLD) factors. The potential connectivity was spatially weighted according to both the natural and cultivated broodstock densities to provide a realistic view of connectivity. We found that the mean pattern of potential connectivity was driven by the southwest and northeast main barotropic circulation structures, with high retention levels in both. Destination locations, spawning sites and PLD were the main drivers of potential connectivity, explaining respectively 26%, 59% and 5% of the variance. Differences between potential and realistic connectivity showed the significant contribution of the pearl oyster broodstock location to its own dynamics. Realistic connectivity showed larger larval supply in the western destination locations, which are preferentially used by farmers for spat collection. In addition, larval supply in the same sectors was enhanced during summer wind conditions. These results provide new cues to understanding the dynamics of bottom-dwelling populations in atoll lagoons, and show how to take advantage of numerical models for pearl oyster management. PMID:24740288

Supramolecular liquid crystalline π-conjugates: the role of aromatic π-stacking and van der Waals forces on the molecular self-assembly of oligophenylenevinylenes.

PubMed

Goel, Mahima; Jayakannan, M

2010-10-07

Here, we report a unique design strategy to trace the role of aromatic π-stacking and van der Waals interactions on the molecular self-organization of π-conjugated building blocks in a single system. A new series of bulky oligophenylenevinylenes (OPVs) bearing a tricyclodecanemethylene (TCD) unit in the aromatic π-core with flexible long methylene chains (n = 0-12 and 16) in the longitudinal position were designed and synthesized. The OPVs were found to be liquid crystalline, and their enthalpies of phase transitions (also entropies) showed odd-even oscillation with respect to the number of carbon atoms in alkyl chains. OPVs with an even number of methylene units in the side chains showed higher enthalpies with respect to their highly packed solid structures compared to odd-numbered ones. Polarized light microscopic analysis confirmed the formation of cholesteric liquid crystalline (LC) phases of fan shaped textures with focal conics in OPVs with 5 ≤ n ≤ 9. OPVs with longer alkyl chains (OPV-10 to OPV-12) produced a birefringence pattern consisting of dark and bright ring-banded suprastructures. The melting temperature followed a sigmoidal trend, indicating the transformation of molecular self-organization in OPVs from solid to ring-banded suprastructures via cholesteric LC intermediates. At longer alkyl chain lengths, the van der Waals interactions among the alkyl chains became predominant and translated the mesogenic effect across the lamellae; as a consequence, the lamellae underwent twisted self-organization along the radial growth direction of the spherulites to produce bright and dark bands. Scanning electron microscope (SEM) analysis of cholesteric LC and ring-banded textures strongly supported the existence of twisted lamellae in the OPVs with ring-banded textures. Variable temperature X-ray diffraction analysis confirmed the reversibility of the molecular self-organization in the solid state and also showed the existence of the higher ordered

Vibrations of double-nanotube systems with mislocation via a newly developed van der Waals model

NASA Astrophysics Data System (ADS)

Kiani, Keivan

2015-06-01

This study deals with transverse vibrations of two adjacent-parallel-mislocated single-walled carbon nanotubes (SWCNTs) under various end conditions. These tubes interact with each other and their surrounding medium through the intertube van der Waals (vdW) forces, and existing bonds between their atoms and those of the elastic medium. The elastic energy of such forces due to the deflections of nanotubes is appropriately modeled by defining a vdW force density function. In the previous works, vdW forces between two identical tubes were idealized by a uniform form of this function. The newly introduced function enables us to investigate the influences of both intertube free distance and longitudinal mislocation on the natural transverse frequencies of the nanosystem which consists of two dissimilar tubes. Such crucial issues have not been addressed yet, even for simply supported tubes. Using nonlocal Timoshenko and higher-order beam theories as well as Hamilton's principle, the strong form of the equations of motion is established. Seeking for an explicit solution to these integro-partial differential equations is a very problematic task. Thereby, an energy-based method in conjunction with an efficient meshfree method is proposed and the nonlocal frequencies of the elastically embedded nanosystem are determined. For simply supported nanosystems, the predicted first five frequencies of the proposed model are checked with those of assumed mode method, and a reasonably good agreement is achieved. Through various studies, the roles of the tube's length ratio, intertube free space, mislocation, small-scale effect, slenderness ratio, radius of SWCNTs, and elastic constants of the elastic matrix on the natural frequencies of the nanosystem with various end conditions are explained. The limitations of the nonlocal Timoshenko beam theory are also addressed. This work can be considered as a vital step towards better realizing of a more complex system that consists of

Engineering Low Dimensional Materials with van der Waals Interaction

NASA Astrophysics Data System (ADS)

Jin, Chenhao

Two-dimensional van der Waals materials grow into a hot and big field in condensed matter physics in the past decade. One particularly intriguing thing is the possibility to stack different layers together as one wish, like playing a Lego game, which can create artificial structures that do not exist in nature. These new structures can enable rich new physics from interlayer interaction: The interaction is strong, because in low-dimension materials electrons are exposed to the interface and are susceptible to other layers; and the screening of interaction is less prominent. The consequence is rich, not only from the extensive list of two-dimensional materials available nowadays, but also from the freedom of interlayer configuration, such as displacement and twist angle, which creates a gigantic parameter space to play with. On the other hand, however, the huge parameter space sometimes can make it challenging to describe consistently with a single picture. For example, the large periodicity or even incommensurability in van der Waals systems creates difficulty in using periodic boundary condition. Worse still, the huge superlattice unit cell and overwhelming computational efforts involved to some extent prevent the establishment of a simple physical picture to understand the evolution of system properties in the parameter space of interlayer configuration. In the first part of the dissertation, I will focus on classification of the huge parameter space into subspaces, and introduce suitable theoretical approaches for each subspace. For each approach, I will discuss its validity, limitation, general solution, as well as a specific example of application demonstrating how one can obtain the most important effects of interlayer interaction with little computation efforts. Combining all the approaches introduced will provide an analytic solution to cover majority of the parameter space, which will be very helpful in understanding the intuitive physical picture behind

Electric-field switching of two-dimensional van der Waals magnets

NASA Astrophysics Data System (ADS)

Jiang, Shengwei; Shan, Jie; Mak, Kin Fai

2018-05-01

Controlling magnetism by purely electrical means is a key challenge to better information technology1. A variety of material systems, including ferromagnetic (FM) metals2-4, FM semiconductors5, multiferroics6-8 and magnetoelectric (ME) materials9,10, have been explored for the electric-field control of magnetism. The recent discovery of two-dimensional (2D) van der Waals magnets11,12 has opened a new door for the electrical control of magnetism at the nanometre scale through a van der Waals heterostructure device platform13. Here we demonstrate the control of magnetism in bilayer CrI3, an antiferromagnetic (AFM) semiconductor in its ground state12, by the application of small gate voltages in field-effect devices and the detection of magnetization using magnetic circular dichroism (MCD) microscopy. The applied electric field creates an interlayer potential difference, which results in a large linear ME effect, whose sign depends on the interlayer AFM order. We also achieve a complete and reversible electrical switching between the interlayer AFM and FM states in the vicinity of the interlayer spin-flip transition. The effect originates from the electric-field dependence of the interlayer exchange bias.

Prediction of intrinsic two-dimensional ferroelectrics in In2Se3 and other III2-VI3 van der Waals materials.

PubMed

Ding, Wenjun; Zhu, Jianbao; Wang, Zhe; Gao, Yanfei; Xiao, Di; Gu, Yi; Zhang, Zhenyu; Zhu, Wenguang

2017-04-07

Interest in two-dimensional (2D) van der Waals materials has grown rapidly across multiple scientific and engineering disciplines in recent years. However, ferroelectricity, the presence of a spontaneous electric polarization, which is important in many practical applications, has rarely been reported in such materials so far. Here we employ first-principles calculations to discover a branch of the 2D materials family, based on In 2 Se 3 and other III 2 -VI 3 van der Waals materials, that exhibits room-temperature ferroelectricity with reversible spontaneous electric polarization in both out-of-plane and in-plane orientations. The device potential of these 2D ferroelectric materials is further demonstrated using the examples of van der Waals heterostructures of In 2 Se 3 /graphene, exhibiting a tunable Schottky barrier, and In 2 Se 3 /WSe 2 , showing a significant band gap reduction in the combined system. These findings promise to substantially broaden the tunability of van der Waals heterostructures for a wide range of applications.

Prediction of intrinsic two-dimensional ferroelectrics in In2Se3 and other III2-VI3 van der Waals materials

PubMed Central

Ding, Wenjun; Zhu, Jianbao; Wang, Zhe; Gao, Yanfei; Xiao, Di; Gu, Yi; Zhang, Zhenyu; Zhu, Wenguang

2017-01-01

Interest in two-dimensional (2D) van der Waals materials has grown rapidly across multiple scientific and engineering disciplines in recent years. However, ferroelectricity, the presence of a spontaneous electric polarization, which is important in many practical applications, has rarely been reported in such materials so far. Here we employ first-principles calculations to discover a branch of the 2D materials family, based on In2Se3 and other III2-VI3 van der Waals materials, that exhibits room-temperature ferroelectricity with reversible spontaneous electric polarization in both out-of-plane and in-plane orientations. The device potential of these 2D ferroelectric materials is further demonstrated using the examples of van der Waals heterostructures of In2Se3/graphene, exhibiting a tunable Schottky barrier, and In2Se3/WSe2, showing a significant band gap reduction in the combined system. These findings promise to substantially broaden the tunability of van der Waals heterostructures for a wide range of applications. PMID:28387225

Prediction of intrinsic two-dimensional ferroelectrics in In2Se3 and other III2-VI3 van der Waals materials

NASA Astrophysics Data System (ADS)

Ding, Wenjun; Zhu, Jianbao; Wang, Zhe; Gao, Yanfei; Xiao, Di; Gu, Yi; Zhang, Zhenyu; Zhu, Wenguang

2017-04-01

Interest in two-dimensional (2D) van der Waals materials has grown rapidly across multiple scientific and engineering disciplines in recent years. However, ferroelectricity, the presence of a spontaneous electric polarization, which is important in many practical applications, has rarely been reported in such materials so far. Here we employ first-principles calculations to discover a branch of the 2D materials family, based on In2Se3 and other III2-VI3 van der Waals materials, that exhibits room-temperature ferroelectricity with reversible spontaneous electric polarization in both out-of-plane and in-plane orientations. The device potential of these 2D ferroelectric materials is further demonstrated using the examples of van der Waals heterostructures of In2Se3/graphene, exhibiting a tunable Schottky barrier, and In2Se3/WSe2, showing a significant band gap reduction in the combined system. These findings promise to substantially broaden the tunability of van der Waals heterostructures for a wide range of applications.

Effect of Dispersion on Surface Interactions of Cobalt(II) Octaethylporphyrin Monolayer on Au(111) and HOPG(0001) Substrates: a Comparative First Principles Study

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

Chilukuri, Bhaskar; Mazur, Ursula; Hipps, Kerry W.

A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly tomore » Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff–Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin–substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.« less

Thermophoretic force and velocity of nanoparticles in the free molecule regime.

PubMed

Li, Zhigang; Wang, Hai

2004-08-01

We extend our previous gas-kinetic theory analysis of drag force in a uniform temperature field [Li and Wang, Phys. Rev. E. 68, 061206 (2003); 68, 061207 (2003)] to particle transport in fluids with nonuniform temperature. Formulations for drag and thermophoretic forces are proposed for nanoparticle transport in low-density gases. We specifically consider the influence of nonrigid body collision due to van der Waals or other forces between the particle and gas molecules and find that these forces play a notable role for particles a few nanometers in size. It is shown that the present formulations can be easily reduced to the classical result of Waldmann [Z. Naturforsch. A 14a, 589 (1959)] by assuming rigid body collision. From the force formulations we also obtain the equation governing the thermophoretic velocity. This velocity is found to be highly sensitive to the potential energy of interactions between gas molecules and particle, and as such Waldmann's thermophoretic velocity is not expected to be accurate for nanosized particles.

Electronic zero-point fluctuation forces inside circuit components

PubMed Central

Leonhardt, Ulf

2018-01-01

One of the most intriguing manifestations of quantum zero-point fluctuations are the van der Waals and Casimir forces, often associated with vacuum fluctuations of the electromagnetic field. We study generalized fluctuation potentials acting on internal degrees of freedom of components in electrical circuits. These electronic Casimir-like potentials are induced by the zero-point current fluctuations of any general conductive circuit. For realistic examples of an electromechanical capacitor and a superconducting qubit, our results reveal the possibility of tunable forces between the capacitor plates, or the level shifts of the qubit, respectively. Our analysis suggests an alternative route toward the exploration of Casimir-like fluctuation potentials, namely, by characterizing and measuring them as a function of parameters of the environment. These tunable potentials may be useful for future nanoelectromechanical and quantum technologies. PMID:29719863

Correlational Effects of the Molecular-Tilt Configuration and the Intermolecular van der Waals Interaction on the Charge Transport in the Molecular Junction.

PubMed

Shin, Jaeho; Gu, Kyungyeol; Yang, Seunghoon; Lee, Chul-Ho; Lee, Takhee; Jang, Yun Hee; Wang, Gunuk

2018-06-25

Molecular conformation, intermolecular interaction, and electrode-molecule contacts greatly affect charge transport in molecular junctions and interfacial properties of organic devices by controlling the molecular orbital alignment. Here, we statistically investigated the charge transport in molecular junctions containing self-assembled oligophenylene molecules sandwiched between an Au probe tip and graphene according to various tip-loading forces ( F L ) that can control the molecular-tilt configuration and the van der Waals (vdW) interactions. In particular, the molecular junctions exhibited two distinct transport regimes according to the F L dependence (i.e., F L -dependent and F L -independent tunneling regimes). In addition, the charge-injection tunneling barriers at the junction interfaces are differently changed when the F L ≤ 20 nN. These features are associated to the correlation effects between the asymmetry-coupling factor (η), the molecular-tilt angle (θ), and the repulsive intermolecular vdW force ( F vdW ) on the molecular-tunneling barriers. A more-comprehensive understanding of these charge transport properties was thoroughly developed based on the density functional theory calculations in consideration of the molecular-tilt configuration and the repulsive vdW force between molecules.

Self-assembled Gemini surfactant film-mediated dispersion stability.

PubMed

Rabinovich, Y I; Kanicky, J R; Pandey, S; Oskarsson, H; Holmberg, K; Moudgil, B M; Shah, D O

2005-08-15

The force-distance curves of 12-2-12 and 12-4-12 Gemini quaternary ammonium bromide surfactants on mica and silica surfaces obtained by atomic force microscopy (AFM) were correlated with the structure of the adsorption layer. The critical micelle concentration was measured in the presence or absence of electrolyte. The electrolyte effect (the decrease of CMC) is significantly more pronounced for Gemini than for single-chain surfactants. The maximum compressive force, F(max), of the adsorbed surfactant aggregates was determined. On the mica surface in the presence of 0.1 M NaCl, the Gemini micelles and strong repulsive barrier appear at surfactant concentrations 0.02-0.05 mM, which is significantly lower than that for the single C(12)TAB (5-10 mM). This difference between single and Gemini surfactants can be explained by a stronger adsorption energy of Gemini surfactants. The low concentration of Gemini at which this surfactant forms the strong micellar layer on the solid/solution interface proves that Gemini aggregates (micelles) potentially act as dispersing agent in processes such as chemical mechanical polishing or collector in flotation. The AFM force-distance results obtained for the Gemini surfactants were used along with turbidity measurements to determine how adsorption of Gemini surfactants affects dispersion stability. It has been shown that Gemini (or two-chain) surfactants are more effective dispersing agents, and that in the presence of electrolyte, the silica dispersion stability at pH 4.0 can also be achieved at very low surfactant concentrations ( approximately 0.02 mM).

Spontaneous doping on high quality talc-graphene-hBN van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Mania, E.; Alencar, A. B.; Cadore, A. R.; Carvalho, B. R.; Watanabe, K.; Taniguchi, T.; Neves, B. R. A.; Chacham, H.; Campos, L. C.

2017-09-01

Steady doping, added to its remarkable electronic properties, would make graphene a valuable commodity in the solar cell market, as energy power conversion could be substantially increased. Here we report a graphene van der Waals heterostructure which is able to spontaneously dope graphene (p-type) up to n ~ 2.2  ×  1013 cm-2 while providing excellent charge mobility (μ ~ 25 000 cm2 V-1 s-1). Such properties are achieved via deposition of graphene on atomically flat layered talc, a natural and abundant dielectric crystal. Raman investigation shows a preferential charge accumulation on graphene-talc van der Waals heterostructures, which are investigated through the electronic properties of talc/graphene/hBN heterostructure devices. These heterostructures preserve graphene’s good electronic quality, verified by the observation of quantum Hall effect at low magnetic fields (B  =  0.4 T) at T  =  4.2 K. In order to investigate the physical mechanisms behind graphene-on-talc p-type doping, we performed first-principles calculations of their interface structural and electronic properties. In addition to potentially improving solar cell efficiency, graphene doping via van der Waals stacking is also a promising route towards controlling the band gap opening in bilayer graphene, promoting a steady n or p type doping in graphene and, eventually, providing a new path to access superconducting states in graphene, predicted to exist only at very high doping.

Pattern-free thermal modulator via thermal radiation between Van der Waals materials

NASA Astrophysics Data System (ADS)

Liu, Xianglei; Shen, Jiadong; Xuan, Yimin

2017-10-01

Modulating heat flux provides a platform for a plethora of emerging devices such as thermal diodes, thermal transistors, and thermal memories. Here, a pattern-free noncontact thermal modulator is proposed based on the mechanical rotation between two Van der Waals films with optical axes parallel to the surfaces. A modulation contrast can reach a value higher than 5 for hexagonal Boron Nitride (hBN) films separated by a nanoscale gap distance. The dominant radiative heat exchange comes from the excitation of both Type I and Type II hyperbolic surface phonon polaritons (HSPhPs) at the vacuum-hBN interface for different orientations, while the large modulation contrast is mainly attributed to the mismatching Type I HSPhPs induced by rotation. This work opens the possibility to design cheap thermal modulators without relying on nanofabrication techniques, and paves the way to apply natural Van der Waals materials in manipulating heat currents in an active way.

Strong enhancement of dispersion forces from microwave radiation

NASA Astrophysics Data System (ADS)

Sernelius, B. E.

2002-11-01

We have studied non-thermal effects of microwave radiation on the forces between objects. This is the first step in a study of possible effects of microwave radiation from cellular phones on biological tissue. We have used a simplified model for human blood cells in blood. We find for the normal radiation level of cellular phones an enhancement of the attractive force with ten orders of magnitude as compared to the corresponding effect at thermal radiation.

Structure and Stability of Molecular Crystals with Many-Body Dispersion-Inclusive Density Functional Tight Binding.

PubMed

Mortazavi, Majid; Brandenburg, Jan Gerit; Maurer, Reinhard J; Tkatchenko, Alexandre

2018-01-18

Accurate prediction of structure and stability of molecular crystals is crucial in materials science and requires reliable modeling of long-range dispersion interactions. Semiempirical electronic structure methods are computationally more efficient than their ab initio counterparts, allowing structure sampling with significant speedups. We combine the Tkatchenko-Scheffler van der Waals method (TS) and the many-body dispersion method (MBD) with third-order density functional tight-binding (DFTB3) via a charge population-based method. We find an overall good performance for the X23 benchmark database of molecular crystals, despite an underestimation of crystal volume that can be traced to the DFTB parametrization. We achieve accurate lattice energy predictions with DFT+MBD energetics on top of vdW-inclusive DFTB3 structures, resulting in a speedup of up to 3000 times compared with a full DFT treatment. This suggests that vdW-inclusive DFTB3 can serve as a viable structural prescreening tool in crystal structure prediction.

Surfactants and Desensitizing Wax Substitutes for TNT-Based Systems.

DTIC Science & Technology

1994-10-01

materials having dispersion (London or van der Waals) forces only. The concept thus had to be refined to take into account additional intermolecular...The column head pressure should have been set to produce a convenient column flow (-l to 5 ml/min) as determined by Van Demmeter plots. 8. Place...current OSHA criteria 2 200 Volatility, Approximate GC Neut . 3 hours at Carbon Typo Distillation Range No. 163 C Clay/SIlica Gel Analysis, Mass % Analysis

Method and Apparatus for the Quantification of Particulate Adhesion Forces on Various Substrates

NASA Technical Reports Server (NTRS)

Wohl, Christopher J.; Atkins, Brad M.; Connell, John W.

2011-01-01

Mitigation strategies for lunar dust adhesion have typically been limited to qualitative analysis. This technical memorandum describes the generation and operation of an adhesion testing device capable of quantitative assessment of adhesion forces between particulates and substrates. An aerosolization technique is described to coat a surface with a monolayer of particulates. Agitation of this surface, via sonication, causes particles to dislodge and be gravitationally fed into an optical particle counter. Experimentally determined adhesion force values are compared to forces calculated from van der Waals interactions and are used to calculate the work of adhesion using Johnson-Kendall-Roberts (JKR) theory. Preliminary results indicate that a reduction in surface energy and available surface area, through topographical modification, improve mitigation of particulate adhesion.

Biomechanics of conidial dispersal in the toxic mold Stachybotrys chartarum

PubMed Central

Tucker, Kathryn; Stolze, Jessica L.; Kennedy, Aaron H.; Money, Nicholas P.

2007-01-01

Conidial dispersal in Stachybotrys chartarum in response to low-velocity airflow was studied using a microflow apparatus. The maximum rate of spore release occurred during the first 5 min of airflow, followed by a dramatic reduction in dispersal that left more than 99% of the conidia attached to their conidiophores. Micromanipulation of undisturbed colonies showed that micronewton (μN) forces were needed to dislodge spore clusters from their supporting conidiophores. Calculations show that airspeeds that normally prevail in the indoor environment disturb colonies with forces that are 1,000-fold lower, in the nanonewton (nN) range. Low-velocity airflow does not, therefore, cause sufficient disturbance to disperse a large proportion of the conidia of S. chartarum. PMID:17267247

Calculation of Non-Bonded Forces Due to Sliding of Bundled Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Frankland, S. J. V.; Bandorawalla, T.; Gates, T. S.

2003-01-01

An important consideration for load transfer in bundles of single-walled carbon nanotubes is the nonbonded (van der Waals) forces between the nanotubes and their effect on axial sliding of the nanotubes relative to each other. In this research, the non-bonded forces in a bundle of seven hexagonally packed (10,10) single-walled carbon nanotubes are represented as an axial force applied to the central nanotube. A simple model, based on momentum balance, is developed to describe the velocity response of the central nanotube to the applied force. The model is verified by comparing its velocity predictions with molecular dynamics simulations that were performed on the bundle with different force histories applied to the central nanotube. The model was found to quantitatively predict the nanotube velocities obtained from the molecular dynamics simulations. Both the model and the simulations predict a threshold force at which the nanotube releases from the bundle. This force converts to a shear yield strength of 10.5-11.0 MPa for (10,10) nanotubes in a bundle.

Layer-dependent band alignment of few layers of blue phosphorus and their van der Waals heterostructures with graphene

NASA Astrophysics Data System (ADS)

Pontes, Renato B.; Miwa, Roberto H.; da Silva, Antônio J. R.; Fazzio, Adalberto; Padilha, José E.

2018-06-01

The structural and electronic properties of few layers of blue phosphorus and their van der Waals heterostructures with graphene were investigated by means of first-principles electronic structure calculations. We study the four energetically most stable stacking configurations for multilayers of blue phosphorus. For all of them, the indirect band-gap semiconductor character, are preserved. We show that the properties of monolayer graphene and single-layer (bilayer) blue phosphorus are preserved in the van der Waals heterostructures. Further, our results reveal that under a perpendicular applied electric field, the position of the band structure of blue phosphorus with respect to that of graphene is tunable, enabling the effective control of the Schottky barrier height. Indeed, for the bilayer blue phosphorene on top of graphene, it is possible to even move the system into an Ohmic contact and induce a doping level of the blue phosphorene. All of these features are fundamental for the design of new nanodevices based on van der Waals heterostructures.

Dispersion Corrected Structural Properties and Quasiparticle Band Gaps of Several Organic Energetic Solids.

PubMed

Appalakondaiah, S; Vaitheeswaran, G; Lebègue, S

2015-06-18

We have performed ab initio calculations for a series of energetic solids to explore their structural and electronic properties. To evaluate the ground state volume of these molecular solids, different dispersion correction methods were accounted in DFT, namely the Tkatchenko-Scheffler method (with and without self-consistent screening), Grimme's methods (D2, D3(BJ)), and the vdW-DF method. Our results reveal that dispersion correction methods are essential in understanding these complex structures with van der Waals interactions and hydrogen bonding. The calculated ground state volumes and bulk moduli show that the performance of each method is not unique, and therefore a careful examination is mandatory for interpreting theoretical predictions. This work also emphasizes the importance of quasiparticle calculations in predicting the band gap, which is obtained here with the GW approximation. We find that the obtained band gaps are ranging from 4 to 7 eV for the different compounds, indicating their insulating nature. In addition, we show the essential role of quasiparticle band structure calculations to correlate the gap with the energetic properties.

Dispersion forces play a role in (Me 2 IPr)Fe(NAd)R 2 (Ad = adamantyl; R = neo Pe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)

DOE PAGES

Cundari, Thomas R.; Jacobs, Brian P.; MacMillan, Samantha N.; ...

2018-01-01

Calculations show that dispersion forces in four-coordinate (Me 2 IPr)Fe(NAd)(1-nor) 2 ( 2b ) contribute to greater D(FeR) and subtly slow its migratory insertion relative to the neopentyl analogue.

Dispersion forces play a role in (Me 2 IPr)Fe(NAd)R 2 (Ad = adamantyl; R = neo Pe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)

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

Cundari, Thomas R.; Jacobs, Brian P.; MacMillan, Samantha N.

Calculations show that dispersion forces in four-coordinate (Me 2 IPr)Fe(NAd)(1-nor) 2 ( 2b ) contribute to greater D(FeR) and subtly slow its migratory insertion relative to the neopentyl analogue.

Lost at sea: genetic, oceanographic and meteorological evidence for storm-forced dispersal.

PubMed

Monzón-Argüello, C; Dell'Amico, F; Morinière, P; Marco, A; López-Jurado, L F; Hays, Graeme C; Scott, Rebecca; Marsh, Robert; Lee, Patricia L M

2012-08-07

For many species, there is broad-scale dispersal of juvenile stages and/or long-distance migration of individuals and hence the processes that drive these various wide-ranging movements have important life-history consequences. Sea turtles are one of these paradigmatic long-distance travellers, with hatchlings thought to be dispersed by ocean currents and adults often shuttling between distant breeding and foraging grounds. Here, we use multi-disciplinary oceanographic, atmospheric and genetic mixed stock analyses to show that juvenile turtles are encountered 'downstream' at sites predicted by currents. However, in some cases, unusual occurrences of juveniles are more readily explained by storm events and we show that juvenile turtles may be displaced thousands of kilometres from their expected dispersal based on prevailing ocean currents. As such, storms may be a route by which unexpected areas are encountered by juveniles which may in turn shape adult migrations. Increased stormy weather predicted under climate change scenarios suggests an increasing role of storms in dispersal of sea turtles and other marine groups with life-stages near the ocean surface.

Lost at sea: genetic, oceanographic and meteorological evidence for storm-forced dispersal

PubMed Central

Monzón-Argüello, C.; Dell'Amico, F.; Morinière, P.; Marco, A.; López-Jurado, L. F.; Hays, Graeme C.; Scott, Rebecca; Marsh, Robert; Lee, Patricia L. M.

2012-01-01

For many species, there is broad-scale dispersal of juvenile stages and/or long-distance migration of individuals and hence the processes that drive these various wide-ranging movements have important life-history consequences. Sea turtles are one of these paradigmatic long-distance travellers, with hatchlings thought to be dispersed by ocean currents and adults often shuttling between distant breeding and foraging grounds. Here, we use multi-disciplinary oceanographic, atmospheric and genetic mixed stock analyses to show that juvenile turtles are encountered ‘downstream’ at sites predicted by currents. However, in some cases, unusual occurrences of juveniles are more readily explained by storm events and we show that juvenile turtles may be displaced thousands of kilometres from their expected dispersal based on prevailing ocean currents. As such, storms may be a route by which unexpected areas are encountered by juveniles which may in turn shape adult migrations. Increased stormy weather predicted under climate change scenarios suggests an increasing role of storms in dispersal of sea turtles and other marine groups with life-stages near the ocean surface. PMID:22319111

Two-dimensional antimonene single crystals grown by van der Waals epitaxy.

PubMed

Ji, Jianping; Song, Xiufeng; Liu, Jizi; Yan, Zhong; Huo, Chengxue; Zhang, Shengli; Su, Meng; Liao, Lei; Wang, Wenhui; Ni, Zhenhua; Hao, Yufeng; Zeng, Haibo

2016-11-15

Unlike the unstable black phosphorous, another two-dimensional group-VA material, antimonene, was recently predicted to exhibit good stability and remarkable physical properties. However, the synthesis of high-quality monolayer or few-layer antimonenes, sparsely reported, has greatly hindered the development of this new field. Here, we report the van der Waals epitaxy growth of few-layer antimonene monocrystalline polygons, their atomical microstructure and stability in ambient condition. The high-quality, few-layer antimonene monocrystalline polygons can be synthesized on various substrates, including flexible ones, via van der Waals epitaxy growth. Raman spectroscopy and transmission electron microscopy reveal that the obtained antimonene polygons have buckled rhombohedral atomic structure, consistent with the theoretically predicted most stable β-phase allotrope. The very high stability of antimonenes was observed after aging in air for 30 days. First-principle and molecular dynamics simulation results confirmed that compared with phosphorene, antimonene is less likely to be oxidized and possesses higher thermodynamic stability in oxygen atmosphere at room temperature. Moreover, antimonene polygons show high electrical conductivity up to 10 4  S m -1 and good optical transparency in the visible light range, promising in transparent conductive electrode applications.

Two-dimensional antimonene single crystals grown by van der Waals epitaxy

PubMed Central

Ji, Jianping; Song, Xiufeng; Liu, Jizi; Yan, Zhong; Huo, Chengxue; Zhang, Shengli; Su, Meng; Liao, Lei; Wang, Wenhui; Ni, Zhenhua; Hao, Yufeng; Zeng, Haibo

2016-01-01

Unlike the unstable black phosphorous, another two-dimensional group-VA material, antimonene, was recently predicted to exhibit good stability and remarkable physical properties. However, the synthesis of high-quality monolayer or few-layer antimonenes, sparsely reported, has greatly hindered the development of this new field. Here, we report the van der Waals epitaxy growth of few-layer antimonene monocrystalline polygons, their atomical microstructure and stability in ambient condition. The high-quality, few-layer antimonene monocrystalline polygons can be synthesized on various substrates, including flexible ones, via van der Waals epitaxy growth. Raman spectroscopy and transmission electron microscopy reveal that the obtained antimonene polygons have buckled rhombohedral atomic structure, consistent with the theoretically predicted most stable β-phase allotrope. The very high stability of antimonenes was observed after aging in air for 30 days. First-principle and molecular dynamics simulation results confirmed that compared with phosphorene, antimonene is less likely to be oxidized and possesses higher thermodynamic stability in oxygen atmosphere at room temperature. Moreover, antimonene polygons show high electrical conductivity up to 104 S m−1 and good optical transparency in the visible light range, promising in transparent conductive electrode applications. PMID:27845327

Exciton–polaritons in van der Waals heterostructures embedded in tunable microcavities

PubMed Central

Dufferwiel, S.; Schwarz, S.; Withers, F.; Trichet, A. A. P.; Li, F.; Sich, M.; Del Pozo-Zamudio, O.; Clark, C.; Nalitov, A.; Solnyshkov, D. D.; Malpuech, G.; Novoselov, K. S.; Smith, J. M.; Skolnick, M. S.; Krizhanovskii, D. N.; Tartakovskii, A. I.

2015-01-01

Layered materials can be assembled vertically to fabricate a new class of van der Waals heterostructures a few atomic layers thick, compatible with a wide range of substrates and optoelectronic device geometries, enabling new strategies for control of light–matter coupling. Here, we incorporate molybdenum diselenide/hexagonal boron nitride (MoSe2/hBN) quantum wells in a tunable optical microcavity. Part-light–part-matter polariton eigenstates are observed as a result of the strong coupling between MoSe2 excitons and cavity photons, evidenced from a clear anticrossing between the neutral exciton and the cavity modes with a splitting of 20 meV for a single MoSe2 monolayer, enhanced to 29 meV in MoSe2/hBN/MoSe2 double-quantum wells. The splitting at resonance provides an estimate of the exciton radiative lifetime of 0.4 ps. Our results pave the way for room-temperature polaritonic devices based on multiple-quantum-well van der Waals heterostructures, where polariton condensation and electrical polariton injection through the incorporation of graphene contacts may be realized. PMID:26446783

The role of van der Waals interaction in the tilted binding of amine molecules to the Au(111) surface

NASA Astrophysics Data System (ADS)

Le, Duy; Aminpour, Maral; Kiejna, Adam; Rahman, Talat S.

2012-06-01

We present the results of ab initio electronic structure calculations for the adsorption characteristics of three amine molecules on Au(111), which show that the inclusion of van der Waals interactions between the isolated molecule and the surface leads in general to good agreement with experimental data on the binding energies. Each molecule, however, adsorbs with a small tilt angle (between -5 and 9°). For the specific case of 1,4-diaminobenzene (BDA) our calculations reproduce the larger tilt angle (close to 24°) measured by photoemission experiments, when intermolecular (van der Waals) interactions (for about 8% coverage) are included. These results point not only to the important contribution of van der Waals interactions to molecule-surface binding energy, but also that of intermolecular interactions, often considered secondary to that between the molecule and the surface, in determining the adsorption geometry and pattern formation.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

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

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

Material transport in a wind and buoyancy forced mixed layer

NASA Astrophysics Data System (ADS)

Mensa, J. A.; Özgökmen, T.; Poje, A. C.; Imberger, J.

2016-02-01

Flows in the upper ocean mixed layer are responsible for the transport and dispersion of biogeochemical tracers, phytoplankton and buoyant pollutants, such as hydrocarbons from an oil spill. Material dispersion in mixed layer flows subject to diurnal buoyancy forcing and weak winds (|u10|=5ms-1) are investigated using a non-hydrostatic model. Both purely buoyancy-forced and combined wind- and buoyancy-forced flows are sampled using passive tracers, as well as 2D and 3D particles to explore characteristics of horizontal and vertical dispersion. It is found that the surface tracer patterns are determined by the convergence zones created by convection cells within a time scale of just a few hours. For pure convection, the results displayed the classic signature of Rayleigh-Benard cells. When combined with a wind stress, the convective cells become anisotropic in that the along-wind length scale gets much larger than the cross-wind scale. Horizontal relative dispersion computed by sampling the flow fields using both 2D and 3D passive particles is found to be consistent with the Richardson regime. Relative dispersion is an order of magnitude higher and 2D surface releases transition to Richardson regime faster in the wind-forced case. We also show that the buoyancy-forced case results in significantly lower amplitudes of scale-dependent horizontal relative diffusivity, kD(l), than those reported by Okubo (1970), while the wind- and buoyancy forced case shows a good agreement with Okubo's diffusivity amplitude, and scaling consistent with Richardson's 4/3rd law, kD(l) l4/3. The modelling results provide a framework for measuring material dispersion by mixed layer flow in future observational programs.

Many-body dispersion effects in the binding of adsorbates on metal surfaces

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

Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

2015-09-14

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic–inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding ofmore » adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate–surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.« less

Quantum Gravitational Force Between Polarizable Objects.

PubMed

Ford, L H; Hertzberg, Mark P; Karouby, J

2016-04-15

Since general relativity is a consistent low energy effective field theory, it is possible to compute quantum corrections to classical forces. Here we compute a quantum correction to the gravitational potential between a pair of polarizable objects. We study two distant bodies and compute a quantum force from their induced quadrupole moments due to two-graviton exchange. The effect is in close analogy to the Casimir-Polder and London-van der Waals forces between a pair of atoms from their induced dipole moments due to two photon exchange. The new effect is computed from the shift in vacuum energy of metric fluctuations due to the polarizability of the objects. We compute the potential energy at arbitrary distances compared to the wavelengths in the system, including the far and near regimes. In the far distance, or retarded, regime, the potential energy takes on a particularly simple form: V(r)=-3987ℏcG^{2}α_{1S}α_{2S}/(4πr^{11}), where α_{1S}, α_{2S} are the static gravitational quadrupole polarizabilities of each object. We provide estimates of this effect.

Low-Voltage Complementary Electronics from Ion-Gel-Gated Vertical Van der Waals Heterostructures

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

Choi, Yongsuk; Kang, Junmo; Jariwala, Deep

2016-03-22

Low-voltage complementary circuits comprising n-type and p-type van der Waals heterojunction vertical field-effect transistors (VFETs) are demonstrated. The resulting VFETs possess high on-state current densities (>3000 A cm-2) and on/off current ratios (>104) in a narrow voltage window (<3 V).

Giant magnetic splitting inducing near-unity valley polarization in van der Waals heterostructures.

PubMed

Nagler, Philipp; Ballottin, Mariana V; Mitioglu, Anatolie A; Mooshammer, Fabian; Paradiso, Nicola; Strunk, Christoph; Huber, Rupert; Chernikov, Alexey; Christianen, Peter C M; Schüller, Christian; Korn, Tobias

2017-11-16

Monolayers of semiconducting transition metal dichalcogenides exhibit intriguing fundamental physics of strongly coupled spin and valley degrees of freedom for charge carriers. While the possibility of exploiting these properties for information processing stimulated concerted research activities towards the concept of valleytronics, maintaining control over spin-valley polarization proved challenging in individual monolayers. A promising alternative route explores type II band alignment in artificial van der Waals heterostructures. The resulting formation of interlayer excitons combines the advantages of long carrier lifetimes and spin-valley locking. Here, we demonstrate artificial design of a two-dimensional heterostructure enabling intervalley transitions that are not accessible in monolayer systems. The resulting giant effective g factor of -15 for interlayer excitons induces near-unity valley polarization via valley-selective energetic splitting in high magnetic fields, even after nonselective excitation. Our results highlight the potential to deterministically engineer novel valley properties in van der Waals heterostructures using crystallographic alignment.

Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates

NASA Astrophysics Data System (ADS)

Bonilla, Manuel; Kolekar, Sadhu; Ma, Yujing; Diaz, Horacio Coy; Kalappattil, Vijaysankar; Das, Raja; Eggers, Tatiana; Gutierrez, Humberto R.; Phan, Manh-Huong; Batzill, Matthias

2018-04-01

Reduced dimensionality and interlayer coupling in van der Waals materials gives rise to fundamentally different electronic1, optical2 and many-body quantum3-5 properties in monolayers compared with the bulk. This layer-dependence permits the discovery of novel material properties in the monolayer regime. Ferromagnetic order in two-dimensional materials is a coveted property that would allow fundamental studies of spin behaviour in low dimensions and enable new spintronics applications6-8. Recent studies have shown that for the bulk-ferromagnetic layered materials CrI3 (ref. 9) and Cr2Ge2Te6 (ref. 10), ferromagnetic order is maintained down to the ultrathin limit at low temperatures. Contrary to these observations, we report the emergence of strong ferromagnetic ordering for monolayer VSe2, a material that is paramagnetic in the bulk11,12. Importantly, the ferromagnetic ordering with a large magnetic moment persists to above room temperature, making VSe2 an attractive material for van der Waals spintronics applications.

Mechanistic Origin of the Ultrastrong Adhesion between Graphene and a-SiO2: Beyond van der Waals.

PubMed

Kumar, Sandeep; Parks, David; Kamrin, Ken

2016-07-26

The origin of the ultrastrong adhesion between graphene and a-SiO2 has remained a mystery. This adhesion is believed to be predominantly van der Waals (vdW) in nature. By rigorously analyzing recently reported blistering and nanoindentation experiments, we show that the ultrastrong adhesion between graphene and a-SiO2 cannot be attributed to vdW forces alone. Our analyses show that the fracture toughness of the graphene/a-SiO2 interface, when the interfacial adhesion is modeled with vdW forces alone, is anomalously weak compared to the measured values. The anomaly is related to an ultrasmall fracture process zone (FPZ): owing to the lack of a third dimension in graphene, the FPZ for the graphene/a-SiO2 interface is extremely small, and the combination of predominantly tensile vdW forces, distributed over such a small area, is bound to result in a correspondingly small interfacial fracture toughness. Through multiscale modeling, combining the results of finite element analysis and molecular dynamics simulations, we show that the adhesion between graphene and a-SiO2 involves two different kinds of interactions: one, a weak, long-range interaction arising from vdW adhesion and, second, discrete, short-range interactions originating from graphene clinging to the undercoordinated Si (≡Si·) and the nonbridging O (≡Si-O·) defects on a-SiO2. A strong resistance to relative opening and sliding provided by the latter mechanism is identified as the operative mechanism responsible for the ultrastrong adhesion between graphene and a-SiO2.

Observation of Pull-in Instability in Graphene Membranes under Interfacial Forces

NASA Astrophysics Data System (ADS)

Liu, Xinghui; Boddeti, Narasimha; Szpunar, Mariah; Wang, Luda; Rodriguez, Miguel; Long, Rong; Xiao, Jianliang; Dunn, Martin; Bunch, Scott; Jianliang Xiao'S Collaboration; Scott Bunch's Team; Martin Dunn's Team

2014-03-01

We present a unique experimental configuration that allows us to determine the interfacial forces on nearly parallel plates made from single and few layer graphene membranes. Our approach consists of using a pressure difference across a graphene membrane to bring the membrane to within ~ 10-20 nm above a circular post covered with SiOx or Au until a critical point is reached whereby the membrane snaps into adhesive contact with the post. Continuous measurements of the deforming membrane with an AFM coupled with a theoretical model allow us to deduce the magnitude of the interfacial forces between graphene and SiOx and graphene and Au. The nature of the interfacial forces at ~ 10 - 20 nm separations is consistent with an inverse fourth power distance dependence, implying that the interfacial forces are dominated by van der Waals interactions. Furthermore, the strength of the interactions is found to increase linearly with the number of graphene layers. The experimental approach can be applied to measure the strength of the interfacial forces for other emerging atomically thin two-dimensional materials.

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

DOE PAGES

Wang, Han; Bang, Junhyeok; Sun, Yiyang; ...

2016-05-10

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

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

Wang, Han; Bang, Junhyeok; Sun, Yiyang

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the

Application of atomic force microscopy to microbial surfaces: from reconstituted cell surface layers to living cells.

PubMed

Dufrêne, Y F

2001-02-01

The application of atomic force microscopy (AFM) to probe the ultrastructure and physical properties of microbial cell surfaces is reviewed. The unique capabilities of AFM can be summarized as follows: imaging surface topography with (sub)nanometer lateral resolution; examining biological specimens under physiological conditions; measuring local properties and interaction forces. AFM is being used increasingly for: (i) visualizing the surface ultrastructure of microbial cell surface layers, including bacterial S-layers, purple membranes, porin OmpF crystals and fungal rodlet layers; (ii) monitoring conformational changes of individual membrane proteins; (iii) examining the morphology of bacterial biofilms, (iv) revealing the nanoscale structure of living microbial cells, including fungi, yeasts and bacteria, (v) mapping interaction forces at microbial surfaces, such as van der Waals and electrostatic forces, solvation forces, and steric/bridging forces; and (vi) probing the local mechanical properties of cell surface layers and of single cells.

Distributed force probe bending model of critical dimension atomic force microscopy bias

NASA Astrophysics Data System (ADS)

Ukraintsev, Vladimir A.; Orji, Ndubuisi G.; Vorburger, Theodore V.; Dixson, Ronald G.; Fu, Joseph; Silver, Rick M.

2013-04-01

Critical dimension atomic force microscopy (CD-AFM) is a widely used reference metrology technique. To characterize modern semiconductor devices, small and flexible probes, often 15 to 20 nm in diameter, are used. Recent studies have reported uncontrolled and significant probe-to-probe bias variation during linewidth and sidewall angle measurements. To understand the source of these variations, tip-sample interactions between high aspect ratio features and small flexible probes, and their influence on measurement bias, should be carefully studied. Using theoretical and experimental procedures, one-dimensional (1-D) and two-dimensional (2-D) models of cylindrical probe bending relevant to carbon nanotube (CNT) AFM probes were developed and tested. An earlier 1-D bending model was refined, and a new 2-D distributed force (DF) model was developed. Contributions from several factors were considered, including: probe misalignment, CNT tip apex diameter variation, probe bending before snapping, and distributed van der Waals-London force. A method for extracting Hamaker probe-surface interaction energy from experimental probe-bending data was developed. Comparison of the new 2-D model with 1-D single point force (SPF) model revealed a difference of about 28% in probe bending. A simple linear relation between biases predicted by the 1-D SPF and 2-D DF models was found. The results suggest that probe bending can be on the order of several nanometers and can partially explain the observed CD-AFM probe-to-probe variation. New 2-D and three-dimensional CD-AFM data analysis software is needed to take full advantage of the new bias correction modeling capabilities.

Interfacial interactions between plastic particles in plastics flotation.

PubMed

Wang, Chong-qing; Wang, Hui; Gu, Guo-hua; Fu, Jian-gang; Lin, Qing-quan; Liu, You-nian

2015-12-01

Plastics flotation used for recycling of plastic wastes receives increasing attention for its industrial application. In order to study the mechanism of plastics flotation, the interfacial interactions between plastic particles in flotation system were investigated through calculation of Lifshitz-van der Waals (LW) function, Lewis acid-base (AB) Gibbs function, and the extended Derjaguin-Landau-Verwey-Overbeek potential energy profiles. The results showed that van der Waals force between plastic particles is attraction force in flotation system. The large hydrophobic attraction, caused by the AB Gibbs function, is the dominant interparticle force. Wetting agents present significant effects on the interfacial interactions between plastic particles. It is found that adsorption of wetting agents promotes dispersion of plastic particles and decreases the floatability. Pneumatic flotation may improve the recovery and purity of separated plastics through selective adsorption of wetting agents on plastic surface. The relationships between hydrophobic attraction and surface properties were also examined. It is revealed that there exists a three-order polynomial relationship between the AB Gibbs function and Lewis base component. Our finding provides some insights into mechanism of plastics flotation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interaction forces between DPPC bilayers on glass

PubMed Central

Orozco-Alcaraz, Raquel; Kuhl, Tonya L.

2013-01-01

The Surface Force Apparatus (SFA) was utilized to obtain force-distance profiles between silica supported membranes formed by Langmuir-Blodgett deposition of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). In the absence of a membrane, a long range electrostatic and short range steric repulsion is measured due to deprotonation of silica in water and roughness of the silica film. The electrostatic repulsion is partially screened by the lipid membrane and a van der Waals adhesion comparable to that measured with well packed DPPC membranes on mica is measured. This finding suggest that electrostatic interactions due to the underlying negatively charged silica are likely present in other systems of glass supported membranes. In contrast, the charge of an underlying mica substrate is almost completely screened when a lipid membrane is deposited on the mica. The difference in the two systems is attributed to stronger physisorption of zwitterionic lipids to molecularly smooth mica compared to rougher silica. PMID:23199333

A van der Waals Equation of State for a Dilute Boson Gas

ERIC Educational Resources Information Center

Deeney, F. A.; O'Leary, J. P.

2012-01-01

An equation of state of a system is a relationship that connects the thermodynamic variables of the system such as pressure and temperature. Such equations are well known for classical gases but less so for quantum systems. In this paper we develop a van der Waals equation of state for a dilute boson gas that may be used to explain the occurrence…

Reasons and remedies for the agglomeration of multilayered graphene and carbon nanotubes in polymers

PubMed Central

Atif, Rasheed

2016-01-01

Summary One of the main issues in the production of polymer nanocomposites is the dispersion state of filler as multilayered graphene (MLG) and carbon nanotubes (CNTs) tend to agglomerate due to van der Waals forces. The agglomeration can be avoided by using organic solvents, selecting suitable dispersion and production methods, and functionalizing the fillers. Another proposed method is the use of hybrid fillers as synergistic effects can cause an improvement in the dispersion state of the fillers. In this review article, various aspects of each process that can help avoid filler agglomeration and improve dispersion state are discussed in detail. This review article would be helpful for both current and prospective researchers in the field of MLG- and CNT-based polymer nanocomposites to achieve maximum enhancement in mechanical, thermal, and electrical properties of produced polymer nanocomposites. PMID:27826492

Optical Modification of Casimir Forces for Improved Function of Micro-and Nano-Scale Devices

NASA Technical Reports Server (NTRS)

Strekalov, Dmitry V.; Yu, Nan

2010-01-01

Recently, there has been a considerable effort to study the Casimir and van der Waals forces, enabled by the improved ability to measure small forces near surfaces. Because of the continuously growing role of micro- and nanomechanical devices, the focus of this activity has shifted towards the ability to control these forces. Possible approaches to manipulating the Casimir force include development of composite materials, engineered nanostructures, mixed-phase materials, or active elements. So far, practical success has been limited. The role of geometrical factors in the Casimir force is significant. It is known, for example, that the Casimir force between two spherical shells enclosed one into the other is repulsive instead of normal attractive. Unfortunately, nanosurfaces with this topology are very difficult to make. A more direct approach to manipulating and neutralizing the Casimir force is using external mechanical or electromagnetic forces. Unfortunately, the technological overhead of such an approach is quite large. Using electromagnetic compensation instead of mechanical will considerably reduce this overhead and at the same time provide the degree of control over the Casimir force that mechanical springs cannot provide. A mechanical analog behind Casimir forces is shown.

Computer Simulation of the Forces Acting on the Polystyrene Probe Submerged into the Succinonitrile Near Phase Transition

NASA Technical Reports Server (NTRS)

Bune, Andris V.; Kaukler, William F.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Modeling approach to simulate both mesoscale and microscopic forces acting in a typical AFM experiment is presented. At mesoscale level interaction between the cantilever tip and the sample surface is primarily described by the balance of attractive Van der Waals and repulsive forces. The model of cantilever oscillations is applicable to both non-contact and "tapping" AFM. This model can be farther enhanced to describe nanoparticle manipulation by cantilever. At microscopic level tip contamination and details of tip-surface interaction can be simulated using molecular dynamics approach. Integration of mesoscale model with molecular dynamic model is discussed.

Casimir forces from conductive silicon carbide surfaces

NASA Astrophysics Data System (ADS)

Sedighi, M.; Svetovoy, V. B.; Broer, W. H.; Palasantzas, G.

2014-05-01

Samples of conductive silicon carbide (SiC), which is a promising material due to its excellent properties for devices operating in severe environments, were characterized with the atomic force microscope for roughness, and the optical properties were measured with ellipsometry in a wide range of frequencies. The samples show significant far-infrared absorption due to concentration of charge carriers and a sharp surface phonon-polariton peak. The Casimir interaction of SiC with different materials is calculated and discussed. As a result of the infrared structure and beyond to low frequencies, the Casimir force for SiC-SiC and SiC-Au approaches very slowly the limit of ideal metals, while it saturates significantly below this limit if interaction with insulators takes place (SiC-SiO2). At short separations (<10 nm) analysis of the van der Waals force yielded Hamaker constants for SiC-SiC interactions lower but comparable to those of metals, which is of significance to adhesion and surface assembly processes. Finally, bifurcation analysis of microelectromechanical system actuation indicated that SiC can enhance the regime of stable equilibria against stiction.

Strong interlayer coupling in phosphorene/graphene van der Waals heterostructure: A first-principles investigation

NASA Astrophysics Data System (ADS)

Hu, Xue-Rong; Zheng, Ji-Ming; Ren, Zhao-Yu

2018-04-01

Based on first-principles calculations within the framework of density functional theory, we study the electronic properties of phosphorene/graphene heterostructures. Band gaps with different sizes are observed in the heterostructure, and charges transfer from graphene to phosphorene, causing the Fermi level of the heterostructure to shift downward with respect to the Dirac point of graphene. Significantly, strong coupling between two layers is discovered in the band spectrum even though it has a van der Waals heterostructure. A tight-binding Hamiltonian model is used to reveal that the resonance of the Bloch states between the phosphorene and graphene layers in certain K points combines with the symmetry matching between band states, which explains the reason for the strong coupling in such heterostructures. This work may enhance the understanding of interlayer interaction and composition mechanisms in van der Waals heterostructures consisting of two-dimensional layered nanomaterials, and may indicate potential reference information for nanoelectronic and optoelectronic applications.

Observing Imperfection in Atomic Interfaces for van der Waals Heterostructures.

PubMed

Rooney, Aidan P; Kozikov, Aleksey; Rudenko, Alexander N; Prestat, Eric; Hamer, Matthew J; Withers, Freddie; Cao, Yang; Novoselov, Kostya S; Katsnelson, Mikhail I; Gorbachev, Roman; Haigh, Sarah J

2017-09-13

Vertically stacked van der Waals heterostructures are a lucrative platform for exploring the rich electronic and optoelectronic phenomena in two-dimensional materials. Their performance will be strongly affected by impurities and defects at the interfaces. Here we present the first systematic study of interfaces in van der Waals heterostructure using cross-sectional scanning transmission electron microscope (STEM) imaging. By measuring interlayer separations and comparing these to density functional theory (DFT) calculations we find that pristine interfaces exist between hBN and MoS 2 or WS 2 for stacks prepared by mechanical exfoliation in air. However, for two technologically important transition metal dichalcogenide (TMDC) systems, MoSe 2 and WSe 2 , our measurement of interlayer separations provide the first evidence for impurity species being trapped at buried interfaces with hBN interfaces that are flat at the nanometer length scale. While decreasing the thickness of encapsulated WSe 2 from bulk to monolayer we see a systematic increase in the interlayer separation. We attribute these differences to the thinnest TMDC flakes being flexible and hence able to deform mechanically around a sparse population of protruding interfacial impurities. We show that the air sensitive two-dimensional (2D) crystal NbSe 2 can be fabricated into heterostructures with pristine interfaces by processing in an inert-gas environment. Finally we find that adopting glovebox transfer significantly improves the quality of interfaces for WSe 2 compared to processing in air.

Dispersive transport and symmetry of the dispersion tensor in porous media

NASA Astrophysics Data System (ADS)

Pride, Steven R.; Vasco, Donald W.; Flekkoy, Eirik G.; Holtzman, Ran

2017-04-01

The macroscopic laws controlling the advection and diffusion of solute at the scale of the porous continuum are derived in a general manner that does not place limitations on the geometry and time evolution of the pore space. Special focus is given to the definition and symmetry of the dispersion tensor that is controlling how a solute plume spreads out. We show that the dispersion tensor is not symmetric and that the asymmetry derives from the advective derivative in the pore-scale advection-diffusion equation. When flow is spatially variable across a voxel, such as in the presence of a permeability gradient, the amount of asymmetry can be large. As first shown by Auriault [J.-L. Auriault et al. Transp. Porous Med. 85, 771 (2010), 10.1007/s11242-010-9591-y] in the limit of low Péclet number, we show that at any Péclet number, the dispersion tensor Di j satisfies the flow-reversal symmetry Di j(+q ) =Dj i(-q ) where q is the mean flow in the voxel under analysis; however, Reynold's number must be sufficiently small that the flow is reversible when the force driving the flow changes sign. We also demonstrate these symmetries using lattice-Boltzmann simulations and discuss some subtle aspects of how to measure the dispersion tensor numerically. In particular, the numerical experiments demonstrate that the off-diagonal components of the dispersion tensor are antisymmetric which is consistent with the analytical dependence on the average flow gradients that we propose for these off-diagonal components.

Strong electrically tunable MoTe2/graphene van der Waals heterostructures for high-performance electronic and optoelectronic devices

NASA Astrophysics Data System (ADS)

Wang, Feng; Yin, Lei; Wang, Zhenxing; Xu, Kai; Wang, Fengmei; Shifa, Tofik Ahmed; Huang, Yun; Wen, Yao; Jiang, Chao; He, Jun

2016-11-01

MoTe2 is an emerging two-dimensional layered material showing ambipolar/p-type conductivity, which makes it an important supplement to n-type two-dimensional layered material like MoS2. However, the properties based on its van der Waals heterostructures have been rarely studied. Here, taking advantage of the strong Fermi level tunability of monolayer graphene (G) and the feature of van der Waals interfaces that is free from Fermi level pinning effect, we fabricate G/MoTe2/G van der Waals heterostructures and systematically study the electronic and optoelectronic properties. We demonstrate the G/MoTe2/G FETs with low Schottky barriers for both holes (55.09 meV) and electrons (122.37 meV). Moreover, the G/MoTe2/G phototransistors show high photoresponse performances with on/off ratio, responsivity, and detectivity of ˜105, 87 A/W, and 1012 Jones, respectively. Finally, we find the response time of the phototransistors is effectively tunable and a mechanism therein is proposed to explain our observation. This work provides an alternative choice of contact for high-performance devices based on p-type and ambipolar two-dimensional layered materials.

Forces between a rigid probe particle and a liquid interface. II. The general case.

PubMed

Dagastine, R R; White, L R

2002-03-15

The semianalytic theory developed previously (Chan, D. Y. C., Dagastine, R. R., and White, L. R., J. Colloid Interface Sci. 236, 141 (2001)) to predict the force curve of an AFM measurement at a liquid interface using a colloidal probe has been expanded to incorporate a general force law with both attractive and repulsive forces. Expressions for the gradient of the force curve are developed to calculate the point at which the probe particle on the cantilever will spontaneously jump in toward the liquid interface. The calculation of the jump instability is reduced to a straightforward embroidery of the simple algorithms presented in Chan et al. In a variety of sample calculations using force laws including van der Waals, electrostatic, and hydrophobic forces for both oil/water and bubble/water interfaces, we have duplicated the general behaviors observed in several AFM investigations at liquid interfaces. The behavior of the drop as a Hookean spring and the numerical difficulties of a full numerical calculation of F(deltaX) are also discussed.

A Scalable Implementation of Van der Waals Density Functionals

NASA Astrophysics Data System (ADS)

Wu, Jun; Gygi, Francois

2010-03-01

Recently developed Van der Waals density functionals[1] offer the promise to account for weak intermolecular interactions that are not described accurately by local exchange-correlation density functionals. In spite of recent progress [2], the computational cost of such calculations remains high. We present a scalable parallel implementation of the functional proposed by Dion et al.[1]. The method is implemented in the Qbox first-principles simulation code (http://eslab.ucdavis.edu/software/qbox). Application to large molecular systems will be presented. [4pt] [1] M. Dion et al. Phys. Rev. Lett. 92, 246401 (2004).[0pt] [2] G. Roman-Perez and J. M. Soler, Phys. Rev. Lett. 103, 096102 (2009).

Amphibian sacculus and the forced Kuramoto model with intrinsic noise and frequency dispersion

NASA Astrophysics Data System (ADS)

Ji, Seung; Bozovic, Dolores; Bruinsma, Robijn

2018-04-01

The amphibian sacculus (AS) is an end organ that specializes in the detection of low-frequency auditory and vestibular signals. In this paper, we propose a model for the AS in the form of an array of phase oscillators with long-range coupling, subject to a steady load that suppresses spontaneous oscillations. The array is exposed to significant levels of frequency dispersion and intrinsic noise. We show that such an array can be a sensitive and robust subthreshold detector of low-frequency stimuli, though without significant frequency selectivity. The effects of intrinsic noise and frequency dispersion are contrasted. Intermediate levels of intrinsic noise greatly enhance the sensitivity through stochastic resonance. Frequency dispersion, on the other hand, only degrades detection sensitivity. However, frequency dispersion can play a useful role in terms of the suppression of spontaneous activity. As a model for the AS, the array parameters are such that the system is poised near a saddle-node bifurcation on an invariant circle. However, by a change of array parameters, the same system also can be poised near an emergent Andronov-Hopf bifurcation and thereby function as a frequency-selective detector.

Two-relaxation-time lattice Boltzmann method for the anisotropic dispersive Henry problem

NASA Astrophysics Data System (ADS)

Servan-Camas, Borja; Tsai, Frank T.-C.

2010-02-01

This study develops a lattice Boltzmann method (LBM) with a two-relaxation-time collision operator (TRT) to cope with anisotropic heterogeneous hydraulic conductivity and anisotropic velocity-dependent hydrodynamic dispersion in the saltwater intrusion problem. The directional-speed-of-sound technique is further developed to address anisotropic hydraulic conductivity and dispersion tensors. Forcing terms are introduced in the LBM to correct numerical errors that arise during the recovery procedure and to describe the sink/source terms in the flow and transport equations. In order to facilitate the LBM implementation, the forcing terms are combined with the equilibrium distribution functions (EDFs) to create pseudo-EDFs. This study performs linear stability analysis and derives LBM stability domains to solve the anisotropic advection-dispersion equation. The stability domains are used to select the time step at which the lattice Boltzmann method provides stable solutions to the numerical examples. The LBM was implemented for the anisotropic dispersive Henry problem with high ratios of longitudinal to transverse dispersivities, and the results compared well to the solutions in the work of Abarca et al. (2007).

The concave iris in pigment dispersion syndrome.

PubMed

Liu, Lance; Ong, Ee Lin; Crowston, Jonathan

2011-01-01

To visualize the changes of the iris contour in patients with pigment dispersion syndrome after blinking, accommodation, and pharmacologic miosis using anterior segment optical coherence tomography. Observational case series. A total of 33 eyes of 20 patients with pigment dispersion syndrome. Each eye was imaged along the horizontal 0- to 180-degree meridian using the Visante Anterior Segment Imaging System (Carl Zeiss Meditec, Dublin, CA). Scans were performed at baseline and after focusing on an internal fixation target for 5 minutes, forced blinking, accommodation, and pharmacologic miosis with pilocarpine 2%. Quantitative analysis of the changes in the iris configuration. After 5 minutes of continual fixation, the iris became planar with the mean ± standard deviation curvature decreasing from 214 ± 74 μm to 67 ± 76 μm (P < 0.05). The iris remained planar in all patients with pigment dispersion syndrome after forced blinking, but the iris concavity recovered to 227 ± 113 μm (P = 0.34) and 238 ± 119 μm (P = 0.19) with the -3.0 and -6.0 diopter lenses, respectively. Pilocarpine-induced miosis caused the iris to assume a planar configuration in all subjects. This study shows that the iris in pigment dispersion syndrome assumes a planar configuration when fixating and that the concavity of the iris surface is not restored by blinking. Accommodation restored the iris concavity, suggesting that the posterior curvature of the iris in pigment dispersion syndrome is induced and probably maintained, at least in part, by accommodation. Copyright © 2011 American Academy of Ophthalmology. Published by Elsevier Inc. All rights reserved.

Inter-layer and intra-layer heat transfer in bilayer/monolayer graphene van der Waals heterostructure: Is there a Kapitza resistance analogous?

NASA Astrophysics Data System (ADS)

Rajabpour, Ali; Fan, Zheyong; Vaez Allaei, S. Mehdi

2018-06-01

Van der Waals heterostructures have exhibited interesting physical properties. In this paper, heat transfer in hybrid coplanar bilayer/monolayer (BL-ML) graphene, as a model layered van der Waals heterostructure, was studied using non-equilibrium molecular dynamics (MD) simulations. The temperature profile and inter- and intra-layer heat fluxes of the BL-ML graphene indicated that, there is no fully developed thermal equilibrium between layers and the drop in the average temperature profile at the step-like BL-ML interface is not attributable to the effect of Kapitza resistance. By increasing the length of the system up to 1 μm in the studied MD simulations, the thermally non-equilibrium region was reduced to a small area near the step-like interface. All MD results were compared to a continuum model and a good match was observed between the two approaches. Our results provide a useful understanding of heat transfer in nano- and micro-scale layered materials and van der Waals heterostructures.

Estimation of Some Parameters from Morse-Morse-Spline-Van Der Waals Intermolecular Potential

NASA Astrophysics Data System (ADS)

Coroiu, I.

2007-04-01

Some parameters such as transport cross-sections and isotopic thermal diffusion factor have been calculated from an improved intermolecular potential, Morse-Morse-Spline-van der Waals (MMSV) potential proposed by R.A. Aziz et al. The treatment was completely classical and no corrections for quantum effects were made. The results would be employed for isotope separations of different spherical and quasi-spherical molecules.

Simulation of nanopowder compaction in terms of granular dynamics

NASA Astrophysics Data System (ADS)

Boltachev, G. Sh.; Volkov, N. B.

2011-07-01

The uniaxial compaction of nanopowders is simulated using the granular dynamics in the 2D geometry. The initial arrangement of particles is represented by (i) a layer of particles executing Brownian motion (isotropic structures) and (ii) particles falling in the gravity field (anisotropic structures). The influence of size effects and the size of a model cell on the properties of the structures are studied. The compaction of the model cell is simulated with regard to Hertz elastic forces between particles, Cattaneo-Mindlin-Deresiewicz shear friction forces, and van der Waals-Hamaker dispersion forces of attraction. Computation is performed for monodisperse powders with particle sizes ranging from 10 to 400 nm and for "cohesionless" powder, in which attractive forces are absent. It is shown that taking into account dispersion forces makes it possible to simulate the size effect in the nanopowder compaction: the compressibility of the nanopowder drops as the particles get finer. The mean coordination number and the axial and lateral pressures in the powder systems are found, and the effect of the density and isotropy of the initial structure on the compressibility is analyzed. The applicability of well-known Rumpf's formula for the size effect is discussed.

Photon polarizability and its effect on the dispersion of plasma waves

NASA Astrophysics Data System (ADS)

Dodin, I. Y.; Ruiz, D. E.

2017-04-01

High-frequency photons travelling in plasma exhibit a linear polarizability that can influence the dispersion of linear plasma waves. We present a detailed calculation of this effect for Langmuir waves as a characteristic example. Two alternative formulations are given. In the first formulation, we calculate the modified dispersion of Langmuir waves by solving the governing equations for the electron fluid, where the photon contribution enters as a ponderomotive force. In the second formulation, we provide a derivation based on the photon polarizability. Then, the calculation of ponderomotive forces is not needed, and the result is more general.

Photon polarizability and its effect on the dispersion of plasma waves

DOE PAGES

Dodin, I. Y.; Ruiz, D. E.

2017-03-06

High-frequency photons travelling in plasma exhibit a linear polarizability that can influence the dispersion of linear plasma waves. We present a detailed calculation of this effect for Langmuir waves as a characteristic example. Here, two alternative formulations are given. In the first formulation, we calculate the modified dispersion of Langmuir waves by solving the governing equations for the electron fluid, where the photon contribution enters as a ponderomotive force. In the second formulation, we provide a derivation based on the photon polarizability. Then, the calculation of ponderomotive forces is not needed, and the result is more general.

Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl 3 crystals

DOE PAGES

McGuire, Michael A.; Clark, Genevieve; KC, Santosh; ...

2017-06-19

CrCl 3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl 3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stagesmore » on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl 3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.« less

Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl 3 crystals

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

McGuire, Michael A.; Clark, Genevieve; KC, Santosh

CrCl 3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl 3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stagesmore » on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl 3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.« less

Orientational ordering of colloidal dispersions by application of time-dependent external forces.

PubMed

Moths, Brian; Witten, T A

2013-08-01

We discuss a method of organizing incoherent motion of a colloidal suspension to produce synchronized, coherent motion, extending the discussion of our recent Letter [Moths and Witten, Phys. Rev. Lett. 110, 028301 (2013)]. The method does not require interaction between the objects. Instead, the effect is controlled by the "twist matrix" which gives the angular velocity of an asymmetric object in a fluid resulting from a weak external force. We analyze the two types of forcing considered in the Letter: a force alternating between two directions and a continuously rotating force. For the alternating force, we justify the claim of the Letter that under appropriate forcing conditions, the orientational entropy of the objects decreases indefinitely with time, on average. We provide a bound on that rate in terms of the twist matrix. For the case of rotating force, we derive conditions for phased-locked motion of the objects to the force and prove that there is only one stable phase-locked orientation under these conditions. We find numerically that the fastest alignment typically occurs for tilt angles of order unity. We discuss how the alignment effect scales with the object size for external forcing caused by gravity or an electric field. Under practical forcing conditions we estimate that the alignment should persist despite rotational diffusion for objects larger than about 10 microns. Potential misalignment owing to hydrodynamic interaction of the objects is estimated to be negligible at volume fractions smaller than about 10(-4.5) (10(-3)) when the forcing is gravitational (electrophoretic).

Material transport in a convective surface mixed layer under weak wind forcing

NASA Astrophysics Data System (ADS)

Mensa, Jean A.; Özgökmen, Tamay M.; Poje, Andrew C.; Imberger, Jörg

2015-12-01

Flows in the upper ocean mixed layer are responsible for the transport and dispersion of biogeochemical tracers, phytoplankton and buoyant pollutants, such as hydrocarbons from an oil spill. Material dispersion in mixed layer flows subject to diurnal buoyancy forcing and weak winds (| u10 | = 5m s-1) are investigated using a non-hydrostatic model. Both purely buoyancy-forced and combined wind- and buoyancy-forced flows are sampled using passive tracers, as well as 2D and 3D particles to explore characteristics of horizontal and vertical dispersion. It is found that the surface tracer patterns are determined by the convergence zones created by convection cells within a time scale of just a few hours. For pure convection, the results displayed the classic signature of Rayleigh-Benard cells. When combined with a wind stress, the convective cells become anisotropic in that the along-wind length scale gets much larger than the cross-wind scale. Horizontal relative dispersion computed by sampling the flow fields using both 2D and 3D passive particles is found to be consistent with the Richardson regime. Relative dispersion is an order of magnitude higher and 2D surface releases transition to Richardson regime faster in the wind-forced case. We also show that the buoyancy-forced case results in significantly lower amplitudes of scale-dependent horizontal relative diffusivity, kD(ℓ), than those reported by Okubo (1970), while the wind- and buoyancy-forced case shows a good agreement with Okubo's diffusivity amplitude, and the scaling is consistent with Richardson's 4/3rd law, kD ∼ ℓ4/3. These modeling results provide a framework for measuring material dispersion by mixed layer flows in future observational programs.

Analysis of dynamic cantilever behavior in tapping mode atomic force microscopy.

PubMed

Deng, Wenqi; Zhang, Guang-Ming; Murphy, Mark F; Lilley, Francis; Harvey, David M; Burton, David R

2015-10-01

Tapping mode atomic force microscopy (AFM) provides phase images in addition to height and amplitude images. Although the behavior of tapping mode AFM has been investigated using mathematical modeling, comprehensive understanding of the behavior of tapping mode AFM still poses a significant challenge to the AFM community, involving issues such as the correct interpretation of the phase images. In this paper, the cantilever's dynamic behavior in tapping mode AFM is studied through a three dimensional finite element method. The cantilever's dynamic displacement responses are firstly obtained via simulation under different tip-sample separations, and for different tip-sample interaction forces, such as elastic force, adhesion force, viscosity force, and the van der Waals force, which correspond to the cantilever's action upon various different representative computer-generated test samples. Simulated results show that the dynamic cantilever displacement response can be divided into three zones: a free vibration zone, a transition zone, and a contact vibration zone. Phase trajectory, phase shift, transition time, pseudo stable amplitude, and frequency changes are then analyzed from the dynamic displacement responses that are obtained. Finally, experiments are carried out on a real AFM system to support the findings of the simulations. © 2015 Wiley Periodicals, Inc.

Modeling and experiments of the adhesion force distribution between particles and a surface.

PubMed

You, Siming; Wan, Man Pun

2014-06-17

Due to the existence of surface roughness in real surfaces, the adhesion force between particles and the surface where the particles are deposited exhibits certain statistical distributions. Despite the importance of adhesion force distribution in a variety of applications, the current understanding of modeling adhesion force distribution is still limited. In this work, an adhesion force distribution model based on integrating the root-mean-square (RMS) roughness distribution (i.e., the variation of RMS roughness on the surface in terms of location) into recently proposed mean adhesion force models was proposed. The integration was accomplished by statistical analysis and Monte Carlo simulation. A series of centrifuge experiments were conducted to measure the adhesion force distributions between polystyrene particles (146.1 ± 1.99 μm) and various substrates (stainless steel, aluminum and plastic, respectively). The proposed model was validated against the measured adhesion force distributions from this work and another previous study. Based on the proposed model, the effect of RMS roughness distribution on the adhesion force distribution of particles on a rough surface was explored, showing that both the median and standard deviation of adhesion force distribution could be affected by the RMS roughness distribution. The proposed model could predict both van der Waals force and capillary force distributions and consider the multiscale roughness feature, greatly extending the current capability of adhesion force distribution prediction.

Atomic layer MoS2-graphene van der Waals heterostructure nanomechanical resonators.

PubMed

Ye, Fan; Lee, Jaesung; Feng, Philip X-L

2017-11-30

Heterostructures play significant roles in modern semiconductor devices and micro/nanosystems in a plethora of applications in electronics, optoelectronics, and transducers. While state-of-the-art heterostructures often involve stacks of crystalline epi-layers each down to a few nanometers thick, the intriguing limit would be hetero-atomic-layer structures. Here we report the first experimental demonstration of freestanding van der Waals heterostructures and their functional nanomechanical devices. By stacking single-layer (1L) MoS 2 on top of suspended single-, bi-, tri- and four-layer (1L to 4L) graphene sheets, we realize an array of MoS 2 -graphene heterostructures with varying thickness and size. These heterostructures all exhibit robust nanomechanical resonances in the very high frequency (VHF) band (up to ∼100 MHz). We observe that fundamental-mode resonance frequencies of the heterostructure devices fall between the values of graphene and MoS 2 devices. Quality (Q) factors of heterostructure resonators are lower than those of graphene but comparable to those of MoS 2 devices, suggesting interface damping related to interlayer interactions in the van der Waals heterostructures. This study validates suspended atomic layer heterostructures as an effective device platform and provides opportunities for exploiting mechanically coupled effects and interlayer interactions in such devices.

Thermal electron attachment to van der Waals molecules containing O/sub 2/

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

Huo, W.M.; Fessenden, R.W.; Bauschlicher C.W. Jr.

1984-12-15

Calculations on O/sub 2/xN/sub 2/ and O/sup -//sub 2/xN/sub 2/ have been carried out to explain the large enhancement in the attachment rate of thermal electrons found in van der Waals molecules containing O/sub 2/. Two geometries, T-shape and linear, are used. SCF wave functions are used to represent both the neutral molecule and the ion. The incoming electron is approximated by a plane wave. The width is determined using a shielded polarization potential. The effect of additional vibrational structures of the van der Waals molecule on the attachment process is investigated by studying the O/sub 2/--N/sub 2/ stretching modemore » using Lennard-Jones potentials. Symmetry breaking, which allows the molecule to attach a p wave electron, is shown to play a primary role. The lowering of resonance energy, due to a deeper Lennard-Jones potential of O/sup -//sub 2/xN/sub 2/ in comparison with O/sub 2/xN/sub 2/, furthers the enhancement. The calculated attachment rate is comparable to that determined by Shimamori and Fessenden, but differs from the recent values obtained by Toriumi and Hatano, who used a different set of reactions to interpret their data.« less

Origins of the Non-DLVO Force between Glass Surfaces in Aqueous Solution.

PubMed

Adler, Joshua J.; Rabinovich, Yakov I.; Moudgil, Brij M.

2001-05-15

Direct measurement of surface forces has revealed that silica surfaces seem to have a short-range repulsion that is not accounted for in classical DLVO theory. The two leading hypotheses for the origin of the non-DLVO force are (i) structuring of water at the silica interface or (ii) water penetration into the surface resulting in a gel layer. In this article, the interaction of silica surfaces will be reviewed from the perspective of the non-DLVO force origin. In an attempt to more accurately describe the behavior of silica and glass surfaces, alternative models of how surfaces with gel layers should interact are proposed. It is suggested that a lessened van der Waals attraction originating from a thin gel layer may explain both the additional stability and the coagulation behavior of silica. It is important to understand the mechanisms underlying the existence of the non-DLVO force which is likely to have a major influence on the adsorption of polymers and surfactants used to modify the silica surface for practical applications in the ceramic, mineral, and microelectronic industries. Copyright 2001 Academic Press.

Heterogeneous nucleation of polymorphs on polymer surfaces: polymer-molecule interactions using a Coulomb and van der Waals model.

PubMed

Wahlberg, Nanna; Madsen, Anders Ø; Mikkelsen, Kurt V

2018-06-09

The nucleation processes of acetaminophen on poly(methyl methacrylate) and poly(vinyl acetate) have been investigated and the mechanisms of the processes are studied. This is achieved by a combination of theoretical models and computational investigations within the framework of a modified QM/MM method; a Coulomb-van der Waals model. We have combined quantum mechanical computations and electrostatic models at the atomistic level for investigating the stability of different orientations of acetaminophen on the polymer surfaces. Based on the Coulomb-van der Waals model, we have determined the most stable orientation to be a flat orientation, and the strongest interaction is seen between poly(vinyl acetate) and the molecule in a flat orientation in vacuum.

Polarizable atomic multipole-based force field for DOPC and POPE membrane lipids

NASA Astrophysics Data System (ADS)

Chu, Huiying; Peng, Xiangda; Li, Yan; Zhang, Yuebin; Min, Hanyi; Li, Guohui

2018-04-01

A polarizable atomic multipole-based force field for the membrane bilayer models 1,2-dioleoyl-phosphocholine (DOPC) and 1-palmitoyl-2-oleoyl-phosphatidylethanolamine (POPE) has been developed. The force field adopts the same framework as the Atomic Multipole Optimized Energetics for Biomolecular Applications (AMOEBA) model, in which the charge distribution of each atom is represented by the permanent atomic monopole, dipole and quadrupole moments. Many-body polarization including the inter- and intra-molecular polarization is modelled in a consistent manner with distributed atomic polarizabilities. The van der Waals parameters were first transferred from existing AMOEBA parameters for small organic molecules and then optimised by fitting to ab initio intermolecular interaction energies between models and a water molecule. Molecular dynamics simulations of the two aqueous DOPC and POPE membrane bilayer systems, consisting of 72 model molecules, were then carried out to validate the force field parameters. Membrane width, area per lipid, volume per lipid, deuterium order parameters, electron density profile, etc. were consistent with experimental values.

Van der Waals Interactions in Aspirin

NASA Astrophysics Data System (ADS)

Reilly, Anthony; Tkatchenko, Alexandre

2015-03-01

The ability of molecules to yield multiple solid forms, or polymorphs, has significance for diverse applications ranging from drug design and food chemistry to nonlinear optics and hydrogen storage. In particular, aspirin has been used and studied for over a century, but has only recently been shown to have an additional polymorphic form, known as form II. Since the two observed solid forms of aspirin are degenerate in terms of lattice energy, kinetic effects have been suggested to determine the metastability of the less abundant form II. Here, first-principles calculations provide an alternative explanation based on free-energy differences at room temperature. The explicit consideration of many-body van der Waals interactions in the free energy demonstrates that the stability of the most abundant form of aspirin is due to a subtle coupling between collective electronic fluctuations and quantized lattice vibrations. In addition, a systematic analysis of the elastic properties of the two forms of aspirin rules out mechanical instability of form II as making it metastable.

Reducing friction and miscibility studies of FEP dispersion/ PDMS fluid blends

NASA Astrophysics Data System (ADS)

Buapool, S.; Thavarungkul, N.; Srisukhumbowornchai, N.

2017-04-01

To develop new polymer blends having reduced friction force of fluorinated ethylene propylene (FEP) dispersion and improved adhesion of polydimethylsiloxane (PDMS) fluid, FEP dispersion was blended with PDMS fluids at different viscosities of 20 cSt and 100 cSt by using solution mixing method. The FEP/PDMS blends were coated on short hollow tubes and examined by penetrating the tubes into the rubber stoppers. It was found that the tubes coated with the blends showed reduced penetration and friction forces and improved adhesion. The tubes coated with the 100 cSt-PDMS blend in the ratio of 5:1.5 demonstrated the penetration and average friction forces as low as 3828 mN and 1524 mN, respectively. The formation of physical blends was characterized and confirmed by FTIR and DSC analyses.

Tailor-made force fields for crystal-structure prediction.

PubMed

Neumann, Marcus A

2008-08-14

A general procedure is presented to derive a complete set of force-field parameters for flexible molecules in the crystalline state on a case-by-case basis. The force-field parameters are fitted to the electrostatic potential as well as to accurate energies and forces generated by means of a hybrid method that combines solid-state density functional theory (DFT) calculations with an empirical van der Waals correction. All DFT calculations are carried out with the VASP program. The mathematical structure of the force field, the generation of reference data, the choice of the figure of merit, the optimization algorithm, and the parameter-refinement strategy are discussed in detail. The approach is applied to cyclohexane-1,4-dione, a small flexible ring. The tailor-made force field obtained for cyclohexane-1,4-dione is used to search for low-energy crystal packings in all 230 space groups with one molecule per asymmetric unit, and the most stable crystal structures are reoptimized in a second step with the hybrid method. The experimental crystal structure is found as the most stable predicted crystal structure both with the tailor-made force field and the hybrid method. The same methodology has also been applied successfully to the four compounds of the fourth CCDC blind test on crystal-structure prediction. For the five aforementioned compounds, the root-mean-square deviations between lattice energies calculated with the tailor-made force fields and the hybrid method range from 0.024 to 0.053 kcal/mol per atom around an average value of 0.034 kcal/mol per atom.

Calculations of predissociative lifetimes of RG...Hal2 Van der Waals complexes

NASA Astrophysics Data System (ADS)

Buchachenko, Alexei A.; Stepanov, N. F.

1992-07-01

Good examples of combined energy- and time-resolved techniques linked by the theoretical solution of a nuclear problem may be found in investigations of the dynamics of weakly bound Van der Waals (VdW) complexes, such as Ar-OH and He-stilbene. Our report concerns only the theoretical aspect of this complex approach. However, we shall stress the importance of energy-resolved spectroscopy for the dynamics and try to illustrate this with some numerical results.

Out-of-plane heat transfer in van der Waals stacks through electron-hyperbolic phonon coupling

NASA Astrophysics Data System (ADS)

Tielrooij, Klaas-Jan; Hesp, Niels C. H.; Principi, Alessandro; Lundeberg, Mark B.; Pogna, Eva A. A.; Banszerus, Luca; Mics, Zoltán; Massicotte, Mathieu; Schmidt, Peter; Davydovskaya, Diana; Purdie, David G.; Goykhman, Ilya; Soavi, Giancarlo; Lombardo, Antonio; Watanabe, Kenji; Taniguchi, Takashi; Bonn, Mischa; Turchinovich, Dmitry; Stampfer, Christoph; Ferrari, Andrea C.; Cerullo, Giulio; Polini, Marco; Koppens, Frank H. L.

2018-01-01

Van der Waals heterostructures have emerged as promising building blocks that offer access to new physics, novel device functionalities and superior electrical and optoelectronic properties1-7. Applications such as thermal management, photodetection, light emission, data communication, high-speed electronics and light harvesting8-16 require a thorough understanding of (nanoscale) heat flow. Here, using time-resolved photocurrent measurements, we identify an efficient out-of-plane energy transfer channel, where charge carriers in graphene couple to hyperbolic phonon polaritons17-19 in the encapsulating layered material. This hyperbolic cooling is particularly efficient, giving picosecond cooling times for hexagonal BN, where the high-momentum hyperbolic phonon polaritons enable efficient near-field energy transfer. We study this heat transfer mechanism using distinct control knobs to vary carrier density and lattice temperature, and find excellent agreement with theory without any adjustable parameters. These insights may lead to the ability to control heat flow in van der Waals heterostructures.

Van der Waals pressure sensors using reduced graphene oxide composites

NASA Astrophysics Data System (ADS)

Jung, Ju Ra; Ahn, Sung Il

2018-04-01

Reduced graphene oxide (RGO) films intercalated with various polymers were fabricated by reaction-based self-assembly, and their characteristics as vacuum pressure sensors based on van der Waals interactions were studied. At low temperature, the electrical resistances of the samples decrease linearly with increasing vacuum pressure, whereas at high temperature the variation of the electrical resistance shows secondary order curves. Among all samples, the poly vinyl alcohol intercalated RGO shows the highest sensitivity, being almost two times more sensitive than reference RGO. All samples show almost the same signal for repetitive sudden pressure changes, indicating reasonable reproducibility and durability.

Spherical and hyperspherical harmonics representation of van der Waals aggregates

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo; Grossi, Gaia; Albernaz, Alessandra F.; Barreto, Patricia R. P.; Cruz, Ana Claudia P. S.

2016-12-01

The representation of the potential energy surfaces of atom-molecule or molecular dimers interactions should account faithfully for the symmetry properties of the systems, preserving at the same time a compact analytical form. To this aim, the choice of a proper set of coordinates is a necessary precondition. Here we illustrate a description in terms of hyperspherical coordinates and the expansion of the intermolecular interaction energy in terms of hypersherical harmonics, as a general method for building potential energy surfaces suitable for molecular dynamics simulations of van der Waals aggregates. Examples for the prototypical case diatomic-molecule-diatomic-molecule interactions are shown.

Development of a picture of the van der Waals interaction energy between clusters of nanometer-range particles

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

Arunachalam, V.; Marlow, W.H.; Lu, J.X.

1998-09-01

The importance of the long-range Lifshitz{endash}van der Waals interaction energy between condensed bodies is well known. However, its implementation for interacting bodies that are highly irregular and separated by distances varying from contact to micrometers has received little attention. As part of a study of collisions of irregular aerosol particles, an approach based on the Lifshitz theory of van der Waals interaction has been developed to compute the interaction energy between a sphere and an aggregate of spheres at all separations. In the first part of this study, the iterated sum-over-dipole interactions between pairs of approximately spherical molecular clusters aremore » compared with the Lifshitz and Lifshitz-Hamaker interaction energies for continuum spheres of radii equal to those of the clusters{close_quote} circumscribed spheres and of the same masses as the clusters. The Lifshitz energy is shown to converge to the iterated dipolar energy for quasispherical molecular clusters for sufficiently large separations, while the energy calculated by using the Lifshitz-Hamaker approach does not. Next, the interaction energies between a contacting pair of these molecular clusters and a third cluster in different relative positions are calculated first by coupling all molecules in the three-cluster system and second by ignoring the interactions between the molecules of the adhering clusters. The error calculated by this omission is shown to be very small, and is an indication of the error in computing the long-range interaction energy between a pair of interacting spheres and a third sphere as a simple sum over the Lifshitz energies between individual, condensed-matter spheres. This Lifshitz energy calculation is then combined with the short-separation, nonsingular van der Waals energy calculation of Lu, Marlow, and Arunachalam, to provide an integrated picture of the van der Waals energy from large separations to contact. {copyright} {ital 1998} {ital The

Probabilistic analysis for identifying the driving force of protein folding

NASA Astrophysics Data System (ADS)

Tokunaga, Yoshihiko; Yamamori, Yu; Matubayasi, Nobuyuki

2018-03-01

Toward identifying the driving force of protein folding, energetics was analyzed in water for Trp-cage (20 residues), protein G (56 residues), and ubiquitin (76 residues) at their native (folded) and heat-denatured (unfolded) states. All-atom molecular dynamics simulation was conducted, and the hydration effect was quantified by the solvation free energy. The free-energy calculation was done by employing the solution theory in the energy representation, and it was seen that the sum of the protein intramolecular (structural) energy and the solvation free energy is more favorable for a folded structure than for an unfolded one generated by heat. Probabilistic arguments were then developed to determine which of the electrostatic, van der Waals, and excluded-volume components of the interactions in the protein-water system governs the relative stabilities between the folded and unfolded structures. It was found that the electrostatic interaction does not correspond to the preference order of the two structures. The van der Waals and excluded-volume components were shown, on the other hand, to provide the right order of preference at probabilities of almost unity, and it is argued that a useful modeling of protein folding is possible on the basis of the excluded-volume effect.

Electrodynamics of Lipid Membrane Interactions in the Presence of Zwitterionic Buffers

PubMed Central

Koerner, Megan M.; Palacio, Luis A.; Wright, Johnnie W.; Schweitzer, Kelly S.; Ray, Bruce D.; Petrache, Horia I.

2011-01-01

Due to thermal motion and molecular polarizability, electrical interactions in biological systems have a dynamic character. Zwitterions are dipolar molecules that typically are highly polarizable and exhibit both a positive and a negative charge depending on the pH of the solution. We use multilamellar structures of common lipids to identify and quantify the effects of zwitterionic buffers that go beyond the control of pH. We use the fact that the repeat spacing of multilamellar lipid bilayers is a sensitive and accurate indicator of the force balance between membranes. We show that common buffers can in fact charge up neutral membranes. However, this electrostatic effect is not immediately recognized because of the concomitant modification of dispersion (van der Waals) forces. We show that although surface charging can be weak, electrostatic forces are significant even at large distances because of reduced ionic screening and reduced van der Waals attraction. The zwitterionic interactions that we identify are expected to be relevant for interfacial biological processes involving lipid bilayers, and for a wide range of biomaterials, including amino acids, detergents, and pharmaceutical drugs. An appreciation of zwitterionic electrodynamic character can lead to a better understanding of molecular interactions in biological systems and in soft materials in general. PMID:21767488

Airpower Projection in the Anti-Access/Area Denial Environment: Dispersed Operations

DTIC Science & Technology

2015-02-01

Raptor Case Study.....................................................................6 Risks to Dispersed Operations...project airpower, this paper breaks down a case study of the Rapid Raptor concept. The risks with executing a dispersed model are analyzed and mitigation...will force leaders to look at alternative ways to project power. Alternative Option: Rapid Raptor Case Study The ability to defend forward operating

Coulomb replica-exchange method: handling electrostatic attractive and repulsive forces for biomolecules.

PubMed

Itoh, Satoru G; Okumura, Hisashi

2013-03-30

We propose a new type of the Hamiltonian replica-exchange method (REM) for molecular dynamics (MD) and Monte Carlo simulations, which we refer to as the Coulomb REM (CREM). In this method, electrostatic charge parameters in the Coulomb interactions are exchanged among replicas while temperatures are exchanged in the usual REM. By varying the atom charges, the CREM overcomes free-energy barriers and realizes more efficient sampling in the conformational space than the REM. Furthermore, this method requires only a smaller number of replicas because only the atom charges of solute molecules are used as exchanged parameters. We performed Coulomb replica-exchange MD simulations of an alanine dipeptide in explicit water solvent and compared the results with those of the conventional canonical, replica exchange, and van der Waals REMs. Two force fields of AMBER parm99 and AMBER parm99SB were used. As a result, the CREM sampled all local-minimum free-energy states more frequently than the other methods for both force fields. Moreover, the Coulomb, van der Waals, and usual REMs were applied to a fragment of an amyloid-β peptide (Aβ) in explicit water solvent to compare the sampling efficiency of these methods for a larger system. The CREM sampled structures of the Aβ fragment more efficiently than the other methods. We obtained β-helix, α-helix, 3(10)-helix, β-hairpin, and β-sheet structures as stable structures and deduced pathways of conformational transitions among these structures from a free-energy landscape. Copyright © 2012 Wiley Periodicals, Inc.

Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality

PubMed Central

Patra, Abhirup; Bates, Jefferson E.; Sun, Jianwei; Perdew, John P.

2017-01-01

We have computed the surface energies, work functions, and interlayer surface relaxations of clean (111), (100), and (110) surfaces of Al, Cu, Ru, Rh, Pd, Ag, Pt, and Au. We interpret the surface energy from liquid metal measurements as the mean of the solid-state surface energies over these three lowest-index crystal faces. We compare experimental (and random phase approximation) reference values to those of a family of nonempirical semilocal density functionals, from the basic local density approximation (LDA) to our most advanced general purpose meta-generalized gradient approximation, strongly constrained and appropriately normed (SCAN). The closest agreement is achieved by the simplest density functional LDA, and by the most sophisticated one, SCAN+rVV10 (Vydrov–Van Voorhis 2010). The long-range van der Waals interaction, incorporated through rVV10, increases the surface energies by about 10%, and increases the work functions by about 3%. LDA works for metal surfaces through two known error cancellations. The Perdew–Burke–Ernzerhof generalized gradient approximation tends to underestimate both surface energies (by about 24%) and work functions (by about 4%), yielding the least-accurate results. The amount by which a functional underestimates these surface properties correlates with the extent to which it neglects van der Waals attraction at intermediate and long range. Qualitative arguments are given for the signs of the van der Waals contributions to the surface energy and work function. A standard expression for the work function in Kohn–Sham (KS) theory is shown to be valid in generalized KS theory. Interlayer relaxations from different functionals are in reasonable agreement with one another, and usually with experiment. PMID:29042509

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

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

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

DOE PAGES

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin; ...

2017-01-26

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

Fourier Transform Microwave Spectroscopy of Multiconformational Molecules and Van Der Waals Complexes.

NASA Astrophysics Data System (ADS)

Hight Walker, Angela Renee

1995-01-01

With the use of a Fourier transform microwave (FTM) spectrometer, structural determinations of two types of species; multiconformational molecules and van der Waals complexes, have been performed. Presented in this thesis are three sections summarizing this research effort. The first section contains a detailed explanation of the FTM instrument. In Section II, the study of three multiconformational molecules is presented as two chapters. Finally, three chapters in Section III outline the work still in progress on many van der Waals complexes. Section I was written to be a "manual" for the FTM spectrometer and to aid new additions to the group in their understanding of the instrument. An instruction guide is necessary for home-built instruments such as this one due to their unique design and application. Vital techniques and theories are discussed and machine operation is outlined. A brief explanation of general microwave spectroscopy as performed on an FTM spectrometer is also given. Section II is composed of two chapters pertaining to multiconformational molecules. In Chapter 2, a complete structural analysis of dipropyl ether is reported. The only conformer assigned had C_{rm s} symmetry. Many transitions are yet unassigned. Chapter 3 summarizes an investigation of two nitrosamines; methyl ethyl and methyl propyl nitrosamine. Only one conformer was observed for methyl ethyl nitrosamine, but two were assigned to methyl propyl nitrosamine. Nuclear hyperfine structure and internal methyl rotation complicated the spectra. The final section, Section III, contains the ongoing progress on weakly bound van der Waals complexes. The analysis of the OCS--HBr complex identified the structure as quasi-linear with large amplitude bending motions. Five separate isotopomers were assigned. Transitions originating from the HBr--DBr complex were measured and presented in Chapter 5. Although early in the analysis, the structure was determined to be bent and deuterium bonded. The

Magnetic domain structure imaging near sample surface with alternating magnetic force microscopy by using AC magnetic field modulated superparamagnetic tip.

PubMed

Cao, Yongze; Nakayama, Shota; Kumar, Pawan; Zhao, Yue; Kinoshita, Yukinori; Yoshimura, Satoru; Saito, Hitoshi

2018-05-03

For magnetic domain imaging with a very high spatial resolution by magnetic force microscopy the tip-sample distance should be as small as possible. However, magnetic imaging near sample surface is very difficult with conventional MFM because the interactive forces between tip and sample includes van der Waals and electrostatic forces along with magnetic force. In this study, we proposed an alternating magnetic force microscopy (A-MFM) which extract only magnetic force near sample surface without any topographic and electrical crosstalk. In the present method, the magnetization of a FeCo-GdOx superparamagnetic tip is modulated by an external AC magnetic field in order to measure the magnetic domain structure without any perturbation from the other forces near the sample surface. Moreover, it is demonstrated that the proposed method can also measure the strength and identify the polarities of the second derivative of the perpendicular stray field from a thin-film permanent magnet with DC demagnetized state and remanent state. © 2018 IOP Publishing Ltd.

Computer Simulation of the Forces Acting on a Submerged Polystyrene Probe as it Approaches the Succinonitrile Melt-Solid Interface

NASA Technical Reports Server (NTRS)

Bune, Andris V.; Kaukler, William; Whitaker, Ann (Technical Monitor)

2001-01-01

A Modeling approach to simulate both mesoscale and microscopic forces acting in a typical AFM experiment is presented. A mesoscale level interaction between the cantilever tip and the sample surface is primarily described by the balance of attractive Van der Waals and repulsive forces. Ultimately, the goal is to measure the forces between a particle and the crystal-melt interface. Two modes of AFM operation are considered in this paper - a stationary and a "tapping" one. The continuous mechanics approach to model tip-surface interaction is presented. At microscopic levels, tip contamination and details of tip-surface interaction are modeled using a molecular dynamics approach for the case of polystyrene - succinonitrile contact. Integration of the mesoscale model with a molecular dynamic model is discussed.

Measurement and modification of forces between lecithin bilayers.

PubMed Central

LeNeveu, D M; Rand, R P

1977-01-01

We probe in two different ways the competing attractive and repulsive forces that create lamellar arrays of the phospholipid lecithin when in equilibrium with pure water. The first probe involves the addition of low molecular weight solutes, glucose and sucrose, to a system where the phospholipid is immersed in a large excess of water. Small solutes can enter the aqueous region between bilayers. Their effect is first to increase and then to decrease the separation between bilayers as sugar concentration increases. We interpret this waxing and waning of the lattice spacing in terms of the successive weakening and strengthening of the attractive van der Waals forces originally responsible for creation of a stable lattice. The second probe is an "osmotic stress method," in which very high molecular weight neutral polymer is added to the pure water phase but is unable to enter the multilayers. The polymer competes for water with the lamellar lattice, and thereby compresses it. From the resulting spacing (determined by X-ray diffraction) and the directly measured osmotic pressure, we find a force vs. distance curve for compressing the lattice (or, equivalently, the free energy of transfer to bulk water of water between bilayers. This method reveals a very strong, exponentially varying "hydration force" with a decay distance of about 2 A. PMID:861359

Flexible ferroelectric element based on van der Waals heteroepitaxy.

PubMed

Jiang, Jie; Bitla, Yugandhar; Huang, Chun-Wei; Do, Thi Hien; Liu, Heng-Jui; Hsieh, Ying-Hui; Ma, Chun-Hao; Jang, Chi-Yuan; Lai, Yu-Hong; Chiu, Po-Wen; Wu, Wen-Wei; Chen, Yi-Chun; Zhou, Yi-Chun; Chu, Ying-Hao

2017-06-01

We present a promising technology for nonvolatile flexible electronic devices: A direct fabrication of epitaxial lead zirconium titanate (PZT) on flexible mica substrate via van der Waals epitaxy. These single-crystalline flexible ferroelectric PZT films not only retain their performance, reliability, and thermal stability comparable to those on rigid counterparts in tests of nonvolatile memory elements but also exhibit remarkable mechanical properties with robust operation in bent states (bending radii down to 2.5 mm) and cycling tests (1000 times). This study marks the technological advancement toward realizing much-awaited flexible yet single-crystalline nonvolatile electronic devices for the design and development of flexible, lightweight, and next-generation smart devices with potential applications in electronics, robotics, automotive, health care, industrial, and military systems.

Flexible ferroelectric element based on van der Waals heteroepitaxy

PubMed Central

Jiang, Jie; Bitla, Yugandhar; Huang, Chun-Wei; Do, Thi Hien; Liu, Heng-Jui; Hsieh, Ying-Hui; Ma, Chun-Hao; Jang, Chi-Yuan; Lai, Yu-Hong; Chiu, Po-Wen; Wu, Wen-Wei; Chen, Yi-Chun; Zhou, Yi-Chun; Chu, Ying-Hao

2017-01-01

We present a promising technology for nonvolatile flexible electronic devices: A direct fabrication of epitaxial lead zirconium titanate (PZT) on flexible mica substrate via van der Waals epitaxy. These single-crystalline flexible ferroelectric PZT films not only retain their performance, reliability, and thermal stability comparable to those on rigid counterparts in tests of nonvolatile memory elements but also exhibit remarkable mechanical properties with robust operation in bent states (bending radii down to 2.5 mm) and cycling tests (1000 times). This study marks the technological advancement toward realizing much-awaited flexible yet single-crystalline nonvolatile electronic devices for the design and development of flexible, lightweight, and next-generation smart devices with potential applications in electronics, robotics, automotive, health care, industrial, and military systems. PMID:28630922

Exfoliation and van der Waals heterostructure assembly of intercalated ferromagnet Cr1/3TaS2

NASA Astrophysics Data System (ADS)

Yamasaki, Yuji; Moriya, Rai; Arai, Miho; Masubuchi, Satoru; Pyon, Sunseng; Tamegai, Tsuyoshi; Ueno, Keiji; Machida, Tomoki

2017-12-01

Ferromagnetic van der Waals (vdW) materials are in demand for spintronic devices with all-two-dimensional-materials heterostructures. Here, we demonstrate mechanical exfoliation of magnetic-atom-intercalated transition metal dichalcogenide Cr1/3TaS2 from its bulk crystal; previously such intercalated materials were thought difficult to exfoliate. Magnetotransport in exfoliated tens-of-nanometres-thick flakes revealed ferromagnetic ordering below its Curie temperature T C ~ 110 K as well as strong in-plane magnetic anisotropy; these are identical to its bulk properties. Further, van der Waals heterostructure assembly of Cr1/3TaS2 with another intercalated ferromagnet Fe1/4TaS2 is demonstrated using a dry-transfer method. The fabricated heterojunction composed of Cr1/3TaS2 and Fe1/4TaS2 with a native Ta2O5 oxide tunnel barrier in between exhibits tunnel magnetoresistance (TMR), revealing possible spin injection and detection with these exfoliatable ferromagnetic materials through the vdW junction.

Structural rearrangement and dispersion of functionalized graphene sheets in aqueous solutions

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

Lee, Yun Jung; Huang, Liwei; Wang, Howard

2015-09-01

Surfactants are widely used for dispersing graphene and functionalized graphene sheets (FGS) in colloidal suspensions, but there have been few studies of the structure of the dispersed graphene-surfactant complexes in suspension and of their time evolution. Here, we combine experimental study of efficiencies of ionic surfactants/polymers in suspending FGS in water with characterization using atomic force microscopy, small angle neutron scattering, and molecular simulations to probe the detailed structures of FGSs. A systematic study of FGS dispersions using ionic surfactants with varying chain lengths revealed that the effective charge density of surfactant layer defines the concentration of dispersed FGS whilemore » the strength of interfacial binding defines the stability of graphene dispersion over long time aging. Ionic surfactants with strong interfacial binding and large molecular weight increase the dispersing power by over an order of magnitude.« less

Thz Spectroscopy and DFT Modeling of Intermolecular Vibrations in Hydrophobic Amino Acids

NASA Astrophysics Data System (ADS)

Williams, michael R. C.; Aschaffenburg, Daniel J.; Schmuttenmaer, Charles A.

2013-06-01

Vibrations that involve intermolecular displacements occur in molecular crystals at frequencies in the 0.5-5 THz range (˜15-165 cm^{-1}), and these motions are direct indicators of the interaction potential between the molecules. The intermolecular potential energy surface of crystalline hydrophobic amino acids is inherently interesting simply because of the wide variety of forces (electrostatic, dipole-dipole, hydrogen-bonding, van der Waals) that are present. Furthermore, an understanding of these particular interactions is immediately relevant to important topics like protein conformation and pharmaceutical polymorphism. We measured the low-frequency absorption spectra of several polycrystalline hydrophobic amino acids using THz time-domain spectroscopy, and in addition we carried out DFT calculations using periodic boundary conditions and an exchange-correlation functional that accounts for van der Waals dispersion forces. We chose to investigate a series of similar amino acids with closely analogous unit cells (leucine, isoleucine, and allo-isoleucine, in racemic or pseudo-racemic mixtures). This allows us to consider trends in the vibrational spectra as a function of small changes in molecular arrangement and/or crystal geometry. In this way, we gain confidence that peak assignments are not based on serendipitous similarities between calculated and observed features.

Method of Manufacturing Micro-Disperse Particles of Sodium Borohydride

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester. Alan P.; Bell, Nelson S.

2008-09-23

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

Dispersion and Mixing in Quasi-two-dimensional Rotating Flows

NASA Astrophysics Data System (ADS)

Wells, M. G.; Clercx, H. J. H.; van Heijst, G. J. F.

A new rotating-tank experiment has been set up to investigate several aspects of dispersion in forced quasi-two-dimensional turbulence. By superimposing a harmonically varying perturbation on the mean rotation rate the mean flow continually interacts with the no-slip boundaries and forms boundary layers with high-amplitude vorticity twice during the forcing period. By choosing the proper amplitude and frequency of the perturbation it is possible to continuously inject small-scale vorticity in the interior of the flow, either in the form of filamentary structures (detached boundary layers) or as small vortices (after the roll-up of detached boundary layers). We present measurements of the passive scalar spectrum which show good agreement with the k -1 spectrum predicted by Batchelor (J. Fluid Mech. 5:113, 1959). Using particle image velocimetry we are able to reconstruct the Lagrangian trajectories of particles. The relative dispersion rates of particle pairs show an initial exponential separation followed by the classical Richardson dispersion, R 2 ∝ t3.0± 0.1. The variance of the absolute particle displacement grows as σ ∝ t1.4, similar to the observations in the previous experiments by Solomon et al. (Phys. Rev. Lett. 71:3975, 1993) and Hansen et al. (Phys. Rev. E 58:7261, 1998). Finally, and indicating future directions of research, we present results of a simple chemical reaction in forced quasi-2D turbulence and show how the bulk reaction rate is controlled by the mixing and filamentation processes.

Cohesive forces prevent the rotational breakup of rubble-pile asteroid (29075) 1950 DA.

PubMed

Rozitis, Ben; MacLennan, Eric; Emery, Joshua P

2014-08-14

Space missions and ground-based observations have shown that some asteroids are loose collections of rubble rather than solid bodies. The physical behaviour of such 'rubble-pile' asteroids has been traditionally described using only gravitational and frictional forces within a granular material. Cohesive forces in the form of small van der Waals forces between constituent grains have recently been predicted to be important for small rubble piles (ten kilometres across or less), and could potentially explain fast rotation rates in the small-asteroid population. The strongest evidence so far has come from an analysis of the rotational breakup of the main-belt comet P/2013 R3 (ref. 7), although that was indirect and poorly constrained by observations. Here we report that the kilometre-sized asteroid (29075) 1950 DA (ref. 8) is a rubble pile that is rotating faster than is allowed by gravity and friction. We find that cohesive forces are required to prevent surface mass shedding and structural failure, and that the strengths of the forces are comparable to, though somewhat less than, the forces found between the grains of lunar regolith.

Observation of aggregation triggered by Resonance Energy Transfer (RET) induced intermolecular pairing force.

PubMed

Pan, Xiaoyong; Wang, Weizhi; Ke, Lin; Zhang, Nan

2017-07-20

In this report, we showed the existence of RET induced intermolecular pairing force by comparing their fluorescence behaviors under room illumination vs standing in dark area for either PFluAnt solution or PFluAnt&PFOBT mixture. Their prominent emission attenuation under room illumination brought out the critical role of photo, i.e. RET induced intermolecular pairing force in induction of polymer aggregation. Constant UV-Vis absorption and fluorescence spectra in terms of both peak shapes and maximum wavelengths implied no chemical decomposition was involved. Recoverable fluorescence intensity, fluorescence lifetime as well as NMR spectra further exclude photo induced decomposition. The controllable on/off state of RET induced intermolecular pairing force was verified by the masking effect of outside PFluAnt solution which function as filter to block the excitation of inside PFluAnt and thus off the RET induced intermolecular pairing force. Theoretical calculation suggest that magnitude of RET induced intermolecular pairing force is on the same scale as that of van der Waals interaction. Although the absolute magnitude of RET induced intermolecular pairing force was not tunable, its effect can be magnified by intentionally turn it "on", which was achieved by irradiance with 5 W desk lamp in this report.

Anomalous dispersion due to hydrocarbons: The secret of reservoir geophysics?

USGS Publications Warehouse

Brown, R.L.

2009-01-01

When P- and S-waves travel through porous sandstone saturated with hydrocarbons, a bit of magic happens to make the velocities of these waves more frequency-dependent (dispersive) than when the formation is saturated with brine. This article explores the utility of the anomalous dispersion in finding more oil and gas, as well as giving a possible explanation about the effect of hydrocarbons upon the capillary forces in the formation. ?? 2009 Society of Exploration Geophysicists.

One-dimensional filtration of pharmaceutical grade phyllosilicate dispersions.

PubMed

Viseras, C; Cerezo, P; Meeten, G H; Lopez-Galindo, A

2001-04-17

The filtration behaviour of some clay-water dispersions was studied. Two Spanish fibrous phyllosilicates (sepiolite from Vicálvaro and palygorskite from Turón) and a commercial bentonite (Bentopharm UK) with similar sizes and different morphologies (fibrous and/or laminar) were selected as model clays. Sepiolite from Vicálvaro is an almost pure fibrous sample, Bentopharm presents a high amount of laminar particles and palygorskite from Turón is made up of similar percentages of laminar and fibrous particles. The disperse systems were made up using a rotor-stator mixer working at two different mixing rates (1000 and 8000 rpm), for periods of 1 and 10 min. Filtration measurements were taken and the corresponding filtration curves obtained. Finally, the desorptivity (S) of the filtration cakes was calculated and correlated to the textural characteristics of the materials, the solid fraction and mixing conditions. Filtration behaviour of the dispersions depended on all three of these factors. Laminar dispersions presented lower S values than fibrous dispersions. In the 2% w/v dispersions the bridging forces between particles did not permit formation of an interconnected network as in 10% w/v dispersions and, consequently, filtration times increased with the solid fraction (i.e. S values decreased). Regarding stability to pH changes, the results showed that filtration behaviour was highly sensitive to basic pH in the fibrous clay dispersions and almost insensitive in the laminar clay dispersions.

Characterizing the surface forces between two individual nanowires using optical microscopy based nanomanipulation

NASA Astrophysics Data System (ADS)

Xie, Hongtao; Mead, James L.; Wang, Shiliang; Fatikow, Sergej; Huang, Han

2018-06-01

The adhesion and friction between two Al2O3 nanowires (NWs) was characterized by the use of optical microscopy based nanomanipulation, with which peeling, shearing and sliding was performed. The elastically deformed shape of the NWs during peeling and shearing was used to calculate the adhesion and frictional forces; force sensing was not required. The obtained adhesion stress between two Al2O3 NWs varied from 0.14 to 0.25 MPa, lower than that observed for carbon nanotube junctions, and was attributed to van der Waals attraction. Stick-slip was observed during the shearing and sliding of two NWs, and was the consequence of discrete contact between surface asperities. The obtained static and kinetic frictional stresses varied from 0.7 to 1.3 MPa and 0.4 to 0.8 MPa, respectively; significantly greater than the obtained adhesion stress.

Characterizing the surface forces between two individual nanowires using optical microscopy based nanomanipulation.

PubMed

Xie, Hongtao; Mead, James L; Wang, Shiliang; Fatikow, Sergej; Huang, Han

2018-06-01

The adhesion and friction between two Al 2 O 3 nanowires (NWs) was characterized by the use of optical microscopy based nanomanipulation, with which peeling, shearing and sliding was performed. The elastically deformed shape of the NWs during peeling and shearing was used to calculate the adhesion and frictional forces; force sensing was not required. The obtained adhesion stress between two Al 2 O 3 NWs varied from 0.14 to 0.25 MPa, lower than that observed for carbon nanotube junctions, and was attributed to van der Waals attraction. Stick-slip was observed during the shearing and sliding of two NWs, and was the consequence of discrete contact between surface asperities. The obtained static and kinetic frictional stresses varied from 0.7 to 1.3 MPa and 0.4 to 0.8 MPa, respectively; significantly greater than the obtained adhesion stress.

Thermal characterization of static and dynamical properties of the confined molecular systems interacting through dispersion force.

PubMed

Ramos, Sergio Luis L M; Ogino, Michihiko; Oguni, Masaharu

2015-01-28

We investigated the thermal properties of liquid methylcyclohexane and racemic sec-butylcyclohexane, as representatives of a molecular system with only dispersion-force intermolecular interactions, confined in the pores (thickness/diameter d = 12, 6, 1.1 nm) of silica gels by adiabatic calorimetry. The results imply a heterogeneous picture for molecular aggregate under confinement consisting of an interfacial region and an inner pore one. In the vicinity of a glass-transition temperature T(g,bulk) of bulk liquid, two distinguishable relaxation phenomena were observed for the confined systems and their origins were attributed to the devitrification, namely glass transition, processes of (1) a layer of interfacial molecules adjacent to the pore walls and (2) the molecules located in the middle of the pore. A third glass-transition phenomenon was observed at lower temperatures and ascribed to a secondary relaxation process. The glass transition of the interfacial-layer molecules was found to proceed at temperatures rather above T(g,bulk), whereas that of the molecules located in the inner pore region occurred at temperatures below T(g,bulk). We discuss the reason why the molecules located in different places in the pores reveal the respectively different dynamical properties.

Electrostatics of electron-hole interactions in van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Cavalcante, L. S. R.; Chaves, A.; Van Duppen, B.; Peeters, F. M.; Reichman, D. R.

2018-03-01

The role of dielectric screening of electron-hole interaction in van der Waals heterostructures is theoretically investigated. A comparison between models available in the literature for describing these interactions is made and the limitations of these approaches are discussed. A simple numerical solution of Poisson's equation for a stack of dielectric slabs based on a transfer matrix method is developed, enabling the calculation of the electron-hole interaction potential at very low computational cost and with reasonable accuracy. Using different potential models, direct and indirect exciton binding energies in these systems are calculated within Wannier-Mott theory, and a comparison of theoretical results with recent experiments on excitons in two-dimensional materials is discussed.

Normal and lateral Casimir forces between deformed plates

NASA Astrophysics Data System (ADS)

Emig, Thorsten; Hanke, Andreas; Golestanian, Ramin; Kardar, Mehran

2003-02-01

The Casimir force between macroscopic bodies depends strongly on their shape and orientation. To study this geometry dependence in the case of two deformed metal plates, we use a path-integral quantization of the electromagnetic field which properly treats the many-body nature of the interaction, going beyond the commonly used pairwise summation (PWS) of van der Waals forces. For arbitrary deformations we provide an analytical result for the deformation induced change in the Casimir energy, which is exact to second order in the deformation amplitude. For the specific case of sinusoidally corrugated plates, we calculate both the normal and the lateral Casimir forces. The deformation induced change in the Casimir interaction of a flat and a corrugated plate shows an interesting crossover as a function of the ratio of the mean plate distance H to the corrugation length λ: For λ≪H we find a slower decay ˜H-4, compared to the H-5 behavior predicted by PWS which we show to be valid only for λ≫H. The amplitude of the lateral force between two corrugated plates which are out of registry is shown to have a maximum at an optimal wavelength of λ≈2.5 H. With increasing H/λ≳0.3 the PWS approach becomes a progressively worse description of the lateral force due to many-body effects. These results may be of relevance for the design and operation of novel microelectromechanical systems (MEMS) and other nanoscale devices.

Sensing properties of pristine boron nitride nanostructures towards alkaloids: A first principles dispersion corrected study

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Dabhi, Shweta D.; Jha, Prafulla K.

2018-05-01

To understand the underlying physics behind the interaction of biomolecules with the nanomaterials to use them practically as bio-nanomaterials is very crucial. A first principles calculation under the frame work of density functional theory is executed to investigate the electronic structures and binding properties of alkaloids (Caffeine and Nicotine) over single walled boron nitride nanotube (BNNT) and boron nitride nanoribbon (BNNR) to determine their suitability towards filtration or sensing of these molecules. We have also used GGA-PBE scheme with the inclusion of Van der Waals (vdW) interaction based on DFT-D2. Increase in the accuracy by incorporating the dispersion correction in the calculation is observed for the long range Van der Waals interaction. Binding energy range of BNNT and BNNR with both alkaloids have been found to be -0.35 to -0.76 eV and -0.45 to -0.91 eV respectively which together with the binding distance shows physisorption binding of these molecules to the both nanostructures. The transfer of charge between the BN nanostructures and the adsorbed molecule has also been analysed by using Lowdin charge analysis. The sensitivity of both nanostructures BNNT and BNNR towards both alkaloids is observed through electronic structure calculations, density of states and quantum conductance. The binding of both alkaloids with BNNR is stronger. The analysis of the calculated properties suggests absence of covalent interaction between the considered species (BNNT/BNNR) and alkaloids. The study may be useful in designing the boron nitride nanostructure based sensing device for alkaloids.

Long-range wetting transparency on top of layered metal-dielectric substrates

NASA Astrophysics Data System (ADS)

Noginov, M. A.; Barnakov, Yuri A.; Liberman, Vladimir; Prayakarao, Srujana; Bonner, Carl E.; Narimanov, Evgenii E.

2016-06-01

It has been recently shown that scores of physical and chemical phenomena (including spontaneous emission, scattering and Förster energy transfer) can be controlled by nonlocal dielectric environments provided by metamaterials with hyperbolic dispersion and simpler metal/dielectric structures. At this time, we have researched van der Waals interactions and experimentally studied wetting of several metallic, dielectric and composite multilayered substrates. We have found that the wetting angle of water on top of MgF2 is highly sensitive to the thickness of the MgF2 layer and the nature of the underlying substrate that could be positioned as far as ~100 nm beneath the water/MgF2 interface. We refer to this phenomenon as long range wetting transparency. The latter effect cannot be described in terms of the most basic model of dispersion van der Waals-London forces based on pair-wise summation of dipole-dipole interactions across an interface or a gap separating the two media. We infer that the experimentally observed gradual change of the wetting angle with increase of the thickness of the MgF2 layer can possibly be explained by the distance dependence of the Hamaker function (describing the strength of interaction), which originates from retardation of electromagnetic waves at the distances comparable to a wavelength.

Long-range wetting transparency on top of layered metal-dielectric substrates.

PubMed

Noginov, M A; Barnakov, Yuri A; Liberman, Vladimir; Prayakarao, Srujana; Bonner, Carl E; Narimanov, Evgenii E

2016-06-21

It has been recently shown that scores of physical and chemical phenomena (including spontaneous emission, scattering and Förster energy transfer) can be controlled by nonlocal dielectric environments provided by metamaterials with hyperbolic dispersion and simpler metal/dielectric structures. At this time, we have researched van der Waals interactions and experimentally studied wetting of several metallic, dielectric and composite multilayered substrates. We have found that the wetting angle of water on top of MgF2 is highly sensitive to the thickness of the MgF2 layer and the nature of the underlying substrate that could be positioned as far as ~100 nm beneath the water/MgF2 interface. We refer to this phenomenon as long range wetting transparency. The latter effect cannot be described in terms of the most basic model of dispersion van der Waals-London forces based on pair-wise summation of dipole-dipole interactions across an interface or a gap separating the two media. We infer that the experimentally observed gradual change of the wetting angle with increase of the thickness of the MgF2 layer can possibly be explained by the distance dependence of the Hamaker function (describing the strength of interaction), which originates from retardation of electromagnetic waves at the distances comparable to a wavelength.

Crystal Growth Rate Dispersion: A Predictor of Crystal Quality in Microgravity?

NASA Technical Reports Server (NTRS)

Kephart, Richard D.; Judge, Russell A.; Snell, Edward H.; vanderWoerd, Mark J.

2003-01-01

In theory macromolecular crystals grow through a process involving at least two transport phenomena of solute to the crystal surface: diffusion and convection. In absence of standard gravitational forces, the ratio of these two phenomena can change and explain why crystal growth in microgravity is different from that on Earth. Experimental evidence clearly shows, however, that crystal growth of various systems is not equally sensitive to reduction in gravitational forces, leading to quality improvement in microgravity for some crystals but not for others. We hypothesize that the differences in final crystal quality are related to crystal growth rate dispersion. If growth rate dispersion exists on Earth, decreases in microgravity, and coincides with crystal quality improvements then this dispersion is a predictor for crystal quality improvement. In order to test this hypothesis, we will measure growth rate dispersion both in microgravity and on Earth and will correlate the data with previously established data on crystal quality differences for the two environments. We present here the first crystal growth rate measurement data for three proteins (lysozyme, xylose isomerase and human recombinant insulin), collected on Earth, using hardware identical to the hardware to be used in microgravity and show how these data correlate with crystal quality improvements established in microgravity.

Determination of the dispersion constant in a constrained vapor bubble thermosyphon

NASA Technical Reports Server (NTRS)

Dasgupta, Sunando; Plawsky, Joel L.; Wayner, Peter C., Jr.

1995-01-01

The isothermal profiles of the extended meniscus in a quartz cuvette were measured in a gravitational field using an image analyzing interferometer which is based on computer enhanced video microscopy of the naturally occurring interference fringes. The experimental results for heptane and pentane menisci were analyzed using the extended Young Laplace Equation. These isothermal results characterized the interfacial force field in-siru at the start of the heat transfer experiments by quantifying the dispersion constant, which is a function of the liquid-solid system and cleaning procedures. The experimentally obtained values of the disjoining pressure and the dispersion constants were compared to that predicted from the DLP theory and good agreements were obtained. The measurements are critical to the subsequent non-isothermal experiments because one of the major variables in the heat sink capability of the Constrained Vapor Bubble Thermosyphon, CVBT, is the dispersion constant. In all previous studies of micro heat pipes the value of the dispersion constant has been 'estimated'. One of the major advantages of the current glass cell is the ability to view the extended meniscus at all times. Experimentally, we find that the extended Young-Laplace Equation is an excellent model for the force field at the solid-liquid-vapor interfaces.

Dispersion of sound in a combustion duct by fuel droplets and soot particles

NASA Technical Reports Server (NTRS)

Miles, J. H.; Raftopoulos, D. D.

1979-01-01

Dispersion and attenuation of acoustic plane wave disturbances propagating in a ducted combustion system are studied. The dispersion and attenuation are caused by fuel droplet and soot emissions from a jet engine combustor. The attenuation and dispersion are due to heat transfer and mass transfer and viscous drag forces between the emissions and the ambient gas. Theoretical calculations show sound propagation at speeds below the isentropic speed of sound at low frequencies. Experimental results are in good agreement with the theory.

Optical spectroscopy of excited exciton states in MoS2 monolayers in van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Robert, C.; Semina, M. A.; Cadiz, F.; Manca, M.; Courtade, E.; Taniguchi, T.; Watanabe, K.; Cai, H.; Tongay, S.; Lassagne, B.; Renucci, P.; Amand, T.; Marie, X.; Glazov, M. M.; Urbaszek, B.

2018-01-01

The optical properties of MoS2 monolayers are dominated by excitons, but for spectrally broad optical transitions in monolayers exfoliated directly onto SiO2 substrates detailed information on excited exciton states is inaccessible. Encapsulation in hexagonal boron nitride (hBN) allows approaching the homogenous exciton linewidth, but interferences in the van der Waals heterostructures make direct comparison between transitions in optical spectra with different oscillator strength more challenging. Here we reveal in reflectivity and in photoluminescence excitation spectroscopy the presence of excited states of the A exciton in MoS2 monolayers encapsulated in hBN layers of calibrated thickness, allowing us to extrapolate an exciton binding energy of ≈220 meV. We theoretically reproduce the energy separations and oscillator strengths measured in reflectivity by combining the exciton resonances calculated for a screened two-dimensional Coulomb potential with transfer matrix calculations of the reflectivity for the van der Waals structure. Our analysis shows a very different evolution of the exciton oscillator strength with principal quantum number for the screened Coulomb potential as compared to the ideal two-dimensional hydrogen model.

Dispersive stresses in wind farms

NASA Astrophysics Data System (ADS)

Segalini, Antonio; Braunbehrens, Robert; Hyvarinen, Ann

2017-11-01

One of the most famous models of wind farms is provided by the assumption that the farm can be approximated as a horizontally-homogeneous forest canopy with vertically-varying force intensity. By means of this approximation, the flow-motion equations become drastically simpler, as many of the three-dimensional effects are gone. However, the application of the horizontal average operator to the RANS equations leads to the appearance of new transport terms (called dispersive stresses) originating from the horizontal (small-scale) variation of the mean velocity field. Since these terms are related to the individual turbine signature, they are expected to vanish outside the roughness sublayer, providing a definition for the latter. In the present work, an assessment of the dispersive stresses is performed by means of a wake-model approach and through the linearised code ORFEUS developed at KTH. Both approaches are very fast and enable the characterization of a large number of wind-farm layouts. The dispersive stress tensor and its effect on the turbulence closure models are investigated, providing guidelines for those simulations where it is impossible to resolve the farm at a turbine scale due to grid requirements (as, for instance, mesoscale simulations).

van der Waals Layered Materials: Opportunities and Challenges.

PubMed

Duong, Dinh Loc; Yun, Seok Joon; Lee, Young Hee

2017-12-26

Since graphene became available by a scotch tape technique, a vast class of two-dimensional (2D) van der Waals (vdW) layered materials has been researched intensively. What is more intriguing is that the well-known physics and chemistry of three-dimensional (3D) bulk materials are often irrelevant, revealing exotic phenomena in 2D vdW materials. By further constructing heterostructures of these materials in the planar and vertical directions, which can be easily achieved via simple exfoliation techniques, numerous quantum mechanical devices have been demonstrated for fundamental research and technological applications. It is, therefore, necessary to review the special features in 2D vdW materials and to discuss the remaining issues and challenges. Here, we review the vdW materials library, technology relevance, and specialties of vdW materials covering the vdW interaction, strong Coulomb interaction, layer dependence, dielectric screening engineering, work function modulation, phase engineering, heterostructures, stability, growth issues, and the remaining challenges.

Adsorption of thiophene on transition metal surfaces with the inclusion of van der Waals effects

NASA Astrophysics Data System (ADS)

Malone, Walter; Matos, Jeronimo; Kara, Abdelkader

2018-03-01

We use density functional theory with the inclusion of the van der Waals interaction to study the adsorption of thiophene, C4H4S, on Pt, Rh, Pd, Au, and Ag (100) surfaces. The five van der Waals (vdW) inclusive functionals we employ are optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2. For comparison we also run calculations with the GGA- Perdew Burke and Ernzerhof (PBE) functional. We examine several adsorption sites with the plane of the molecule parallel or perpendicular to the surface. The most stable configuration on all metals was the site where the center of the thiophene lies over a 4-fold hollow site with the sulfur atom lying close to a top site. Furthermore, we examine several electronic and geometric properties of the adsorbate including charge transfer, modification of the d-band, adsorption energy, tilt angle, and adsorption height. For the coinage metals PBE gives the lowest adsorption energy. For reactive transition metal substrates, revPBE-vdW and rPW86-vdW2 give lower adsorption energies than PBE.

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.; Pedersen, M.J.

1993-01-01

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids

DOE PAGES

Lian, Cheng; Univ. of California, Riverside, CA; Zhao, Shuangliang; ...

2016-11-29

Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this paper, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the durationmore » of charging. Finally and furthermore, we investigate the effects of van der Waals attraction between electrode/ionic-liquid interactions on the charging processes.« less

The nature of the interlayer interaction in bulk and few-layer phosphorus

DOE PAGES

Shulenburger, Luke; Baczewski, A. D.; Zhu, Z.; ...

2015-11-02

Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called van der Waals (vdW) solids . We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. Lastly, these findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.

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

Shulenburger, Luke; Baczewski, A. D.; Zhu, Z.

Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called van der Waals (vdW) solids . We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. Lastly, these findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.

The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus.

PubMed

Shulenburger, L; Baczewski, A D; Zhu, Z; Guan, J; Tománek, D

2015-12-09

Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called "van der Waals (vdW) solids". We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. These findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures.

PubMed

Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J; Li, Lain-Jong; Wallace, Robert M; Datta, Suman; Robinson, Joshua A

2015-06-19

Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics.

Computations of Lifshitz-van der Waals interaction energies between irregular particles and surfaces at all separations for resuspension modelling

NASA Astrophysics Data System (ADS)

Priye, Aashish; Marlow, William H.

2013-10-01

The phenomenon of particle resuspension plays a vital role in numerous fields. Among many aspects of particle resuspension dynamics, a dominant concern is the accurate description and formulation of the van der Waals (vdW) interactions between the particle and substrate. Current models treat adhesion by incorporating a material-dependent Hamaker's constant which relies on the heuristic Hamaker's two-body interactions. However, this assumption of pairwise summation of interaction energies can lead to significant errors in condensed matter as it does not take into account the many-body interaction and retardation effects. To address these issues, an approach based on Lifshitz continuum theory of vdW interactions has been developed to calculate the principal many-body interactions between arbitrary geometries at all separation distances to a high degree of accuracy through Lifshitz's theory. We have applied this numerical implementation to calculate the many-body vdW interactions between spherical particles and surfaces with sinusoidally varying roughness profile and also to non-spherical particles (cubes, cylinders, tetrahedron etc) orientated differently with respect to the surface. Our calculations revealed that increasing the surface roughness amplitude decreases the adhesion force and non-spherical particles adhere to the surfaces more strongly when their flatter sides are oriented towards the surface. Such practical shapes and structures of particle-surface systems have not been previously considered in resuspension models and this rigorous treatment of vdW interactions provides more realistic adhesion forces between the particle and the surface which can then be coupled with computational fluid dynamics models to improve the predictive capabilities of particle resuspension dynamics.

Sensitivity study of cloud parameterizations with relative dispersion in CAM5.1: impacts on aerosol indirect effects

NASA Astrophysics Data System (ADS)

Xie, Xiaoning; Zhang, He; Liu, Xiaodong; Peng, Yiran; Liu, Yangang

2017-05-01

Aerosol-induced increase of relative dispersion of cloud droplet size distribution ɛ exerts a warming effect and partly offsets the cooling of aerosol indirect radiative forcing (AIF) associated with increased droplet concentration by increasing the cloud droplet effective radius (Re) and enhancing the cloud-to-rain autoconversion rate (Au) (labeled as the dispersion effect), which can help reconcile global climate models (GCMs) with the satellite observations. However, the total dispersion effects on both Re and Au are not fully considered in most GCMs, especially in different versions of the Community Atmospheric Model (CAM). In order to accurately evaluate the dispersion effect on AIF, the new complete cloud parameterizations of Re and Au explicitly accounting for ɛ are implemented into the CAM version 5.1 (CAM5.1), and a suite of sensitivity experiments is conducted with different representations of ɛ reported in the literature. It is shown that the shortwave cloud radiative forcing is much better simulated with the new cloud parameterizations as compared to the standard scheme in CAM5.1, whereas the influences on longwave cloud radiative forcing and surface precipitation are minimal. Additionally, consideration of the dispersion effect can significantly reduce the changes induced by anthropogenic aerosols in the cloud-top effective radius and the liquid water path, especially in the Northern Hemisphere. The corresponding AIF with the dispersion effect considered can also be reduced substantially by a range of 0.10 to 0.21 W m-2 at the global scale and by a much bigger margin of 0.25 to 0.39 W m-2 for the Northern Hemisphere in comparison with that of fixed relative dispersion, mainly dependent on the change of relative dispersion and droplet concentrations (Δɛ/ΔNc).

Ecological considerations for the use of dispersants in oil spill response

USGS Publications Warehouse

Lindstedt-Siva, J.; Albers, P.H.; Fucik, K.W.; Maynard, N.G.; Allen, Tom E.

1984-01-01

A multidisciplinary task force with membership from government agencies, academia, and industry is developing ecologically based guidelines for dispersant use in marine and estuarine environments. The guidelines are organized by habitat type (e.g., coral reefs, rocky shores, bird habitats) and consider dispersant use to protect the habitats from impact, to mitigate impacts, and to clean the habitats after a spill. Each guideline contains a description of the habitat type covered, recommendations for dispersant use, and a background section reviewing the relevant literature. The goal is to minimize the ecological impacts of oil spills. Aesthetic, socioeconomic, and political factors are not considered, although it is recognized that these are important concerns during spill response. Use of dispersants is considered along with other appropriate countermeasures and compared with the “no cleanup” alternative.

Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

PubMed

Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

2017-02-01

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer-grafted gold nanorods in polymer thin films: Dispersion and plasmonic coupling

NASA Astrophysics Data System (ADS)

Hore, Michael-Jon Ainsley

This dissertation describes complementary experimental and theoretical studies to deter- mine the thermodynamic factors that affect the dispersion of polymer-grafted Au nanorods within polymer thin films. Au nanorods exhibit a uniform dispersion with a regular spacing for favorable brush / matrix interactions, such as poly(ethylene glycol) (PEG)-Au / poly(methyl methacrylate) (PMMA) and polystyrene (PS)-Au / poly(2,6-dimethyl-p-phenylene oxide) (PPO). For PEG-Au / PMMA, the nanorods are locally oriented and their dispersion is independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), α = P/N, whereas for chemically similar brush / matrix combinations, such as PS-Au / PS and PEG-Au / poly(ethylene oxide) (PEO), nanorods are randomly dispersed for α 2. For aggregated systems (α > 2), nanorods are found primarily within aggregates containing side-by-side aligned nanorods with a spacing that scales with N. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that coupling between surface plasmons within the aggregates leads to a blue shift in the optical absorption as α increases, indicating the sensitivity of spectroscopy for determining nanorod dispersion in polymer nanocomposite films. Self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations show that the aggregation of nanorods for α > 2 can be attributed to depletion-attraction forces caused by autophobic dewetting of the brush and matrix. Finally, miscible blends of PS and PPO are investigated as a route to control depletion-attraction interactions between PS-Au nanorods. Initially, nanorods aggregate in matrices having 50 vol. % PPO and then gradually disperse as PPO becomes the majority component. The brush and matrix density profiles, determined by SCFT, show that PPO segregates into the PS brush, and acts as a compatibilizer, which improves dispersion. As dispersion improves, coupling between surface

Nuclear spin-spin coupling in a van der Waals-bonded system: xenon dimer.

PubMed

Vaara, Juha; Hanni, Matti; Jokisaari, Jukka

2013-03-14

Nuclear spin-spin coupling over van der Waals bond has recently been observed via the frequency shift of solute protons in a solution containing optically hyperpolarized (129)Xe nuclei. We carry out a first-principles computational study of the prototypic van der Waals-bonded xenon dimer, where the spin-spin coupling between two magnetically non-equivalent isotopes, J((129)Xe - (131)Xe), is observable. We use relativistic theory at the four-component Dirac-Hartree-Fock and Dirac-density-functional theory levels using novel completeness-optimized Gaussian basis sets and choosing the functional based on a comparison with correlated ab initio methods at the nonrelativistic level. J-coupling curves are provided at different levels of theory as functions of the internuclear distance in the xenon dimer, demonstrating cross-coupling effects between relativity and electron correlation for this property. Calculations on small Xe clusters are used to estimate the importance of many-atom effects on J((129)Xe - (131)Xe). Possibilities of observing J((129)Xe - (131)Xe) in liquid xenon are critically examined, based on molecular dynamics simulation. A simplistic spherical model is set up for the xenon dimer confined in a cavity, such as in microporous materials. It is shown that the on the average shorter internuclear distance enforced by the confinement increases the magnitude of the coupling as compared to the bulk liquid case, rendering J((129)Xe - (131)Xe) in a cavity a feasible target for experimental investigation.

Statistical substantiation of the van der Waals theory of inhomogeneous fluids

NASA Astrophysics Data System (ADS)

Baidakov, V. G.; Protsenko, S. P.; Chernykh, G. G.; Boltachev, G. Sh.

2002-04-01

Computer experiments on simulation of thermodynamic properties and structural characteristics of a Lennard-Jones fluid in one- and two-phase models have been performed for the purpose of checking the base concepts of the van der Waals theory. Calculations have been performed by the method of molecular dynamics at cutoff radii of the intermolecular potential rc,1=2.6σ and rc,2=6.78σ. The phase equilibrium parameters, surface tension, and density distribution have been determined in a two-phase model with a flat liquid-vapor interface. The strong dependence of these properties on the value of rc is shown. The p,ρ,T properties and correlation functions have been calculated in a homogeneous model for a stable and a metastable fluid. An equation of state for a Lennard-Jones fluid describing stable, metastable, and labile regions has been built. It is shown that at T>=1.1 the properties of a flat interface within the computer experimental error can be described by the van der Waals square-gradient theory with an influence parameter κ independent of the density. Taking into account the density dependence of κ through the second moment of the direct correlation function will deteriorate the agreement of the theory with data of computer simulation. The contribution of terms of a higher order than (∇ρ)2 to the Helmholtz free energy of an inhomogeneous system has been considered. It is shown that taking into account terms proportional to (∇ρ)4 leaves no way of obtaining agreement between the theory and simulation data, while taking into consideration of terms proportional to (∇ρ)6 makes it possible to describe with adequate accuracy all the properties of a flat interface in the temperature range from the triple to the critical point.

Dispersion, controlled dispersion, and three applications

NASA Astrophysics Data System (ADS)

Bradshaw, Douglas H.

Causality dictates that all physical media must be dispersive. (We will call a medium dispersive if its refractive index varies with frequency.) Ordinarily, strong dispersion is accompanied either by strong absorption or strong gain. However, over the past 15 years several groups have demonstrated that it is possible to have media that are both strongly dispersive and roughly transparent for some finite bandwidth. In these media, group and phase velocities may differ from each other by many orders of magnitude and even by sign. Relationships and intuitive models that are satisfactory when it is reasonable to neglect dispersion may then fail dramatically. In this dissertation we analyze three such cases of failure. Before looking at the specific cases, we review some basic ideas relating to dispersion. We review some of the geometric meanings of group velocity, touch on the relationship between group velocity and causality, and give some examples of techniques by which the group velocity may be manipulated. We describe the interplay between group velocity and energy density for non-absorbing dispersive media. We discuss the ideas of temporary absorption and emission as dictated by an instantaneous spectrum. We then apply these concepts in three specific areas. First, non-dispersive formulations for the momentum of light in a medium must be adjusted to account for dispersion. For over 100 years, there has been a gradual discussion of the proper form for the per-photon momentum. Two forms, each of which has experimental relevance in a 'dispersionless' medium, are the Abraham momentum, and the Minkowski momentum. If h is the angular frequency, n is the refractive index, h is Planck's constant, and c is the speed of light, then these reduce in a dispersionless medium to per-photon momenta of ho/(nc), and nho/c respectively. A simple generalization of the two momenta to dispersive media entails multiplying each per-photon momentum by n/ng, where ng is the group

Communication: THz absorption spectrum of the CO2-H2O complex: observation and assignment of intermolecular van der Waals vibrations.

PubMed

Andersen, J; Heimdal, J; Mahler, D W; Nelander, B; Larsen, R Wugt

2014-03-07

Terahertz absorption spectra have been recorded for the weakly bound CO2-H2O complex embedded in cryogenic neon matrices at 2.8 K. The three high-frequency van der Waals vibrational transitions associated with out-of-plane wagging, in-plane rocking, and torsional motion of the isotopic H2O subunit have been assigned and provide crucial observables for benchmark theoretical descriptions of this systems' flat intermolecular potential energy surface. A (semi)-empirical value for the zero-point energy of 273 ± 15 cm(-1) from the class of intermolecular van der Waals vibrations is proposed and the combination with high-level quantum chemical calculations provides a value of 726 ± 15 cm(-1) for the dissociation energy D0.

Superconducting Ga/GaSe layers grown by van der Waals epitaxy

NASA Astrophysics Data System (ADS)

Desrat, W.; Moret, M.; Briot, O.; Ngo, T.-H.; Piot, B. A.; Jabakhanji, B.; Gil, B.

2018-04-01

We report on the growth of GaSe films by molecular beam epitaxy on both (111)B GaAs and sapphire substrates. X-ray diffraction reveals the perfect crystallinity of GaSe with the c-axis normal to the substrate surface. The samples grown under Ga rich conditions possess an additional gallium film on top of the monochalcogenide layer. This metallic film shows two normal-to-superconducting transitions which are detected at T c ≈ 1.1 K and 6.0 K. They correspond likely to the β and α-phases of gallium in the form of bulk and droplets respectively. Our results demonstrate that van der Waals epitaxy can lead to future high quality hybrid superconductor/monochalcogenide heterostructures.

Meteorological Controls on Local and Regional Volcanic Ash Dispersal.

PubMed

Poulidis, Alexandros P; Phillips, Jeremy C; Renfrew, Ian A; Barclay, Jenni; Hogg, Andrew; Jenkins, Susanna F; Robertson, Richard; Pyle, David M

2018-05-02

Volcanic ash has the capacity to impact human health, livestock, crops and infrastructure, including international air traffic. For recent major eruptions, information on the volcanic ash plume has been combined with relatively coarse-resolution meteorological model output to provide simulations of regional ash dispersal, with reasonable success on the scale of hundreds of kilometres. However, to predict and mitigate these impacts locally, significant improvements in modelling capability are required. Here, we present results from a dynamic meteorological-ash-dispersion model configured with sufficient resolution to represent local topographic and convectively-forced flows. We focus on an archetypal volcanic setting, Soufrière, St Vincent, and use the exceptional historical records of the 1902 and 1979 eruptions to challenge our simulations. We find that the evolution and characteristics of ash deposition on St Vincent and nearby islands can be accurately simulated when the wind shear associated with the trade wind inversion and topographically-forced flows are represented. The wind shear plays a primary role and topographic flows a secondary role on ash distribution on local to regional scales. We propose a new explanation for the downwind ash deposition maxima, commonly observed in volcanic eruptions, as resulting from the detailed forcing of mesoscale meteorology on the ash plume.

The formation process and responsive impacts of single oil droplet in submerged process.

PubMed

Li, Haoshuai; Meng, Long; Shen, Tiantian; Zhang, Jianrui; Bao, Mutai; Sun, Peiyan

2017-11-15

Simulated column was applied to research forming progress of single oil droplet in submerged process, floating progress, and study effects of environment factors and dispersants on the concentration of oil hydrocarbon in water as well as changing rules of oil droplet sizes. As expected, particular formation mechanism of single oil droplet was presented. When necking down length L is 0.5 time of oil droplet diameter (d) after expansion phase, necking down becomes long and thin; when L=2d, necking down begins to break. In floating progress, the shape changes oval and its motion trail becomes an auger-type. Fluctuation occurs at horizontal direction. Dispersants decrease oil droplet size by its dispersion effect, and cut down effect of Van Der Waals force among oil droplets. More broadly, these findings provide rare empirical evidence expounding formation mechanism of single oil droplet to increasing ability of oil spill response. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of rarefaction waves in van der Waals fluids

NASA Astrophysics Data System (ADS)

Yuen, Albert; Barnard, John J.

2015-12-01

We calculate the isentropic evolution of an instantaneously heated foil, assuming a van der Waals equation of state with the Maxwell construction. The analysis by Yuen and Barnard [Phys. Rev. E 92, 033019 (2015), 10.1103/PhysRevE.92.033019] is extended for the particular case of three degrees of freedom. We assume heating to temperatures in the vicinity of the critical point. The self-similar profiles of the rarefaction waves describing the evolution of the foil display plateaus in density and temperature due to a phase transition from the single-phase to the two-phase regime. The hydrodynamic equations are expressed in a dimensionless form and the solutions form a set of universal curves, depending on a single parameter: the dimensionless initial entropy. We characterize the rarefaction waves by calculating how the plateau length, density, pressure, temperature, velocity, internal energy, and sound speed vary with dimensionless initial entropy.

On the evolution of dispersal via heterogeneity in spatial connectivity

PubMed Central

Henriques-Silva, Renato; Boivin, Frédéric; Calcagno, Vincent; Urban, Mark C.; Peres-Neto, Pedro R.

2015-01-01

Dispersal has long been recognized as a mechanism that shapes many observed ecological and evolutionary processes. Thus, understanding the factors that promote its evolution remains a major goal in evolutionary ecology. Landscape connectivity may mediate the trade-off between the forces in favour of dispersal propensity (e.g. kin-competition, local extinction probability) and those against it (e.g. energetic or survival costs of dispersal). It remains, however, an open question how differing degrees of landscape connectivity may select for different dispersal strategies. We implemented an individual-based model to study the evolution of dispersal on landscapes that differed in the variance of connectivity across patches ranging from networks with all patches equally connected to highly heterogeneous networks. The parthenogenetic individuals dispersed based on a flexible logistic function of local abundance. Our results suggest, all else being equal, that landscapes differing in their connectivity patterns will select for different dispersal strategies and that these strategies confer a long-term fitness advantage to individuals at the regional scale. The strength of the selection will, however, vary across network types, being stronger on heterogeneous landscapes compared with the ones where all patches have equal connectivity. Our findings highlight how landscape connectivity can determine the evolution of dispersal strategies, which in turn affects how we think about important ecological dynamics such as metapopulation persistence and range expansion. PMID:25673685

Thermodynamically consistent force fields for the assembly of inorganic, organic, and biological nanostructures: the INTERFACE force field.

PubMed

Heinz, Hendrik; Lin, Tzu-Jen; Mishra, Ratan Kishore; Emami, Fateme S

2013-02-12

The complexity of the molecular recognition and assembly of biotic-abiotic interfaces on a scale of 1 to 1000 nm can be understood more effectively using simulation tools along with laboratory instrumentation. We discuss the current capabilities and limitations of atomistic force fields and explain a strategy to obtain dependable parameters for inorganic compounds that has been developed and tested over the past decade. Parameter developments include several silicates, aluminates, metals, oxides, sulfates, and apatites that are summarized in what we call the INTERFACE force field. The INTERFACE force field operates as an extension of common harmonic force fields (PCFF, COMPASS, CHARMM, AMBER, GROMACS, and OPLS-AA) by employing the same functional form and combination rules to enable simulations of inorganic-organic and inorganic-biomolecular interfaces. The parametrization builds on an in-depth understanding of physical-chemical properties on the atomic scale to assign each parameter, especially atomic charges and van der Waals constants, as well as on the validation of macroscale physical-chemical properties for each compound in comparison to measurements. The approach eliminates large discrepancies between computed and measured bulk and surface properties of up to 2 orders of magnitude using other parametrization protocols and increases the transferability of the parameters by introducing thermodynamic consistency. As a result, a wide range of properties can be computed in quantitative agreement with experiment, including densities, surface energies, solid-water interface tensions, anisotropies of interfacial energies of different crystal facets, adsorption energies of biomolecules, and thermal and mechanical properties. Applications include insight into the assembly of inorganic-organic multiphase materials, the recognition of inorganic facets by biomolecules, growth and shape preferences of nanocrystals and nanoparticles, as well as thermal transitions and

A simulation of atomic force microscope microcantilever in the tapping mode utilizing couple stress theory.

PubMed

Abbasi, Mohammad

2018-04-01

The nonlinear vibration behavior of a Tapping mode atomic force microscopy (TM-AFM) microcantilever under acoustic excitation force has been modeled and investigated. In dynamic AFM, the tip-surface interactions are strongly nonlinear, rapidly changing and hysteretic. First, the governing differential equation of motion and boundary conditions for dynamic analysis are obtained using the modified couple stress theory. Afterwards, closed-form expressions for nonlinear frequency and effective nonlinear damping ratio are derived utilizing perturbation method. The effect of tip connection position on the vibration behavior of the microcantilever are also analyzed. The results show that nonlinear frequency is size dependent. According to the results, an increase in the equilibrium separation between the tip and the sample surface reduces the overall effect of van der Waals forces on the nonlinear frequency, but its effect on the effective nonlinear damping ratio is negligible. The results also indicate that both the change in the distance between tip and cantilever free end and the reduction of tip radius have significant effects on the accuracy and sensitivity of the TM-AFM in the measurement of surface forces. The hysteretic behavior has been observed in the near resonance frequency response due to softening and hardening of the forced vibration response. Copyright © 2018 Elsevier Ltd. All rights reserved.

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures

PubMed Central

Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M.; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J.; Li, Lain-Jong; Wallace, Robert M.; Datta, Suman; Robinson, Joshua A.

2015-01-01

Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2–WSe2–graphene and WSe2–MoS2–graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics. PMID:26088295

Porous silicon film formation from silicon-nanoparticle inks: The possibility of effects of van der Waals interactions on uniform film formation

NASA Astrophysics Data System (ADS)

Tanaka, Kazuki; Nagoya, Wataru; Moriki, Kazuya; Sato, Seiichi

2018-02-01

Porous Si films were formed on electrically insulative, semiconductive, and conductive substrates by depositing aqueous and nonaqueous Si nanoparticle inks. In this study, we focused on whether the Si ink deposition resulted in the formation of uniform porous Si films on various substrates. As a result of the experiments, we found that the inks showing better substrate wettabilities did not necessarily result in more uniform film formation on the substrates. This implies that the ink-solvent wettability and the nanoparticle-substrate interactions play important roles in the uniform film formation. As one of the interactions, we discussed the influence of van der Waals interactions by calculating the Hamaker constants. The calculation results indicated that the uniform film formation was hampered when the nanoparticle surface had a repulsive van der Waals interaction with the substrate.

Sensitivity study of cloud parameterizations with relative dispersion in CAM5.1: impacts on aerosol indirect effects

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

Xie, Xiaoning; Zhang, He; Liu, Xiaodong

Aerosol-induced increase of relative dispersion of cloud droplet size distribution ε exerts a warming effect and partly offsets the cooling of aerosol indirect radiative forcing (AIF) associated with increased droplet concentration by increasing the cloud droplet effective radius ( R e) and enhancing the cloud-to-rain autoconversion rate (Au) (labeled aBut, the total dispersion effects on both R e and Au are not fully considered in most GCMs, especially in different versions of the Community Atmospheric Model (CAM). Furthermore, in order to accurately evaluate the dispersion effect on AIF, the new complete cloud parameterizations of R e and Au explicitly accountingmore » for ε are implemented into the CAM version 5.1 (CAM5.1), and a suite of sensitivity experiments is conducted with different representations of ε reported in the literature. It is shown that the shortwave cloud radiative forcing is much better simulated with the new cloud parameterizations as compared to the standard scheme in CAM5.1, whereas the influences on longwave cloud radiative forcing and surface precipitation are minimal. In addition, consideration of the dispersion effect can significantly reduce the changes induced by anthropogenic aerosols in the cloud-top effective radius and the liquid water path, especially in the Northern Hemisphere. The corresponding AIF with the dispersion effect considered can also be reduced substantially by a range of 0.10 to 0.21 W m -2 at the global scale and by a much bigger margin of 0.25 to 0.39 W m -2 for the Northern Hemisphere in comparison with that of fixed relative dispersion, mainly dependent on the change of relative dispersion and droplet concentrations (Δε/ΔN).« less

Sensitivity study of cloud parameterizations with relative dispersion in CAM5.1: impacts on aerosol indirect effects

DOE PAGES

Xie, Xiaoning; Zhang, He; Liu, Xiaodong; ...

2017-05-12

Aerosol-induced increase of relative dispersion of cloud droplet size distribution ε exerts a warming effect and partly offsets the cooling of aerosol indirect radiative forcing (AIF) associated with increased droplet concentration by increasing the cloud droplet effective radius ( R e) and enhancing the cloud-to-rain autoconversion rate (Au) (labeled aBut, the total dispersion effects on both R e and Au are not fully considered in most GCMs, especially in different versions of the Community Atmospheric Model (CAM). Furthermore, in order to accurately evaluate the dispersion effect on AIF, the new complete cloud parameterizations of R e and Au explicitly accountingmore » for ε are implemented into the CAM version 5.1 (CAM5.1), and a suite of sensitivity experiments is conducted with different representations of ε reported in the literature. It is shown that the shortwave cloud radiative forcing is much better simulated with the new cloud parameterizations as compared to the standard scheme in CAM5.1, whereas the influences on longwave cloud radiative forcing and surface precipitation are minimal. In addition, consideration of the dispersion effect can significantly reduce the changes induced by anthropogenic aerosols in the cloud-top effective radius and the liquid water path, especially in the Northern Hemisphere. The corresponding AIF with the dispersion effect considered can also be reduced substantially by a range of 0.10 to 0.21 W m -2 at the global scale and by a much bigger margin of 0.25 to 0.39 W m -2 for the Northern Hemisphere in comparison with that of fixed relative dispersion, mainly dependent on the change of relative dispersion and droplet concentrations (Δε/ΔN).« less

Interfacial interaction track of amorphous solid dispersions established by water-soluble polymer and indometacin.

PubMed

Li, Jing; Fan, Na; Wang, Xin; Li, Chang; Sun, Mengchi; Wang, Jian; Fu, Qiang; He, Zhonggui

2017-08-30

The present work studied interfacial interactions of amorphous solid dispersions matrix of indometacin (IMC) that established using PVP K30 (PVP) and PEG 6000 (PEG) by focusing on their interaction forces and wetting process. Infrared spectroscopy (IR), raman spectroscopy, X-ray photoelectron spectra and contact angle instrument were used throughout the study. Hydrogen bond energy formed between PEG and IMC were stronger than that of PVP and IMC evidenced by molecular modeling measurement. The blue shift of raman spectroscopy confirmed that hydrogen bonding forces were formed between IMC and two polymers. The contact angle study can be used as an easy method to determine the dissolution mechanism of amorphous solid dispersions through fitting the profile of contact angle of water on a series of tablets. It is believed that the track of interfacial interactions will certainly become powerful tools to for designing and evaluating amorphous solid dispersions. Copyright © 2017 Elsevier B.V. All rights reserved.

Dispersion corrected hartree-fock and density functional theory for organic crystal structure prediction.

PubMed

Brandenburg, Jan Gerit; Grimme, Stefan

2014-01-01

We present and evaluate dispersion corrected Hartree-Fock (HF) and Density Functional Theory (DFT) based quantum chemical methods for organic crystal structure prediction. The necessity of correcting for missing long-range electron correlation, also known as van der Waals (vdW) interaction, is pointed out and some methodological issues such as inclusion of three-body dispersion terms are discussed. One of the most efficient and widely used methods is the semi-classical dispersion correction D3. Its applicability for the calculation of sublimation energies is investigated for the benchmark set X23 consisting of 23 small organic crystals. For PBE-D3 the mean absolute deviation (MAD) is below the estimated experimental uncertainty of 1.3 kcal/mol. For two larger π-systems, the equilibrium crystal geometry is investigated and very good agreement with experimental data is found. Since these calculations are carried out with huge plane-wave basis sets they are rather time consuming and routinely applicable only to systems with less than about 200 atoms in the unit cell. Aiming at crystal structure prediction, which involves screening of many structures, a pre-sorting with faster methods is mandatory. Small, atom-centered basis sets can speed up the computation significantly but they suffer greatly from basis set errors. We present the recently developed geometrical counterpoise correction gCP. It is a fast semi-empirical method which corrects for most of the inter- and intramolecular basis set superposition error. For HF calculations with nearly minimal basis sets, we additionally correct for short-range basis incompleteness. We combine all three terms in the HF-3c denoted scheme which performs very well for the X23 sublimation energies with an MAD of only 1.5 kcal/mol, which is close to the huge basis set DFT-D3 result.

Non-pairwise additivity of the leading-order dispersion energy

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

Hollett, Joshua W., E-mail: j.hollett@uwinnipeg.ca

2015-02-28

The leading-order (i.e., dipole-dipole) dispersion energy is calculated for one-dimensional (1D) and two-dimensional (2D) infinite lattices, and an infinite 1D array of infinitely long lines, of doubly occupied locally harmonic wells. The dispersion energy is decomposed into pairwise and non-pairwise additive components. By varying the force constant and separation of the wells, the non-pairwise additive contribution to the dispersion energy is shown to depend on the overlap of density between neighboring wells. As well separation is increased, the non-pairwise additivity of the dispersion energy decays. The different rates of decay for 1D and 2D lattices of wells is explained inmore » terms of a Jacobian effect that influences the number of nearest neighbors. For an array of infinitely long lines of wells spaced 5 bohrs apart, and an inter-well spacing of 3 bohrs within a line, the non-pairwise additive component of the leading-order dispersion energy is −0.11 kJ mol{sup −1} well{sup −1}, which is 7% of the total. The polarizability of the wells and the density overlap between them are small in comparison to that of the atomic densities that arise from the molecular density partitioning used in post-density-functional theory (DFT) damped dispersion corrections, or DFT-D methods. Therefore, the nonadditivity of the leading-order dispersion observed here is a conservative estimate of that in molecular clusters.« less

van der Waals Heterostructures with High Accuracy Rotational Alignment.

PubMed

Kim, Kyounghwan; Yankowitz, Matthew; Fallahazad, Babak; Kang, Sangwoo; Movva, Hema C P; Huang, Shengqiang; Larentis, Stefano; Corbet, Chris M; Taniguchi, Takashi; Watanabe, Kenji; Banerjee, Sanjay K; LeRoy, Brian J; Tutuc, Emanuel

2016-03-09

We describe the realization of van der Waals (vdW) heterostructures with accurate rotational alignment of individual layer crystal axes. We illustrate the approach by demonstrating a Bernal-stacked bilayer graphene formed using successive transfers of monolayer graphene flakes. The Raman spectra of this artificial bilayer graphene possess a wide 2D band, which is best fit by four Lorentzians, consistent with Bernal stacking. Scanning tunneling microscopy reveals no moiré pattern on the artificial bilayer graphene, and tunneling spectroscopy as a function of gate voltage reveals a constant density of states, also in agreement with Bernal stacking. In addition, electron transport probed in dual-gated samples reveals a band gap opening as a function of transverse electric field. To illustrate the applicability of this technique to realize vdW heterostructuctures in which the functionality is critically dependent on rotational alignment, we demonstrate resonant tunneling double bilayer graphene heterostructures separated by hexagonal boron-nitride dielectric.

Infrared photodetectors based on graphene van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Ryzhii, V.; Ryzhii, M.; Svintsov, D.; Leiman, V.; Mitin, V.; Shur, M. S.; Otsuji, T.

2017-08-01

We propose and evaluate the graphene layer (GL) infrared photodetectors (GLIPs) based on the van der Waals (vdW) heterostructures with the radiation absorbing GLs. The operation of the GLIPs is associated with the electron photoexcitation from the GL valence band to the continuum states above the inter-GL barriers (either via tunneling or direct transitions to the continuum states). Using the developed device model, we calculate the photodetector characteristics as functions of the GL-vdW heterostructure parameters. We show that due to a relatively large efficiency of the electron photoexcitation and low capture efficiency of the electrons propagating over the barriers in the inter-GL layers, GLIPs should exhibit the elevated photoelectric gain and detector responsivity as well as relatively high detectivity. The possibility of high-speed operation, high conductivity, transparency of the GLIP contact layers, and the sensitivity to normally incident IR radiation provides additional potential advantages in comparison with other IR photodetectors. In particular, the proposed GLIPs can compete with unitravelling-carrier photodetectors.

Crossing the front: contrasting storm-forced dispersal dynamics revealed by biological, geological and genetic analysis of beach-cast kelp.

PubMed

Waters, Jonathan M; King, Tania M; Fraser, Ceridwen I; Craw, Dave

2018-03-01

The subtropical front (STF) generally represents a substantial oceanographic barrier to dispersal between cold-sub-Antarctic and warm-temperate water masses. Recent studies have suggested that storm events can drastically influence marine dispersal and patterns. Here we analyse biological and geological dispersal driven by two major, contrasting storm events in southern New Zealand, 2017. We integrate biological and physical data to show that a severe southerly system in July 2017 disrupted this barrier by promoting movement of substantial numbers of southern sub-Antarctic Durvillaea kelp rafts across the STF, to make landfall in mainland NZ. By contrast, a less intense easterly storm (Cyclone Cook, April 2017) resulted in more moderate dispersal distances, with minimal dispersal between the sub-Antarctic and mainland New Zealand. These quantitative analyses of approximately 200 freshly beach-cast kelp specimens indicate that storm intensity and wind direction can strongly influence marine dispersal and landfall outcomes. © 2018 The Author(s).

Pair mobility functions for rigid spheres in concentrated colloidal dispersions: Force, torque, translation, and rotation

NASA Astrophysics Data System (ADS)

Zia, Roseanna N.; Swan, James W.; Su, Yu

2015-12-01

The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations is the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16-29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375-400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1-29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to particle translation

Pair mobility functions for rigid spheres in concentrated colloidal dispersions: Force, torque, translation, and rotation.

PubMed

Zia, Roseanna N; Swan, James W; Su, Yu

2015-12-14

The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations is the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16-29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375-400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1-29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to particle translation

Pair mobility functions for rigid spheres in concentrated colloidal dispersions: Force, torque, translation, and rotation

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

Zia, Roseanna N., E-mail: zia@cbe.cornell.edu; Su, Yu; Swan, James W.

2015-12-14

The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations ismore » the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261–290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16–29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375–400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1–29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to

Recent progress in the assembly of nanodevices and van der Waals heterostructures by deterministic placement of 2D materials.

PubMed

Frisenda, Riccardo; Navarro-Moratalla, Efrén; Gant, Patricia; Pérez De Lara, David; Jarillo-Herrero, Pablo; Gorbachev, Roman V; Castellanos-Gomez, Andres

2018-01-02

Designer heterostructures can now be assembled layer-by-layer with unmatched precision thanks to the recently developed deterministic placement methods to transfer two-dimensional (2D) materials. This possibility constitutes the birth of a very active research field on the so-called van der Waals heterostructures. Moreover, these deterministic placement methods also open the door to fabricate complex devices, which would be otherwise very difficult to achieve by conventional bottom-up nanofabrication approaches, and to fabricate fully-encapsulated devices with exquisite electronic properties. The integration of 2D materials with existing technologies such as photonic and superconducting waveguides and fiber optics is another exciting possibility. Here, we review the state-of-the-art of the deterministic placement methods, describing and comparing the different alternative methods available in the literature, and we illustrate their potential to fabricate van der Waals heterostructures, to integrate 2D materials into complex devices and to fabricate artificial bilayer structures where the layers present a user-defined rotational twisting angle.

Carbon nanotube dispersed conductive network for microbial fuel cells

NASA Astrophysics Data System (ADS)

Matsumoto, S.; Yamanaka, K.; Ogikubo, H.; Akasaka, H.; Ohtake, N.

2014-08-01

Microbial fuel cells (MFCs) are promising devices for capturing biomass energy. Although they have recently attracted considerable attention, their power densities are too low for practical use. Increasing their electrode surface area is a key factor for improving the performance of MFC. Carbon nanotubes (CNTs), which have excellent electrical conductivity and extremely high specific surface area, are promising materials for electrodes. However, CNTs are insoluble in aqueous solution because of their strong intertube van der Waals interactions, which make practical use of CNTs difficult. In this study, we revealed that CNTs have a strong interaction with Saccharomyces cerevisiae cells. CNTs attach to the cells and are dispersed in a mixture of water and S. cerevisiae, forming a three-dimensional CNT conductive network. Compared with a conventional two-dimensional electrode, such as carbon paper, the three-dimensional conductive network has a much larger surface area. By applying this conductive network to MFCs as an anode electrode, power density is increased to 176 μW/cm2, which is approximately 25-fold higher than that in the case without CNTs addition. Maximum current density is also increased to approximately 8-fold higher. These results suggest that three-dimensional CNT conductive network contributes to improve the performance of MFC by increasing surface area.

Electrostatic forces in planetary rings

NASA Technical Reports Server (NTRS)

Goertz, C. K.; Shan, Linhua; Havnes, O.

1988-01-01

The average charge on a particle in a particle-plasma cloud, the plasma potential inside the cloud, and the Coulomb force acting on the particle are calculated. The net repulsive electrostatic force on a particle depends on the plasma density, temperature, density of particles, particle size, and the gradient of the particle density. In a uniformly dense ring the electrostatic repulsion is zero. It is also shown that the electrostatic force acts like a pressure force, that even a collisionless ring can be stable against gravitational collapse, and that a finite ring thickness does not necessarily imply a finite velocity dispersion. A simple criterion for the importance of electrostatic forces in planetary rings is derived which involves the calculation of the vertical ring thickness which would result if only electrostatic repulsion were responsible for the finite ring thickness. Electrostatic forces are entirely negligible in the main rings of Saturn and the E and G rings. They may also be negligible in the F ring. However, the Uranian rings and Jupiter's ring seem to be very much influenced by electrostatic repulsion. In fact, electrostatic forces could support a Jovian ring which is an order of magnitude more dense than observed.

Kinetic theory-based numerical modeling and analysis of bi-disperse segregated mixture fluidized bed

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

Konan, N. A.; Huckaby, E. D.

We discuss a series of continuum Euler-Euler simulations of an initially mixed bi-disperse fluidized bed which segregates under certain operating conditions. The simulations use the multi-phase kinetic theory-based description of the momentum and energy exchanges between the phases by Simonin’s Group [see e.g. Gourdel, Simonin and Brunier (1999). Proceedings of 6th International Conference on Circulating Fluidized Beds, Germany, pp. 205-210]. The discussion and analysis of the results focus on the fluid-particle momentum exchange (i.e. drag). Simulations using mono- and poly-disperse fluid-particle drag correlations are analyzed for the Geldart D-type size bi-disperse gas-solid experiments performed by Goldschmidt et al. [Powder Tech.,more » pp. 135-159 (2003)]. The poly-disperse gas-particle drag correlations account for the local particle size distribution by using an effective mixture diameter when calculating the Reynolds number and then correcting the resulting force coefficient. Simulation results show very good predictions of the segregation index for bidisperse beds with the mono-disperse drag correlations contrary to the poly-disperse drag correlations for which the segregation rate is systematically under-predicted. The statistical analysis of the results shows a clear separation in the distribution of the gas-particle mean relaxation times of the small and large particles with simulations using the mono-disperse drag. In contrast, the poly-disperse drag simulations have a significant overlap and also a smaller difference in the mean particle relaxation times. This results in the small and large particles in the bed to respond to the gas similarly without enough relative time lag. The results suggest that the difference in the particle response time induce flow dynamics favorable to a force imbalance which results in the segregation.« less

Kinetic theory-based numerical modeling and analysis of bi-disperse segregated mixture fluidized bed

DOE PAGES

Konan, N. A.; Huckaby, E. D.

2017-06-21

We discuss a series of continuum Euler-Euler simulations of an initially mixed bi-disperse fluidized bed which segregates under certain operating conditions. The simulations use the multi-phase kinetic theory-based description of the momentum and energy exchanges between the phases by Simonin’s Group [see e.g. Gourdel, Simonin and Brunier (1999). Proceedings of 6th International Conference on Circulating Fluidized Beds, Germany, pp. 205-210]. The discussion and analysis of the results focus on the fluid-particle momentum exchange (i.e. drag). Simulations using mono- and poly-disperse fluid-particle drag correlations are analyzed for the Geldart D-type size bi-disperse gas-solid experiments performed by Goldschmidt et al. [Powder Tech.,more » pp. 135-159 (2003)]. The poly-disperse gas-particle drag correlations account for the local particle size distribution by using an effective mixture diameter when calculating the Reynolds number and then correcting the resulting force coefficient. Simulation results show very good predictions of the segregation index for bidisperse beds with the mono-disperse drag correlations contrary to the poly-disperse drag correlations for which the segregation rate is systematically under-predicted. The statistical analysis of the results shows a clear separation in the distribution of the gas-particle mean relaxation times of the small and large particles with simulations using the mono-disperse drag. In contrast, the poly-disperse drag simulations have a significant overlap and also a smaller difference in the mean particle relaxation times. This results in the small and large particles in the bed to respond to the gas similarly without enough relative time lag. The results suggest that the difference in the particle response time induce flow dynamics favorable to a force imbalance which results in the segregation.« less

Imaging Carbon Nanotubes in High Performance Polymer Composites via Magnetic Force Microscope

NASA Technical Reports Server (NTRS)

Lillehei, Peter T.; Park, Cheol; Rouse, Jason H.; Siochi, Emilie J.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

Application of carbon nanotubes as reinforcement in structural composites is dependent on the efficient dispersion of the nanotubes in a high performance polymer matrix. The characterization of such dispersion is limited by the lack of available tools to visualize the quality of the matrix/carbon nanotube interaction. The work reported herein demonstrates the use of magnetic force microscopy (MFM) as a promising technique for characterizing the dispersion of nanotubes in a high performance polymer matrix.

2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

NASA Astrophysics Data System (ADS)

Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

2017-09-01

Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

Long-range wetting transparency on top of layered metal-dielectric substrates

PubMed Central

Noginov, M. A.; Barnakov, Yuri A.; Liberman, Vladimir; Prayakarao, Srujana; Bonner, Carl E.; Narimanov, Evgenii E.

2016-01-01

It has been recently shown that scores of physical and chemical phenomena (including spontaneous emission, scattering and Förster energy transfer) can be controlled by nonlocal dielectric environments provided by metamaterials with hyperbolic dispersion and simpler metal/dielectric structures. At this time, we have researched van der Waals interactions and experimentally studied wetting of several metallic, dielectric and composite multilayered substrates. We have found that the wetting angle of water on top of MgF2 is highly sensitive to the thickness of the MgF2 layer and the nature of the underlying substrate that could be positioned as far as ~100 nm beneath the water/MgF2 interface. We refer to this phenomenon as long range wetting transparency. The latter effect cannot be described in terms of the most basic model of dispersion van der Waals-London forces based on pair-wise summation of dipole-dipole interactions across an interface or a gap separating the two media. We infer that the experimentally observed gradual change of the wetting angle with increase of the thickness of the MgF2 layer can possibly be explained by the distance dependence of the Hamaker function (describing the strength of interaction), which originates from retardation of electromagnetic waves at the distances comparable to a wavelength. PMID:27324650

Controlling exfoliation in order to minimize damage during dispersion of long SWCNTs for advanced composites

PubMed Central

Yoon, Howon; Yamashita, Motoi; Ata, Seisuke; Futaba, Don N.; Yamada, Takeo; Hata, Kenji

2014-01-01

We propose an approach to disperse long single-wall carbon nanotubes (SWCNTs) in a manner that is most suitable for the fabrication of high-performance composites. We compare three general classes of dispersion mechanisms, which encompass 11 different dispersion methods, and we have dispersed long SWCNTs, short multi-wall carbon nanotubes, and short SWCNTs in order to understand the most appropriate dispersion methods for the different types of CNTs. From this study, we have found that the turbulent flow methods, as represented by the Nanomizer and high-pressure jet mill methods, produced unique and superior dispersibility of long SWCNTs, which was advantageous for the fabrication of highly conductive composites. The results were interpreted to imply that the biaxial shearing force caused an exfoliation effect to disperse the long SWCNTs homogeneously while suppressing damage. A conceptual model was developed to explain this dispersion mechanism, which is important for future work on advanced CNT composites. PMID:24469607

Spatial seed and pollen games: dispersal, sex allocation, and the evolution of dioecy.

PubMed

Fromhage, Lutz; Kokko, Hanna

2010-09-01

The evolutionary forces shaping within- and across-species variation in the investment in male and female sex function are still incompletely understood. Despite earlier suggestions that in plants the evolution or cosexuality vs. dioecy, as well as sex allocation among cosexuals, is affected by seed and pollen dispersal, no formal model has explicitly used dispersal distances to address this problem. Here, we present a game-theory model as well as a simulation study that fills in this gap. Our model predicts that dioecy should evolve if seeds and pollen disperse widely and that sex allocation among cosexuals should be biased towards whichever sex function produces more widely dispersing units. Dispersal limitations stabilize cosexuality by reinforcing competition between spatially clumped dispersal units from the same source, leading to saturating fitness returns that render sexual specialization unprofitable. However, limited pollen dispersal can also increase the risk of selfing, thus potentially selecting for dioecy as an outbreeding mechanism. Finally, we refute a recent claim that cosexuals should always invest equally in both sex functions.

Modeling the influence of the Casimir force on the pull-in instability of nanowire-fabricated nanotweezers

NASA Astrophysics Data System (ADS)

Farrokhabadi, Amin; Mokhtari, Javad; Rach, Randolph; Abadyan, Mohamadreza

2015-09-01

The Casimir force can strongly interfere with the pull-in performance of ultra-small structures. The strength of the Casimir force is significantly affected by the geometries of interacting bodies. Previous investigators have exclusively studied the effect of the Casimir force on the electromechanical instability of nanostructures with planar geometries. However no work has yet considered this effect on the pull-in instability of systems with cylindrical geometries such as nanotweezers fabricated from nanotube/nanowires. In our present work, the influence of the Casimir attraction on the electrostatic response and pull-in instability of nanotweezers fabricated from cylindrical conductive nanowires/nanotubes is theoretically investigated. An asymptotic solution, based on scattering theory, is applied to consider the effect of vacuum fluctuations in the theoretical model. The Euler-Bernoulli beam model is employed, in conjunction with the size-dependent modified couple stress continuum theory, to derive the governing equation of the nanotweezers. The governing nonlinear equations are solved by two different approaches, i.e., the modified Adomian-Padé method (MAD-Padé) and a numerical solution. Various aspects of the problem, i.e., the variation of pull-in parameters, effect of geometry, coupling between the Casimir force and size dependency effects and comparison with the van der Waals force regime are discussed.

Dual-Gated MoTe2/MoS2 van der Waals Heterojunction p-n Diode

NASA Astrophysics Data System (ADS)

Rai, Amritesh; Movva, Hema C. P.; Kang, Sangwoo; Larentis, Stefano; Roy, Anupam; Tutuc, Emanuel; Banerjee, Sanjay K.

2D materials are promising for future electronic and optoelectronic applications. In this regard, it is important to realize p-n diodes, the most fundamental building block of all modern semiconductor devices, based on these 2D materials. While it is challenging to achieve homojunction diodes in 2D semiconductors due to lack of reliable selective doping techniques, it is relatively easier to achieve diode-like behavior in van der Waals (vdW) heterostructures comprising different 2D semiconductors. Here, we demonstrate dual-gated vdW heterojunction p-n diodes based on p-type MoTe2 and n-type MoS2, with hBN as the top and bottom gate dielectric. The heterostructure stack is assembled using a polymer-based `dry-transfer' technique. Pt contact is used for hole injection in MoTe2, whereas Ag is used for electron injection in MoS2. The dual-gates allow for independent electrostatic tuning of the carriers in MoTe2 and MoS2. Room temperature interlayer current-voltage characteristics reveal a strong gate-tunable rectification behavior. At low temperatures, the diode turn-on voltage increases, whereas the reverse saturation current decreases, in accordance with conventional p-n diode behavior. Dual-Gated MoTe2/MoS2 van der Waals Heterojunction p-n Diode.

Ab-initio study of structural and electronic properties of WS2/h-BN van der Waals heterostructure

NASA Astrophysics Data System (ADS)

Ghasemi majd, Zahra; Amiri, Peiman; Taghizadeh, Seyed Fardin

2018-06-01

First-principle calculations with different exchange-correlation functionals, including LDA, GGA, semi-empirical and ab-initio van der Waals in the forms of vdW-DF2B86R and vdW-DF2 were performed to evaluate the performance of different functionals in describing the bonding mechanism, adsorption energy and interlayer distance of WS2 monolayer on and between h-BN layers. The finding was that the vdW-DF2B86R seems to be the approach best lending itself to this purpose. In order to include the van der Waals (vdW) interactions in our calculations, we used the DFT-D2 and vdW methods, which gave rise to a physical adsorption with no net charge transfer between the WS2 layer and the corresponding substrates. In addition, we investigated the electronic and structural properties of WS2 and h-BN heterolayers, using vdW-DF2B86R functional. Based on density functional theory calculations, WS2 on and between h-BN layers showed a direct band gap at the K-point, which was experimentally observed.

When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures.

PubMed

Gobbi, Marco; Orgiu, Emanuele; Samorì, Paolo

2018-05-01

van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on-demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self-assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Schottky barrier in van der Waals heterostructures of graphene and g-GaN

NASA Astrophysics Data System (ADS)

Sun, Minglei; Chou, Jyh-Pin; Ren, Qingqiang; Zhao, Yiming; Yu, Jin; Tang, Wencheng

2017-04-01

Using first-principles calculations, we systematically investigated the electronic properties of graphene/g-GaN van der Waals (vdW) heterostructures. We discovered that the Dirac cone of graphene could be quite well preserved in the vdW heterostructures. Moreover, a transition from an n-type to p-type Schottky contact at the graphene/g-GaN interface was induced with a decreased interlayer distance from 4.5 to 2.5 Å. This relationship is expected to enable effective control of the Schottky barrier, which is an important development in the design of Schottky devices.

Optimizing Dispersed Air Operations: A Concept To Use Highways As Improved Airfields In A Contested Environment

DTIC Science & Technology

2015-04-01

capability to conduct airfield surveys outside of a permissive environment. Optimizing the Rapid Raptor Forward Arming and Refueling Point (FARP...9] An Initial Approach at Dispersing Air Operations: Rapid Raptor Concept ................... [12] Rapid Raptor : Optimized...Approach at Dispersing Air Operations: Rapid Raptor Concept The Air Force Rapid Raptor Fighter Forward Arming and Refueling (FARP) concept is an

Force Generation by Flapping Foils

NASA Astrophysics Data System (ADS)

Bandyopadhyay, P. R.; Donnelly, M.

1996-11-01

Aquatic animals like fish use flapping caudal fins to produce axial and cross-stream forces. During WW2, German scientists had built and tested an underwater vehicle powered by similar flapping foils. We have examined the forces produced by a pair of flapping foils. We have examined the forced produced by a pair of flapping foils attached to the tail end of a small axisymmetric cylinder. The foils operate in-phase (called waving), or in anti-phase (called clapping). In a low-speed water tunnel, we have undertaken time-dependent measurements of axial and cross-stream forces and moments that are exerted by the vortex shedding process over the entire body. Phase-matched LDV measurements of vorticity-velocity vectors, as well as limited flow visualization of the periodic vortex shedding process have also been carried out. The direction of the induced velocity within a pair of shed vortices determines the nature of the forces produced, viz., thrust or drag or cross-stream forces. The clapping mode produces a widely dispersed symmetric array of vortices which results in axial forces only (thrust and rag). On the other hand, the vortex array is staggered in the waving mode and cross-stream (maneuvering) forces are then generated.

Van der Waals heterojunction diode composed of WS2 flake placed on p-type Si substrate

NASA Astrophysics Data System (ADS)

Aftab, Sikandar; Farooq Khan, M.; Min, Kyung-Ah; Nazir, Ghazanfar; Afzal, Amir Muhammad; Dastgeer, Ghulam; Akhtar, Imtisal; Seo, Yongho; Hong, Suklyun; Eom, Jonghwa

2018-01-01

P-N junctions represent the fundamental building blocks of most semiconductors for optoelectronic functions. This work demonstrates a technique for forming a WS2/Si van der Waals junction based on mechanical exfoliation. Multilayered WS2 nanoflakes were exfoliated on the surface of bulk p-type Si substrates using a polydimethylsiloxane stamp. We found that the fabricated WS2/Si p-n junctions exhibited rectifying characteristics. We studied the effect of annealing processes on the performance of the WS2/Si van der Waals p-n junction and demonstrated that annealing improved its electrical characteristics. However, devices with vacuum annealing have an enhanced forward-bias current compared to those annealed in a gaseous environment. We also studied the top-gate-tunable rectification characteristics across the p-n junction interface in experiments as well as density functional theory calculations. Under various temperatures, Zener breakdown occurred at low reverse-bias voltages, and its breakdown voltage exhibited a negative coefficient of temperature. Another breakdown voltage was observed, which increased with temperature, suggesting a positive coefficient of temperature. Therefore, such a breakdown can be assigned to avalanche breakdown. This work demonstrates a promising application of two-dimensional materials placed directly on conventional bulk Si substrates.

Effect of relative humidity on onset of capillary forces for rough surfaces.

PubMed

Zarate, Nyah V; Harrison, Aaron J; Litster, James D; Beaudoin, Stephen P

2013-12-01

Atomic force microscopy (AFM) was used to investigate the effect of relative humidity (RH) on the adhesion forces between silicon nitride AFM probes, hydrophilic stainless steel, and hydrophobic Perspex® (polymethylmethacrylate, PMMA). In addition, AFM-based phase contrast imaging was used to quantify the amount and location of adsorbed water present on these substrates at RH levels ranging from 15% to 65% at 22°C. Both the adhesion forces and the quantities of adsorbed moisture were seen to vary with RH, and the nature of this variation depended on the hydrophobicity of the substrate. For the Perspex®, both the adhesion force and the amount of adsorbed moisture were essentially independent of RH. For the stainless steel substrate, adsorbed moisture increased continuously with increasing RH, while the adhesion force rose from a minimum at 15% RH to a broad maximum between 25% and 35% RH. From 35% to 55% RH, the adhesion force dropped continuously to an intermediate level before rising again as 65% RH was approached. The changes in adhesion force with increasing relative humidity in the case of the stainless steel substrate were attributed to a balance of effects associated with adsorbed, sub-continuum water on the cantilever and steel. Hydrogen bonding interactions between these adsorbed water molecules were thought to increase the adhesion force. However, when significant quantities of molecular water adsorbed, these molecules were expect to decrease adhesion by screening the van der Waals interactions between the steel and the cantilever tip, and by increasing the separation distance between these solid surfaces when they were 'in contact'. Finally, the slight increase in adhesion between 55% and 65% RH was attributed to true capillary forces exerted by continuum water on the two solid surfaces. Copyright © 2013 Elsevier Inc. All rights reserved.

Dispersion in deep polar firn driven by synoptic-scale surface pressure variability

NASA Astrophysics Data System (ADS)

Buizert, Christo; Severinghaus, Jeffrey P.

2016-09-01

Commonly, three mechanisms of firn air transport are distinguished: molecular diffusion, advection, and near-surface convective mixing. Here we identify and describe a fourth mechanism, namely dispersion driven by synoptic-scale surface pressure variability (or barometric pumping). We use published gas chromatography experiments on firn samples to derive the along-flow dispersivity of firn, and combine this dispersivity with a dynamical air pressure propagation model forced by surface air pressure time series to estimate the magnitude of dispersive mixing in the firn. We show that dispersion dominates mixing within the firn lock-in zone. Trace gas concentrations measured in firn air samples from various polar sites confirm that dispersive mixing occurs. Including dispersive mixing in a firn air transport model suggests that our theoretical estimates have the correct order of magnitude, yet may overestimate the true dispersion. We further show that strong barometric pumping, such as at the Law Dome site, may reduce the gravitational enrichment of δ15N-N2 and other tracers below gravitational equilibrium, questioning the traditional definition of the lock-in depth as the depth where δ15N enrichment ceases. Last, we propose that 86Kr excess may act as a proxy for past synoptic activity (or paleo-storminess) at the site.

Interfacial force field characterization of a constrained vapor bubble thermosyphon using IAI

NASA Technical Reports Server (NTRS)

Dasgupta, Sunando; Plawsky, Joel L.; Wayner, Peter C., Jr.

1994-01-01

The isothermal profiles of the extended meniscus in a quartz cuvette were measured in a gravitational field using IAI (image analyzing interferometer) which is based on computer enhanced video microscopy of the naturally occurring interference fringes. The experimental results for heptane and pentane menisci were analyzed using the extended Young-Laplace Equation. These isothermal results characterized the interfacial force field in-situ at the start of the heat transfer experiments by quantifying the dispersion constant for the specific liquid-solid system. The experimentally obtained values of the disjoining pressures and the dispersion constants are compared to the subsequent non-isothermal experiments because one of the major variables in the heat sink capability of the CVBT is the dispersion constant. In all previous studies of micro heat pipes the value of the dispersion constant has been 'guesstimated'. The major advantages of the current glass cell is the ability to view the extended meniscus at all times. Experimentally, we find that the extended Young-Laplace Equation is an excellent model for for the force field at the solid-liquid vapor interfaces.

Interplay of temperature, spatial dispersion, and topology in silicene Casimir interactions

NASA Astrophysics Data System (ADS)

Woods, Lilia; Rodriguez-Lopez, Pablo; Kort-Kamp, Wilton; Dalvit, Diego

Graphene materials have given an impetus to the field of electromagnetic fluctuation interactions, such as Casimir forces. The discovery of unusual distance asymptotics, pronounced thermal effects, and strong dependence on the chemical potential in graphene Casimir interactions have shown new directions for control of this universal force. Recently discovered silicene, a graphene-like material with staggered lattice and significant spin-orbit coupling, offers new opportunities to re-evaluate these unusual Casimir interaction functionalities. Utilizing the Lifshitz formalism we investigate how the spatial dispersion and temperature affect the Casimir interaction in silicene undergoing various topological phase transitions under an applied electric field and laser illumination. This study is facilitated by the comprehensive examination of the conductivity components calculated via the Kubo formalism. We show that the interplay between temperature, spatial dispersion, and topology result in novel features in Casimir interactions involving staggered graphene-like lattices. Support from the US Department of Energy under Grant Number DE-FG02-06ER46297 and the LANL LDRD program is acknowledged.

Polymer Nanocomposite Films: Dispersion of Polymer Grafted Nanorods and Optical Properties

NASA Astrophysics Data System (ADS)

Composto, Russell

2013-03-01

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NR) in polymer matrix films have been studied by experiment and theory. When brush and matrix have a favorable interaction, such as poly(ethylene oxide) (PEO)-NR/ poly(methyl methacrylate) (PMMA) and polystyrene (PS)-NR / poly(2,6-dimethyl-p-phenylene oxide) (PPO), nanorods are uniformly dispersed. For PEO-NRs in PMMA, the NRs are regularly spaced and well dispersed, independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), namely P/N. As the NR volume fraction increases, the local orientation of the nanorods increases, whereas the macroscopic orientation remains isotropic. When the brush and matrix are similar (i.e., PS-NR / PS and PEO-NR / PEO), the nanorods randomly disperse for P/N < 2 (i.e., wet brush), but align side-by-side in aggregates for P/N > 2. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that surface plasmon coupling leads to a blue shift in the longitudinal surface plasmon resonance (LSPR) as P/N increases. For P/N > 2, self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations indicate that nanorod aggregation is caused by depletion-attraction forces. Starting with a dry brush system, namely, a PS matrix where P/N = 30, these attractive forces can be mediated by adding a compatibilizing agent (e.g., PPO) that drives the NRs to disperse. Finally, dry and wet brush behavior is observed for NR aspect ratios varying from 2.5 to 7. However, compared at the same volume fraction, long rods for the dry case exhibit much better local order than lower aspect ratio nanorods, suggesting that long rods may exhibit nematic-like ordering at higher loadings. NSF Polymer and CEMRI Programs.

Two-Dimensional Semiconductor Optoelectronics Based on van der Waals Heterostructures.

PubMed

Lee, Jae Yoon; Shin, Jun-Hwan; Lee, Gwan-Hyoung; Lee, Chul-Ho

2016-10-27

Two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDCs) and black phosphorous have drawn tremendous attention as an emerging optical material due to their unique and remarkable optical properties. In addition, the ability to create the atomically-controlled van der Waals (vdW) heterostructures enables realizing novel optoelectronic devices that are distinct from conventional bulk counterparts. In this short review, we first present the atomic and electronic structures of 2D semiconducting TMDCs and their exceptional optical properties, and further discuss the fabrication and distinctive features of vdW heterostructures assembled from different kinds of 2D materials with various physical properties. We then focus on reviewing the recent progress on the fabrication of 2D semiconductor optoelectronic devices based on vdW heterostructures including photodetectors, solar cells, and light-emitting devices. Finally, we highlight the perspectives and challenges of optoelectronics based on 2D semiconductor heterostructures.

Two-Dimensional Semiconductor Optoelectronics Based on van der Waals Heterostructures

PubMed Central

Lee, Jae Yoon; Shin, Jun-Hwan; Lee, Gwan-Hyoung; Lee, Chul-Ho

2016-01-01

Two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDCs) and black phosphorous have drawn tremendous attention as an emerging optical material due to their unique and remarkable optical properties. In addition, the ability to create the atomically-controlled van der Waals (vdW) heterostructures enables realizing novel optoelectronic devices that are distinct from conventional bulk counterparts. In this short review, we first present the atomic and electronic structures of 2D semiconducting TMDCs and their exceptional optical properties, and further discuss the fabrication and distinctive features of vdW heterostructures assembled from different kinds of 2D materials with various physical properties. We then focus on reviewing the recent progress on the fabrication of 2D semiconductor optoelectronic devices based on vdW heterostructures including photodetectors, solar cells, and light-emitting devices. Finally, we highlight the perspectives and challenges of optoelectronics based on 2D semiconductor heterostructures. PMID:28335321

Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures

DOE PAGES

Song, Tiancheng; Cai, Xinghan; Tu, Matisse Wei-Yuan; ...

2018-05-03

Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI3) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance which is drastically enhanced with increasing CrI 3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI 3. In conclusion, ourmore » work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI 3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.« less

Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures

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

Song, Tiancheng; Cai, Xinghan; Tu, Matisse Wei-Yuan

Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI3) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance which is drastically enhanced with increasing CrI 3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI 3. In conclusion, ourmore » work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI 3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.« less

Graphene Casimir Interactions and Some Possible Applications

NASA Astrophysics Data System (ADS)

Phan, Anh D.

Scientific development requires profound understandings of micromechanical and nanomechanical systems (MEMS/NEMS) due to their applications not only in the technological world, but also for scientific understanding. At the micro- or nano-scale, when two objects are brought close together, the existence of stiction or adhesion is inevitable and plays an important role in the behavior operation of these systems. Such effects are due to surface dispersion forces, such as the van der Waals or Casimir interactions. The scientific understanding of these forces is particularly important for low-dimensional materials. In addition, the discovery of materials, such as graphitic systems has provided opportunities for new classes of devices and challenging fundamental problems. Therefore, investigations of the van der Waals or Caismir forces in graphene-based systems, in particular, and the solution generating non-touching systems are needed. In this study, the Casimir force involving 2D graphene is investigated under various conditions. The Casimir interaction is usually studied in the framework of the Lifshitz theory. According to this theory, it is essential to know the frequency-dependent reflection coefficients of materials. Here, it is found that the graphene reflection coefficients strongly depend on the optical conductivity of graphene, which is described by the Kubo formalism. When objects are placed in vacuum, the Casimir force is attractive and leads to adhesion on the surface. We find that the Casimir repulsion can be obtained by replacing vacuum with a suitable liquid. Our studies show that bromobenzene is the liquid providing this effect. We also find that this long-range force is temperature dependent and graphene/bromobenzene/metal substrate configuration can be used to demonstrate merely thermal Casimir interaction at room temperature and micrometer distances. These findings would provide good guidance and predictions for practical studies.

Inelastic neutron scattering, Raman, vibrational analysis with anharmonic corrections, and scaled quantum mechanical force field for polycrystalline L-alanine

NASA Astrophysics Data System (ADS)

Williams, Robert W.; Schlücker, Sebastian; Hudson, Bruce S.

2008-01-01

A scaled quantum mechanical harmonic force field (SQMFF) corrected for anharmonicity is obtained for the 23 K L-alanine crystal structure using van der Waals corrected periodic boundary condition density functional theory (DFT) calculations with the PBE functional. Scale factors are obtained with comparisons to inelastic neutron scattering (INS), Raman, and FT-IR spectra of polycrystalline L-alanine at 15-23 K. Calculated frequencies for all 153 normal modes differ from observed frequencies with a standard deviation of 6 wavenumbers. Non-bonded external k = 0 lattice modes are included, but assignments to these modes are presently ambiguous. The extension of SQMFF methodology to lattice modes is new, as are the procedures used here for providing corrections for anharmonicity and van der Waals interactions in DFT calculations on crystals. First principles Born-Oppenheimer molecular dynamics (BOMD) calculations are performed on the L-alanine crystal structure at a series of classical temperatures ranging from 23 K to 600 K. Corrections for zero-point energy (ZPE) are estimated by finding the classical temperature that reproduces the mean square displacements (MSDs) measured from the diffraction data at 23 K. External k = 0 lattice motions are weakly coupled to bonded internal modes.

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy

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

Krajina, Brad A.; Kocherlakota, Lakshmi S.; Overney, René M., E-mail: roverney@u.washington.edu

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO{sub 2}) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS{sub 2}) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called “intrinsic friction analysis” (IFA) provided direct access to the Hamaker constants for HOPG and MoS{sub 2}, as well as the control sample, calcium fluoride (CaF{sub 2}). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with largermore » scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.« less

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy

NASA Astrophysics Data System (ADS)

Krajina, Brad A.; Kocherlakota, Lakshmi S.; Overney, René M.

2014-10-01

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO2) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS2) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called "intrinsic friction analysis" (IFA) provided direct access to the Hamaker constants for HOPG and MoS2, as well as the control sample, calcium fluoride (CaF2). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with larger scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy.

PubMed

Krajina, Brad A; Kocherlakota, Lakshmi S; Overney, René M

2014-10-28

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO2) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS2) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called "intrinsic friction analysis" (IFA) provided direct access to the Hamaker constants for HOPG and MoS2, as well as the control sample, calcium fluoride (CaF2). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with larger scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.

Adsorption of DNA/RNA nucleobases onto single-layer MoS2 and Li-Doped MoS2: A dispersion-corrected DFT study

NASA Astrophysics Data System (ADS)

Sadeghi, Meisam; Jahanshahi, Mohsen; Ghorbanzadeh, Morteza; Najafpour, Ghasem

2018-03-01

The kind of sensing platform in nano biosensor plays an important role in nucleic acid sequence detection. It has been demonstrated that graphene does not have an intrinsic band gap; therefore, transition metal dichalcogenides (TMDs) are desirable materials for electronic base detection. In the present work, a comparative study of the adsorption of the DNA/RNA nucleobases [Adenine (A), Cytosine (C) Guanine (G), Thymine (T) and Uracil (U)] onto the single-layer molybdenum disulfide (MoS2) and Li-doped MoS2 (Li-MoS2) as a sensing surfaces was investigated by using Dispersion-corrected Density Functional Theory (D-DFT) calculations and different measure of equilibrium distances, charge transfers and binding energies for the various nucleobases were calculated. The results revealed that the interactions between the nucleobases and the MoS2 can be strongly enhanced by introducing metal atom, due to significant charge transfer from the Li atom to the MoS2 when Lithium is placed on top of the MoS2. Furthermore, the binding energies of the five nucleobases were in the range of -0.734 to -0.816 eV for MoS2 and -1.47 to -1.80 eV for the Li-MoS2. Also, nucleobases were adsorbed onto MoS2 sheets via the van der Waals (vdW) force. This high affinity and the renewable properties of the biosensing platform demonstrated that Li-MoS2 nanosheet is biocompatible and suitable for nucleic acid analysis.

Phonon dispersion evolution in uniaxially strained aluminum crystal

NASA Astrophysics Data System (ADS)

Parthasarathy, Ranganathan; Misra, Anil; Aryal, Sitaram; Ouyang, Lizhi

2018-04-01

The influence of loading upon the phonon dispersion of crystalline materials could be highly nonlinear with certain particular trends that depend upon the loading path. In this paper, we have calculated the influence of [100] uniaxial strain on the phonon dispersion and group velocities in fcc aluminum using second moments of position obtained from molecular dynamics (MD) simulation at 300 K. In contrast to nonlinear monotonic variation of both longitudinal and transverse phonon frequencies along the Δ , Λ and Σ lines of the first Brillouin zone under tension, transverse phonon branches along the Λ line show inflection at specific wavevectors when the compressive strain exceeds 5%. Further, the longitudinal group velocities along the high-symmetry Δ line vary non-monotonically with strain, reaching a minimum at 5% compressive strain. Throughout the strain range studied, the equilibrium positions of atoms displace in an affine manner preserving certain static structural symmetry. We attribute the anomalies in the phonon dispersion to the non-affine evolution of second moments of atomic position, and the associated plateauing of force constants under the applied strain path.

The Kadomtsev-Petviashvili equation under rapid forcing

NASA Astrophysics Data System (ADS)

Moroz, Irene M.

1997-06-01

We consider the initial value problem for the forced Kadomtsev-Petviashvili equation (KP) when the forcing is assumed to be fast compared to the evolution of the unforced equation. This suggests the introduction of two time scales. Solutions to the forced KP are sought by expanding the dependent variable in powers of a small parameter, which is inversely related to the forcing time scale. The unforced system describes weakly nonlinear, weakly dispersive, weakly two-dimensional wave propagation and is studied in two forms, depending upon whether gravity dominates surface tension or vice versa. We focus on the effect that the forcing has on the one-lump solution to the KPI equation (where surface tension dominates) and on the one- and two-line soliton solutions to the KPII equation (when gravity dominates). Solutions to second order in the expansion are computed analytically for some specific choices of the forcing function, which are related to the choice of initial data.

ff14ipq: A Self-Consistent Force Field for Condensed-Phase Simulations of Proteins

PubMed Central

2015-01-01

We present the ff14ipq force field, implementing the previously published IPolQ charge set for simulations of complete proteins. Minor modifications to the charge derivation scheme and van der Waals interactions between polar atoms are introduced. Torsion parameters are developed through a generational learning approach, based on gas-phase MP2/cc-pVTZ single-point energies computed of structures optimized by the force field itself rather than the quantum benchmark. In this manner, we sacrifice information about the true quantum minima in order to ensure that the force field maintains optimal agreement with the MP2/cc-pVTZ benchmark for the ensembles it will actually produce in simulations. A means of making the gas-phase torsion parameters compatible with solution-phase IPolQ charges is presented. The ff14ipq model is an alternative to ff99SB and other Amber force fields for protein simulations in programs that accommodate pair-specific Lennard–Jones combining rules. The force field gives strong performance on α-helical and β-sheet oligopeptides as well as globular proteins over microsecond time scale simulations, although it has not yet been tested in conjunction with lipid and nucleic acid models. We show how our choices in parameter development influence the resulting force field and how other choices that may have appeared reasonable would actually have led to poorer results. The tools we developed may also aid in the development of future fixed-charge and even polarizable biomolecular force fields. PMID:25328495

Placing Local Aggregations in a Larger-Scale Context: Hierarchical Modeling of Black-Footed Albatross Dispersion.

PubMed

Michael, P E; Jahncke, J; Hyrenbach, K D

2016-01-01

At-sea surveys facilitate the study of the distribution and abundance of marine birds along standardized transects, in relation to changes in the local environmental conditions and large-scale oceanographic forcing. We analyzed the form and the intensity of black-footed albatross (Phoebastria nigripes: BFAL) spatial dispersion off central California, using five years (2004-2008) of vessel-based surveys of seven replicated survey lines. We related BFAL patchiness to local, regional and basin-wide oceanographic variability using two complementary approaches: a hypothesis-based model and an exploratory analysis. The former tested the strength and sign of hypothesized BFAL responses to environmental variability, within a hierarchical atmosphere-ocean context. The latter explored BFAL cross-correlations with atmospheric / oceanographic variables. While albatross dispersion was not significantly explained by the hierarchical model, the exploratory analysis revealed that aggregations were influenced by static (latitude, depth) and dynamic (wind speed, upwelling) environmental variables. Moreover, the largest BFAL patches occurred along the survey lines with the highest densities, and in association with shallow banks. In turn, the highest BFAL densities occurred during periods of negative Pacific Decadal Oscillation index values and low atmospheric pressure. The exploratory analyses suggest that BFAL dispersion is influenced by basin-wide, regional-scale and local environmental variability. Furthermore, the hypothesis-based model highlights that BFAL do not respond to oceanographic variability in a hierarchical fashion. Instead, their distributions shift more strongly in response to large-scale ocean-atmosphere forcing. Thus, interpreting local changes in BFAL abundance and dispersion requires considering diverse environmental forcing operating at multiple scales.

Influence of long-range forces and capillarity on the function of underwater superoleophobic wrinkled surfaces.

PubMed

Owais, Ahmed; Smith-Palmer, Truis; Gentle, Angus; Neto, Chiara

2018-06-26

Underwater superoleophobic surfaces can be considered a particular type of lubricant-infused surface, that have anti-fouling properties by virtue of a trapped water layer that repels oils. However, as their function relies on a water layer being trapped in the surface roughness, it is crucial to understand the factors that determine the layer stability. In this work, the forces that are responsible for the stability of thin liquid films within structured surfaces were quantified, and the conclusions were tested against the performance of wrinkled surfaces as underwater superoleophobic coatings. Here, the system studied was a family of wrinkled surfaces made of hydrophilic poly(4-vinylpyridine) (P4VP), whereby the wrinkle width could be controllably tuned in the range 90 nm to 8000 nm. The van der Waals free energy was quantified and the capillary forces trapping water in the surface micro- and nano-wrinkle structure were estimated. P4VP surfaces with micro-scale wrinkles had underwater superoleophobic properties, and low adhesion to different oils with droplet roll-off angle below 6° ± 1°. Despite the van der Waals free energy of the system pointing to the dewetting of a water film under oil on top of a smooth P4VP film, the wrinkled structure is sufficient to induce a Cassie state with a trapped water layer. The micro-scale wrinkles (average width 4-12 μm) were found to be particularly effective in the trapping of the water in a Cassie non-adhesive state. The P4VP wrinkled surfaces are superamphiphobic, as when they were first infused with oil, and then exposed to a droplet of water under oil, they exhibited superhydrophobic behavior. The P4VP wrinkles have the additional useful feature of being transparent underwater, which makes them useful candidates for the protection of underwater cameras and sensors.

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

PubMed

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

Modeling compressible multiphase flows with dispersed particles in both dense and dilute regimes

NASA Astrophysics Data System (ADS)

McGrath, T.; St. Clair, J.; Balachandar, S.

2018-05-01

Many important explosives and energetics applications involve multiphase formulations employing dispersed particles. While considerable progress has been made toward developing mathematical models and computational methodologies for these flows, significant challenges remain. In this work, we apply a mathematical model for compressible multiphase flows with dispersed particles to existing shock and explosive dispersal problems from the literature. The model is cast in an Eulerian framework, treats all phases as compressible, is hyperbolic, and satisfies the second law of thermodynamics. It directly applies the continuous-phase pressure gradient as a forcing function for particle acceleration and thereby retains relaxed characteristics for the dispersed particle phase that remove the constituent material sound velocity from the eigenvalues. This is consistent with the expected characteristics of dispersed particle phases and can significantly improve the stable time-step size for explicit methods. The model is applied to test cases involving the shock and explosive dispersal of solid particles and compared to data from the literature. Computed results compare well with experimental measurements, providing confidence in the model and computational methods applied.

Regionally Aligned Forces and Megacities

DTIC Science & Technology

2015-05-21

the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed , and completing and reviewing this...3 isolation of dispersed enemy forces impossible. Additionally, doctrine presents an argument that cities are complex “systems of systems.”8 While...Dimension in TP 523-3-7 as “the cognitive , physical, and social components of Soldier, Army Civilians, leader, and organizational development and

Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit.

PubMed

Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén; Klein, Dahlia R; Cheng, Ran; Seyler, Kyle L; Zhong, Ding; Schmidgall, Emma; McGuire, Michael A; Cobden, David H; Yao, Wang; Xiao, Di; Jarillo-Herrero, Pablo; Xu, Xiaodong

2017-06-07

Since the discovery of graphene, the family of two-dimensional materials has grown, displaying a broad range of electronic properties. Recent additions include semiconductors with spin-valley coupling, Ising superconductors that can be tuned into a quantum metal, possible Mott insulators with tunable charge-density waves, and topological semimetals with edge transport. However, no two-dimensional crystal with intrinsic magnetism has yet been discovered; such a crystal would be useful in many technologies from sensing to data storage. Theoretically, magnetic order is prohibited in the two-dimensional isotropic Heisenberg model at finite temperatures by the Mermin-Wagner theorem. Magnetic anisotropy removes this restriction, however, and enables, for instance, the occurrence of two-dimensional Ising ferromagnetism. Here we use magneto-optical Kerr effect microscopy to demonstrate that monolayer chromium triiodide (CrI 3 ) is an Ising ferromagnet with out-of-plane spin orientation. Its Curie temperature of 45 kelvin is only slightly lower than that of the bulk crystal, 61 kelvin, which is consistent with a weak interlayer coupling. Moreover, our studies suggest a layer-dependent magnetic phase, highlighting thickness-dependent physical properties typical of van der Waals crystals. Remarkably, bilayer CrI 3 displays suppressed magnetization with a metamagnetic effect, whereas in trilayer CrI 3 the interlayer ferromagnetism observed in the bulk crystal is restored. This work creates opportunities for studying magnetism by harnessing the unusual features of atomically thin materials, such as electrical control for realizing magnetoelectronics, and van der Waals engineering to produce interface phenomena.

Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit

DOE PAGES

Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén; ...

2017-06-07

Since the celebrated discovery of graphene, the family of two-dimensional (2D) materials has grown to encompass a broad range of electronic properties. Recent additions include spin-valley coupled semiconductors, Ising superconductors that can be tuned into a quantum metal, possible Mott insulators with tunable charge-density waves, and topological semi-metals with edge transport. Despite this progress, there is still no 2D crystal with intrinsic magnetism, which would be useful for many technologies such as sensing, information, and data storage. Theoretically, magnetic order is prohibited in the 2D isotropic Heisenberg model at finite temperatures by the Mermin-Wagner theorem. However, magnetic anisotropy removes thismore » restriction and enables, for instance, the occurrence of 2D Ising ferromagnetism. Here, we use magneto-optical Kerr effect (MOKE) microscopy to demonstrate that monolayer chromium triiodide (CrI 3) is an Ising ferromagnet with out-of-plane spin orientation. Its Curie temperature of 45 K is only slightly lower than the 61 K of the bulk crystal, consistent with a weak interlayer coupling. Moreover, our studies suggest a layer-dependent magnetic phases, showcasing the hallmark thickness dependent physical properties typical of van der Waals crystals. Remarkably, bilayer CrI3 displays suppressed magnetization with a metamagnetic effect, while in trilayer the interlayer ferromagnetism observed in the bulk crystal is restored. Our work creates opportunities for studying magnetism by harnessing the unique features of atomically-thin materials, such as electrical control for realizing magnetoelectronics, and van der Waals engineering for novel interface phenomena.« less

Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit

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

Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén

Since the celebrated discovery of graphene, the family of two-dimensional (2D) materials has grown to encompass a broad range of electronic properties. Recent additions include spin-valley coupled semiconductors, Ising superconductors that can be tuned into a quantum metal, possible Mott insulators with tunable charge-density waves, and topological semi-metals with edge transport. Despite this progress, there is still no 2D crystal with intrinsic magnetism, which would be useful for many technologies such as sensing, information, and data storage. Theoretically, magnetic order is prohibited in the 2D isotropic Heisenberg model at finite temperatures by the Mermin-Wagner theorem. However, magnetic anisotropy removes thismore » restriction and enables, for instance, the occurrence of 2D Ising ferromagnetism. Here, we use magneto-optical Kerr effect (MOKE) microscopy to demonstrate that monolayer chromium triiodide (CrI 3) is an Ising ferromagnet with out-of-plane spin orientation. Its Curie temperature of 45 K is only slightly lower than the 61 K of the bulk crystal, consistent with a weak interlayer coupling. Moreover, our studies suggest a layer-dependent magnetic phases, showcasing the hallmark thickness dependent physical properties typical of van der Waals crystals. Remarkably, bilayer CrI3 displays suppressed magnetization with a metamagnetic effect, while in trilayer the interlayer ferromagnetism observed in the bulk crystal is restored. Our work creates opportunities for studying magnetism by harnessing the unique features of atomically-thin materials, such as electrical control for realizing magnetoelectronics, and van der Waals engineering for novel interface phenomena.« less

Dynamic Image Forces Near a Metal Surface and the Point-Charge Motion

ERIC Educational Resources Information Center

Gabovich, A. M.; Voitenko, A. I.

2012-01-01

The problem of charge motion governed by image force attraction near a plane metal surface is considered and solved self-consistently. The temporal dispersion of metal dielectric permittivity makes the image forces dynamic and, hence, finite, contrary to the results of the conventional approach. Therefore, the maximal attainable velocity turns out…

Polarizable Multipole-Based Force Field for Dimethyl and Trimethyl Phosphate

PubMed Central

2015-01-01

Phosphate groups are commonly observed in biomolecules such as nucleic acids and lipids. Due to their highly charged and polarizable nature, modeling these compounds with classical force fields is challenging. Using quantum mechanical studies and liquid-phase simulations, the AMOEBA force field for dimethyl phosphate (DMP) ion and trimethyl phosphate (TMP) has been developed. On the basis of ab initio calculations, it was found that ion binding and the solution environment significantly impact both the molecular geometry and the energy differences between conformations. Atomic multipole moments are derived from MP2/cc-pVQZ calculations of methyl phosphates at several conformations with their chemical environments taken into account. Many-body polarization is handled via a Thole-style induction model using distributed atomic polarizabilities. van der Waals parameters of phosphate and oxygen atoms are determined by fitting to the quantum mechanical interaction energy curves for water with DMP or TMP. Additional stretch-torsion and angle-torsion coupling terms were introduced in order to capture asymmetry in P–O bond lengths and angles due to the generalized anomeric effect. The resulting force field for DMP and TMP is able to accurately describe both the molecular structure and conformational energy surface, including bond and angle variations with conformation, as well as interaction of both species with water and metal ions. The force field was further validated for TMP in the condensed phase by computing hydration free energy, liquid density, and heat of vaporization. The polarization behavior between liquid TMP and TMP in water is drastically different. PMID:26574325

van der Waals forces and confinement in carbon nanopores: Interaction between CH 4, COOH, NH 3, OH, SH and single-walled carbon nanotubes

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

2016-04-13

Interactions between CH 4, COOH, NH 3, OH, SH and armchair (n,n)(n=4,7,14) and zigzag (n,0)(n=7,12,25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C 6/r 6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Furthermore, chemisorption of COOH, NH 3, OH and SH at SWCNT edge sites was examined using a H-capped (7,0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks wasmore » predicted by means of Fukui functions.« less

Combinations of coupled cluster, density functionals, and the random phase approximation for describing static and dynamic correlation, and van der Waals interactions

NASA Astrophysics Data System (ADS)

Garza, Alejandro J.; Bulik, Ireneusz W.; Alencar, Ana G. Sousa; Sun, Jianwei; Perdew, John P.; Scuseria, Gustavo E.

2016-04-01

Contrary to standard coupled cluster doubles (CCD) and Brueckner doubles (BD), singlet-paired analogues of CCD and BD (denoted here as CCD0 and BD0) do not break down when static correlation is present, but neglect substantial amounts of dynamic correlation. In fact, CCD0 and BD0 do not account for any contributions from multielectron excitations involving only same-spin electrons at all. We exploit this feature to add - without introducing double counting, self-interaction, or increase in cost - the missing correlation to these methods via meta-GGA (generalised gradient approximation) density functionals (Tao-Perdew-Staroverov-Scuseria and strongly constrained and appropriately normed). Furthermore, we improve upon these CCD0+DFT blends by invoking range separation: the short- and long-range correlations absent in CCD0/BD0 are evaluated with density functional theory and the direct random phase approximation, respectively. This corrects the description of long-range van der Waals forces. Comprehensive benchmarking shows that the combinations presented here are very accurate for weakly correlated systems, while also providing a reasonable description of strongly correlated problems without resorting to symmetry breaking.

The evaluation and validation of copper (II) force field parameters of the Auxiliary Activity family 9 enzymes

NASA Astrophysics Data System (ADS)

Moses, Vuyani; Tastan Bishop, Özlem; Lobb, Kevin A.

2017-06-01

The Auxiliary Activity family 9 (AA9) proteins are Cu2+ coordinating enzymes which are crucial for the early stages of cellulose degradation. In this study, the force field parameters for copper-containing bonds in the Type 1 AA9 protein active site were established and used in a molecular dynamics simulation on a solvated, neutralized system containing an AA9 protein, Cu2+ and a β-cellulose surface. The copper to cellulose interaction was evident during the dynamics, which could also be accelerated by the use of high Cusbnd O van der Waals parameters. The interaction of AA9, Cu2+ and cellulose is described in detail.

Self-bridging of vertical silicon nanowires and a universal capacitive force model for spontaneous attraction in nanostructures.

PubMed

Sun, Zhelin; Wang, Deli; Xiang, Jie

2014-11-25

Spontaneous attractions between free-standing nanostructures have often caused adhesion or stiction that affects a wide range of nanoscale devices, particularly nano/microelectromechanical systems. Previous understandings of the attraction mechanisms have included capillary force, van der Waals/Casimir forces, and surface polar charges. However, none of these mechanisms universally applies to simple semiconductor structures such as silicon nanowire arrays that often exhibit bunching or adhesions. Here we propose a simple capacitive force model to quantitatively study the universal spontaneous attraction that often causes stiction among semiconductor or metallic nanostructures such as vertical nanowire arrays with inevitably nonuniform size variations due to fabrication. When nanostructures are uniform in size, they share the same substrate potential. The presence of slight size differences will break the symmetry in the capacitive network formed between the nanowires, substrate, and their environment, giving rise to electrostatic attraction forces due to the relative potential difference between neighboring wires. Our model is experimentally verified using arrays of vertical silicon nanowire pairs with varied spacing, diameter, and size differences. Threshold nanowire spacing, diameter, or size difference between the nearest neighbors has been identified beyond which the nanowires start to exhibit spontaneous attraction that leads to bridging when electrostatic forces overcome elastic restoration forces. This work illustrates a universal understanding of spontaneous attraction that will impact the design, fabrication, and reliable operation of nanoscale devices and systems.

Layered uranium(VI) hydroxides: structural and thermodynamic properties of dehydrated schoepite α-UO₂(OH)₂.

PubMed

Weck, Philippe F; Kim, Eunja

2014-12-07

The structure of dehydrated schoepite, α-UO2(OH)2, was investigated using computational approaches that go beyond standard density functional theory and include van der Waals dispersion corrections (DFT-D). Thermal properties of α-UO2(OH)2, were also obtained from phonon frequencies calculated with density functional perturbation theory (DFPT) including van der Waals dispersion corrections. While the isobaric heat capacity computed from first-principles reproduces available calorimetric data to within 5% up to 500 K, some entropy estimates based on calorimetric measurements for UO3·0.85H2O were found to overestimate by up to 23% the values computed in this study.

SMED - Sulphur MEditerranean Dispersion

NASA Astrophysics Data System (ADS)

Salerno, Giuseppe G.; Sellitto, Pasquale; Corradini, Stefano; Di Sarra, Alcide Giorgio; Merucci, Luca; Caltabiano, Tommaso; La Spina, Alessandro

2016-04-01

Emissions of volcanic gases and particles can have profound impacts on terrestrial environment, atmospheric composition, climate forcing, and then on human health at various temporal and spatial scales. Volcanic emissions have been identified as one of the largest sources of uncertainty in our understanding of recent climate change trends. In particular, a primary role is acted by sulphur dioxide emission due to its conversion to volcanic sulphate aerosol via atmospheric oxidation. Aerosols may play a key role in the radiative budget and then in photochemistry and tropospheric composition. Mt. Etna is one of the most prodigious and persistent emitters of gasses and particles on Earth, accounting for about 10% of global average volcanic emission of CO2 and SO2. Its sulphur emissions stand for 0.7 × 106 t S/yr9 and then about 10 times bigger than anthropogenic sulphur emissions in the Mediterranean area. Centrepiece of the SMED project is to advance the understanding of volcanogenic sulphur dioxide and sulphate aerosol particles dispersion and radiative impact on the downwind Mediterranean region by an integrated approach between ground- and space-based observations and modelling. Research is addressed by exploring the potential relationship between proximal SO2 flux and aerosol measured remotely in the volcanic plume of Mt. Etna between 2000 and 2014 and distal aerosol ground-based measurements in Lampedusa, Greece, and Malta from AERONET network. Ground data are combined with satellite multispectral polar and geostationary imagers able to detect and retrieve volcanic ash and SO2. The high repetition time of SEVIRI (15 minutes) will ensure the potential opportunity to follow the entire evolution of the volcanic cloud, while, the higher spatial resolution of MODIS (1x1 km2), are exploited for investigating the probability to retrieve volcanic SO2 abundances from passive degassing. Ground and space observations are complemented with atmospheric Lagrangian model

Improving nanoparticle dispersion and charge transfer in cadmium telluride tetrapod and conjugated polymer blends.

PubMed

Monson, Todd C; Hollars, Christopher W; Orme, Christine A; Huser, Thomas

2011-04-01

The dispersion of CdTe tetrapods in a conducting polymer and the resulting charge transfer is studied using a combination of confocal fluorescence microscopy and atomic force microscopy (AFM). The results of this work show that both the tetrapod dispersion and charge transfer between the CdTe and conducting polymer (P3HT) are greatly enhanced by exchanging the ligands on the surface of the CdTe and by choosing proper solvent mixtures. The ability to experimentally probe the relationship between particle dispersion and charge transfer through the combination of AFM and fluorescence microscopy provides another avenue to assess the performance of polymer/semiconductor nanoparticle composites. © 2011 American Chemical Society

Simple Physics-Based Analytical Formulas for the Potentials of Mean Force of the Interaction of Amino Acid Side Chains in Water. VII. Charged-Hydrophobic/Polar and Polar-Hydrophobic/Polar Side Chains.

PubMed

Makowski, Mariusz; Liwo, Adam; Scheraga, Harold A

2017-01-19

The physics-based potentials of side-chain-side-chain interactions corresponding to pairs composed of charged and polar, polar and polar, charged and hydrophobic, and hydrophobic and hydrophobic side chains have been determined. A total of 144 four-dimensional potentials of mean force (PMFs) of all possible pairs of molecules modeling these pairs were determined by umbrella-sampling molecular dynamics simulations in explicit water as functions of distance and orientation, and the analytical expressions were then fitted to the PMFs. Depending on the type of interacting sites, the analytical approximation to the PMF is a sum of terms corresponding to van der Waals interactions and cavity-creation involving the nonpolar sections of the side chains and van der Waals, cavity-creation, and electrostatic (charge-dipole or dipole-dipole) interaction energies and polarization energies involving the charged or polar sections of the side chains. The model used in this work reproduces all features of the interacting pairs. The UNited RESidue force field with the new side-chain-side-chain interaction potentials was preliminarily tested with the N-terminal part of the B-domain of staphylococcal protein A (PDBL 1BDD ; a three-α-helix bundle) and UPF0291 protein YnzC from Bacillus subtilis (PDB: 2HEP ; an α-helical hairpin).

Genetics of dispersal.

PubMed

Saastamoinen, Marjo; Bocedi, Greta; Cote, Julien; Legrand, Delphine; Guillaume, Frédéric; Wheat, Christopher W; Fronhofer, Emanuel A; Garcia, Cristina; Henry, Roslyn; Husby, Arild; Baguette, Michel; Bonte, Dries; Coulon, Aurélie; Kokko, Hanna; Matthysen, Erik; Niitepõld, Kristjan; Nonaka, Etsuko; Stevens, Virginie M; Travis, Justin M J; Donohue, Kathleen; Bullock, James M; Del Mar Delgado, Maria

2018-02-01

Dispersal is a process of central importance for the ecological and evolutionary dynamics of populations and communities, because of its diverse consequences for gene flow and demography. It is subject to evolutionary change, which begs the question, what is the genetic basis of this potentially complex trait? To address this question, we (i) review the empirical literature on the genetic basis of dispersal, (ii) explore how theoretical investigations of the evolution of dispersal have represented the genetics of dispersal, and (iii) discuss how the genetic basis of dispersal influences theoretical predictions of the evolution of dispersal and potential consequences. Dispersal has a detectable genetic basis in many organisms, from bacteria to plants and animals. Generally, there is evidence for significant genetic variation for dispersal or dispersal-related phenotypes or evidence for the micro-evolution of dispersal in natural populations. Dispersal is typically the outcome of several interacting traits, and this complexity is reflected in its genetic architecture: while some genes of moderate to large effect can influence certain aspects of dispersal, dispersal traits are typically polygenic. Correlations among dispersal traits as well as between dispersal traits and other traits under selection are common, and the genetic basis of dispersal can be highly environment-dependent. By contrast, models have historically considered a highly simplified genetic architecture of dispersal. It is only recently that models have started to consider multiple loci influencing dispersal, as well as non-additive effects such as dominance and epistasis, showing that the genetic basis of dispersal can influence evolutionary rates and outcomes, especially under non-equilibrium conditions. For example, the number of loci controlling dispersal can influence projected rates of dispersal evolution during range shifts and corresponding demographic impacts. Incorporating more realism in

Long-Range Repulsion Between Spatially Confined van der Waals Dimers

NASA Astrophysics Data System (ADS)

Sadhukhan, Mainak; Tkatchenko, Alexandre

2017-05-01

It is an undisputed textbook fact that nonretarded van der Waals (vdW) interactions between isotropic dimers are attractive, regardless of the polarizability of the interacting systems or spatial dimensionality. The universality of vdW attraction is attributed to the dipolar coupling between fluctuating electron charge densities. Here, we demonstrate that the long-range interaction between spatially confined vdW dimers becomes repulsive when accounting for the full Coulomb interaction between charge fluctuations. Our analytic results are obtained by using the Coulomb potential as a perturbation over dipole-correlated states for two quantum harmonic oscillators embedded in spaces with reduced dimensionality; however, the long-range repulsion is expected to be a general phenomenon for spatially confined quantum systems. We suggest optical experiments to test our predictions, analyze their relevance in the context of intermolecular interactions in nanoscale environments, and rationalize the recent observation of anomalously strong screening of the lateral vdW interactions between aromatic hydrocarbons adsorbed on metal surfaces.

Consistent van der Waals radii for the whole main group.

PubMed

Mantina, Manjeera; Chamberlin, Adam C; Valero, Rosendo; Cramer, Christopher J; Truhlar, Donald G

2009-05-14

Atomic radii are not precisely defined but are nevertheless widely used parameters in modeling and understanding molecular structure and interactions. The van der Waals radii determined by Bondi from molecular crystals and data for gases are the most widely used values, but Bondi recommended radius values for only 28 of the 44 main-group elements in the periodic table. In the present Article, we present atomic radii for the other 16; these new radii were determined in a way designed to be compatible with Bondi's scale. The method chosen is a set of two-parameter correlations of Bondi's radii with repulsive-wall distances calculated by relativistic coupled-cluster electronic structure calculations. The newly determined radii (in A) are Be, 1.53; B, 1.92; Al, 1.84; Ca, 2.31; Ge, 2.11; Rb, 3.03; Sr, 2.49; Sb, 2.06; Cs, 3.43; Ba, 2.68; Bi, 2.07; Po, 1.97; At, 2.02; Rn, 2.20; Fr, 3.48; and Ra, 2.83.

Spherical solid model system: Exact evaluation of the van der Waals interaction between a microscopic or submacroscopic spherical solid and a deformable fluid interface

NASA Astrophysics Data System (ADS)

Wang, Y. Z.; Wang, B.; Xiong, X. M.; Zhang, J. X.

2011-03-01

In many previous research work associated with studying the deformation of the fluid interface interacting with a solid, the theoretical calculation of the surface energy density on the deformed fluid interface (or its interaction surface pressure) is often approximately obtained by using the expression for the interaction energy per unit area (or pressure) between two parallel macroscopic plates, e.g. σ(D) = - A / 12 πD2or π(D) = - A / 6 πD3for the van der Waals (vdW) interaction, through invoking the Derjaguin approximation (DA). This approximation however would result in over- or even inaccurate-prediction of the interaction force and the corresponding deformation of the fluid interface due to the invalidation of Derjaguin approximation in cases of microscopic or submacroscopic solids. To circumvent the above limitations existing in the previous DA-based theoretical work, a more accurate and quantitative theoretical model, available for exactly calculating the vdW-induced deformation of a planar fluid interface interacting with a sphere, and the interaction forces taking into account its change, is presented in this paper. The validity and advantage of the new mathematical and physical technique is rigorously verified by comparison with the numerical results on basis of the previous Paraboloid solid (PS) model and the Hamaker's sphere-flat expression (viz. F = - 2 Aa3 / (3 D2( D + 2 a) 2)), as well as its well-known DA-based general form of F / a = - A / 6z p02.

The Conductivity and pH Values of Dispersions of Nanospheres for Targeted Drug Delivery in the Course of Forced Equilibrium Dialysis.

PubMed

Musiał, Witold; Pluta, Janusz; Byrski, Tomasz; Valh, Julija V

2015-01-01

In the available literature, the problem of pH and conductivity in FED is evaluated separately, and limited mainly to the final purity of the synthesized polymer. In this study data from conductivity and pH measurements were evaluated in the context of the structure of the macromolecule. The aim of the study was to evaluate the conductivity and pH of dispersions of nanospheres synthesized with the use of N-isopropyl acrylamide (NIPA) as the main monomer, N,N'-methylenebisacrylamide (MBA) as the cross-linker and acrylic acid (AcA) as the anionic comonomer during the purification of dispersions via forced equilibrium dialysis (FED). Six batches of nanospheres were obtained in the process of surfactant free precipitation polymerization (SFPP) under inert nitrogen. The conductivity and pH of the dispersions of nanospheres were measured at the beginning of FED and after finishing that process. The conductivity in the systems being studied decreased significantly in the process of FED. The initial values of conductivity ranged from 736.85±8.13 μS×cm(-1) to 1048.90±67.53 μS×cm(-1) After 10 days, when the systems being assessed gained stability in terms of conductivity level, the values of conductivity were between 4.29±0.01 μS×cm(-1) and 33.56±0.04 μS×cm(-1). The pH values inreased significantly after FED. The resulting pH was between 6.92±0.07 and 8.21±0.07, while the initial values were between 3.42±0.23 μS×cm(-1) and 4.30±0.22 μS×cm(-1). Conductivity and pH measurements performed during purification via FED provide important information on the composition of the resulting nanospheres, including the functional groups embedded in the structure of the polymer in the course of the synthesis, as well as the purity of the structures. The presence of a cross-linker and acidic comonomer in the poly-N-isopropyl acrylamide (polyNIPA) macromolecule may be confirmed by both the pH and the conductivity measurements.