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Sample records for intermolecular interaction energies

  1. The same number of optimized parameters scheme for determining intermolecular interaction energies

    DEFF Research Database (Denmark)

    Kristensen, Kasper; Ettenhuber, Patrick; Eriksen, Janus Juul; Jensen, Frank; Jørgensen, Poul

    2015-01-01

    We propose the Same Number Of Optimized Parameters (SNOOP) scheme as an alternative to the counterpoise method for treating basis set superposition errors in calculations of intermolecular interaction energies. The key point of the SNOOP scheme is to enforce that the number of optimized wave...... numerically. Numerical results for second-order Møller-Plesset perturbation theory (MP2) and coupled-cluster with single, double, and approximate triple excitations (CCSD(T)) show that the SNOOP scheme in general outperforms the uncorrected and counterpoise approaches. Furthermore, we show that SNOOP...

  2. Local intermolecular interactions for selective CO2 capture by zeolitic imidazole frameworks: energy decomposition analysis

    International Nuclear Information System (INIS)

    Intermolecular energy decomposition analysis (EDA) is reported for the binding of CO2 with zeolitic imidazole frameworks (ZIF) to provide a molecular level interpretation of the recent capacity and selectivity measurements of several ZIFs and to suggest a theoretical guideline to improve their performance further, using 1 nm size of organic linker fragment of the ZIFs as a target molecule. The EDA suggests that the local electronic interaction of CO2 and the substituent groups, mainly frozen density and polarization interactions with little charge transfer, is the primary binding interaction, but the electron correlation effects can be equally or more important depending on the binding geometry and functional groups. The present correlated calculations identify the preferred ZIF binding sites for various gases including CO2 to be mostly near the benzene substituent groups rather than the plane of imidazole rings. We predict that the NH2-substituted ZIF would have an enhanced capacity of CO2 as compared to the NO2-substituted ZIF that was recently synthesized and reported to be one of the materials with the best capacity results along with high gas selectivity. The present calculations may imply that the local functionality of the linking organics, rather than detailed framework structures, may be of primary importance in designing certain high capacity MOF or ZIF materials.

  3. Specific intermolecular interactions of organic compounds

    CERN Document Server

    Baev, Alexei K

    2012-01-01

    This volume sets out the development of the thermodynamic theory of specific intermolecular interactions for a wide spectrum of organic compounds, laying down the framework of an unconventional approach to H-bonding based on a pentacoordinate carbon atom.

  4. Hyperspherical representation of potential energy surfaces: intermolecular interactions in tetra-atomic and penta-atomic systems

    International Nuclear Information System (INIS)

    In this paper, we discuss the applications of spherical and hyperspherical harmonics expansions for potential energy surfaces for intermolecular interactions, focusing on four- and five-body problems. Case studies include diatomic-molecule-diatomic-molecule systems, floppy-molecule-rare-gas-atom cases, atom-triatomic, and nonlinear-molecule-linear-molecule systems. Among these systems, the important ones regarding water interaction with atoms and diatomic molecules are presented here to illustrate the use of spherical and hyperspherical coordinates and harmonics for weakly interacting systems. The interaction potential representation involves the distance between the centers of mass of the two molecules and a set of angles that defines the mutual orientation of the molecules, whose geometries are assumed to be either 'frozen' in their equilibrium configurations or to vary according to specific large-amplitude modes. The potential energy surfaces in the given examples of water-hydrogen, nitrogen and oxygen interactions are generated at the CCSD(T)/aug-cc-pVTZ level. Comparisons to the theoretical and experimental results of recent works for these and similar systems are presented.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Using the CCSD(T) model, we evaluated the intermolecular potential energy surfaces of the He-, Ne-, and Ar-phosgene complexes. We considered a representative number of intermolecular geometries for which we calculated the corresponding interaction energies with the augmented (He complex) and doub...

  6. Intermolecular electrostatic energies using density fitting.

    Science.gov (United States)

    Cisneros, G Andrs; Piquemal, Jean-Philip; Darden, Thomas A

    2005-07-22

    A method is presented to calculate the electron-electron and nuclear-electron intermolecular Coulomb interaction energy between two molecules by separately fitting the unperturbed molecular electron density of each monomer. This method is based on the variational Coulomb fitting method which relies on the expansion of the ab initio molecular electron density in site-centered auxiliary basis sets. By expanding the electron density of each monomer in this way the integral expressions for the intermolecular electrostatic calculations are simplified, lowering the operation count as well as the memory usage. Furthermore, this method allows the calculation of intermolecular Coulomb interactions with any level of theory from which a one-electron density matrix can be obtained. Our implementation is initially tested by calculating molecular properties with the density fitting method using three different auxiliary basis sets and comparing them to results obtained from ab initio calculations. These properties include dipoles for a series of molecules, as well as the molecular electrostatic potential and electric field for water. Subsequently, the intermolecular electrostatic energy is tested by calculating ten stationary points on the water dimer potential-energy surface. Results are presented for electron densities obtained at four different levels of theory using two different basis sets, fitted with three auxiliary basis sets. Additionally, a one-dimensional electrostatic energy surface scan is performed for four different systems (H2O dimer, Mg2+-H2O, Cu+-H2O, and n-methyl-formamide dimer). Our results show a very good agreement with ab initio calculations for all properties as well as interaction energies. PMID:16095348

  7. Probing intermolecular protein-protein interactions in the calcium-sensing receptor homodimer using bioluminescence resonance energy transfer (BRET)

    DEFF Research Database (Denmark)

    Jensen, Anders A.; Hansen, Jakob L; Sheikh, Søren P; Bräuner-Osborne, Hans

    2002-01-01

    -induced intermolecular movements in the CaR homodimer using the new bioluminescence resonance energy transfer technique, BRET2, which is based on the transference of energy from Renilla luciferase (Rluc) to the green fluorescent protein mutant GFP2. We tagged CaR with Rluc and GFP2 at different intracellular locations...

  8. Influence of intermolecular interactions on magnetic observables

    Science.gov (United States)

    Schnack, Jürgen

    2016-02-01

    Very often it is an implied paradigm of molecular magnetism that magnetic molecules in a crystal interact so weakly that measurements of dc magnetic observables reflect ensemble properties of single molecules. But the number of cases where the assumption of virtually noninteracting molecules does not hold grows steadily. A deviation from the noninteracting case can especially clearly be seen in clusters with antiferromagnetic couplings, where steps of the low-temperature magnetization curve are smeared out with increasing intermolecular interaction. In this investigation we demonstrate with examples in one, two, and three space dimensions how intermolecular interactions influence typical magnetic observables such as magnetization, susceptibility, and specific heat.

  9. Bowl inversion state controlled by intermolecular interactions

    International Nuclear Information System (INIS)

    Full text: Bowl-shaped pi-conjugated compounds are important not only as model compounds of fullerenes but also as possible hosts for different guest molecules. Recent studies regarding the storage of possible energy carriers such as hydrogen and methane in nano-structured carbon materials have further increased the interest in well defined model compounds that allow for a detailed investigation of host-guest interactions in order to optimize the storage capacity of technologically relevant carbon-based materials. Within this context we investigated the structural properties of monolayer films of sumanene (C21H12) deposited on Ag(111). Based on STM experiments we find that the fraction of molecules having a bowl-down adsorption geometry is coverage-dependent, indicating that the bowl-inversion state is determined by intermolecular interactions. The experimental findings are rationalized by density functional theory (DFT) calculations, which reveal a subtle interplay between molecule-substrate and molecule- molecule interactions that is responsible for the abrupt structural change involving inversion of a fraction of the molecules and reorientation of the molecules with respect to the surface normal. (author)

  10. Intermolecular Interactions of Noble-Gas-Containing Species

    OpenAIRE

    Lignell, Antti

    2008-01-01

    The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from str...

  11. Energy-Dispersive NEXAFS: A Novel Tool for the Investigation of Intermolecular Interaction and Structural Phase Dynamics

    OpenAIRE

    Scholz, Markus

    2013-01-01

    In the context of this thesis, the novel method soft X-ray energy-dispersive NEXAFS spectroscopy was explored and utilized to investigate intermolecular coupling and post-growth processes with a temporal resolution of seconds. 1,4,5,8- naphthalene tetracarboxylic acid dianhydride (NTCDA)multilayer films were the chosen model system for these investigations. The core hole-electron correlation in coherently coupled molecules was studied by means of energy-dispersive near-edge X-ray absorption f...

  12. An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

    Science.gov (United States)

    Azar, R. Julian; Head-Gordon, Martin

    2012-01-01

    We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the Cs-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

  13. An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

    Energy Technology Data Exchange (ETDEWEB)

    Azar, R. Julian; Head-Gordon, Martin [Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720 (United States) and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2012-01-14

    We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the C{sub s}-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

  14. An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

    International Nuclear Information System (INIS)

    We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the Cs-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

  15. Energy-dispersive NEXAFS. A novel tool for the investigation of intermolecular interaction and structural phase dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Scholz, Markus

    2013-06-27

    In the context of this thesis, the novel method soft X-ray energy-dispersive NEXAFS spectroscopy was explored and utilized to investigate intermolecular coupling and post-growth processes with a temporal resolution of seconds. 1,4,5,8- naphthalene tetracarboxylic acid dianhydride (NTCDA)multilayer films were the chosen model system for these investigations. The core hole-electron correlation in coherently coupled molecules was studied by means of energy-dispersive near-edge X-ray absorption fine-structure spectroscopy. A transient phase was found which exists during the transition between a disordered condensed phase and the bulk structure. This phase is characterized by distinct changes in the spectral line shape and energetic position of the X-ray absorption signal at the C K-edge. The findings were explained with the help of theoretical models based on the coupling of transition dipole moments, which are well established for optically excited systems. In consequence, the experimental results provides evidence for a core hole-electron pair delocalized over several molecules. Furthermore, the structure formation of NTCDA multilayer films on Ag(111) surfaces was investigated. With time-resolved and energy-dispersive NEXAFS experiments the intensity evolution in s- and p-polarization showed a very characteristic behavior. By combining these findings with the results of time-dependent photoemission measurements, several sub-processes were identified in the post- growth behavior. Upon annealing, the amorphous but preferentially flat-lying molecules flip into an upright orientation. After that follows a phase characterized by strong intermolecular coupling. Finally, three-dimensional islands are established. Employing the Kolmogorov-Johnson-Mehl-Avrami model, the activation energies of the sub-processes were determined.

  16. Energy-dispersive NEXAFS. A novel tool for the investigation of intermolecular interaction and structural phase dynamics

    International Nuclear Information System (INIS)

    In the context of this thesis, the novel method soft X-ray energy-dispersive NEXAFS spectroscopy was explored and utilized to investigate intermolecular coupling and post-growth processes with a temporal resolution of seconds. 1,4,5,8- naphthalene tetracarboxylic acid dianhydride (NTCDA)multilayer films were the chosen model system for these investigations. The core hole-electron correlation in coherently coupled molecules was studied by means of energy-dispersive near-edge X-ray absorption fine-structure spectroscopy. A transient phase was found which exists during the transition between a disordered condensed phase and the bulk structure. This phase is characterized by distinct changes in the spectral line shape and energetic position of the X-ray absorption signal at the C K-edge. The findings were explained with the help of theoretical models based on the coupling of transition dipole moments, which are well established for optically excited systems. In consequence, the experimental results provides evidence for a core hole-electron pair delocalized over several molecules. Furthermore, the structure formation of NTCDA multilayer films on Ag(111) surfaces was investigated. With time-resolved and energy-dispersive NEXAFS experiments the intensity evolution in s- and p-polarization showed a very characteristic behavior. By combining these findings with the results of time-dependent photoemission measurements, several sub-processes were identified in the post- growth behavior. Upon annealing, the amorphous but preferentially flat-lying molecules flip into an upright orientation. After that follows a phase characterized by strong intermolecular coupling. Finally, three-dimensional islands are established. Employing the Kolmogorov-Johnson-Mehl-Avrami model, the activation energies of the sub-processes were determined.

  17. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    Directory of Open Access Journals (Sweden)

    Venkatesha R. Hathwar

    2015-09-01

    Full Text Available Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended ?-conjugated core between molecules. We present here the electron density distribution in rubrene at 20?K and at 100?K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of C?...C? interactions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by HH interactions. The electron density features of HH bonding, and the interaction energy of molecular dimers connected by HH interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. The quantitative nature of the intermolecular interactions is virtually unchanged between 20?K and 100?K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.

  18. Density matrix based microscopic theory of molecule metal-nanoparticle interactions: linear absorbance and plasmon enhancement of intermolecular excitation energy transfer.

    Science.gov (United States)

    Kyas, Gerold; May, Volkhard

    2011-01-21

    A microscopic theory of interacting molecule metal-nanoparticle (MNP) systems is presented and used to compute absorption spectra and the plasmon enhancement of intermolecular excitation energy transfer (EET). The approach is based on a nonperturbative consideration of the Coulomb coupling matrix elements responsible for EET between the molecules and the MNP. In this way, the need to determine the local fields induced by surface plasmon excitations of the MNP is removed, but the whole description is restricted to distances among the interacting species less than the wavelength of absorbed photons. Based on a density matrix theory, the approach accounts for the vibrational level structure of the molecules, intramolecular vibrational energy redistribution (IVR), and plasmon damping. Numerical results for linear absorbance spectra and EET dynamics are offered. In this respect the importance of energy dissipation in the MNP due to rapid surface plasmon decay is emphasized. PMID:21261378

  19. Resonant intermolecular transfer of vibrational energy in liquid water

    Science.gov (United States)

    Woutersen, Sander; Bakker, Huib J.

    1999-12-01

    Many biological, chemical and physical processes involve the transfer of energy. In the case of electronic excitations, transfer between molecules is rapid, whereas for vibrations in the condensed phase, resonant energy transfer is an unlikely process because the typical timescale of vibrational relaxation (a few picoseconds) is much shorter than that of resonant intermolecular vibrational energy transfer. For the OH-stretch vibration in liquid water, which is of particular importance due to its coupling to the hydrogen bond, extensive investigations have shown that vibrational relaxation takes place with a time constant of 740 +/- 25 femtoseconds (ref. 7). So for resonant intermolecular energy transfer to occur in liquid water, the interaction between the OH-stretch modes of different water molecules needs to be extremely strong. Here we report time-resolved pump-probe laser spectroscopy measurements that reveal the occurrence of fast resonant intermolecular transfer of OH-stretch excitations over many water molecules before the excitation energy is dissipated. We find that the transfer process is mediated by dipole-dipole interactions (the Förster transfer mechanism) and additional mechanisms that are possibly based on intermolecular anharmonic interactions involving hydrogen bonds. Our findings suggest that liquid water may play an important role in transporting vibrational energy between OH groups located on either different biomolecules or along extended biological structures. OH groups in a hydrophobic environment should accordingly be able to remain in a vibrationally excited state longer than OH groups in a hydrophilic environment.

  20. The diversity of physical forces and mechanisms in intermolecular interactions

    International Nuclear Information System (INIS)

    Intermolecular interactions became an inherent part of the structure–function paradigm. Therefore, the generalized concept of protein stability and interactions should consider the balance of stabilizing forces working in different types of intermolecular interactions. We consider here two 'extremes' of protein interactions, viral protein with high intrinsic disorder and hyperthermostable protein complexes. Intermolecular interactions provide folding upon binding as a part of function in the viral case, while they secure and stabilize specific native interfaces as a prerequisite for function in hyperthermostable complexes. We propose a generalized concept of protein stability and interactions, which includes intermolecular interactions comprising distinct combinations of stabilizing forces depending on the types of interacting partners

  1. Ab initio ground state phenylacetylene-argon intermolecular potential energy surface and rovibrational spectrum

    DEFF Research Database (Denmark)

    Cybulski, Hubert; Fernandez, Berta; Henriksen, Christian; Felker, Peter M.

    2012-01-01

    We evaluate the phenylacetylene-argon intermolecular potential energy surface by fitting a representative number of ab initio interaction energies to an analytic function. These energies are calculated at a grid of intermolecular geometries, using the CCSD(T) method and the aug-cc-pVDZ basis set...

  2. Intermolecular interactions and the thermodynamic properties of supercritical fluids.

    Science.gov (United States)

    Yigzawe, Tesfaye M; Sadus, Richard J

    2013-05-21

    The role of different contributions to intermolecular interactions on the thermodynamic properties of supercritical fluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercritical fluids. PMID:23697423

  3. Spectral manifestation of intermolecular interaction in phthalimide and isatin dimers

    International Nuclear Information System (INIS)

    A theoretical analysis of vibrational spectra of phthalimide and isatin is carried out by the DFT/b3LYP method. The influence of intermolecular interaction in dimers of the compounds is estimated. It is shown that one can reliably interpret vibrational spectra of conjugated cyclic compounds, construct structural-dynamic models for dimers of such compounds, and predict a mechanism for intermolecular interaction based on nonempirical quantum calculations of the adiabatic potential. (authors)

  4. Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies.

    Science.gov (United States)

    Horn, Paul R; Mao, Yuezhi; Head-Gordon, Martin

    2016-03-21

    In energy decomposition analysis of Kohn-Sham density functional theory calculations, the so-called frozen (or pre-polarization) interaction energy contains contributions from permanent electrostatics, dispersion, and Pauli repulsion. The standard classical approach to separate them suffers from several well-known limitations. We introduce an alternative scheme that employs valid antisymmetric electronic wavefunctions throughout and is based on the identification of individual fragment contributions to the initial supersystem wavefunction as determined by an energetic optimality criterion. The density deformations identified with individual fragments upon formation of the initial supersystem wavefunction are analyzed along with the distance dependence of the new and classical terms for test cases that include the neon dimer, ammonia borane, water-Na(+), water-Cl(-), and the naphthalene dimer. PMID:27004862

  5. Non-covalent intermolecular carbon-carbon interactions in polyynes.

    Science.gov (United States)

    Remya, Karunakaran; Suresh, Cherumuttathu H

    2015-10-28

    Polyynes, the smaller analogues of one dimensional infinite chain carbon allotrope carbyne, have been studied for the type and strength of the intermolecular interactions in their dimer and tetramer complexes using density functional theory. The nature of end group functionalities and the chain length of the polyynes are varied to assess their role in modulating the non-covalent interaction energy. As seen in molecular electrostatic potential analysis, all the polyyne complexes showed a multitude of non-covalent CC interactions, resulting from complementary electrostatic interactions between relatively electron rich formal triple bond region of one monomer and the electron deficient formal single bond region of the other monomer. This type of paired (C[triple bond, length as m-dash]C)(C-C) bonding interaction, also characterized using quantum theory of atoms-in-molecules, increases with increase in the monomer chain length leading to substantial increase in interaction energy (Eint); -1.07 kcal mol(-1) for the acetylene dimer to -45.83 kcal mol(-1) for the 50yne dimer. The magnitude of Eint increases with substitutions at end positions of the polyyne and this effect persists even up to 50 triple bonds, the largest chain length analyzed in this paper. The role of CC interactions in stabilizing the polyyne dimers is also shown by sliding one monomer in a dimer over the other, which resulted in multiple minima with a reduced number of CC interactions and lower values of Eint. Furthermore, strong cooperativity in the CC bond strength in tetramers is observed as the interaction energy per monomer (Em) of the polyyne is 2.5-2.8 times higher compared to that of the dimer in a test set of four tetramers. The huge gain in energy observed in large polyyene dimers and tetramers predicts the formation of polyyne bundles which may find use in the design of new functional molecular materials. PMID:26412713

  6. Learning about Intermolecular Interactions from the Cambridge Structural Database

    Science.gov (United States)

    Battle, Gary M.; Allen, Frank H.

    2012-01-01

    A clear understanding and appreciation of noncovalent interactions, especially hydrogen bonding, are vitally important to students of chemistry and the life sciences, including biochemistry, molecular biology, pharmacology, and medicine. The opportunities afforded by the IsoStar knowledge base of intermolecular interactions to enhance the

  7. Intermolecular interaction in TeO2 crystal.

    Science.gov (United States)

    Gabuda, Svyatoslav P; Kozlova, Svetlana G

    2006-09-21

    It is shown that the abnormal long-range Te-Te intermolecular interaction in TeO(2) crystals may be related to the tunneling of electrons from the 5s(2) active lone pairs of Te(4+) ions and their partial delocalization on neighboring Te(4+). PMID:16970416

  8. Covalent intermolecular interaction of the nitric oxide dimer (NO)2

    Science.gov (United States)

    Zhang, Hui; Zheng, Gui-Li; Lv, Gang; Geng, Yi-Zhao; Ji, Qing

    2015-09-01

    Covalent bonds arise from the overlap of the electronic clouds in the internucleus region, which is a pure quantum effect and cannot be obtained in any classical way. If the intermolecular interaction is of covalent character, the result from direct applications of classical simulation methods to the molecular system would be questionable. Here, we analyze the special intermolecular interaction between two NO molecules based on quantum chemical calculation. This weak intermolecular interaction, which is of covalent character, is responsible for the formation of the NO dimer, (NO)2, in its most stable conformation, a cis conformation. The natural bond orbital (NBO) analysis gives an intuitive illustration of the formation of the dimer bonding and antibonding orbitals concomitant with the breaking of the π bonds with bond order 0.5 of the monomers. The dimer bonding is counteracted by partially filling the antibonding dimer orbital and the repulsion between those fully or nearly fully occupied nonbonding dimer orbitals that make the dimer binding rather weak. The direct molecular mechanics (MM) calculation with the UFF force fields predicts a trans conformation as the most stable state, which contradicts the result of quantum mechanics (QM). The lesson from the investigation of this special system is that for the case where intermolecular interaction is of covalent character, a specific modification of the force fields of the molecular simulation method is necessary. Project supported by the National Natural Science Foundation of China (Grant Nos. 90403007 and 10975044), the Key Subject Construction Project of Hebei Provincial Universities, China, the Research Project of Hebei Education Department, China (Grant Nos. Z2012067 and Z2011133), the National Natural Science Foundation of China (Grant No. 11147103), and the Open Project Program of State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, China (Grant No. Y5KF211CJ1).

  9. Abstracts of 6. International Conference on Intermolecular Interactions in Matter

    International Nuclear Information System (INIS)

    6. International Conference on Intermolecular Interactions in Matter is cyclically organised international forum for discussion of most important problems connected with solid state physics, material engineering and crystallography. Especially investigations of low dimensional systems as multilayers, thin films, nanocrystalline systems have been extensively presented and discussed. The methods of crystal growth as well as modern methods for crystal manufacturing process control and material properties investigations have been also performed in the course of the conference

  10. Cation-π interactions: accurate intermolecular potential from symmetry-adapted perturbation theory.

    Science.gov (United States)

    Ansorg, Kay; Tafipolsky, Maxim; Engels, Bernd

    2013-09-01

    Symmetry-adapted perturbation theory (SAPT) is used to decompose the total intermolecular interaction energy between the ammonium cation and a benzene molecule into four physically motivated individual contributions: electrostatics, exchange, dispersion, and induction. Based on this rigorous decomposition, it is shown unambiguously that both the electrostatic and the induction energy components contribute almost equally to the attractive forces stabilizing the dimer with a nonnegligible contribution coming from the dispersion term. A polarizable potential model for the interaction of ammonium cation with benzene is parametrized by fitting these four energy components separately using the functional forms of the AMOEBA force field augmented with the missing charge penetration energy term calculated as a sum over pairwise electrostatic energies between spherical atoms. It is shown that the proposed model is able to produce accurate intermolecular interaction energies as compared to ab initio results, thus avoiding error compensation to a large extent. PMID:23924321

  11. Intermolecular Sulfur···Oxygen Interactions: Theoretical and Statistical Investigations.

    Science.gov (United States)

    Zhang, Xuejin; Gong, Zhen; Li, Jian; Lu, Tao

    2015-10-26

    Intermolecular S···O interactions are very common and are important in biological systems, but until recently, the presence of these contacts in protein-ligand systems largely depended on serendipitous discovery instead of rational design. Here we provide insight into the phenomenon of intermolecular S···O contacts by focusing on three sulfur-containing aromatic rings. Quantum mechanics is employed to characterize the strength and directionality of the S···O interactions and to determine their energy dependence on their geometric parameters. Protein Data Bank mining is performed to systematically determine the occurrence and geometry of intermolecular S···O interactions, and several representative examples are discussed. Three typical cases are investigated using a combined quantum mechanics/molecular mechanics approach to demonstrate the potential of these interactions in improving binding affinities and physiochemical properties. Overall, our work elucidates the structures and energy features of intermolecular S···O interactions and addresses their use in molecular design. PMID:26393532

  12. Towards the biaxial nematic phase via specific intermolecular interactions

    International Nuclear Information System (INIS)

    The work described in this thesis has been focussed on the search of an elusive liquid crystal phase, known as the biaxial nematic phase. Indeed, despite nearly thirty years of intense research, no-one has been able to characterise unambiguously a biaxial nematic phase in a low-molar-mass thermotropic system. Our research is based on the concept of molecular biaxiality as distinct from shape biaxiality. Thus, we are seeking to design palladium complexes where specific intermolecular interactions could exist. Therefore, a few original synthetic strategies were developed to tackle the challenge of discovering the biaxial nematic phase

  13. Weak intermolecular interactions in gas-phase NMR

    CERN Document Server

    Garbacz, Piotr; Jackowski, Karol; Moszynski, Robert; Jaszunski, Michal

    2011-01-01

    Gas-phase NMR spectra demonstrating the effect of weak intermolecular forces on the NMR shielding constants of the interacting species are reported. We analyse the interaction of the molecular hydrogen isotopomers with He, Ne, and Ar, and the interaction in the He-CO_2 dimer. The same effects are studied for all these systems in the ab initio calculations. The comparison of the experimental and computed shielding constants is shown to depend strongly on the treatment of the bulk susceptibility effects, which determine in practice the pressure dependence of the experimental values. Best agreement of the results is obtained when the bulk susceptibility correction in rare gas solvents is evaluated from the analysis of the He-rare gas interactions, and when the shielding of deuterium in D_2-rare gas systems is considered.

  14. Distinguishability and chiral stability in solution: Effects of decoherence and intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Han, Heekyung [Dalla Lana School of Public Health, University of Toronto, Toronto, Ontario M5T 3M7 (Canada); Wardlaw, David M., E-mail: dwardlaw@mun.ca [Department of Chemistry, Memorial University of Newfoundland, St. John' s, Newfoundland and Labrador A1C 5S7 (Canada); Frolov, Alexei M., E-mail: afrolov@uwo.ca [Department of Applied Mathematics, University of Western Ontario, London, Ontario N6H 5B7 (Canada)

    2014-05-28

    We examine the effect of decoherence and intermolecular interactions (chiral discrimination energies) on the chiral stability and the distinguishability of initially pure versus mixed states in an open chiral system. Under a two-level approximation for a system, intermolecular interactions are introduced by a mean-field theory, and interaction between a system and an environment is modeled by a continuous measurement of a population difference between the two chiral states. The resultant equations are explored for various parameters, with emphasis on the combined effects of the initial condition of the system, the chiral discrimination energies, and the decoherence in determining: the distinguishability as measured by a population difference between the initially pure and mixed states, and the decoherence process; the chiral stability as measured by the purity decay; and the stationary state of the system at times long relative to the time scales of the system dynamics and of the environmental effects.

  15. Nanophotonic boost of intermolecular energy transfer

    Science.gov (United States)

    de Roque, P. M.; van Hulst, N. F.; Sapienza, R.

    2015-11-01

    We propose a scheme for efficient long-range energy transfer between two distant light emitters separated by more than one wavelength of light, i.e. much beyond the classical Frster radius. A hybrid nanoantenna-waveguide system mediates the transmission of energy, showing enhancements up to 108 as compared to vacuum. Our model shows how energy transfer in nanostructured media can be boosted, beyond the simple donor Purcell enhancement, and in particular for large donoracceptor separations. The scheme we propose connects realistic emitters and could lead to practical on-chip implementations.

  16. Nanophotonic boost of intermolecular energy transfer

    CERN Document Server

    de Roque, P M; Sapienza, R

    2015-01-01

    We propose a scheme for efficient long-range energy transfer between two distant light emitters separated by more than one wavelength of light, i.e. much beyond the classical Forster radius. A hybrid nanoantenna-waveguide system mediates the transmission of energy, showing enhancements up to 10^8 as compared to vacuum. Our model shows how energy transfer in nanostructured media can be boosted, beyond the simple donor Purcell enhancement, and in particular for large donor-acceptor separations. The scheme we propose connects realistic emitters and could lead to practical on-chip implementations.

  17. Intermolecular Interactions in Ternary GlycerolSampleH2O

    DEFF Research Database (Denmark)

    Westh, Peter; Rasmussen, Erik Lumby; Koga, Yoshikata

    2011-01-01

    We studied the intermolecular interactions in ternary glycerol (Gly)sample (S)H2O systems at 25?C. By measuring the excess partial molar enthalpy of Gly, HGlyEHEGly, we evaluated the GlyGly enthalpic interaction, HGly-GlyEHEGly--Gly, in the presence of various samples (S). For S, tert...... little effect on HGly-GlyEHEGly--Gly. This contrasts with our earlier studies on 1PSH2O in that Na+, F? and Cl? are found as hydration centers from the induced changes on HIP-IPEHEIP--IP in the presence of S, while Br?, I?, and SCN? are found to act as hydrophiles. In comparison with the Hofmeister...... ranking of these ions, the kosmotropes are hydration centers and the more kosmotropic the higher the hydration number, consistent with the original Hofmeisters concept of H2O withdrawing power. Br?, I? and SCN?, on the other hand, acted as hydrophiles and the more chaotropic they are the more...

  18. Ab initio investigation of intermolecular interactions in solid benzene

    OpenAIRE

    Bludsky, O.; Rubes, M.; Soldan, P.

    2008-01-01

    A computational strategy for the evaluation of the crystal lattice constants and cohesive energy of the weakly bound molecular solids is proposed. The strategy is based on the high level ab initio coupled-cluster determination of the pairwise additive contribution to the interaction energy. The zero-point-energy correction and non-additive contributions to the interaction energy are treated using density functional methods. The experimental crystal lattice constants of the solid benzene are r...

  19. Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

    CERN Document Server

    Christensen, Anders S; Cui, Qiang

    2015-01-01

    Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O and S are presented. The RMSD interaction energy is improved from 6.07 kcal/mol to 1...

  20. Intermolecular interactions in rifabutin—2-hydroxypropyl-β-cyclodextrin—water solutions

    Science.gov (United States)

    Anshakova, A. V.; Yermolenko, Yu. V.; Konyukhov, V. Yu.; Polshakov, V. I.; Maksimenko, O. O.; Gelperina, S. E.

    2015-05-01

    The possibility of a intermolecular complex rifabutin (RB)-2-hydroxypropyl-β-cyclodextrin (HP-β-CD) formed as a result of the interaction of the piperidine fragment of the RB molecule and the hydrophobic cavity of the HP-β-CD molecule was found. The stability constant of the intermolecular complex was determined.

  1. Determination of stepsize parameters for intermolecular vibrational energy transfer

    International Nuclear Information System (INIS)

    The understanding of intermolecular vibrational energy transfer (IVET) is important since it is involved in any mechanism in which internal energy is added or removed from molecules. The database for the details of IVET for highly excited polyatomic molecules is inadequate and must be expanded. The overall objectives of this project are: (1) to determine the dependence of energy relaxation on excitation energy and on the molecular complexity of substrate and deactivator, (2) to assess the importance of intermolecular attractions on IVET, (3) to obtain more detailed information on the energy distribution after collision, and (4) to evaluate the importance of IVET on high temperature unimolecular reactions. The first three objectives are being met by experimentally measuring the time evolution of the average energy of the vibrationally excited species (hydro- and fluoro- carbons excited by a pulsed CO2 laser) and the average energy transferred into relative translation via time resolved IR spectrometry, interferometry and optoacoustic techniques. Trajectory calculations simulating IVET are being performed for model substrate/deactivator pairs to provide additional details and insight on the critical parameters. Our calculations for high temperature unimolecular reactions indicate that IVET effects are significant and must be correctly taken into account. 9 refs., 3 figs., 6 tabs

  2. Ab initio investigation of intermolecular interactions in solid benzene

    CERN Document Server

    Bludsky, O; Soldan, P; 10.1103/PhysRevB.77.092103

    2009-01-01

    A computational strategy for the evaluation of the crystal lattice constants and cohesive energy of the weakly bound molecular solids is proposed. The strategy is based on the high level ab initio coupled-cluster determination of the pairwise additive contribution to the interaction energy. The zero-point-energy correction and non-additive contributions to the interaction energy are treated using density functional methods. The experimental crystal lattice constants of the solid benzene are reproduced, and the value of 480 meV/molecule is calculated for its cohesive energy.

  3. Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

    International Nuclear Information System (INIS)

    Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O, and S are presented. The Root Mean Square Deviation (RMSD) interaction energy is improved from 6.07 kcal/mol to 1.49 kcal/mol for interactions with one charged species, whereas the RMSD is improved from 5.60 kcal/mol to 1.73 for a set of 9 salt bridges, compared to uncorrected DFTB3. For large water clusters and complexes that are dominated by dispersion interactions, the already satisfactory performance of the DFTB3-D3 model is retained; polarizabilities of neutral molecules are also notably improved. Overall, the CPE extension of DFTB3-D3 provides a more balanced description of different types of non-covalent interactions than Neglect of Diatomic Differential Overlap type of semi-empirical methods (e.g., PM6-D3H4) and PBE-D3 with modest basis sets

  4. Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

    Science.gov (United States)

    Christensen, Anders S.; Elstner, Marcus; Cui, Qiang

    2015-08-01

    Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O, and S are presented. The Root Mean Square Deviation (RMSD) interaction energy is improved from 6.07 kcal/mol to 1.49 kcal/mol for interactions with one charged species, whereas the RMSD is improved from 5.60 kcal/mol to 1.73 for a set of 9 salt bridges, compared to uncorrected DFTB3. For large water clusters and complexes that are dominated by dispersion interactions, the already satisfactory performance of the DFTB3-D3 model is retained; polarizabilities of neutral molecules are also notably improved. Overall, the CPE extension of DFTB3-D3 provides a more balanced description of different types of non-covalent interactions than Neglect of Diatomic Differential Overlap type of semi-empirical methods (e.g., PM6-D3H4) and PBE-D3 with modest basis sets.

  5. Identification and measurement of intermolecular interaction in polyester/polystyrene blends by FTIR-photoacoustic spectrometry

    Science.gov (United States)

    Fourier transform infrared photoacoustic spectrometry was used to reveal and identify n-p type intermolecular interaction formed in plastic comprising binary blends of polystyrene and a biodegradable polymer, either polylactic acid, polycaprolactone or poly(tetramethyleneadipate-co-terephthalate)....

  6. Intermolecular interactions in poly(vinylidene fluoride) and ?-caprolactam mixtures

    OpenAIRE

    Liu, Zehui; Marchal, Philippe; Jrme, Robert

    1996-01-01

    Mixtures of poly(vinylidene fluoride) (PVDF) and caprolactam (CPL) have been investigated as models for possible cross-interactions between vinylidene fluoride and amide structural units, that might account for the very fine phase morphology previously observed in PVDF/polyamide 6 blends. Over the entire composition range, the PVDF/CPL mixtures are monophase above the PVDF melting temperature. From the depression of the PVDF melting point, a negative interaction energy density, B, has been ca...

  7. Double strand interaction is the predominant pathway for intermolecular recombination of adeno-associated viral genomes

    International Nuclear Information System (INIS)

    Intermolecular recombination is the foundation for dual vector mediated larger gene transfer by recombinant adeno-associated virus (rAAV). To identify precursors for intermolecular recombination, we sequentially infected skeletal muscle with AAV LacZ trans-splicing viruses. At 1 month postinfection, nearly all inputting single-strand (ss) AAV genomes were cleared out in muscle. If ss-ss interaction is absolutely required for intermolecular recombination, LacZ expression from sequential infection will be negligible to that from coinfection. Interestingly, expression from sequential infection reached ?50% of that from coinfection at the 1-month time-point in BL6 mice. In immune deficient SCID mice, expression from sequential infection was comparable to that from coinfection at the 4- and 13-month time points. Our results suggest that ds interaction represents the predominant pathway for AAV intermolecular recombination

  8. Determination of stepsize parameters for intermolecular vibrational energy transfer

    Energy Technology Data Exchange (ETDEWEB)

    Tardy, D.C.

    1992-03-01

    Intermolecular energy transfer of highly excited polyatomic molecules plays an important role in many complex chemical systems: combustion, high temperature and atmospheric chemistry. By monitoring the relaxation of internal energy we have observed trends in the collisional efficiency ({beta}) for energy transfer as a function of the substrate's excitation energy and the complexities of substrate and deactivator. For a given substrate {beta} increases as the deactivator's mass increase to {approximately}30 amu and then exhibits a nearly constant value; this is due to a mass mismatch between the atoms of the colliders. In a homologous series of substrate molecules (C{sub 3}{minus}C{sub 8}) {beta} decreases as the number of atoms in the substrate increases; replacing F with H increases {beta}. All substrates, except for CF{sub 2}Cl{sub 2} and CF{sub 2}HCl below 10,000 cm{sup {minus}1}, exhibited that {beta} is independent of energy, i.e. <{Delta}E>{sub all} is linear with energy. The results are interpreted with a simple model which considers that {beta} is a function of the ocillators energy and its vibrational frequency. Limitations of current approximations used in high temperature unimolecular reactions were evaluated and better approximations were developed. The importance of energy transfer in product yields was observed for the photoactivation of perfluorocyclopropene and the photoproduction of difluoroethyne. 3 refs., 18 figs., 4 tabs.

  9. A Colloidal Description of Intermolecular Interactions Driving Fibril-Fibril Aggregation of a Model Amphiphilic Peptide.

    Science.gov (United States)

    Owczarz, Marta; Motta, Anna C; Morbidelli, Massimo; Arosio, Paolo

    2015-07-14

    We apply a kinetic analysis platform to study the intermolecular interactions underlying the colloidal stability of dispersions of charged amyloid fibrils consisting of a model amphiphilic peptide (RADA 16-I). In contrast to the aggregation mechanisms observed in the large majority of proteins and peptides, where several elementary reactions involving both monomers and fibrils are present simultaneously, the system selected in this work allows the specific investigation of the fibril-fibril aggregation process. We examine the intermolecular interactions driving the aggregation reaction at pH 2.0 by changing the buffer composition in terms of salt concentration, type of ion as well as type and concentration of organic solvent. The aggregation kinetics are followed by dynamic light scattering, and the experimental data are simulated by Smoluchowski population balance equations, which allow to estimate the energy barrier between two colliding fibrils in terms of the Fuchs stability ratio (W). When normalized on a dimensionless time weighted on the Fuchs stability ratio, the aggregation profiles under a broad range of conditions collapse on a single master curve, indicating that the buffer composition modifies the aggregation kinetics without affecting the aggregation mechanism. Our results show that the aggregation process does not occur under diffusion-limited conditions. Rather, the reaction rate is limited by the presence of an activation energy barrier that is largely dominated by electrostatic repulsive interactions. Such interactions could be reduced by increasing the concentration of salt, which induces charge screening, or the concentration of organic solvent, which affects the dielectric constant. It is remarkable that the dependence of the activation energy on the ionic strength can be described quantitatively in terms of charge screening effects in the frame of the DLVO theory, although specific anion and cation effects are also observed. While anion effects are mainly related to the binding to the positive groups of the fibril surface and to the resulting decrease of the surface charge, cation effects are more complex and involve additional solvation forces. PMID:26125620

  10. MODELS OF AMPHOTERICIN MEMBRANE CHANNEL BASED ON CONCERTED INTERMOLECULAR =C-HO INTERACTIONS

    Directory of Open Access Journals (Sweden)

    Lisnyak Yu. V

    2012-10-01

    Full Text Available To study the possibility for amphotericin to form membrane channel via intermolecular interactions mimicing the association mode of polyene macrolides in crystal structures we have built two channel models in vacuo: amphotericin B octamer and hexamer. The octamer model does not reproduce the concerted weak =C-HO intermolecular interactions within the whole aggregate structure and has too large pore diameter. For hexamer model, the pore diameter is within experimental estimates. The hexamer model rather well reproduces characteristic features of a channel with such concerted weak interactions: association mode, H-bonding pattern within the whole assembly and accessibility of polyene hydroxyl groups for hydrophyllic interactions in the pore.

  11. Reversible electron-induced cis-trans isomerization mediated by intermolecular interactions

    International Nuclear Information System (INIS)

    Reversible isomerization processes are rarely found when organic molecular switches are adsorbed on metal surfaces. One obstacle is the large energy difference of the isomeric forms, since usually the most planar conformer has the largest adsorption energy. In the example of an imine derivative, we show a strategy for also stabilizing the non-planar isomer by intermolecular bonding to its neighbors. Tunneling electrons from the tip of a scanning tunneling microscope can then be used to induce reversible switching between the trans and cis-like state. Supported by model force-field calculations, we illustrate that the most probable cause of the enhanced stability of the three-dimensional cis state at specific adsorption sites is the electrostatic interaction with N sites of the neighboring molecule.

  12. Modulation of the intermolecular interaction of myoglobin by removal of the heme

    Energy Technology Data Exchange (ETDEWEB)

    Imamura, Hiroshi; Morita, Takeshi [Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan); Sumi, Tomonari [Okayama University, 3-1-1 Tsushima-Naka, Kita-ku, Okayama 700-8530 (Japan); Isogai, Yasuhiro [Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama 939-0398 (Japan); Kato, Minoru [Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577 (Japan); Nishikawa, Keiko, E-mail: k.nishikawa@faculty.chiba-u.jp [Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)

    2013-11-01

    The present study analysed small-angle X-ray scattering profiles of myoglobin to examine how removal of the heme changes the intermolecular interaction. Toward understanding intermolecular interactions governing self-association of proteins, the present study investigated a model protein, myoglobin, using a small-angle X-ray scattering technique. It has been known that removal of the heme makes myoglobin aggregation-prone. The interparticle interferences of the holomyoglobin and the apomyoglobin were compared in terms of the structure factor. Analysis of the structure factor using a model potential of Derjaguin–Laudau–Verwey–Overbeek (DLVO) suggests that the intermolecular interaction potential of apomyoglobin is more attractive than that of holomyoglobin at short range from the protein molecule.

  13. Influence of Electrostatic and Intermolecular Interactions on the Solution Behavior and Electrospinning of Functional Nanofibers

    OpenAIRE

    Hunley, Matthew T

    2010-01-01

    The solution rheological and electrospinning behavior of a series of charge-containing polymers, surface-active agents, and carbon nanotube composites was studied to investigate the effect of intermolecular interactions, including electrostatic interactions, hydrogen bonding, surface activity, and surface functionalization of carbon nanotubes. The synthesis of novel polyelectrolytes with varied topologies, charge content, and counterions tailored the charged macromolecules to elucidate struc...

  14. Application of atomic force microscopy for characteristics of single intermolecular interactions.

    Science.gov (United States)

    Safenkova, I V; Zherdev, A V; Dzantievf, B B

    2012-12-01

    Atomic force microscopy (AFM) can be used to make measurements in vacuum, air, and water. The method is able to gather information about intermolecular interaction forces at the level of single molecules. This review encompasses experimental and theoretical data on the characterization of ligand-receptor interactions by AFM. The advantage of AFM in comparison with other methods developed for the characterization of single molecular interactions is its ability to estimate not only rupture forces, but also thermodynamic and kinetic parameters of the rupture of a complex. The specific features of force spectroscopy applied to ligand-receptor interactions are examined in this review from the stage of the modification of the substrate and the cantilever up to the processing and interpretation of the data. We show the specificities of the statistical analysis of the array of data based on the results of AFM measurements, and we discuss transformation of data into thermodynamic and kinetic parameters (kinetic dissociation constant, Gibbs free energy, enthalpy, and entropy). Particular attention is paid to the study of polyvalent interactions, where the definition of the constants is hampered due to the complex stoichiometry of the reactions. PMID:23379527

  15. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions

    Science.gov (United States)

    Azar, Richard Julian; Head-Gordon, Martin

    2015-05-01

    Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the "(2)"-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order.

  16. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Azar, Richard Julian, E-mail: julianazar2323@berkeley.edu; Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu [Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-05-28

    Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the “(2)”-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order.

  17. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions.

    Science.gov (United States)

    Azar, Richard Julian; Head-Gordon, Martin

    2015-05-28

    Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the "(2)"-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order. PMID:26026428

  18. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions

    International Nuclear Information System (INIS)

    Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the “(2)”-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order

  19. Effect of intermolecular interactions on the nucleation, growth, and propagation of like-spin domains in spin-crossover materials

    Science.gov (United States)

    Slimani, A.; Boukheddaden, K.; Yamashita, K.

    2015-07-01

    The nucleation, growth, and propagation of like-spin domains in spin-crossover materials was investigated during the relaxation process of a metastable HS state at low temperature using an electroelastic model running on a deformable two-dimensional square lattice. We distinguish the onset of patterns formation of low-spin domain as the intermolecular interaction is increased, passing successively through random dispersion to clustering pattern and ending up with an impressive single macroscopic domain growth. Attaining and maintaining a single-domain configuration through the transition is attributed to the long-range character of interactions. Qualitative investigation of the elastic energy, of the propagation of the low-spin domain, and of the displacement field are presented. We demonstrate that as the intermolecular interaction increases the propagation of the like-spin domain slowdown. The deformations are believed as the prolonged effect of the intermolecular interactions that are at the origin of the onset of dispersed, poly-, and single-domain nucleation. Spatial autocorrelation of the deformations analysis based on Moran's I index is used. We demonstrate that at short distance significant spatially autocorrelated patterns are detected, and the extent of the autocorrelation decreases with the distance.

  20. Ab initio intermolecular potential energy surface and thermophysical properties of nitrous oxide

    International Nuclear Information System (INIS)

    We present an analytical intermolecular potential energy surface (PES) for two rigid nitrous oxide (N2O) molecules derived from high-level quantum-chemical ab initio calculations. Interaction energies for 2018 N2O–N2O configurations were computed utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory using basis sets up to aug-cc-pVQZ supplemented with bond functions. A site-site potential function with seven sites per N2O molecule was fitted to the pair interaction energies. We validated our PES by computing the second virial coefficient as well as shear viscosity and thermal conductivity in the dilute-gas limit. The values of these properties are substantiated by the best experimental data

  1. Vibrational spectroscopy on intermolecular interactions in solutions and at interfaces

    OpenAIRE

    Nissink, Johannes Wilhelmus Maria

    1999-01-01

    In recent years, considerable progress has been made in the areas of molecular recognition and surface analysis. These fields meet in the field of sensor development, where the interaction between molecules and a suitably modified surface is of utmost importance. Vibrational spectroscopy is quite useful in these areas of research, as it may reveal the processes taking place at a molecular level. This thesis describes a number of applications of vibrational spectroscopy in the anal...

  2. Investigation of Intermolecular Interaction in Organic Thin Films by means of NEXAFS Spectroscopy

    OpenAIRE

    Holch, Florian

    2010-01-01

    The present work reports on the electron–vibron coupling in large organic molecules and particularly on the intermolecular interaction in molecular condensates. The optical and electrical properties of these organic systems are in the focus of attention due to their crucial importance for the development of (hybrid) organic electronic devices. In particular, the charge transport mechanism and hence the interaction between condensed molecules is a matter of debate [1–4]. In order to shed light...

  3. DFT calculation of the intermolecular exchange interaction in the magnetic Mn$_4$ dimer

    OpenAIRE

    Park, Kyungwha; Pederson, Mark R.; Richardson, Steven L.; Aliaga-Alcalde, Nuria; Christou, George

    2003-01-01

    The dimeric form of the single-molecule magnet [Mn$_4$O$_3$Cl$_4$(O$_2$CEt)$_3$(py)$_3$]$_2$ recently revealed interesting phenomena: no quantum tunneling at zero field and tunneling before magnetic field reversal. This is attributed to substantial antiferromagnetic exchange interaction between different monomers. The intermolecular exchange interaction, electronic structure and magnetic properties of this molecular magnet are calculated using density-functional theory within generalized-grad...

  4. Ab initio investigation of intermolecular interactions in solid benzene

    Czech Academy of Sciences Publication Activity Database

    Bludský, Ota; Rubeš, Miroslav

    2008-01-01

    Roč. 77, - (2008), 092103/1-092103/4. ISSN 1098-0121 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550613 Institutional research plan: CEZ:AV0Z40550506 Keywords : augmented-wawe method * rare-gas solids * energies Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.322, year: 2008

  5. Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions

    International Nuclear Information System (INIS)

    The polarization energy in intermolecular interactions treated by self-consistent field electronic structure theory is often evaluated using a constraint that the atomic orbital (AO) to molecular orbital transformation is blocked by fragments. This approach is tied to AO basis sets, overestimates polarization energies in the overlapping regime, particularly in large AO basis sets, and lacks a useful complete basis set limit. These problems are addressed by the construction of polarization subspaces based on the responses of isolated fragments to weak electric fields. These subspaces are spanned by fragment electric-field response functions, which can capture effects up to the dipole (D), or quadrupole (DQ) level, or beyond. Schemes are presented for the creation of both non-orthogonal and orthogonal fragment subspaces, and the basis set convergence of the polarization energies computed using these spaces is assessed. Numerical calculations for the water dimer, water–Na+, water–Mg2+, water–F−, and water–Cl− show that the non-orthogonal DQ model is very satisfactory, with small differences relative to the orthogonalized model. Additionally, we prove a fundamental difference between the polarization degrees of freedom in the fragment-blocked approaches and in constrained density schemes. Only the former are capable of properly prohibiting charge delocalization during polarization

  6. Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions.

    Science.gov (United States)

    Horn, Paul R; Head-Gordon, Martin

    2015-09-21

    The polarization energy in intermolecular interactions treated by self-consistent field electronic structure theory is often evaluated using a constraint that the atomic orbital (AO) to molecular orbital transformation is blocked by fragments. This approach is tied to AO basis sets, overestimates polarization energies in the overlapping regime, particularly in large AO basis sets, and lacks a useful complete basis set limit. These problems are addressed by the construction of polarization subspaces based on the responses of isolated fragments to weak electric fields. These subspaces are spanned by fragment electric-field response functions, which can capture effects up to the dipole (D), or quadrupole (DQ) level, or beyond. Schemes are presented for the creation of both non-orthogonal and orthogonal fragment subspaces, and the basis set convergence of the polarization energies computed using these spaces is assessed. Numerical calculations for the water dimer, water-Na(+), water-Mg(2+), water-F(-), and water-Cl(-) show that the non-orthogonal DQ model is very satisfactory, with small differences relative to the orthogonalized model. Additionally, we prove a fundamental difference between the polarization degrees of freedom in the fragment-blocked approaches and in constrained density schemes. Only the former are capable of properly prohibiting charge delocalization during polarization. PMID:26395691

  7. Intermolecular interactions in the bilirubin-cholate-silica system

    Science.gov (United States)

    Vlasova, N. N.; Golovkova, L. P.; Severinovskaya, O. V.

    2007-06-01

    Bilirubin-cholate interactions in aqueous solutions were studied. The constants of binding of bilirubin with taurocholate dimers and taurodeoxycholate trimers were calculated. The adsorption of bilirubin and cholates on the surface of highly dispersed silica was studied. It was shown that taurine-conjugated cholates are poorly adsorbed from micellar solutions on the silica surface, the specific amount of bilirubin adsorbed decreases with increasing concentration of cholates in the solution, the affinity of free bilirubin for the silica surface is independent of the nature of the cholic acid, and that the affinity of cholate-bilirubin complexes for the silica surface is lower than the affinity of free bilirubin.

  8. Changes of microstructure characteristics and intermolecular interactions of preserved egg white gel during pickling.

    Science.gov (United States)

    Zhao, Yan; Chen, Zhangyi; Li, Jianke; Xu, Mingsheng; Shao, Yaoyao; Tu, Yonggang

    2016-07-15

    Changes in gel microstructure characteristics and in intermolecular interactions of preserved egg whites during pickling were investigated. Spin-spin relaxation times of preserved egg whites significantly decreased in the first 8days and remained unchanged after the 16th day. SEM images revealed a three-dimensional gel network, interwoven with a loose linear fibrous mesh structure. The protein gel mesh structure became more regular, smaller, and compacted with pickling time. Free sulfhydryl contents in the egg whites increased significantly, while total sulfhydryl contents dramatically decreased during pickling. The primary intermolecular forces in the preserved egg white gels were ionic and disulfide bonds. Secondary forces included hydrophobic interaction and relatively few hydrogen bonds. During the first 8days, the proportion of ionic bonds sharply decreased, and that of disulfide bonds increased over the first 24days. PMID:26948621

  9. Investigation of intermolecular interactions and hydrogen bonds in the gas phase. Possibilities and perspectives

    International Nuclear Information System (INIS)

    The band shape of the νHF in B ..HF complexes was studied in the gas phase at 293 K, where B = HCN, H2O, (CH3)2O and (CH3)2CO. The band shape was reconstructed non empirically as a superposition of ro-vibrational bands of the fundamental, hot and combination transitions from excited states of low-frequency modes. Anharmonic interactions between different intermolecular motions are also analyzed in detail. (authors)

  10. The Molecular Oxygen Tetramer: Intermolecular Interactions and Implications for the $\\epsilon$ Solid Phase

    OpenAIRE

    Bartolomei, Massimiliano; Carmona-Novillo, Estela; Hernández, Marta. I.; Pérez-Ríos, J.; Campos-Martínez, José; Hernández Lamoneda, Ramón

    2011-01-01

    Recent data have determined that the structure of the high-pressure ε phase of solid oxygen consists of clusters composed of four O2 molecules. This finding has opened the question about the nature of the intermolecular interactions within the molecular oxygen tetramer. We use multiconfigurational ab initio calculations to obtain an adequate characterization of the ground singlet state of (O2)4, which is compatible with the nonmagnetic character of the ε phase. In contrast to previous suggest...

  11. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    International Nuclear Information System (INIS)

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN)4] layers to form a solid of formula unit T(ImD)2[Ni(CN)4]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN)4] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives

  12. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    Energy Technology Data Exchange (ETDEWEB)

    González, M.; Lemus-Santana, A.A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Rodríguez-Hernández, J. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, Havana (Cuba); Aguirre-Velez, C.I. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico); Knobel, M. [Institute of Physics “Gleb Wataghin”, UNICAMP, 13083-970 Campinas, SP (Brazil); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México, DF (Mexico)

    2013-08-15

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN){sub 4}] layers to form a solid of formula unit T(ImD){sub 2}[Ni(CN){sub 4}]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN){sub 4}] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives.

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

    International Nuclear Information System (INIS)

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

  14. Determination of Intermolecular Interactions Using Polarization Compensated Heteronuclear Overhauser Effect of Hyperpolarized Spins.

    Science.gov (United States)

    Kim, Jihyun; Liu, Mengxiao; Chen, Hsueh-Ying; Hilty, Christian

    2015-11-01

    The nuclear Overhauser effect (NOE) has long been used as a selective indicator for intermolecular interactions. Due to relatively small changes of signal intensity, often on the order of several percent, quantitative NOE measurements can be challenging. Hyperpolarization of nuclear spins can dramatically increase the NOE intensity by increasing population differences, but poses its own challenge in quantifying the original polarization level. Here, we demonstrate a method for the accurate measurement of intermolecular heteronuclear cross-relaxation rates by simultaneous acquisition of signals from both nuclei. Using this method, we measure cross-relaxation rates between water protons and (19)F of trifluoroacetic acid at concentrations ranging from 23 to 72 mM. A concentration-independent value of 2.46 10(-4) 1.02 10(-5) s(-1) M(-1) is obtained at a temperature of 301 K and validated using a nonhyperpolarized measurement. In a broader context, accurate measurement of heteronuclear cross-relaxation rates may enable the study of intermolecular interactions including those involving macromolecules where (19)F atoms can be introduced as site-selective labels. PMID:26426882

  15. Physical nature of intermolecular interactions inside Sir2 homolog active site: molecular dynamics and ab initio study.

    Science.gov (United States)

    Czeleń, Przemysław; Czyżnikowska, Żaneta

    2016-06-01

    In the present study, we analyze the interactions of NAD+-dependent deacetylase (Sir2 homolog yeast Hst2) with carba-nicotinamide-adenine-dinucleotide (ADP-HPD). For the Sir2 homolog, a yeast Hst2 docking procedure was applied. The structure of the protein-ADP-HPD complex obtained during the docking procedure was used as a starting point for molecular dynamics simulation. The intermolecular interaction energy partitioning was performed for protein-ADP-HPD complex resulting from molecular dynamics simulation. The analysis was performed for ADP-HPD and 15 amino acids forming a deacetylase binding pocket. Although the results indicate that the first-order electrostatic interaction energy is substantial, the presence of multiple hydrogen bonds in investigated complexes can lead to significant value of induction component. PMID:27154340

  16. An isotopic mass effect on the intermolecular potential

    Science.gov (United States)

    Herman, Michael F.; Currier, Robert P.; Clegg, Samuel M.

    2015-10-01

    The impact of isotopic variation on the electronic energy and intermolecular potentials is often suppressed when calculating isotopologue thermodynamics. Intramolecular potential energy surfaces for distinct isotopologues are in fact equivalent under the Born-Oppenheimer approximation, which is sometimes used to imply that the intermolecular interactions are independent of isotopic mass. In this communication, the intermolecular dipole-dipole interaction between hetero-nuclear diatomic molecules is considered. It is shown that the intermolecular potential contains mass-dependent terms even though each nucleus moves on a Born-Oppenheimer surface. The analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.

  17. Vibrational Circular Dichroism (VCD) Reveals Subtle Conformational Aspects and Intermolecular Interactions in the Carnitine Family.

    Science.gov (United States)

    Mazzeo, Giuseppe; Abbate, Sergio; Longhi, Giovanna; Castiglioni, Ettore; Villani, Claudio

    2015-12-01

    Vibrational circular dichroism spectra (VCD) in the mid-IR region and electronic circular dichroism (ECD) spectra for three carnitine derivatives in the form of hydrochloride salts were recorded in deuterated methanol solutions. Density Functional Theory calculations help one to understand the significance of the observed VCD bands. VCD and ECD spectra are informative about the absolute configuration of the molecule, but VCD data reveal also some conformational aspects in the N,N,N-trimethyl moiety and inform us about intermolecular interactions gained from the carbonyl stretching region for the acyl substituted carnitines. PMID:26447810

  18. Relativistic effects in the intermolecular interaction-induced nuclear magnetic resonance parameters of xenon dimer

    DEFF Research Database (Denmark)

    Hanni, Matti; Lantto, Perttu; Ilias, Miroslav; Jensen, Hans Jørgen Aagaard; Vaara, Juha

    2007-01-01

    Relativistic effects on the 129Xe nuclear magnetic resonance shielding and 131Xe nuclear quadrupole coupling (NQC) tensors are examined in the weakly bound Xe2 system at different levels of theory including the relativistic four-component Dirac-Hartree-Fock (DHF) method. The intermolecular...... interaction-induced binary chemical shift d, the anisotropy of the shielding tensor ?s, and the NQC constant along the internuclear axis ?ll are calculated as a function of the internuclear distance. DHF shielding calculations are carried out using gauge-including atomic orbitals. For comparison, the full...

  19. Intermolecular Interactions and the Release Pattern of Electrospun Curcumin-Polyvinyl(pyrrolidone) Fiber.

    Science.gov (United States)

    Rahma, Annisa; Munir, Muhammad Miftahul; Khairurrijal; Prasetyo, Anton; Suendo, Veinardi; Rachmawati, Heni

    2016-01-01

    An electrospun fiber of polyvinyl(pyrrolidone) (PVP)-Tween 20 (T20) with curcumin as the encapsulated drug has been developed. A study of intermolecular interactions was performed using Raman spectroscopy, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The Raman and FT-IR studies showed that curcumin preferrably interacted with T20 and altered PVP chain packing, as supported by XRD and physical stability data. The hydroxyl stretching band in PVP shifted to a lower wavenumber with higher intenstity in the presence of curcumin and PVP, indicating that hydrogen bond formation is more intense in a curcumin or curcumin-T20 containing fiber. The thermal pattern of the fiber did not indicate phase separation. The conversion of curcumin into an amorphous state was confirmed by XRD analysis. An in vitro release study in phosphate buffer pH 6.8 showed that intermolecular interactions between each material influenced the drug release rate. However, low porosity was found to limit the hydrogen bond-mediated release. PMID:26830478

  20. Intermolecular interactions during complex coacervation of pea protein isolate and gum arabic.

    Science.gov (United States)

    Liu, Shuanghui; Cao, Yuan-Long; Ghosh, Supratim; Rousseau, Dérick; Low, Nicholas H; Nickerson, Michael T

    2010-01-13

    The nature of intermolecular interactions during complexation between pea protein isolate (PPI) and gum arabic (GA) was investigated as a function of pH (4.30-2.40) by turbidimetric analysis and confocal scanning microscopy in the presence of destabilizing agents (100 mM NaCl or 100 mM urea) and at different temperatures (6-60 degrees C). Complex formation followed two pH-dependent structure-forming events associated with the formation of soluble and insoluble complexes and involved interactions between GA and PPI aggregates. Complex formation was driven by electrostatic attractive forces between complementary charged biopolymers, with secondary stabilization by hydrogen bonding. Hydrophobic interactions were found to enhance complex stability at lower pH (pH 3.10), but not with its formation. PMID:19938857

  1. Permutationally invariant fitting of intermolecular potential energy surfaces: A case study of the Ne-C2H2 system

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2015-12-01

    The permutation invariant polynomial-neural network (PIP-NN) approach is extended to fit intermolecular potential energy surfaces (PESs). Specifically, three PESs were constructed for the Ne-C2H2 system. PES1 is a full nine-dimensional PIP-NN PES directly fitted to ˜42 000 ab initio points calculated at the level of CCSD(T)-F12a/cc-pCVTZ-F12, while the other two consist of the six-dimensional PES for C2H2 [H. Han, A. Li, and H. Guo, J. Chem. Phys. 141, 244312 (2014)] and an intermolecular PES represented in either the PIP (PES2) or PIP-NN (PES3) form. The comparison of fitting errors and their distributions, one-dimensional cuts and two-dimensional contour plots of the PESs, as well as classical trajectory collisional energy transfer dynamics calculations shows that the three PESs are very similar. We conclude that full-dimensional PESs for non-covalent interacting molecular systems can be constructed efficiently and accurately by the PIP-NN approach for both the constituent molecules and intermolecular parts.

  2. Generalized Intermolecular Interaction Tensor Applied to Long-Range Interactions in Hydrogen and Coinage Metal (Cu, Ag, and Au) Clusters.

    Science.gov (United States)

    Hatz, Richard; Korpinen, Markus; Hnninen, Vesa; Halonen, Lauri

    2015-12-01

    We present a novel formulation for the intermolecular interaction tensor, which is used to describe the long-range electrostatic, induction, and dispersion interactions. Our formulation is based on concepts drawn from combinatorial analysis and Clifford calculus and enables us to present the interaction tensor in a form that is simple to use and suitable for both numerical and symbolic analyses. We apply the derived formulas to calculate the long-range interaction coefficients in hydrogen and coinage metal (Cu, Ag, and Au) clusters. The electronic structure calculations are performed at the CCSD(T) level, with triple-? and quadruple-? basis sets. The multipole moments and dispersion coefficients are obtained as fits to the derived interaction formulas. The most important interaction parameters are obtained accurately and are in good agreement with other results. PMID:26501212

  3. Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D., E-mail: sdchao@spring.iam.ntu.edu.tw [Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan (China)

    2014-10-07

    We perform an ab initio computational study of molecular complexes with the general formula CF{sub 3}X—B that involve one trifluorohalomethane CF{sub 3}X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH{sub 3} and PH{sub 3}), two n-pairs (H{sub 2}O and H{sub 2}S), two n-pairs with an unsaturated bond (H{sub 2}CO and H{sub 2}CS), and a single π-pair (C{sub 2}H{sub 4}) and two π-pairs (C{sub 2}H{sub 2}). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C–X bond lengths shorten, while the C–X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

  4. Gold behaves as hydrogen in the intermolecular self-interaction of metal aurides MAu4 (M = Ti, Zr, and Hf).

    Science.gov (United States)

    Jung, Jaehoon; Kim, Hyemi; Kim, Jong Chan; Park, Min Hee; Han, Young-Kyu

    2011-03-01

    We performed density functional calculations to examine the intermolecular self-interaction of metal tetraauride MAu(4) (M = Ti, Zr, and Hf) clusters. We found that the metal auride clusters have strong dimeric interactions (2.8-3.1 eV) and are similar to the metal hydride analogues with respect to structure and bonding nature. Similarly to (MH(4))(2), the (μ-Au)(3) C(s) structures with three three-center two-electron (3c-2e) bonds were found to be the most stable. Natural orbital analysis showed that greater than 96 % of the Au 6s orbital contributes to the 3c-2e bonds, and this predominant s orbital is responsible for the similarity between metal aurides and metal hydrides (>99 % H 1s). The favorable orbital interaction between occupied Au 6s and unoccupied metal d orbitals leads to a stronger dimeric interaction for MAu(4)-MAu(4) than the interaction for MH(4)-MH(4). There is a strong relationship between the dimeric interaction energy and the chemical hardness of its monomer for (MAu(4))(2) and (MH(4))(2). PMID:21225974

  5. Crystal structures and intermolecular interactions of two novel antioxidant triazolyl-benzimidazole compounds

    Energy Technology Data Exchange (ETDEWEB)

    Karayel, A., E-mail: matchlessjimmy@163.com, E-mail: yccaoh@hotmail.com; Özbey, S. [Hacettepe University, Physics Engineering Department (Turkey); Ayhan-Kılcıgil, G.; Kuş, C. [Ankara University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)

    2015-12-15

    The crystal structures of 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(3-fluorophenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G6C) and 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(2-methylphenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G4C) have been determined by single-crystal X-ray diffraction. Benzimidazole ring systems in both molecules are planar. The triazole part is almost perpendicular to the phenyl and the benzimidazole parts of the molecules in order to avoid steric interactions between the rings. The crystal structures are stabilized by intermolecular hydrogen bonds between the amino group of the triazole and the nitrogen atom of benzimidazole of a neighboring molecule.

  6. Intermolecular interactions in binary mixtures of 2-Chloroethanol with 2-Dimethylaminoethanol and 2-Diethylaminoethanol at different temperatures

    International Nuclear Information System (INIS)

    Highlights: • Ultrasonic, volumetric and spectroscopic properties of 2-CletOH + DMAE/DEAE liquid mixtures were studied. • Results showed the presence of intermolecular hydrogen bonding between the unlike molecules. • H-bonding occurred between hydrogen atom of –OH group of 2-CletOH and oxygen atom of –OH group of DMAE/DEAE. • The strength of intermolecular interactions was found in order: 2-CletOH + DEAE > 2-CletOH + DMAE. - Abstract: The ultrasonic velocity (u) and density (ρ) of binary mixtures of 2-Chloroethanol (2-CletOH) with 2-Dimethylaminoethanol (DMAE) and 2-Diethylaminoethanol (DEAE) have been measured over the entire concentration range at temperatures 293.15, 303.15 and 313.15 K. The ultrasonic velocity and density data are used to estimate adiabatic compressibility (βS), intermolecular free length (Lf), molar sound velocity (R), molar compressibility (B) and specific acoustic impedance (Z) along with excess values of ultrasonic velocity (uE), adiabatic compressibility (βSE), intermolecular free length (LfE), acoustic impedance (ZE) and molar volume (VmE). The infrared spectra of both of the systems, 2-CletOH + DMAE and 2-CletOH + DEAE, have also been recorded at room temperature (298.15 K). The observed variations of these parameters, with concentration and temperature, are discussed in terms of the intermolecular interactions between the unlike molecules of the binary mixtures

  7. Spectroscopic studies on weak intermolecular interactions of fluoranthene derivatives with benzene or ethanol in cyclohexane

    International Nuclear Information System (INIS)

    Complete text of publication follows. We have published on the spectroscopic study on the formation of a 1:1 molecular complex of fluoranthene (F) with benzene (B) in cyclohexane and estimated the equilibrium constant K(F-B) (0.147 dm3 mol-1 at 298 K), enthalpy change DH(F-B) (-5.9 kJ mol-1) and entropy change DS(F-B) (-36 JK-1mol-1 at 298 K) for this complex formation (S. Enomoto et al., Bull. Chem. Soc. Jpn., 75 (2002) 689-693). In this study, the electronic absorption spectra have been observed for the fluoranthene derivatives in cyclohexane-benzene and/or cyclohexane-ethanol mixed solvents to investigate the weak intermolecular interactions between fluoranthene derivatives and benzene or ethanol. The electronic absorption spectra of 3-aminofluoranthene (AF) in the mixed solvent mentioned above showed isosbestic points with varying B and ethanol (E) concentrations. These observations indicate that AF forms a 1:1 molecular complex with B or E, the K(AF-B) and K(AF-E) values for these complex formations being estimated as 0.146 and 0.647 dm3 mol-1 at 298 K, respectively. Temperature dependence of K(AF-B) and K(AF-E) yielded ?H(AF-B) and ?H(AF-E) values of -6.3 and -14.2 kJ mol-1, respectively, ?S(AF-B) and ?S(AF-E) values being respectively calculated as -40 and -51 JK-1mol-1 at 298 K. Applying similar experimental and calculational procedures to 3-nitrofluoranthene (NF) in cyclohexane-B mixed solvent, K(NF-B), ?H(NF-B) and ?S(NF-B) values were estimated as 0.064 dm3 mol-1 at 298 K, -14.6 kJ mol-1 and -72 JK-1 mol1 at 298 K, respectively, for the 1:1 molecular complex formation of NF with B. It is interesting to note that the amino group has almost no effect on the stability of F-B molecular complex since K(AF-B) is comparable to K(F-B) value. It is, further, noted that AF-E and NF-B complexes are enthalpically easier and entropically harder to be formed, respectively, than AF-B one. Assuming that the dispersion energy involved in ?H(NF-B) is the same in magnitude as ?H(F-B) which is considered to be purely dispersion energy, the induction energy contributed to ?H(NF-B) is calculated as -8.7 kJ mol-1. Concerning the conformations of AF-B and NF-B molecular complexes, both the ab initio and PPP calculations support the sandwich- or parallel-type.

  8. Intermolecular interactions and 3D structure in cellulose-NaOH-urea aqueous system.

    Science.gov (United States)

    Jiang, Zhiwei; Fang, Yan; Xiang, Junfeng; Ma, Yanping; Lu, Ang; Kang, Hongliang; Huang, Yong; Guo, Hongxia; Liu, Ruigang; Zhang, Lina

    2014-08-28

    The dissolution of cellulose in NaOH/urea aqueous solution at low temperature is a key finding in cellulose science and technology. In this paper, (15)N and (23)Na NMR experiments were carried out to clarify the intermolecular interactions in cellulose/NaOH/urea aqueous solution. It was found that there are direct interactions between OH(-) anions and amino groups of urea through hydrogen bonds and no direct interaction between urea and cellulose. Moreover, Na(+) ions can interact with both cellulose and urea in an aqueous system. These interactions lead to the formation of cellulose-NaOH-urea-H2O inclusion complexes (ICs). (23)Na relaxation results confirmed that the formation of urea-OH(-) clusters can effectively enhance the stability of Na(+) ions that attracted to cellulose chains. Low temperature can enhance the hydrogen bonding interaction between OH(-) ions and urea and improve the binding ability of the NaOH/urea/H2O clusters that attached to cellulose chains. Cryo-TEM observation confirmed the formation of cellulose-NaOH-urea-H2O ICs, which is in extended conformation with mean diameter of about 3.6 nm and mean length of about 300 nm. Possible 3D structure of the ICs was proposed by the M06-2X/6-31+G(d) theoretical calculation, revealing the O3H···O5 intramolecular hydrogen bonds could remain in the ICs. This work clarified the interactions in cellulose/NaOH/urea aqueous solution and the 3D structure of the cellulose chain in dilute cellulose/NaOH/urea aqueous solution. PMID:25111839

  9. Intermolecular interactions in binary mixtures of 2-Chloroethanol with 2-Dimethylaminoethanol and 2-Diethylaminoethanol at different temperatures

    Science.gov (United States)

    Pandey, Puneet Kumar; Awasthi, Anjali; Awasthi, Aashees

    2013-09-01

    The ultrasonic velocity (u) and density (ρ) of binary mixtures of 2-Chloroethanol (2-CletOH) with 2-Dimethylaminoethanol (DMAE) and 2-Diethylaminoethanol (DEAE) have been measured over the entire concentration range at temperatures 293.15, 303.15 and 313.15 K. The ultrasonic velocity and density data are used to estimate adiabatic compressibility (βS), intermolecular free length (Lf), molar sound velocity (R), molar compressibility (B) and specific acoustic impedance (Z) along with excess values of ultrasonic velocity (uE), adiabatic compressibility (βSE), intermolecular free length (LfE), acoustic impedance (ZE) and molar volume (VmE). The infrared spectra of both of the systems, 2-CletOH + DMAE and 2-CletOH + DEAE, have also been recorded at room temperature (298.15 K). The observed variations of these parameters, with concentration and temperature, are discussed in terms of the intermolecular interactions between the unlike molecules of the binary mixtures.

  10. Intermolecular interaction between a branching ribozyme and associated homing endonuclease mRNA

    DEFF Research Database (Denmark)

    Birgisdottir, Asa B; Nielsen, Henrik; Beckert, Bertrand; Masquida, Benot; Johansen, Steinar D

    2011-01-01

    tetraloop in a small branching ribozyme (DiGIR1) and a receptor motif (HEG P1 motif) present in a hairpin structure on a separate mRNA molecule. DiGIR1 generates a 2', 5' lariat cap at the 5' end of its downstream homing endonuclease mRNA by catalysing a self-cleavage branching reaction at an internal......-like motif (UCUAAG-CAAGA) found within the HEG P1. The biological role of this interaction appears to be linked to the homing endonuclease expression by promoting post-cleavage release of the lariat capped mRNA. These findings add to our understanding of how protein-coding genes embedded in nuclear ribosomal...... processing site. Upon release, the 5' end of the mRNA forms a distinct hairpin structure termed HEG P1. Our biochemical data, in concert with molecular 3D modelling, provide experimental support for an intermolecular tetraloop receptor interaction between the L9 GAAA in DiGIR1 and a GNRA tetraloop receptor...

  11. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    Science.gov (United States)

    Osiry, H.; Cano, A.; Lemus-Santana, A. A.; Rodríguez, A.; Carbonio, R. E.; Reguera, E.

    2015-10-01

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π-π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting.

  12. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    International Nuclear Information System (INIS)

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework

  13. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Osiry, H.; Cano, A.; Lemus-Santana, A.A.; Rodríguez, A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico); Carbonio, R.E. [INFIQC-CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba (Argentina); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico)

    2015-10-15

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework.

  14. Energy relaxation of intermolecular motions in supercooled water and ice: A molecular dynamics study

    Science.gov (United States)

    Yagasaki, Takuma; Saito, Shinji

    2011-12-01

    We investigate the energy relaxation of intermolecular motions in liquid water at temperatures ranging from 220 K to 300 K and in ice at 220 K using molecular dynamics simulations. We employ the recently developed frequency resolved transient kinetic energy analysis, which provides detailed information on energy relaxation in condensed phases like two-color pump-probe spectroscopy. It is shown that the energy cascading in liquid water is characterized by four processes. The temperature dependences of the earlier three processes, the rotational-rotational, rotational-translational, and translational-translational energy transfers, are explained in terms of the density of states of the intermolecular motions. The last process is the slow energy transfer arising from the transitions between potential energy basins caused by the excitation of the low frequency translational motion. This process is absent in ice because the hydrogen bond network rearrangement, which accompanies the interbasin transitions in liquid water, cannot take place in the solid phase. We find that the last process in supercooled water is well approximated by a stretched exponential function. The stretching parameter, ?, decreases from 1 to 0.72 with decreasing temperature. This result indicates that the dynamics of liquid water becomes heterogeneous at lower temperatures.

  15. The origins of intra- and inter-molecular vibrational couplings: A case study of H2O-Ar on full and reduced-dimensional potential energy surface

    Science.gov (United States)

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Li, Hui

    2016-01-01

    The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H2O-Ar, which explicitly incorporates interdependence on the intramolecular (Q1, Q2, Q3) normal-mode coordinates of the H2O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averaged interaction energies for the (v1, v2, v3) = (0, 0, 0), (0, 0, 1), (1, 0, 0), (0, 1, 0) states of H2O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm-1, and required only 58 parameters. With the 3D PESs of H2O-Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm-1 for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H2O in H2O-Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings.

  16. Thermal dissociation of protein-oligosaccharide complexes in the gas phase: mapping the intrinsic intermolecular interactions.

    Science.gov (United States)

    Kitova, Elena N; Bundle, David R; Klassen, John S

    2002-05-22

    Blackbody infrared radiative dissociation (BIRD) and functional group replacement are used to map the location and strength of hydrogen bonds between an antibody single chain fragment (scFv) and its natural trisaccharide receptor, alpha-D-Galp (1-->2)[alpha-D-Abep (1-->3)]alpha-D-Manp1-->OMe (1), in the gaseous, multiply protonated complex. Arrhenius activation parameters (E(a) and A) are reported for the loss of 1 and a series of monodeoxy trisaccharide congeners (5-8 identical with tri) from the (scFv + tri + 10H)(+10) complex. The energetic contribution of the specific oligosaccharide OH groups to the stability of the (scFv + 1 + 10H)(+10) complex is determined from the differences in E(a) measured for the trisaccharide analogues and 1 (55.2 kcal/mol). A decrease of 6 to 11 kcal/mol in E(a), measured for the monodeoxy trisaccharides, indicates that the deleted OH groups interact strongly with the scFv and that they account for a majority of the stabilizing intermolecular interactions. A partial map of the hydrogen bond donor/acceptor groups of 1 and the strength of the interactions is presented for the protonated +10 complex. A comparison of the gas-phase map with the crystal structure indicates that significant structural differences exist. The hydroxyl groups located outside of the binding pocket, and exposed to solvent in solution, participate in new protein-oligosaccharide hydrogen bonds in the gas phase. The decrease in kinetic and energetic stability of the (scFv + 2 + nH)(n)()(+) complex with increasing charge-state is attributed to conformational differences in the binding region induced by electrostatic repulsion. The similarity in the Arrhenius parameters for the +9 and +10 charge states suggests that repulsion effects on the structure of the binding region are negligible below +11. PMID:12010066

  17. Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001

    Directory of Open Access Journals (Sweden)

    Michael Roos

    2011-07-01

    Full Text Available The competition between intermolecular interactions and long-range lateral variations in the substrate–adsorbate interaction was studied by scanning tunnelling microscopy (STM and force field based calculations, by comparing the phase formation of (sub- monolayers of the organic molecules (i 2-phenyl-4,6-bis(6-(pyridin-3-yl-4-(pyridin-3-ylpyridin-2-ylpyrimidine (3,3'-BTP and (ii 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA on graphene/Ru(0001. For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results.

  18. Intermolecular interactions in binary mixtures of 2-Chloroethanol with 2-Dimethylaminoethanol and 2-Diethylaminoethanol at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Puneet Kumar [Material Science Research Laboratory, Department of Physics, University of Lucknow, Lucknow 226 007 (India); Awasthi, Anjali [Department of Physics, BBD University, Lucknow 227 015 (India); Awasthi, Aashees, E-mail: aasheesawasthi@rediffmail.com [Material Science Research Laboratory, Department of Physics, University of Lucknow, Lucknow 226 007 (India)

    2013-09-23

    Highlights: • Ultrasonic, volumetric and spectroscopic properties of 2-CletOH + DMAE/DEAE liquid mixtures were studied. • Results showed the presence of intermolecular hydrogen bonding between the unlike molecules. • H-bonding occurred between hydrogen atom of –OH group of 2-CletOH and oxygen atom of –OH group of DMAE/DEAE. • The strength of intermolecular interactions was found in order: 2-CletOH + DEAE > 2-CletOH + DMAE. - Abstract: The ultrasonic velocity (u) and density (ρ) of binary mixtures of 2-Chloroethanol (2-CletOH) with 2-Dimethylaminoethanol (DMAE) and 2-Diethylaminoethanol (DEAE) have been measured over the entire concentration range at temperatures 293.15, 303.15 and 313.15 K. The ultrasonic velocity and density data are used to estimate adiabatic compressibility (β{sub S}), intermolecular free length (L{sub f}), molar sound velocity (R), molar compressibility (B) and specific acoustic impedance (Z) along with excess values of ultrasonic velocity (u{sup E}), adiabatic compressibility (β{sub S}{sup E}), intermolecular free length (L{sub f}{sup E}), acoustic impedance (Z{sup E}) and molar volume (V{sub m}{sup E}). The infrared spectra of both of the systems, 2-CletOH + DMAE and 2-CletOH + DEAE, have also been recorded at room temperature (298.15 K). The observed variations of these parameters, with concentration and temperature, are discussed in terms of the intermolecular interactions between the unlike molecules of the binary mixtures.

  19. Intermolecular interaction between rare earth and manganese precursors in metalorganic chemical vapor deposition of perovskite manganite films

    International Nuclear Information System (INIS)

    The gas-phase reaction mechanism was investigated in liquid delivery metalorganic chemical vapor deposition (MOCVD) of praseodymium and lanthanum manganite films. We studied the gas-phase behavior of praseodymium, lanthanum, and manganese precursors under actual CVD conditions by in situ infrared absorption spectroscopy. The rate of the decrease of the infrared absorbance due to Pr(DPM)3 was almost constant even if Mn(DPM)3 was added, indicating that the intermolecular interaction between Pr and Mn precursors in the gas phase is relatively weak in MOCVD of praseodymium manganite films. On the other hand, the temperature dependence of the infrared absorption indicates that the thermal decomposition of La(DPM)3 was promoted in the presence of Mn(DPM)3. The significant intermolecular interaction occurs between La and Mn precursors in the gas phase in MOCVD of lanthanum manganite films. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Intermolecular energy transfer in the presence of dispersing and absorbing media

    CERN Document Server

    Dung, H T; Welsch, D G; Dung, Ho Trung; Kn\\"{o}ll, Ludwig; Welsch, Dirk-Gunnar

    2002-01-01

    By making use of the Green function concept of quantization of the electromagnetic field in Kramers--Kronig consistent media, a rigorous quantum mechanical derivation of the rate of intermolecular energy transfer in the presence of arbitrarily shaped, dispersing, and absorbing material bodies is given. Applications to bulk material, multi-slab planar structures, and microspheres are studied. It is shown that when the two molecules are near a planar interface, then surface-guided waves can strongly affect the energy transfer and essentially modify both the (F\\"{o}rster) short-range $R^{-6}$ dependence of the transfer rate and the long-range $R^{-2}$ dependence, which are typically observed in free space. In particular, enhancement (inhibition) of energy transfer can be accompanied by inhibition (enhancement) of donor decay. Results for four- and five-layered planar structures are given and compared with experimental results. Finally, the energy transfer between two molecules located at diametrically opposite p...

  1. Theory of intermolecular forces

    CERN Document Server

    Margenau, H; Ter Haar, D

    1971-01-01

    Theory of Intermolecular Forces deals with the exposition of the principles and techniques of the theory of intermolecular forces. The text focuses on the basic theory and surveys other aspects, with particular attention to relevant experiments. The initial chapters introduce the reader to the history of intermolecular forces. Succeeding chapters present topics on short, intermediate, and long range atomic interactions; properties of Coulomb interactions; shape-dependent forces between molecules; and physical adsorption. The book will be of good use to experts and students of quantum mechanics

  2. Analysis of intermolecular interactions in 3-(4-fluoro-3-phenoxyphenyl)-1-((4-methylpiperazin-1-yl)methyl)-1H-1,2,4-triazole-5-thiol

    Indian Academy of Sciences (India)

    Piyush Panini; Rahul Shukla; T P Mohan; B Vishalakshi; Deepak Chopra

    2014-09-01

    In the present study, we have prepared and structurally characterized a derivative of 1,2,4 triazoles, namely 3-(4-fluoro-3-phenoxyphenyl)-1-((4-methylpiperazin-1-yl)methyl)-1H-1,2,4-triazole-5-thiol (T-1) via single crystal X-ray diffraction. The crystal structure was observed to be stabilized by the presence of various intermolecular interactions in the crystalline solid such as O-H…S, C-H…F, C-H…S, C-H…N, C-H…O, C-H$\\ldots$ , $\\ldots$ and $\\ldots$ intermolecular interactions. The interaction energy of these interactions was evaluated through PIXEL method with decomposition of the total energy into the coulombic, polarization, dispersion and repulsion contribution. The study of the nature of H-bonds with sulfur reveals that stabilization due to contribution from polarization plays a significant role. It is noteworthy that the presence of the solvent molecules in the crystal structure were observed to provide stabilization to an otherwise destabilized molecular pair (comprising of two molecules of 1,2,4 triazoles in the asymmetric unit).

  3. Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state

    KAUST Repository

    Sutton, Christopher

    2015-06-15

    Rubrene is one of the most studied molecular semiconductors; its chemical structure consists of a tetracene backbone with four phenyl rings appended to the two central fused rings. Derivatization of these phenyl rings can lead to two very different solid-state molecular conformations and packings: One in which the tetracene core is planar and there exists substantive overlap among neighboring π-conjugated backbones; and another where the tetracene core is twisted and the overlap of neighboring π-conjugated backbones is completely disrupted. State-of-the-art electronic-structure calculations show for all isolated rubrene derivatives that the twisted conformation is more favorable (by -1.7 to -4.1 kcal mol-1), which is a consequence of energetically unfavorable exchange-repulsion interactions among the phenyl side groups. Calculations based on available crystallographic structures reveal that planar conformations of the tetracene core in the solid state result from intermolecular interactions that can be tuned through well-chosen functionalization of the phenyl side groups, and lead to improved intermolecular electronic couplings. Understanding the interplay of these intramolecular and intermolecular interactions provides insight into how to chemically modify rubrene and similar molecular semiconductors to improve the intrinsic materials electronic properties.

  4. Noncovalent intermolecular interactions between dehydroepiandrosterone and the active site of human dehydroepiandrosterone sulphotransferase: A density functional theory based treatment

    Science.gov (United States)

    Astani, Elahe; Heshmati, Emran; Chen, Chun-Jung; Hadipour, Nasser L.; Shekarsaraei, Setareh

    2016-04-01

    A theoretical study was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond (HB), in the active site of enzyme human dehydroepiandrosterone sulphotransferase (SULT2A1/DHEA) using the local (M06-L) and hybrid (M06, M06-2X) meta-GGA functionals of density functional theory (DFT). Results revealed that DHEA is able to form HBs with residues His99, Tyr231, Met137 and Met16 in the active site of the SULT2A1/DHEA. It was found that DHEA interacts with the other residues through electrostatic and Van der Waals interactions.

  5. A quantum chemical insight to intermolecular hydrogen bonding interaction between cytosine and nitrosamine: Structural and energetic investigations

    Science.gov (United States)

    Khalili, Behzad

    2016-03-01

    Hydrogen bond interactions which are formed during complex formation between cytosine and nitrosamine have been fully investigated using B3LYP, B3PW91 and MP2 methods in conjunction with various basis sets including 6-311++G (d,p), 6-311++G (2d,2p), 6-311++G (df,pd) and AUG-cc-pVDZ. Three regions around the most stable conformer of cytosine in the gas phase with six possible double H-bonded interactions were considered. Two intermolecular hydrogen bonds of type NC-N-HNA and O-H(N-H)C-ONA were found on the potential energy surface in a cyclic system with 8-member in CN1, CN3, CN5 and 7-member in CN2, CN4, CN6 systems. Results of binding energy calculation at all applied methods reveal that the CN1 structure is the most stable one which is formed by interaction of nitrosamine with cytosine in S1 region. The BSSE-corrected binding energy for six complex system is ranging from -23.8 to -43.6 kJ/mol at MP2/6-311++G (df,pd) level and the stability order is as CN1 > CN2 > CN3 > CN4 > CN5 > CN6 in all studied levels of theories. The NBO results reveal that the charge transfer occurred from cytosine to nitrosamine in CN1, CN3, CN5 and CN6 whereas this matter in the case of CN2 and CN4 was reversed. The relationship between BEs with red shift of H-bond involved bonds vibrational frequencies, charge transfer energies during complex formation and electron densities at H-bond BCPs were discussed. In addition activation energetic properties related to the proton transfer process between cytosine and nitrosamine have been calculated at MP2/6-311++G (df,pd) level. AIM results imply that H-bond interactions are electrostatic with partially covalent characteristic in nature.

  6. Intermolecular resonance energy transfer in the presence of a dielectric cylinder

    International Nuclear Information System (INIS)

    Using a Green's tensor method, we investigate the rate of resonance electronic energy transfer between two molecules near a dielectric cylinder. Both the case of a real and frequency-independent dielectric constant ε and the case of a Drude-Lorentz model for ε(ω) are considered, the latter case including dispersion and absorption. If the donor is placed at a fixed position near the cylinder, we find that the energy transfer rate to the acceptor is enhanced compared to its vacuum value in a number of discrete hotspots, centered at the cylinder's surface. In the absence of dispersion and absorption the rate of energy transfer may be enhanced at most a few times. On the other hand, for the Drude-Lorentz model the enhancement may be huge (up to 106) and the hotspots are sharply localized at the surface. We show that these observations can be explained from the fact that in the resonance region of the Drude-Lorentz dielectric surface plasmons occur, which play the dominant role in transferring the electronic energy between the donor and the acceptor. The dependence of the energy transfer rate on the molecular transition frequency is investigated as well. For small intermolecular distances, the cylinder hardly affects the transfer rate, independent of frequency. For larger distances, the frequency dependence is quite strong, in particular in the stop-gap region. The role of the intermolecular distance in the frequency dependence may be explained qualitatively using Heisenberg's uncertainty principle to calculate the spread in the frequencies of the intermediate photons.

  7. On the representation of the electric charge distribution in ethane for calculations of the molecular quadrupole moment and intermolecular electrostatic energy

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Alldredge, G. P.; Bruch, L. W.; Taub, H.

    1985-01-01

    and gives a repulsive rather than an attractive electrostatic interaction at typical intermolecular distances. In the local multipole model, the atom-site dipoles give the largest contribution to both the molecular quadrupole moment and the intermolecular interaction. The Journal of Chemical Physics...

  8. Intermolecular interaction of thiosemicarbazone derivatives to solvents and a potential Aedes aegypti target

    Science.gov (United States)

    da Silva, João Bosco P.; Hallwass, Fernando; da Silva, Aluizio G.; Moreira, Diogo Rodrigo; Ramos, Mozart N.; Espíndola, José Wanderlan P.; de Oliveira, Ana Daura T.; Brondani, Dalci José; Leite, Ana Cristina L.; Merz, Kenneth M.

    2015-08-01

    DFT calculations were used to access information about structure, energy and electronic properties of series of phenyl- and phenoxymethyl-(thio)semicarbazone derivatives with demonstrated activity against the larvae of Aedes aegypti in stage L4. The way as the thiosemicarbazone derivatives can interact with solvents like DMSO and water were analyzed from the comparison between calculated and experimental 1H NMR chemical shifts. The evidences of thiosemicarbazone derivatives making H-bond interaction to solvent have provide us insights on how they can interact with a potential A. aegypti's biological target, the Sterol Carrier Protein-2.

  9. Self-Assembly and Intermolecular Forces When Cellulose and Water Interact Using Molecular Modeling

    OpenAIRE

    Ali Chami Khazraji; Sylvain Robert

    2013-01-01

    Cellulose chains are linear and aggregation occurs via both intra- and intermolecular hydrogen bonds. Cellulose has a strong affinity to itself and toward materials containing hydroxyls groups. Based on the preponderance of hydroxyl functional groups, cellulose is very reactive with water. At room temperature, cellulose chains will have at least a monomolecular layer of water associated to it. The formation of hydrogen bonds at the cellulose/water interface is shown to depend essentially on t...

  10. Intermolecular interactions at early stage of protein/detergent particle association induced by salt/polyethylene glycol mixtures.

    Science.gov (United States)

    Odahara, Takayuki; Odahara, Koji

    2016-04-01

    Mixtures of neutral salts and polyethylene glycol are used for various purposes in biological studies. Although the effects of each component of the mixtures are theoretically well investigated, comprehension of their integrated effects remains insufficient. In this work, their roles and effects as a precipitant were clarified by studying dependence of precipitation curves on salt concentration for integral membrane protein/detergent particles of different physicochemical properties. The dependence of precipitation curves was reasonably related to intermolecular interactions among relevant molecules such as protein, detergent and polyethylene glycol by considering their physicochemical properties. The obtained relationships are useful as basic information to learn the early stage of biological macromolecular associations. PMID:26705098

  11. Lack of evidence for intermolecular epistatic interactions between adiponectin and resistin gene polymorphisms in Malaysian male subjects

    Directory of Open Access Journals (Sweden)

    Cia-Hin Lau

    2012-01-01

    Full Text Available Epistasis (gene-gene interaction is a ubiquitous component of the genetic architecture of complex traits such as susceptibility to common human diseases. Given the strong negative correlation between circulating adiponectin and resistin levels, the potential intermolecular epistatic interactions between ADIPOQ (SNP+45T > G, SNP+276G > T, SNP+639T > C and SNP+1212A > G and RETN (SNP-420C > G and SNP+299G > A gene polymorphisms in the genetic risk underlying type 2 diabetes (T2DM and metabolic syndrome (MS were assessed. The potential mutual influence of the ADIPOQ and RETN genes on their adipokine levels was also examined. The rare homozygous genotype (risk alleles of SNP-420C > G at the RETN locus tended to be co-inherited together with the common homozygous genotypes (protective alleles of SNP+639T > C and SNP+1212A > G at the ADIPOQ locus. Despite the close structural relationship between the ADIPOQ and RETN genes, there was no evidence of an intermolecular epistatic interaction between these genes. There was also no reciprocal effect of the ADIPOQ and RETN genes on their adipokine levels, i.e., ADIPOQ did not affect resistin levels nor did RETN affect adiponectin levels. The possible influence of the ADIPOQ gene on RETN expression warrants further investigation.

  12. Structural aspects of intermolecular interactions in the solid state of 1,4-dibenzylpiperazines bearing nitrile or amidine groups

    International Nuclear Information System (INIS)

    X-ray diffraction analyses for new pentamidine analogs are presented: 1,4-bis(4-cyanobenzyl)piperazine (1) crystallizes in the triclinic space group and 1,4-bis(4-amidinobenzyl)piperazine tetrahydrochloride tetrahydrate (2) in the monoclinic space group (P21/n) revealing a complex system of hydrogen bonds for (2). The crystal structures of the title 1,4-bis(4-cyanobenzyl)piperazine (1) and 1,4-bis(4-amidinobenzyl)piperazine tetrahydrochloride tetrahydrate (2) are reported. Compound (1) crystallizes in the triclinic space group and compound (2) in the monoclinic space group P21/n. In both (1) and (2) the asymmetric unit contains one half of the molecule because the central piperazine rings were located across a symmetry center. The packing of both molecules was dominated by hydrogen bonds. The crystal lattice of (1) was formed by weak CH?N and CH?? interactions. The crystal structure of (2) was completely different, with cations as well as chloride anions and water molecules taking part in intermolecular interactions. Single-crystal X-ray diffraction studies combined with density functional theory (DFT) calculations allowed the characterization of the intermolecular interactions in those two systems having different types of very strong electrophilic groups: non-ionic nitrile and ionic amidine. Chemical shift data from 13C CP/MAS (Cross Polarization Magic Angle Spinning) NMR spectra were analyzed using the different procedures for the theoretical computation of shielding constants

  13. Electronic Mechanisms of Intra and Intermolecular J Couplings in Systems with C-HO Interactions

    OpenAIRE

    Cavasotto, Claudio N.; Vizioli, Celia V.; Martin C. Ruiz de Azua; Claudia G. Giribet

    2003-01-01

    Abstract: Correlation effects on the change of 1J(CH) couplings in model systems I:NCH...H2O and II:CH4...H2O as a function of the H...O distance are discussed. RPA and SOPPA results follow a similar trend in system II. In system I RPA values decrease monotonously as the H...O distance decreases, while SOPPA ones exhibit flat maximum near equilibrium. Such different behavior is ascribed to the €-transmitted component. Intermolecular couplings at the equilibrium geometry of I are analyzed by...

  14. Effect of Intra-molecular Disorder and Inter-molecular Electronic Interactions on the Electronic Structure of Poly-p-Phenylene Vinylene (PPV)

    OpenAIRE

    Yang, Ping; Batista, Enrique R.; Tretiak, Sergei; Saxena, Avadh; Martin, Richard L.; Smith, D. L.

    2007-01-01

    We investigate the role of intra-molecular conformational disorder and inter-molecular electronic interactions on the electronic structure of disorder clusters of poly-p-phenylene vinylene (PPV) oligomers. Classical molecular dynamics is used to determine probable molecular geometries, and first-principle density functional theory (DFT) calculations are used to determine electronic structure. Intra-molecular and inter-molecular effects are disentangled by contrasting results for densely packe...

  15. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates.

    Science.gov (United States)

    Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice. PMID:26342376

  16. Intermolecular interactions and proton transfer in the hydrogen halide-superoxide anion complexes.

    Science.gov (United States)

    Lee, Sebastian J R; Mullinax, J Wayne; Schaefer, Henry F

    2016-02-17

    The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the hydrogen halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 Å) hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier hydrogen halides with the resulting complexes characterized as long (>1.89 Å) hydrogen bonds between halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier hydrogen halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI. PMID:26852733

  17. Method for Slater-Type Density Fitting for Intermolecular Electrostatic Interactions with Charge Overlap. I. The Model.

    Science.gov (United States)

    Öhrn, Anders; Hermida-Ramon, Jose M; Karlström, Gunnar

    2016-05-10

    The effects of charge overlap, or charge penetration, are neglected in most force fields and interaction terms in QM/MM methods. The effects are however significant at intermolecular distances near the van der Waals minimum. In the present study, we propose a method to evaluate the intermolecular Coloumb interaction using Slater-type functions, thus explicitly modeling the charge overlap. The computational cost of the method is low, which allows it to be used in large systems with most force fields as well as in QM/MM schemes. The charge distribution is modeled as a distributed multipole expansion up to quadrupole and Slater-type functions of angular momentum up to L = 1. The exponents of the Slater-type functions are obtained using a divide-and-conquer method to avoid the curse of dimensionality that otherwise is present for large nonlinear optimizations. A Levenberg-Marquardt algorithm is applied in the fitting process. A set of parameters is obtained for each molecule, and the process is fully automated. Calculations have been performed in the carbon monoxide and the water dimers to illustrate the model. Results show a very good accuracy of the model with relative errors in the electrostatic potential lower than 3% over all reasonable separations. At very short distances where the charge overlaps is the most significant, errors are lower than 8% and lower than 3.5% at distances near the van der Waals minimum. PMID:27015000

  18. Investigation on Intermolecular Interaction in Supersaturation State of Cadmium Sulphate Mixed Zinc tris-THIOUREA Sulphate Solutions

    Science.gov (United States)

    Muley, G. G.; Naik, A. B.; Gambhire, A. B.

    2014-06-01

    Zinc tris-thiourea sulphate (ZTS) is a well known nonlinear optical (NLO) crystal widely used for various NLO applications. The NLO, physical and chemical properties can be modified by adding impurities and/or modifying crystal growth conditions. The impurities present in the growth solution and growth conditions can affect the crystal growth parameters at great extent. Thus, the study on the nature of intermolecular interaction with the dopant in the solution during crystal growth process becomes important. In the present investigation, the ultrasonic velocity was measured in the aqueous solutions of pure and cadmium sulphate mixed ZTS in the supersaturation state at 313.15 K. The thermodynamic parameters such as adiabatic compressibility, inter molecular free length, acoustic impedance and relative associations have been calculated from the ultrasonic data and densities of water and solutions at 313.15 K, and the nature of intermolecular interaction has been discussed. FT-IR spectra of all mixtures in the solid form at room temperature were recorded and the shifts in the absorption peaks corresponding to the functional groups of ZTS have been reported.

  19. Intermolecular interaction between rare earth and manganese precursors in metalorganic chemical vapor deposition of perovskite manganite films

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Toshihiro [Department of Engineering Science, Osaka Electro-Communication University, 18-8 Hatsu-cho, Neyagawa, Osaka 572-8530 (Japan)

    2015-07-15

    The gas-phase reaction mechanism was investigated in liquid delivery metalorganic chemical vapor deposition (MOCVD) of praseodymium and lanthanum manganite films. We studied the gas-phase behavior of praseodymium, lanthanum, and manganese precursors under actual CVD conditions by in situ infrared absorption spectroscopy. The rate of the decrease of the infrared absorbance due to Pr(DPM){sub 3} was almost constant even if Mn(DPM){sub 3} was added, indicating that the intermolecular interaction between Pr and Mn precursors in the gas phase is relatively weak in MOCVD of praseodymium manganite films. On the other hand, the temperature dependence of the infrared absorption indicates that the thermal decomposition of La(DPM){sub 3} was promoted in the presence of Mn(DPM){sub 3}. The significant intermolecular interaction occurs between La and Mn precursors in the gas phase in MOCVD of lanthanum manganite films. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Intermolecular interactions in mixtures of poly (ethylene glycol) with methoxybenzene and ethoxybenzene: Volumetric and viscometric studies

    International Nuclear Information System (INIS)

    Highlights: • Density and viscosity values of PEG400 + methoxybenzene or + ethoxybenzene were measured. • The excess molar volume and thermodynamic functions of activation were calculated. • The results were interpreted in light of polymer–solvent interactions. • The changes in activation function indicate the viscous flow process. • The thermodynamic functions were correlated with the suitable equations. -- Abstract: The density and viscosity values of the binary mixtures of {poly (ethylene glycol) (PEG400) + methoxybenzene, or + ethoxybenzene} have been measured at T = (298.15, 308.15, and 318.15) K. From these experimental values, the excess molar volume, apparent specific volume, partial specific volume of solute, partial specific volume of solvent and excess Gibbs free energy of activation have been computed over the entire range of composition at three temperatures. From the experimental data, the thermodynamic functions of activation have been estimated for each binary mixture. The obtained results have been interpreted in light of polymer–solvent interactions and packing effects. The signs of excess molar volume and deviations of excess Gibbs free energy of activation have been used to obtain some information in regard to existence of specific interactions between PEG400 and solvents molecules. The changes in entropy and enthalpy of activation from the initial state to the transition state were also calculated in order to see which one of these functions controls viscous flow process in the studied polymer solutions. The excess molar volume and excess Gibbs free energy of activation values have been adequately fitted to the Redlich–Kister polynomial. Apparent specific volume values were correlated with the suitable equation. The different models proposed for correlating the viscosity of polymer solutions or liquid mixtures (segment-based-Eyring–NRTL, segment-based-Eyring–Wilson, Grunbreg–Nissan, Frenkel, Hind et al., Katti–Chauddhri, Tamura–Kurata, Auslander and McAllister) have also been used to fit the viscosity values

  1. Perturbation theory of intermolecular interactions: What is the problem, are there solutions?

    International Nuclear Information System (INIS)

    We review the nature of the problem in the framework of Rayleigh-Schroedinger perturbation theory (the polarization approximation) considering explicitly two examples: the interaction of two hydrogen atoms and the interaction of Li with H. We show, in agreement with the work of Claverie and of Morgan and Simon, that the LiH problem is dramatically different from the H2 problem. In particular, the physical states of LiH are higher in energy than an infinite number of discrete, unphysical states and they are buried in a continuum of unbound, unphysical states, which starts well below the lowest physical state. Clavrie has shown that the perturbation expansion, under these circumstances, is likely to converge to an unphysical state of lower energy than the physical ground state, if it converges at all. We review, also, the application of two classes of exchange perturbation theory to LiH and larger systems. We show that the spectra of three Eisenschitz-London (EL) class, exchange perturbation theories have no continuum of unphysical states overlaying the physical states and no discrete, unphysical states below the lowest physical state. In contrast, the spectra of two Hirschfelder-Silbey class theories differ hardly at all from that found with the polarization approximation. Not one of the EL class of perturbation theories, however, eliminates all of the discrete unphysical states

  2. Theoretical Studies on the Intermolecular Interactions of Potentially Primordial Base-Pair Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Leszczynski, Jerzy [Computational Center for Molecular Structure and Interactions, Jackson, MS; Sponer, Judit [Academy of Sciences of the Czech Republic; Sponer, Jiri [Academy of Sciences of the Czech Republic; Sumpter, Bobby G [ORNL; Fuentes-Cabrera, Miguel A [ORNL; Vazquez-Mayagoitia, Alvaro [ORNL

    2010-01-01

    Recent experimental studies on the Watson Crick type base pairing of triazine and aminopyrimidine derivatives suggest that acid/base properties of the constituent bases might be related to the duplex stabilities measured in solution. Herein we use high-level quantum chemical calculations and molecular dynamics simulations to evaluate the base pairing and stacking interactions of seven selected base pairs, which are common in that they are stabilized by two NH O hydrogen bonds separated by one NH N hydrogen bond. We show that neither the base pairing nor the base stacking interaction energies correlate with the reported pKa data of the bases and the melting points of the duplexes. This suggests that the experimentally observed correlation between the melting point data of the duplexes and the pKa values of the constituent bases is not rooted in the intrinsic base pairing and stacking properties. The physical chemistry origin of the observed experimental correlation thus remains unexplained and requires further investigations. In addition, since our calculations are carried out with extrapolation to the complete basis set of atomic orbitals and with inclusion of higher electron correlation effects, they provide reference data for stacking and base pairing energies of non-natural bases.

  3. Identification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice.

    Science.gov (United States)

    Tamboli, Majid I; Krishnaswamy, Shobhana; Gonnade, Rajesh G; Shashidhar, Mysore S

    2013-09-16

    Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)?the favorable geometry of the nucleophile (-OH) and the electrophile (C-O) and 2)?the molecular assembly, reinforced by C-H???? interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity. PMID:23934729

  4. Intermolecular CH?O interactions in cyclopentanone: An inelastic neutron scattering study

    Energy Technology Data Exchange (ETDEWEB)

    Vaz, Pedro D., E-mail: pmvaz@fc.ul.pt [CQB, Department of Chemistry and Biochemistry, Faculty of Science, University of Lisbon, 1749-016 Lisbon (Portugal); Nolasco, Mariela M. [Departamento de Qumica CICECO, Universidade de Aveiro, P-3810-193 Aveiro (Portugal); Ribeiro-Claro, Paulo J.A., E-mail: prc@ua.pt [Departamento de Qumica CICECO, Universidade de Aveiro, P-3810-193 Aveiro (Portugal)

    2013-12-12

    Highlights: The inelastic neutron spectrum of cyclopentanone was obtained. The neutron spectrum of the pure compound reveals presence of CH?O hydrogen bonds. Almost exact match between simulated CH?O bonded dimer and experimental spectra. Anti-translational ?H?O mode assigned to band at 95 cm{sup ?1} and confirmed by DFT results. - Abstract: The inelastic neutron scattering (INS) spectra of cyclopentanone were obtained for pure and 50% CCl{sub 4} solution forms. Spectra are compared with infrared and Raman data, and with DFT calculated eigenvectors. This exercise aims to find spectroscopic evidence in the neutron spectra for the presence of CH?O hydrogen bonds. These are weak interactions with an energy of ca. ?6 kJ mol{sup ?1} as predicted by DFT. The neutron spectra show narrow and sharp bands which allows for an assignment of the vibrational modes. The simulated neutron spectrum of CH?O bonded cyclopentanone dimers matches the experimental spectrum of the pure compound, whereas the monomer simulation monomer matches the experimental spectrum of the diluted solution, meaning that such interaction can be probed by INS. Assignment of the 95 cm{sup ?1} band to the ?H?O anti-translational mode, being supported by DFT results and in agreement with previous literature data, is considered and discussed.

  5. New aspects of weak CH⋯π bonds: intermolecular interactions between alicyclic and aromatic rings in crystals of small compounds, peptides and proteins

    Science.gov (United States)

    Ciunik, Z.; Berski, S.; Latajka, Z.; Leszczyński, J.

    1998-02-01

    The geometry of intermolecular contacts between alicyclic and aromatic rings in a number of crystal structures suggests an attractive interaction between the rings. An analysis of molecular packing of 444 different crystal structures collected in the Cambridge Structural Database shows that phenyl…cyclohexanonyl, cyclohexyl, and/or cyclopentyl ring interactions occur in 59-82% of studied crystals. Similar interactions are observed between aromatic rings and heterocyclic pyrrolidine rings of proline in peptides and proteins. An analysis of data collected in the Brookhaven Protein Data Bank reveals that interactions between proline CH groups and aromatic rings of phenylalanine, tyrosine, and tryptophan as acceptors are frequently observed in proteins. Based on these results, several geometric models of these interactions are proposed. Two of these models are fully optimized using quantum chemical calculations at the density functional theory level. Calculated energies suggest that the most important interaction between the cyclohexanone and benzene rings is described by the face-to-face model, in which three axial hydrogen atoms are directed toward the aromatic partner.

  6. Formation of intermolecular crosslinks by the actinocin derivatives with DNA in interaction under conditions of semidilute solution

    International Nuclear Information System (INIS)

    Interaction of native calf thymus DNA (ctDNA) with the actinocin derivatives containing protonated diethylamino groups, dimethylamino groups and unsubstituted amino groups and having different length of the alkyl chain have been studied by the method of viscometry. An anomalous hydrodynamic behavior of solutions of DNA with very low amount of ligands prepared under conditions of semidilute solution was revealed. We assumed that such an anomalous behavior of solutions of DNA complexes with actinocin derivatives associated with the formation of intermolecular crosslinks while the preparation of the complex was in terms of overlapping of macromolecular coils in solution. Comparative study of the hydrodynamic behavior of the DNA complexes with various actinocin structures lead us to the conclusion of the formation of crosslinks by the compounds containing protonated diethylamino groups

  7. Determination of stepsize parameters for intermolecular vibrational energy transfer: Progress report, May 1, 1987-April 30, 1988

    International Nuclear Information System (INIS)

    Intermolecular vibrational energy transfer for highly excited polyatomic molecules is involved in any mechanism in which excitation energy is required (pyrolysis) or in which energy must be removed from a hot source (cooling). The average energy removed per collision, , is a useful quantity to compare efficiency for energy transfer. The objectives of this work are: to determine the dependence of on excitation energy and on the molecular complexity (number of vibrational modes) of substrate and deactivator; to assess the importance of intermolecular attractions (complex formation) on vibrational energy transfer; to obtain detailed information on the energy distribution after collision and to evaluate the importance of on high-temperature unimolecular reactions. This information will be obtained by monitoring the time dependence of the infrared emission, ultraviolet absorption, refractive index and pressure. The results from these complementary techniques will be benchmarked with values from previous studies on the relaxation of chemically activated alkyl and fluoroalkyl radicals. Trajectory calculations simulating energy transfer are being performed for ''generic'' substrate/deactivator pairs to provide additional details and insight on the important parameters. Model calculations are also being performed to determine the feasibility of obtaining information from experimental data for high-temperature unimolecular reactions

  8. Study of intermolecular interactions in binary mixtures of 2-(dimethylamino)ethanol with methanol and ethanol at various temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Puneet Kumar; Pandey, Vrijesh Kumar [Material Science Research Laboratory, Department of Physics, University of Lucknow, Lucknow 226 007 (India); Awasthi, Anjali [Department of Physics, B. B. D. University, Lucknow 227 015 (India); Nain, Anil Kumar [Department of Chemistry, Dyal Singh College, University of Delhi, New Delhi 110 003 (India); Awasthi, Aashees, E-mail: aasheesawasthi@rediffmail.com [Material Science Research Laboratory, Department of Physics, University of Lucknow, Lucknow 226 007 (India)

    2014-06-01

    Graphical abstract: The densities and ultrasonic speeds of the binary mixtures over the entire composition range were measured at various temperatures at atmospheric pressure. The excess molar volumes, isentropic compressibilities, and molar isentropic compressions have been calculated. The variations of these parameters with composition and temperature are discussed. The IR spectra were recorded they further supported the conclusion drawn from excess parameters, which indicates the presence of intermolecular hydrogen bonding between the oxygen atom of DMAE molecules and hydrogen atom of methanol and ethanol molecules in these mixtures.. - Highlights: • The study reports density and ultrasonic velocity data of 2-(dimethylamino)ethanol + methanol/ethanol mixtures. • To elucidate the interactions in 2-(dimethylamino)ethanol + methanol/ethanol binary mixtures. • Provides information on nature and relative strength of interactions in these mixtures. • Correlates physicochemical properties with interactions in these mixtures. - Abstract: The densities, ρ and ultrasonic speeds, u of the binary mixtures of 2-(dimethylamino)ethanol (DMAE) with methanol/ethanol, including those of pure liquids, over the entire composition range were measured at 298.15, 308.15 and 318.15 K. From the experimental data, the excess molar volumes, V{sub m}{sup E} and excess isentropic compressibilities, κ{sub s}{sup E} have been calculated. The excess partial molar volumes, V{sup ¯}{sub m,1}{sup E} and V{sup ¯}{sub m,2}{sup E} and excess partial molar isentropic compressions, K{sup ¯}{sub s,m,1}{sup E} and K{sup ¯}{sub s,m,2}{sup E} over the whole composition range; and partial molar volumes, V{sup ¯}{sub m,1}{sup °} and V{sup ¯}{sub m,2}{sup °}, partial molar isentropic compressions, K{sup ¯}{sub s,m,1}{sup °} and K{sup ¯}{sub s,m,2}{sup °}, excess partial molar volumes, V{sup ¯}{sub m,1}{sup °E} and V{sup ¯}{sub m,2}{sup °E}, and excess partial molar isentropic compressions, K{sup ¯}{sub s,m,1}{sup °E} and K{sup ¯}{sub s,m,2}{sup °E} at infinite dilution have also been calculated. The variations of these parameters with composition and temperature are discussed in terms of intermolecular interactions. The IR spectra of these mixtures have also been recorded at 298.15 K.

  9. Study of intermolecular interactions in binary mixtures of 2-(dimethylamino)ethanol with methanol and ethanol at various temperatures

    International Nuclear Information System (INIS)

    Graphical abstract: The densities and ultrasonic speeds of the binary mixtures over the entire composition range were measured at various temperatures at atmospheric pressure. The excess molar volumes, isentropic compressibilities, and molar isentropic compressions have been calculated. The variations of these parameters with composition and temperature are discussed. The IR spectra were recorded they further supported the conclusion drawn from excess parameters, which indicates the presence of intermolecular hydrogen bonding between the oxygen atom of DMAE molecules and hydrogen atom of methanol and ethanol molecules in these mixtures.. - Highlights: • The study reports density and ultrasonic velocity data of 2-(dimethylamino)ethanol + methanol/ethanol mixtures. • To elucidate the interactions in 2-(dimethylamino)ethanol + methanol/ethanol binary mixtures. • Provides information on nature and relative strength of interactions in these mixtures. • Correlates physicochemical properties with interactions in these mixtures. - Abstract: The densities, ρ and ultrasonic speeds, u of the binary mixtures of 2-(dimethylamino)ethanol (DMAE) with methanol/ethanol, including those of pure liquids, over the entire composition range were measured at 298.15, 308.15 and 318.15 K. From the experimental data, the excess molar volumes, VmE and excess isentropic compressibilities, κsE have been calculated. The excess partial molar volumes, V¯m,1E and V¯m,2E and excess partial molar isentropic compressions, K¯s,m,1E and K¯s,m,2E over the whole composition range; and partial molar volumes, V¯m,1° and V¯m,2°, partial molar isentropic compressions, K¯s,m,1° and K¯s,m,2°, excess partial molar volumes, V¯m,1°E and V¯m,2°E, and excess partial molar isentropic compressions, K¯s,m,1°E and K¯s,m,2°E at infinite dilution have also been calculated. The variations of these parameters with composition and temperature are discussed in terms of intermolecular interactions. The IR spectra of these mixtures have also been recorded at 298.15 K

  10. Investigation of intermolecular interactions between single walled nanotubes and conjugated oligomers using the dispersion-corrected DFT methods

    Science.gov (United States)

    Lagowski, Jolanta B.; Aljohani, Suad; Khan, M. Zahidul H.; Zhao, Yuming

    The area of carbon nanotubes (CNT)-polymer composites has been progressing rapidly in recent years. Pure CNT and CNT-polymer composites have many useful (industry related) properties: ranging from electronic electrical conductivity to superior strength. However the full potential of using CNTs as reinforcements (in say a polymer matrix) has been severely limited because of complications associated with the dispersion of CNTs. CNTs tend to entangle with each other forming materials that have properties that fall short of the expectations. The goal of this work is to identify the type of conjugated oligomers that are best suited for the dispersion of single walled CNT (SWCNT). For this purpose, various methods of dispersion corrected density functional theory (DFT-D/B97D, /WB97XD, /CAM-B3LYP) have been used to investigate the interaction between the SWCNT and the organic conjugated oligomers with different end groups (aldehyde (ALD) and dithiafulvenyl (DTF)). We investigate the effect of intermolecular interactions on the structure, polarity and energetics of the oligomers and SWCNT combinations. The comparison of results obtained using different DFT approximations is made. Our results show that DFT-endcapped oligomer interact more strongly with CNT than ALD-endcapped oligomer. The financial support from NSERC, SACBC and Memorial University and the computational resources from Compute Canada were received.

  11. Useful lower limits to polarization contributions to intermolecular interactions using a minimal basis of localized orthogonal orbitals: Theory and analysis of the water dimer

    Science.gov (United States)

    Azar, R. Julian; Horn, Paul Richard; Sundstrom, Eric Jon; Head-Gordon, Martin

    2013-02-01

    The problem of describing the energy-lowering associated with polarization of interacting molecules is considered in the overlapping regime for self-consistent field wavefunctions. The existing approach of solving for absolutely localized molecular orbital (ALMO) coefficients that are block-diagonal in the fragments is shown based on formal grounds and practical calculations to often overestimate the strength of polarization effects. A new approach using a minimal basis of polarized orthogonal local MOs (polMOs) is developed as an alternative. The polMO basis is minimal in the sense that one polarization function is provided for each unpolarized orbital that is occupied; such an approach is exact in second-order perturbation theory. Based on formal grounds and practical calculations, the polMO approach is shown to underestimate the strength of polarization effects. In contrast to the ALMO method, however, the polMO approach yields results that are very stable to improvements in the underlying AO basis expansion. Combining the ALMO and polMO approaches allows an estimate of the range of energy-lowering due to polarization. Extensive numerical calculations on the water dimer using a large range of basis sets with Hartree-Fock theory and a variety of different density functionals illustrate the key considerations. Results are also presented for the polarization-dominated Na+CH4 complex. Implications for energy decomposition analysis of intermolecular interactions are discussed.

  12. Reliable prediction of three-body intermolecular interactions using dispersion-corrected second-order Møller-Plesset perturbation theory

    Science.gov (United States)

    Huang, Yuanhang; Beran, Gregory J. O.

    2015-07-01

    Three-body and higher intermolecular interactions can play an important role in molecular condensed phases. Recent benchmark calculations found problematic behavior for many widely used density functional approximations in treating 3-body intermolecular interactions. Here, we demonstrate that the combination of second-order Møller-Plesset (MP2) perturbation theory plus short-range damped Axilrod-Teller-Muto (ATM) dispersion accurately describes 3-body interactions with reasonable computational cost. The empirical damping function used in the ATM dispersion term compensates both for the absence of higher-order dispersion contributions beyond the triple-dipole ATM term and non-additive short-range exchange terms which arise in third-order perturbation theory and beyond. Empirical damping enables this simple model to out-perform a non-expanded coupled Kohn-Sham dispersion correction for 3-body intermolecular dispersion. The MP2 plus ATM dispersion model approaches the accuracy of O(N6) methods like MP2.5 or even spin-component-scaled coupled cluster models for 3-body intermolecular interactions with only O(N5) computational cost.

  13. Studies of intermolecular interactions in solid dispersions using advanced surface chemical analysis

    OpenAIRE

    Maniruzzaman, M.; Snowden, Martin J; Bradely, Mike S; Douroumis, D.

    2015-01-01

    The aim of this study is to utilise an advanced surface chemical analysis based on X-ray photoelectron spectroscopy (XPS) to determine and characterise drug/polymer interactions in solid dispersions manufactured via hot melt extrusion (HME). Cetirizine HCl (CTZ) and verapamil HCl (VRP) were used as model cationic drugs while Eudragit grade L100 and L100-55 polymers were used as anionic carriers. A molecular dynamics (MD) based simulation approach predicted drug/polymer interactions while sca...

  14. Synthesis and description of intermolecular interactions in new sulfonamide derivatives of tranexamic acid

    Science.gov (United States)

    Ashfaq, Muhammad; Arshad, Muhammad Nadeem; Danish, Muhammad; Asiri, Abdullah M.; Khatoon, Sadia; Mustafa, Ghulam; Zolotarev, Pavel N.; Butt, Rabia Ayub; Şahin, Onur

    2016-01-01

    Tranexamic acid (4-aminomethyl-cyclohexanecarboxylic acid) was reacted with sulfonyl chlorides to produce structurally related four sulfonamide derivatives using simple and environmental friendly method to check out their three-dimensional behavior and van der Walls interactions. The molecules were crystallized in different possibilities, as it is/after alkylation at its O and N atoms/along with a co-molecule. All molecules were crystallized in monoclinic crystal system with space group P21/n, P21/c and P21/a. X-ray studies reveal that the molecules stabilized themselves by different kinds of hydrogen bonding interactions. The molecules are getting connected through O-H⋯O hydrogen bonds to form inversion dimers which are further connected through N-H⋯O interactions. The molecules in which N and O atoms were alkylated showed non-classical interaction and generated centro-symmetric R22(24) ring motif. The co-crystallized host and guest molecules are connected to each other via O-H⋯O interactions to generate different ring motifs. By means of the ToposPro software an analysis of the topologies of underlying nets that correspond to molecular packings and hydrogen-bonded networks in structures under consideration was carried out.

  15. 12C/13C and H/D vapor pressure isotope effects of fluoroform: intermolecular interactions in liquid fluoroform

    International Nuclear Information System (INIS)

    A precision cryostat of the Bigeleisen-Brooks-Ribnikar-Ishida (BBIR) type with associated vacuum systems has been constructed and the appropriate temperature/pressure measurement and control systems designed and implemented. Various improvements in the cryostat design were incorporated in order to facilitate the assembly and repair processes. A major design change involved the incorporation of a digital stand alone computer to control cryostat operations. This apparatus was used to measure the 12C/13C and H/D Vapor Pressure Isotope Effects of Fluoroform. Analysis of the measured VPIE results, in light of existing experimental data and theories, has demonstrated the need of a temperature dependent liquid force field, specifically a temperature-dependent interaction force constant between the C-H stretching motion and translational motion in the direction of the figure axis of CHF3. This result is consistent with the observed spectroscopic data and vibrational and configurational models of fluoroform dimers. The intermolecular interaction is believed to be a weak hydrogen-bond in nature

  16. Gibb's energy and intermolecular free length of 'Borassus Flabellifier' (BF) and Adansonia digitata (AnD) aqueous binary mixture

    International Nuclear Information System (INIS)

    One of the potential driving forces behind a chemical reaction is favourable a new quantity known as the Gibbs free energy (G) of the system, which reflects the balance between these forces. Ultrasonic velocity and absorption measurements in liquids and liquid mixtures find extensive application to study the nature of intermolecular forces. Ultrasonic velocity measurements have been successfully employed to detect weak and strong molecular interactions present in binary and ternary liquid mixtures. After measuring the density and ultrasonic velocity of aqueous solution of 'Borassus Flabellifier' BF and Adansonia digitata And, we calculated Gibb's energy and intermolecular free length. The velocity of ultrasonic waves was measured, using a multi-frequency ultrasonic interferometer with a high degree of accuracy operating Model M-84 by M/s Mittal Enterprises, New Delhi, at a fixed frequency of 2 MHz. Natural sample 'Borassus Flabellifier' BF fruit pulp and Adansonia digitata AnD powder was collected from Dhar, District of MP, India for this study.

  17. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    International Nuclear Information System (INIS)

    Highlights: ► The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. ► Acetone molecules in the dimer are stacked with an antiparallel way. ► The structure of the acetone trimer and the tetramer are the cyclic structures. ► The carbonyl groups would interact with the methyl groups in acetone clusters. ► These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR–VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 ∼ 3550 cm−1 of neutral acetone and its clusters (CH3COCH3)n (n = 1–4). Features around 3440 cm−1 in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm−1 as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  18. Oligophenylenevinylenes in spatially confined nanochannels: Monitoring intermolecular interactions by UV/Vis and Raman spectroscopy

    DEFF Research Database (Denmark)

    Aloshyna, Mariya; Medina, Begona Milian; Poulsen, Lars; Moreau, Juliette; Beljonne, David; Cornil, Jerome; Silvestro, Giuseppe Di; Cerminara, Michele; Meinardi, Francesco; Tubino, Riccardo; Detert, Heiner; Schrader, Sigurd; Egelhaaf, Hans-Joachim; Botta, Chiara; Gierschner, Johannes

    2008-01-01

    -guest interactions are elucidated by UV/Vis and Raman spectroscopy. The impact of the local environment of the chromophore on the optical and photophysical properties is discussed in light of quantum-chemical calculations. In stark contrast to thin films where preferential side-by-side orientation leads to quenching...

  19. De novo design of protein-protein interactions through modification of inter-molecular helix-helix interface residues.

    Science.gov (United States)

    Yagi, Sota; Akanuma, Satoshi; Yamagishi, Manami; Uchida, Tatsuya; Yamagishi, Akihiko

    2016-05-01

    For de novo design of protein-protein interactions (PPIs), information on the shape and chemical complementarity of their interfaces is generally required. Recent advances in computational PPI design have allowed for de novo design of protein complexes, and several successful examples have been reported. In addition, a simple and easy-to-use approach has also been reported that arranges leucines on a solvent-accessible region of an α-helix and places charged residues around the leucine patch to induce interactions between the two helical peptides. For this study, we adopted this approach to de novo design a new PPI between the helical bundle proteins sulerythrin and LARFH. A non-polar patch was created on an α-helix of LARFH around which arginine residues were introduced to retain its solubility. The strongest interaction found was for the LARFH variant cysLARFH-IV-3L3R and the sulerythrin mutant 6L6D (KD=0.16 μM). This artificial protein complex is maintained by hydrophobic and ionic interactions formed by the inter-molecular helical bundle structure. Therefore, by the simple and easy-to-use approach to create de novo interfaces on the α-helices, we successfully generated an artificial PPI. We also created a second LARFH variant with the non-polar patch surrounded by positively charged residues at each end. Upon mixing this LARFH variant with 6L6D, mesh-like fibrous nanostructures were observed by atomic force microscopy. Our method may, therefore, also be applicable to the de novo design of protein nanostructures. PMID:26867971

  20. Redetermined structure of diphenylphosphonimidotriphenylphosphorane: location of the hydrogen atoms and analysis of the intermolecular interactions

    Directory of Open Access Journals (Sweden)

    Richard Betz

    2011-05-01

    Full Text Available The title compound, C30H25NOP2, is a bulky phosphazene derivative. Its previous crystal structure [Cameron et al. (1979. Acta Cryst. B35, 13731377] is confirmed and its H atoms have been located in the present study. The formal P=N double bond is about 0.05? shorter than the PN single bond and the large P=NP bond angle reflects the steric strain in the molecule. An intramolecular CH...O interaction occurs. In the crystal, short CH...O contacts connect the molecules into chains propagating in [011], which are cross-linked via CH...? interactions, generating a three-dimensional network. Aromatic ?? stacking also occurs [shortest centroidcentroid separation = 3.6012?(11?].

  1. Tuning of intermolecular interactions results in packing diversity in imidazolin-5-ones

    Indian Academy of Sciences (India)

    Ashish Singh; Basanta Kumar Rajbongshi; Gurunath Ramanathan

    2014-09-01

    Crystal structures of four green fluorescent protein (GFP) chromophore analogues with different packing interactions could be tuned by appropriate substitutions around the imidazolin-5-one ring are reported here. Compound 1 was crystallized from tetrahydrofuran at room temperature while compounds 2-4 have been crystallized from a mixture of methanol and dichloromethane in 3:1 ratio. Molecule 1, 2 and 3 crystallized in monoclinic lattice while molecule 4 preferred to crystallize in a triclinic crystal system. The crystal packing of these molecules was stabilized by C-H$\\ldots$ stacking and C-H $\\ldots$ O type of supramolecular interactions. The results reveal that packing diversity can be easily accomplished in these molecules by tuning the substituents around the imidazolin-5-one ring. Photophysical studies also reveal that all have good quantum yield and fluoresce typically in red region due to presence of electron donating groups around the imidazolin-5-one ring.

  2. Co-amorphous simvastatin and glipizide combinations show improved physical stability without evidence of intermolecular interactions

    DEFF Research Database (Denmark)

    Löbmann, Korbinian; Strachan, Clare; Grohganz, Holger; Rades, Thomas; Korhonen, Ossi; Laitinen, Riikka

    2012-01-01

    The objective of this study was to prepare a co-amorphous drug/drug combination between two BCS class II drugs, simvastatin (SVS) and glipizide (GPZ). This pharmacologically relevant combination of two drugs could produce a promising candidate for formulations intended for combination therapy of...... metabolic disorders. The co-amorphous SVS-GPZ mixtures (molar ratios 2:1, 1:1 and 1:2) were prepared by mechanical activation (ball milling or cryomilling) and characterized with respect to their thermal properties, possible molecular interactions, dissolution properties and physical stability, and compared...... to the behaviour of pure amorphous forms and their physical mixtures. It was found that even though a molecular mixture was achieved with all SVS-GPZ mixture ratios, no molecular interactions between the drugs could be detected. By formation of co-amorphous single-phase mixtures, only the dissolution...

  3. Intermolecular interactions in cyclic complexes with hydrogen bond of bifunctional N-containing compounds in solution

    International Nuclear Information System (INIS)

    The structure of molecular and ionic hydrogen-bonded complexes formed by bifunctional N-containing molecules, which can act as proton donor and proton acceptor simultaneously, and the nature of molecular interactions in these complexes were studied in solution. The spectroscopic, steric and thermodynamic characteristics of self-associates of 3,5-dimethylpyrazole, diphenylformamidine, diphenylguanidine and diphenyltriazene and complexes of these compounds with carboxylic acids were obtained. The quantum chemical calculations of the structure of complexes and the vibrational frequencies in IR spectra were carried out in the harmonic approximation and with the anharmonic effects taken into account. It was shown that under the interaction with weak carboxylic acids (HCOOH, CH3COOH, CH2ClCOOH) the complexes have molecular structure with two H-bonds NH...O=C and OH...N, and the interaction with strong acids (CHCl2COOH, CCl3COOH, CF3COOH) results in formation of cyclic hydrogen-bonded ionic pairs with proton transfer from hydroxyl group to the N atom of the azo-compound. (authors)

  4. Conductance switching in a molecular device: The role of side groups and intermolecular interactions

    DEFF Research Database (Denmark)

    Taylor, Jeremy Philip; Brandbyge, Mads; Stokbro, Kurt

    2003-01-01

    We report first-principles studies of electronic transport in monolayers of Tour wires functionalized with different side groups. An analysis of the scattering states and transmission eigenchannels suggests that the functionalization does not strongly affect the resonances responsible for current...... flow through the monolayer. However, functionalization has a significant effect on the interactions within the monolayer, so that monolayers with NO2 side groups exhibit local minima associated with twisted conformations of the molecules. We use our results to interpret observations of negative...

  5. Macrocyclic β-Sheet Peptides that Mimic Protein Quaternary Structure through Intermolecular β-Sheet Interactions

    OpenAIRE

    Khakshoor, Omid; Demeler, Borries; Nowick, James S.

    2007-01-01

    This paper reports the design, synthesis, and characterization of a family of cyclic peptides that mimic protein quaternary structure through β-sheet interactions. These peptides are 54-membered-ring macrocycles comprising an extended heptapeptide β-strand, two Hao β-strand mimics [JACS 2000, 122, 7654] joined by one additional α-amino acid, and two δ-linked ornithine β-turn mimics [JACS 2003, 125, 876]. Peptide 3a, as the representative of these cyclic peptides, contains a heptapeptide seque...

  6. Competing intermolecular interactions of artemisinin-type agents and aspirin with membrane phospholipids: Combined model mass spectrometry and quantum-chemical study

    International Nuclear Information System (INIS)

    Highlights: • Competitive binding of artemisinin agents and aspirin with phospholipids is shown. • Complexation between the antimalarial drugs and aspirin molecules is also found. • Energetically favorable structures of the model complexes are identified by DFT. • Membranotropic activity of the studied drugs can be modified under joint usage. - Abstract: Study of intermolecular interactions of antimalarial artemisinin-type drugs and aspirin with membrane phospholipids is important in term of elucidation of the drugs activity modification under their joint usage. Combined experimental and computational study of the interaction of dihydroartemisinin, α-artemether, and artesunate with aspirin (ASP) and dipalmitoylphosphatidylcholine (DPPC) is performed by electrospray ionization (ESI) mass spectrometry and by DFT B3LYP/aug-cc-pVDZ methods. The results of the ESI investigation of systems containing artemisinin-type agent, ASP and DPPC, reveal a competition between the antimalarial agents and ASP for binding with DPPC molecules. The complexation between the antimalarial drugs and ASP is also found. Observed phenomena suggest that membranotropic activity of artemisin-type agents and aspirin is modified under their combined usage. To elucidate structure-energy characteristics of the non-covalent complexes studied the model DFT calculations are performed for dihydroartemisinin · ASP complex and complexes of the each drug with phosphatidylcholine head of DPPC in neutral and cationized forms

  7. Competing intermolecular interactions of artemisinin-type agents and aspirin with membrane phospholipids: Combined model mass spectrometry and quantum-chemical study

    Energy Technology Data Exchange (ETDEWEB)

    Pashynska, Vlada, E-mail: vlada@vl.kharkov.ua [B.Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, Lenin Ave., 47, 61103 Kharkov (Ukraine); Stepanian, Stepan [B.Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, Lenin Ave., 47, 61103 Kharkov (Ukraine); Gömöry, Agnes; Vekey, Karoly [Institute of Organic Chemistry of Research Centre for Natural Sciences of the Hungarian Academy of Sciences, Magyar tudosok korutja, 2, Budapest H-1117 (Hungary); Adamowicz, Ludwik [University of Arizona, Department of Chemistry and Biochemistry, Tucson, AZ 85721 (United States)

    2015-07-09

    Highlights: • Competitive binding of artemisinin agents and aspirin with phospholipids is shown. • Complexation between the antimalarial drugs and aspirin molecules is also found. • Energetically favorable structures of the model complexes are identified by DFT. • Membranotropic activity of the studied drugs can be modified under joint usage. - Abstract: Study of intermolecular interactions of antimalarial artemisinin-type drugs and aspirin with membrane phospholipids is important in term of elucidation of the drugs activity modification under their joint usage. Combined experimental and computational study of the interaction of dihydroartemisinin, α-artemether, and artesunate with aspirin (ASP) and dipalmitoylphosphatidylcholine (DPPC) is performed by electrospray ionization (ESI) mass spectrometry and by DFT B3LYP/aug-cc-pVDZ methods. The results of the ESI investigation of systems containing artemisinin-type agent, ASP and DPPC, reveal a competition between the antimalarial agents and ASP for binding with DPPC molecules. The complexation between the antimalarial drugs and ASP is also found. Observed phenomena suggest that membranotropic activity of artemisin-type agents and aspirin is modified under their combined usage. To elucidate structure-energy characteristics of the non-covalent complexes studied the model DFT calculations are performed for dihydroartemisinin · ASP complex and complexes of the each drug with phosphatidylcholine head of DPPC in neutral and cationized forms.

  8. Weak interactions in barbituric acid derivatives. Unusually steady intermolecular organic “sandwich” complexes. π π Stacking versus hydrogen bonding interactions

    Science.gov (United States)

    Khrustalev, Victor N.; Krasnov, Konstantin A.; Timofeeva, Tatiana V.

    2008-04-01

    The 4-methoxy-6,6-dimethyl-5,6,7,8-tetrahydro[1,3]dioxolo[4,5- g]isoquinolin-6-ium ( 1) and 2-(1 H-indol-3-yl)-1-ethanaminium (tryptaminium) ( 2) salts of 1,3-dimethyl-2,4,6-trioxoperhydro-pyrimidine-5-spiro-6'-{4'-methoxy-7'-(1,3-dimethyl-2,4,6-trioxoper-hydropyrimidin-5-yl)-5',6',7',8'-tetrahydro[1,3]dioxolo[4,5- g]naphthalene} ( 3) have been prepared and their structures have been investigated by single-crystal X-ray diffraction analysis. It has been found on the basis of the crystal packing arrangement as well as physical and chemical properties that derivatives 1 and 2 form unusually steady intermolecular sandwich-like complexes both in the crystal and in solution, which are stabilized by weak C sbnd H… n(O dbnd C) hydrogen bonds and π-π stacking. The interplay between the intermolecular π-π stacking and strong N sbnd H…O hydrogen bond interactions and its influence on the "sandwich" structures of 1 and 2 are discussed.

  9. Fabrication and Intermolecular Interactions of Silk Fibroin/Hydroxybutyl Chitosan Blended Nanofibers

    Directory of Open Access Journals (Sweden)

    Xiu-Mei Mo

    2011-03-01

    Full Text Available The native extracellular matrix (ECM is composed of a cross-linked porous network of multifibril collagens and glycosaminoglycans. Nanofibrous scaffolds of silk fibroin (SF and hydroxybutyl chitosan (HBC blends were fabricated using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP and trifluoroacetic acid (TFA as solvents to biomimic the native ECM via electrospinning. Scanning electronic microscope (SEM showed that relatively uniform nanofibers could be obtained when 12% SF was blended with 6% HBC at the weight ratio of 50:50. Meanwhile, the average nanofibrous diameter increased when the content of HBC in SF/HBC blends was raised from 20% to 100%. Fourier transform infrared spectra (FTIR and 13C nuclear magnetic resonance (NMR showed SF and HBC molecules existed in hydrogen bonding interactions but HBC did not induce conformation of SF transforming from random coil form to β-sheet structure. X-ray diffraction (XRD confirmed the different structure of SF/HBC blended nanofibers from both SF and HBC. Thermogravimetry-Differential thermogravimetry (TG-DTG results demonstrated that the thermal stability of SF/HBC blend nanofibrous scaffolds was improved. The results indicated that the rearrangement of HBC and SF molecular chain formed a new structure due to stronger hydrogen bonding between SF and HBC. These electrospun SF/HBC blended nanofibers may provide an ideal tissue engineering scaffold and wound dressing.

  10. Fine structures in vibrational circular dichroism spectra of chiral molecules with rotatable hydroxyl groups and their application in the analysis of local intermolecular interactions

    Science.gov (United States)

    Konno, Kohzo; Shiina, Isamu; Yui, Hiroharu

    2013-03-01

    The effect of hydroxyl group on vibrational circular dichroism is addressed. (-)-Menthol is investigated as a representative chiral molecule which has been widely used as a chiral starting material. Free rotation of the hydroxyl group in (-)-menthol allows it to exist in various conformations in solution. The variety of conformations inevitably affects local intermolecular interactions and the resultant efficiency of asymmetric syntheses. However, the precise relationship between the conformations and intermolecular interactions arising from rotation of the hydroxyl group has remained an unsolved issue despite the molecule's importance. Here, the conformations and interactions are investigated using vibrational circular dichroism (VCD). VCD is quite sensitive to slight differences in the conformation of chiral molecules and their local environment. We examined various conformers in (-)-menthol and compared the VCD spectrum with that of (-)-menthone. It revealed the rotation of the polar hydroxyl group sensitively affects the VCD activity, resulting in the emergence of various patterns in the corresponding VCD spectra, especially in the wavenumber regions at around 1064 cm-1 and 1254 cm-1. Among these regions, the latter one is further investigated to examine the feasibility of applying the sensitive response to the analysis on the local intermolecular environment. It includes solute-solvent interactions via hydroxyl groups, which is important for biomacromolecule structural stability and efficient stereoselective syntheses. As a consequence, distinctive fine structures in the VCD spectra, including an unpredicted band, are observed when varying temperature and concentration. Their possible assignment is also discussed.

  11. Toward more efficient CCSD(T) calculations of intermolecular interactions in model hydrogen-bonded and stacked dimers.

    Science.gov (United States)

    Dedíková, Pavlína; Pitonák, Michal; Neogrády, Pavel; Cernusák, Ivan; Urban, Miroslav

    2008-07-31

    Interaction energies of the model H-bonded complexes, the formamide and formamidine dimers, as well as the stacked formaldehyde and ethylene dimers are calculated by the coupled cluster CCSD(T) method. These systems serve as a model for H-bonded and stacking interactions, typical in molecules participating in biological systems. We use the optimized virtual orbital space (OVOS) technique, by which the dimension of the space of virtual orbitals in coupled cluster CCSD(T) calculations can be significantly reduced. We demonstrate that when the space of virtual orbitals is reduced to 50% of the full space, which means reducing computational demands by 1 order of magnitude, the interaction energies for both H-bonded and stacked dimers are affected by no more than 0.1 kcal/mol. This error is much smaller than the error when interaction energies are calculated using limited basis sets. PMID:18593134

  12. Determination of stepsize parameters for intermolecular vibrational energy transfer. Final report, May 1, 1987--December 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Tardy, D.C.

    1992-03-01

    Intermolecular energy transfer of highly excited polyatomic molecules plays an important role in many complex chemical systems: combustion, high temperature and atmospheric chemistry. By monitoring the relaxation of internal energy we have observed trends in the collisional efficiency ({beta}) for energy transfer as a function of the substrate`s excitation energy and the complexities of substrate and deactivator. For a given substrate {beta} increases as the deactivator`s mass increase to {approximately}30 amu and then exhibits a nearly constant value; this is due to a mass mismatch between the atoms of the colliders. In a homologous series of substrate molecules (C{sub 3}{minus}C{sub 8}) {beta} decreases as the number of atoms in the substrate increases; replacing F with H increases {beta}. All substrates, except for CF{sub 2}Cl{sub 2} and CF{sub 2}HCl below 10,000 cm{sup {minus}1}, exhibited that {beta} is independent of energy, i.e. <{Delta}E>{sub all} is linear with energy. The results are interpreted with a simple model which considers that {beta} is a function of the ocillators energy and its vibrational frequency. Limitations of current approximations used in high temperature unimolecular reactions were evaluated and better approximations were developed. The importance of energy transfer in product yields was observed for the photoactivation of perfluorocyclopropene and the photoproduction of difluoroethyne. 3 refs., 18 figs., 4 tabs.

  13. Intramolecular photo-switching and intermolecular energy transfer as primary photoevents in photoreceptive processes: The case of Euglena gracilis

    International Nuclear Information System (INIS)

    In this paper we report the results of measurements performed by FLIM on the photoreceptor of Euglenagracilis. This organelle consists of optically bistable proteins, characterized by two thermally stable isomeric forms: A498, non fluorescent and B462, fluorescent. Our data indicate that the primary photoevent of Euglena photoreception upon photon absorption consists of two contemporaneous different phenomena: an intramolecular photo-switch (i.e., A498 becomes B462), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B462 form acts as donor for the non-fluorescent A498 form of the protein nearby, which acts as acceptor. We hypothesize that in nature these phenomena follow each other with a domino progression along the orderly organized and closely packed proteins in the photoreceptor layer(s), modulating the isomeric composition of the photoreceptive protein pool. This mechanism guarantees that few photons are sufficient to produce a signal detectable by the cell.

  14. Landau-Zener tunneling in the presence of weak intermolecular interactions in a crystal of Mn4 single-molecule magnets

    OpenAIRE

    Wernsdorfer, W.; Bhaduri, S.; Vinslava, A.; Christou, G

    2005-01-01

    A Mn4 single-molecule magnet (SMM), with a well isolated spin ground state of S = 9/2, is used as a model system to study Landau-Zener (LZ) tunneling in the presence of weak intermolecular dipolar and exchange interactions. The anisotropy constants D and B are measured with minor hysteresis loops. A transverse field is used to tune the tunnel splitting over a large range. Using the LZ and inverse LZ method, it is shown that these interactions play an important role in the tunnel rates. Three ...

  15. Design, synthesis, and optoelectronic properties of dendrimeric Pt(II) complexes and their ability to inhibit intermolecular interaction.

    Science.gov (United States)

    Li, Hui; Li, Jing; Ding, Junqiao; Yuan, Wei; Zhang, Zilong; Zou, Luyi; Wang, Xingdong; Zhan, Hongmei; Xie, Zhiyuan; Cheng, Yanxiang; Wang, Lixiang

    2014-01-21

    Dendrimeric Pt(II) complexes [(C(?)N)Pt(dpm)] and [Pt(C(?)N)2] (Hdpm = dipivaloylmethane, HC(?)N = 1,2-diphenylbenzoimidazole and its derivatives containing the carbazole dendrons) have been synthesized and characterized systematically. All of the complexes display green emission in the range of 495-535 nm that originated from the 360-440 nm absorption bands, which are assigned to d?(Pt)??*(L) metal-to-ligand charge transfer (MLCT) mixed with intraligand ?(L)??*(L) transition. Solution photoluminescence quantum yield (?p 0.26-0.31) of the heteroleptic complexes [(C(?)N)Pt(dpm)] obviously increases when compared with that of complex [(C(?)N)Pt(acac)]. Organic light-emitting diode devices based on these Pt(II) complexes with a multilayer configuration were fabricated and gave desirable electroluminescent (EL) performances, such as non- or less red-shifted EL spectra, in comparison with the photoluminescence spectra and slow efficiency roll-off with increasing brightness or current density. Complex [(t-BuCzCzPBI)Pt(dpm)] (where t-BuCzCzPBI = 1-(4-(3,6-di-(3,6-di-t-butyl-carbazol-9-yl))carbazol-9-yl)phenyl-2-phenylbenzoimidazole) showed the best performance, with a maximum current efficiency of 29.31 cd/A and a maximum external quantum efficiency (EQE) of 9.04% among the fabricated devices. Likewise, for homoleptic [Pt(t-BuCzCzPBI)2] dendrimer, the powder ?p (0.14) and maximum EQE (0.74%) improve by 7 and 7.4 times, respectively, as high as they do for nondendrimeric [Pt(1,2-diphenylbenzoimidazole)2] (0.02, 0.10%), although its efficiency is still lower than that of the heteroleptic counterpart due to the severely distorted square-planar geometry of the emitting core. These results reveal that large steric hindrance from ancillary ligand (dpm) or the homoleptic conformation can effectively inhibit intermolecular interaction for these dendrimeric Pt(II) complexes. PMID:24393007

  16. Benchmark Calculations of Three-Body Intermolecular Interactions and the Performance of Low-Cost Electronic Structure Methods

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Huang, Y.; Hobza, Pavel; Beran, G. J. O.

    2015-01-01

    Roč. 11, č. 7 (2015), s. 3065-3079. ISSN 1549-9618 R&D Projects: GA ČR GP13-01214P; GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * Plesset perturbation theory * noncovalent interactions * interaction energies Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.498, year: 2014

  17. Renewable energy liberation by nonthermal intermolecular bond dissociation in water and ethanol

    Science.gov (United States)

    Graneau, N.; Verdoold, S.; Oudakker, G.; Yurteri, C. U.; Marijnissen, J. C. M.

    2011-02-01

    Prior indication that renewable energy can be extracted from hydrogen bonds in water has led to several investigations of the energy balance when bulk liquid is converted into micron scale droplets by directional (nonthermal) forces. The demonstration of this effect has previously involved pulsed high current arcs in water which produce large electrodynamic forces. Here, we show that renewable energy is also liberated during the creation of droplets by electrostatic forces in electrohydrodynamic atomization (electrospray) experiments. Using both ethanol and water, the energy outputs, primarily the droplet kinetic energy, were always greater than the energy inputs, implying that stored energy was liberated from the liquid. The energetics of generic chemical bonding are investigated to demonstrate that although this discovery was not publicly anticipated, it is consistent with conventional theory. This experimental breakthrough should have a major impact on the quest for renewable energy sources, capable of powering electricity generators.

  18. Intermolecular interactions of inorganic and organic molecules embedded in zeolite-type materials probed by near-infrared Fourier transform Raman spectroscopy

    Science.gov (United States)

    Wirnsberger, Gernot; Fritzer, Harald P.; Koller, Hubert; Behrens, Peter; Popitsch, Alois

    1999-05-01

    Near-infrared Fourier transform Raman spectroscopy represents an excellently suited tool to investigate spectroscopically inorganic and organic molecules occluded in zeolite-type materials as well as interactions between them. Two examples are presented: First, insertion compounds of iodine in various microporous SiO 2 modifications (deca-dodecasil 3R, all-silica theta-1 and silicalite-1) are discussed. Intermolecular interaction between the inserted molecules is prevented by occlusion of iodine in the cages of deca-dodecasil 3R, but is allowed in the insertion compounds of hosts with higher pore dimensionalities. The intermolecular coupling is confirmed by an appreciable reduction of the Raman shifts, as observed similarly for liquid and amorphous iodine. The second example deals with pyridine and n-alkylamines ( n-propyl-, n-butyl- or n-pentylamine) occluded during synthesis in all-silica ferrierite. Raman spectra reveal for all compounds, regardless of the n-alkylamine used, an interaction between the n-alkylamine and neighboring pyridine molecules, with both amines being located in the ten-membered ring channels. For this reason, it is proposed that bimolecular complexes, consisting of an n-alkylamine weakly bound to a pyridine molecule act as structure-directing agents during synthesis.

  19. The role of weak intermolecular C-H…F interactions in supramolecular assembly: Structural investigations on 3,5- dibenzylidene-piperidin-4-one and database analysis

    Indian Academy of Sciences (India)

    R S Rathore; N S Karthikeyan; Y Alekhya; K Sathiyanarayanan; P G Aravindan

    2011-07-01

    The fluorinated and non-fluorinated dibenzylidene-4-piperidones were synthesized and their structures examined using X-ray crystallography. Interestingly, the para-fluorosubstituted dibenzylidene compound, in contrast to other analogs, is characterized by C-H…F bonded one-dimensional packing motif. To evaluate the ability of hydrogen bond donors and acceptors for forming interactions, in general and competitive situation, we have defined statistical descriptors. Analysis of Cambridge Structural Database using these newly defined parameters reveals high propensity of C-H…F interactions in organic crystals. The present structural study suggests much larger role of fluorine driven intermolecular interactions that are even though weak, but possess significant ability to direct and alter the packing.

  20. Intramolecular photo-switching and intermolecular energy transfer as primary photoevents in photoreceptive processes: The case of Euglena gracilis

    Energy Technology Data Exchange (ETDEWEB)

    Mercatelli, Raffaella; Quercioli, Franco [Istituto Sistemi Complessi, CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino (Italy); Barsanti, Laura; Evangelista, Valter [Istituto di Biofisica, CNR, Via Moruzzi 1, 56124 Pisa (Italy); Coltelli, Primo [ISTI, CNR, Via Moruzzi 1, 56124 Pisa (Italy); Passarelli, Vincenzo; Frassanito, Anna Maria [Istituto di Biofisica, CNR, Via Moruzzi 1, 56124 Pisa (Italy); Gualtieri, Paolo, E-mail: paolo.gualtieri@pi.ibf.cnr.it [Istituto di Biofisica, CNR, Via Moruzzi 1, 56124 Pisa (Italy)

    2009-07-24

    In this paper we report the results of measurements performed by FLIM on the photoreceptor of Euglenagracilis. This organelle consists of optically bistable proteins, characterized by two thermally stable isomeric forms: A{sub 498,} non fluorescent and B{sub 462}, fluorescent. Our data indicate that the primary photoevent of Euglena photoreception upon photon absorption consists of two contemporaneous different phenomena: an intramolecular photo-switch (i.e., A{sub 498} becomes B{sub 462}), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B{sub 462} form acts as donor for the non-fluorescent A{sub 498} form of the protein nearby, which acts as acceptor. We hypothesize that in nature these phenomena follow each other with a domino progression along the orderly organized and closely packed proteins in the photoreceptor layer(s), modulating the isomeric composition of the photoreceptive protein pool. This mechanism guarantees that few photons are sufficient to produce a signal detectable by the cell.

  1. Polyelectrolyte and non-polyelectrolyte polyacrylamide copolymer solutions: the role of salt on the intra- and intermolecular interactions

    Scientific Electronic Library Online (English)

    Ana M. S., Maia; Marcos A., Villetti; Redouane, Borsali; Rosangela C., Balaban.

    2013-11-01

    Full Text Available Poli(acrilamida-co-dihexilacrilamida) (PAHM-0) e poli(acrilamida-co-acrilato de sdio-co-dihexilacrilamida) (PAHM-21) foram estudadas por espalhamento de raios-X a baixos ngulos (SAXS), espalhamento de luz (LS) e reologia. Os resultados de SAXS ressaltaram o carter polieletroltico da PAHM-21, com [...] uma conformao altamente estendida em soluo aquosa devido s repulses entre as cargas, enquanto a PAHM-0 tem uma conformao em novelo aleatrio. As medidas de LS indicaram que a PAHM-0 forma aglomerados intermoleculares em soluo, na presena e na ausncia de sal, mesmo com um contedo hidrofbico menor que o descrito na literatura para poliacrilamidas associativas. Contudo, os resultados reolgicos mostraram que, apesar de haver associao hidrofbica, no h um aumento da viscosidade. Os resultados de LS da PAHM-21 sugerem que esse polmero forma, predominantemente, associaes intramoleculares na presena de sais. Alm disso, as medidas viscosimtricas mostram que a sua viscosidade diminui com a blindagem das cargas pela adio de sais. Abstract in english Poly(acrylamide-co-dihexylacrylamide) (PAHM-0) and poly(acrylamide-co-sodium acrylate-co-dihexylacrylamide) (PAHM-21) were studied through small-angle X-ray scattering (SAXS), light scattering (LS) and rheology. SAXS results highlighted the polyelectrolyte character of PAHM-21, with highly extended [...] conformation in aqueous solution owing to charge repulsion, while the PAHM-0 has a coil conformation. LS measurements indicated that PAHM-0 makes intermolecular clusters in solution, in presence and absence of salt, even with a lower hydrophobic content than that described in the literature to the associative polyacrylamides. However, the rheological results showed that there is not an enhancement of the viscosity although hydrophobic association takes place. LS results for PAHM-21 suggest that this polymer makes intramolecular associations mainly in the presence of salts. Furthermore, the viscosity measurements show that its viscosity decreases due to screening of the charges by the addition of salts.

  2. Interacting Agegraphic Dark Energy

    OpenAIRE

    Wei, Hao; Cai, Rong-Gen(State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Beijing, 100190, China)

    2007-01-01

    A new dark energy model, named "agegraphic dark energy", has been proposed recently, based on the so-called K\\'{a}rolyh\\'{a}zy uncertainty relation, which arises from quantum mechanics together with general relativity. In this note, we extend the original agegraphic dark energy model by including the interaction between agegraphic dark energy and pressureless (dark) matter. In the interacting agegraphic dark energy model, there are many interesting features different from the original agegrap...

  3. Specific intermolecular interactions of conserved water molecules with amino acids in the Galectin-1 carbohydrate recognition domain

    Science.gov (United States)

    Di Lella, Santiago; Petruk, Ariel A.; Armiño, Diego J. Alonso de; Álvarez, Rosa M. S.

    2010-08-01

    Water molecules, rigidly associated to protein surfaces, play a key role in stabilizing biomolecules and participating in their biological functions. Recent studies on the solvation properties of the carbohydrate recognition domain of Galectin-1 by means of molecular dynamic simulations have revealed the existence of several water sites which were well correlated to both the bound water molecules observed in the crystal structure of the protein in the free state and to some of the hydroxyl groups of the carbohydrate ligand observed in the crystal structure of the complexed protein. In this work, we present a study using quantum mechanical methods (B3LYP/6-311++G(3df,3dp)//B3LYP/6-31+G(d)) to determine the energy involved in the binding of these water molecules to specific amino acids in the carbohydrate recognition domain of the protein. By modeling the hydroxyl groups of the carbohydrate by methanol, the energies associated to the local interactions between the ligand and the protein have been evaluated by replacing specific water molecules with methanol. The values of the binding energies have been compared to those previously obtained by the molecular dynamic method.

  4. Vapour pressures of 1-methyl derivatives of benzimidazole, pyrazole and indole. The energy of the intermolecular hydrogen bond N-H⋯N

    International Nuclear Information System (INIS)

    Highlights: • Vapour pressures of 1-methyl derivatives of benzimidazole, pyrazole and indole. • Enthalpies, entropies and Gibbs free energies of sublimation/vaporisation were derived. • Temperatures and enthalpies of fusion were determined. • Energy of the intermolecular hydrogen bond N-H⋯N was estimated. - Abstract: The vapour pressures of the liquid phase of 1-methylpyrazole, 1-methylbenzimidazole and 1-methylindole were measured over the temperature ranges (253.9 to 293.3) K, (303.2 to 372.5) K, and (268.6 to 341.9) K, respectively, using a static method. The vapour pressures of the crystalline phase of the two latter compounds were also measured at temperatures between (301.2 to 328.9) K and (267.6 to 275.5) K, respectively. The results obtained enabled the determination of the standard molar enthalpies and entropies of sublimation and of vaporisation at the mean temperatures of the measurements and at T = 298.15 K. The temperatures and molar enthalpies of fusion were determined using differential scanning calorimetry. The enthalpies of the intermolecular hydrogen bonds N-H⋯N in the crystalline phase of benzimidazole and pyrazole were determined and compared with the result previously determined for the energy of the intermolecular hydrogen bond in crystalline imidazole

  5. Data in support of intermolecular interactions at early stage of protein/detergent particle association induced by salt/polyethylene glycol mixtures

    Science.gov (United States)

    Odahara, Takayuki; Odahara, Koji

    2016-01-01

    The data provide information in support of the research article, “Intermolecular interactions at early stage of protein/detergent particle association induced by salt/polyethylene glycol mixtures” [1]. The data regarding variation of absorption spectra is used as an indicator of the duration of Rp. viridis PRU and RC, Rb. sphaeroides RC and LH2, and Rb. capsulatus LH2 in the native state in the presence of NaCl/polyethylene glycol (PEG) mixture. The data about minimum concentrations of salt and PEG whose aqueous phases are mutually separated presents information on additional influence of Tris buffer and N-octyl-β-d-glucoside on the salt–PEG phase separation. PMID:27135050

  6. Mapping intermolecular bonding in C??.

    Science.gov (United States)

    Sundqvist, Bertil

    2014-01-01

    The formation of intermolecular bonds in C?? has been investigated in detail at pressures below 2.2?GPa and up to 750?K. Fullerene samples were heated in a temperature gradient to obtain data on the formation of dimers and low-dimensional polymers along isobars. Intermolecular bonding was analyzed ex situ by Raman scattering, using both intramolecular modes and intermolecular stretching modes. Semi-quantitative reaction maps are given for the formation of dimers and chains. The activation energy for dimer formation decreases by 0.2?meV pm(-1) when intermolecular distances decrease and dimer formation is noticeably affected by the rotational state of molecules. Above 400-450?K larger oligomers are formed; below 1.4?GPa most of these are disordered, with small domains of linear chains, but above this the appearance of stretching modes indicates the existence of ordered one-dimensional polymers. At the highest pressures and temperatures two-dimensional polymers are also observed. PMID:25145952

  7. Interactive Energy Planning

    DEFF Research Database (Denmark)

    Blarke, Morten Boje

    2006-01-01

    tools. This paper presents an “Interactive Energy Planning” framework, which is intended to support interactivity in planning, building on important theoretical and experimental advances in planning. In particular, the paper explores the potential significance of allowing a critical perspective on...... context analysis and problem-orientation to define the course of the planning process, and deploying value-rational planning tools primarily as a platform for interactivity. The focus on interactivity in energy planning will allow contemporary government planners, consultants, researchers, and...

  8. Landau-Zener tunneling in the presence of weak intermolecular interactions in a crystal of Mn4 single-molecule magnets

    Science.gov (United States)

    Wernsdorfer, W.; Bhaduri, S.; Vinslava, A.; Christou, G.

    2005-12-01

    A Mn4 single-molecule magnet (SMM), with a well-isolated spin ground state of S=9/2 , is used as a model system to study Landau-Zener (LZ) tunneling in the presence of weak intermolecular dipolar and exchange interactions. The anisotropy constants D and B are measured with minor hysteresis loops. A transverse field is used to tune the tunnel splitting over a large range. Using the LZ and inverse LZ method, it is shown that these interactions play an important role in the tunnel rates. Three regions are identified: (i) at small transverse fields, tunneling is dominated by single tunnel transitions, (ii) at intermediate transverse fields, the measured tunnel rates are governed by reshuffling of internal fields, and (iii) at larger transverse fields, the magnetization reversal starts to be influenced by the direct relaxation process, and many-body tunnel events may occur. The hole digging method is used to study the next-nearest-neighbor interactions. At small external fields, it is shown that magnetic ordering occurs which does not quench tunneling. An applied transverse field can increase the ordering rate. Spin-spin cross-relaxations, mediated by dipolar and weak exchange interactions, are proposed to explain additional quantum steps.

  9. Structural Analysis of Intermolecular Interactions in the Kinesin Adaptor Complex Fasciculation and Elongation Protein Zeta 1/ Short Coiled-Coil Protein (FEZ1/SCOCO)

    Science.gov (United States)

    da Silva, Jlio Csar; Sfora, Maurcio Lus; Honorato, Rodrigo Vargas; Granato, Daniela Campos; dos Santos Migueleti, Deivid Lucas; Neves, Jorge L.; de Oliveira, Paulo Sergio Lopes; Paes-Leme, Adriana Franco; Zeri, Ana Carolina de Mattos; de Torriani, Iris Concepcion Linares; Kobarg, Jrg

    2013-01-01

    Cytoskeleton and protein trafficking processes, including vesicle transport to synapses, are key processes in neuronal differentiation and axon outgrowth. The human protein FEZ1 (fasciculation and elongation protein zeta 1 / UNC-76, in C. elegans), SCOCO (short coiled-coil protein / UNC-69) and kinesins (e.g. kinesin heavy chain / UNC116) are involved in these processes. Exploiting the feature of FEZ1 protein as a bivalent adapter of transport mediated by kinesins and FEZ1 protein interaction with SCOCO (proteins involved in the same path of axonal growth), we investigated the structural aspects of intermolecular interactions involved in this complex formation by NMR (Nuclear Magnetic Resonance), cross-linking coupled with mass spectrometry (MS), SAXS (Small Angle X-ray Scattering) and molecular modelling. The topology of homodimerization was accessed through NMR (Nuclear Magnetic Resonance) studies of the region involved in this process, corresponding to FEZ1 (92-194). Through studies involving the protein in its monomeric configuration (reduced) and dimeric state, we propose that homodimerization occurs with FEZ1 chains oriented in an anti-parallel topology. We demonstrate that the interaction interface of FEZ1 and SCOCO defined by MS and computational modelling is in accordance with that previously demonstrated for UNC-76 and UNC-69. SAXS and literature data support a heterotetrameric complex model. These data provide details about the interaction interfaces probably involved in the transport machinery assembly and open perspectives to understand and interfere in this assembly and its involvement in neuronal differentiation and axon outgrowth. PMID:24116125

  10. Theoretical studies for the N2–N2O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies

    International Nuclear Information System (INIS)

    Theoretical studies of the potential energy surface (PES) and bound states are performed for the N2–N2O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N2O monomer is near the N2 monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency for intermolecular disrotation mode is 23.086 cm−1, which is in good agreement with the available experimental data of 22.334 cm−1. A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers 14N2–N2O and 15N2–N2O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters

  11. Intra and inter-molecular interactions dictate the aggregation state of irinotecan co-encapsulated with floxuridine inside liposomes

    DEFF Research Database (Denmark)

    Dicko, A.; Frazier, A.A.; Liboiron, B.D.; Hinderliter, A.; Ellena, J.F.; Xie, X.; Cho, C.; Weber, T.; Tardi, P.G.; Cabral-Lilly, D.; Cafiso, D.S.; Mayer, L.D.

    2008-01-01

    PURPOSE: The inter/intramolecular interactions between drugs (floxuridine, irinotecan) and excipients (copper gluconate, triethanolamine) in the dual-drug liposomal formulation CPX-1 were elucidated in order to identify the physicochemical properties that allow coordinated release of irinotecan and...... required to achieve the highest solubility of irinotecan, direct drug-excipient binding interactions were absent. CONCLUSIONS: Long-range interactions between irinotecan, floxuridine and excipients modulate the aggregation state of irinotecan, allowing for simultaneous release of both drugs from the...

  12. Analysis of Cl…Cl and C-H…Cl intermolecular interactions involving chlorine in substituted 2-chloroquinoline derivatives

    Indian Academy of Sciences (India)

    Venkatesha R Hathwar; S Mohana Roopan; R Subashini; F Nawaz Khan; T N Guru Row

    2010-09-01

    Six crystal structures of substituted 2-chloroquinoline derivatives have been analysed to evaluate the role of Cl atom as a self recognizing unit resulting in the formation of Cl…Cl and C-H…Cl interactions to generate supramolecular assembly in the solid state. The features of Type I and Type II geometries associated with Cl…Cl interactions have been analysed to show directional preferences leading to differences in the packing motifs in these crystal structures. C-H…Cl interactions are generated exclusively in structures depicting Type II Cl…Cl interaction have been observed in these structures.

  13. Intermolecular, ion-molecular and interionic interactions in solutions of lithium and tetrabutylammonium salts in mixtures of methanol with propylene carbonate

    International Nuclear Information System (INIS)

    Interparticle interactions are investigated in solutions of LiI, LiBr, LiCl, LiNCS, (C4H9)4NI, (C4H9)4NBr, (C4H9)4NCl in mixtures of methanol with propylene carbonate in absence of self-association of molecules of methanol and in different salt concentrations by the methods of IR spectroscopy. Intermolecular and ion-molecular interactions are studied on IR absorption lines of valent vibrations of OH-groups of methanol (3300-3500 cm-1), interionic interaction - on lines of valent CN (2000-2100 cm-1) and deformation O-Cl-O (625 cm-1) vibrations of NVS- and ClO4- correspondingly. Concentrations of lithium complexes forming in solutions are calculated on intensities of valent absorption lines of OH-groups of methanol. In the case of salt concentration increase the content of complexes decreases. Ousting of solvent molecule by anions in complex happens so faster as electron-donor ability of it is higher

  14. Landau-Zener tunneling in the presence of weak intermolecular interactions in a crystal of Mn4 single-molecule magnets

    CERN Document Server

    Wernsdorfer, W; Vinslava, A; Christou, G

    2005-01-01

    A Mn4 single-molecule magnet (SMM), with a well isolated spin ground state of S = 9/2, is used as a model system to study Landau-Zener (LZ) tunneling in the presence of weak intermolecular dipolar and exchange interactions. The anisotropy constants D and B are measured with minor hysteresis loops. A transverse field is used to tune the tunnel splitting over a large range. Using the LZ and inverse LZ method, it is shown that these interactions play an important role in the tunnel rates. Three regions are identified: (i) at small transverse fields, tunneling is dominated by single tunnel transitions; (ii) at intermediate transverse fields, the measured tunnel rates are governed by reshuffling of internal fields, (iii) at larger transverse fields, the magnetization reversal starts to be influenced by the direct relaxation process, and many-body tunnel events may occur. The hole digging method is used to study the next-nearest neighbor interactions. At small external fields, it is shown that magnetic ordering occ...

  15. Intramolecular versus intermolecular hydrogen bonding in solution

    OpenAIRE

    Vliegenthart, J. F. G.; Kroon, Jan; Kroon-Batenburg, L.M.J.; Leeflang, B.R.

    1994-01-01

    The balance between intra- and intermolecular hydrogen bonding is studied for a solution of methyl beta-cellobioside in water and dimethylsulfoxide by 1H NMR and molecular dynamics simulations. In water O(3) predominantly interacts with water molecules, whereas in dimethylsulfoxide it is intramolecularly hydrogen bonded to O(5Œ). The temperature coefficient of the chemical shift of the hydroxy groups appears to be a reliable indicator of intermolecular hydrogen-bond formation, whereas the ex...

  16. Electronic transitions and intermolecular forces

    International Nuclear Information System (INIS)

    This thesis describes two different subjects - electronic transitions and intermolecular forces - that are related mainly by the following observation: The wavenumber at which an electronic transition in an atom or molecule occurs, depends on the environment of that atom or molecule. This implies, for instance, that when a molecule becomes solvated its absorption spectrum may be shifted either to the blue or to the red side of the original gasphase spectrum. In part I attention is paid to the experimental aspects of VUV spectroscopy, both in the gasphase and in the condensed phase. In part II a series of papers are presented, dealing with the calculation of intermolecular forces (and some related topics) both for the ground state and for the excited state interactions, using different non-empirical methods. The calculations provide, among other results, a semiquantitative interpretation of the spectral blue shifts encountered in our experiments. (Auth.)

  17. Relationship between molecular weight of poly(ethylene)glycol and intermolecular interaction of Taka-amylase A monomers

    Science.gov (United States)

    Onuma, Kazuo; Furubayashi, Naoki; Shibata, Fujiko; Kobayashi, Yoshiko; Kaito, Sachiko; Ohnishi, Yuki; Inaka, Koji

    2010-04-01

    Dynamic and static light scattering investigations of Taka-amylase A (TAA) protein monomers were done using solutions containing poly(ethylene)glycol (PEG) with molecular weights of 1500, 4000, 8000, and 20 000. The anomalies observed in a previous study using a weight of 8000, in which the hydrodynamic TAA monomer radius at a zero protein concentration and the molecular weight of the monomers decreased when the PEG concentration was increased, were observed for all four weights. These anomalies became more pronounced as the PEG molecular weight was increased. The overall interaction parameter did not move further in the direction of the attractive force despite an increase in the PEG concentration from 6% to 12.5% for the PEG 8000 and 20 000 solutions. This was due to the change in the relative contributions of the static structure factor (direct interaction) and the hydrodynamic interaction factor (indirect interaction) against the overall interaction parameter. For the PEG 1500 and 4000 solutions, the change in the overall interaction parameter with an increase in the PEG concentration was controlled by changing the static structure factor. For the PEG 8000 and 20 000 solutions, a change in the hydrodynamic interaction factor with an increase in the PEG concentration offset the change in the static structure factor, unexpectedly resulting in the overall interaction parameter being independent of the PEG concentration. This suggests that the scale and density of a PEG network structure, which are thought to be the origin of the observed anomalies, change nonlinearly with the PEG molecular weight.

  18. Interacting Dark Energy

    OpenAIRE

    Zhang, Xinmin

    2004-01-01

    In this paper I discuss some of the phenomenologies of models of the dark energy interacting with the ordinary matter. After a very brief review about the current constraint on the equation of the state of the dark energy from the SN and a new scenario of dark energy {\\it the Quintom}, I present models of Quintessential Baryo(Lepto)genesis, Quintessino dark matter and mass varying neutrinos in details.

  19. Interacting dark energy

    International Nuclear Information System (INIS)

    In this paper I discuss some of the phenomenologies of models of the dark energy interacting with the ordinary matter. After a very brief review about the current constraint on the equation of the state of the dark energy from the SN and a new scenario of dark energy the Quintom, I present models of Quintessential Baryo(Lepto) genesis, Quintessino dark matter and mass varying neutrinos in details. (author)

  20. Ab initio Intermolecular Potential Energy Surface and Calculation of Second Virial Coefficients for the Cl2–Cl2 Dimer

    OpenAIRE

    Nguyen Thanh Duoc; Nguyen Thi Ai Nhung; Tran Duong; Pham Van Tat

    2015-01-01

    The results presented in this paper are the ab initio intermolecular potentials and the second virial coefficient, B2 (T) of the dimer Cl2-Cl2. These ab initio potentials were proposed by the quantum chemical calculations at high level of theory CCSD (T) with basis sets of Dunning’s valence correlation-consistent aug-cc-pVmZ (m = 2, 3); these results were extrapolated to complete basis set limit aug-cc-pV23Z. The ab initio energies of complete basis set limit aug-cc-pV23Z resulted from the ex...

  1. A quantum-chemical validation about the formation of hydrogen bonds and secondary interactions in intermolecular heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Boaz Galdino Oliveira

    2009-08-01

    Full Text Available We have performed a detailed theoretical study in order to understand the charge density topology of the C2H4O···C2H2 and C2H4S···C2H2 heterocyclic hydrogen-bonded complexes. Through the calculations derived from Quantum Theory of Atoms in Molecules (QTAIM, it was observed the formation of hydrogen bonds and secondary interactions. Such analysis was performed through the determination of optimized geometries at B3LYP/6-31G(d,p level of theory, by which is that QTAIM topological operators were computed, such as the electronic density ρ(r, Laplacian Ñ2ρ(r, and ellipticity ε. The examination of the hydrogen bonds has been performed through the measurement of ρ(r, Ñ2ρ(r and ε between (O···H—C and (S···H—C, whereas the secondary interaction between axial hydrogen atoms Hα and carbon of acetylene. In this insight, it was verified the existence of secondary interaction only in C2H4S···C2H2 complex because its structure is propitious to form multiple interactions.

  2. Refined ab initio intermolecular ground-state potential energy surface for the He-C2H2 van der Waals complex

    DEFF Research Database (Denmark)

    Fernández, Berta; Henriksen, Christian; Farrelly, David

    A refined CCSD(T) intermolecular potential energy surface is developed for the He-C2H2 van der Waals complex. For this, 206 points on the intermolecular potential energy surface, evaluated using the CCSD(T) method and the aug-cc-pVQZ basis set extended with a set of 3s3p2d1f1g midbond functions...... developed previously by Munteanu and Fernández (J. Chem. Phys., 123, 014309, 2005) but differs notably at short range. The improved potential energy surface should, therefore, be particularly useful for computations of collision line broadening. Dynamical calculations of a number of rovibrational bound......, are fitted to a 15-parameter analytic function. The potential is characterised by minima of-24.21 cm-1 at distances between the rare gas atom and the C2H2 centre of mass of 4.3453 Å, and with the complex in a linear configuration. At intermediate distances the surface is rather similar to that...

  3. Solid-State [2+2] Photodimerization and Photopolymerization of α,ω-Diarylpolyene Monomers: Effective Utilization of Noncovalent Intermolecular Interactions in Crystals

    Directory of Open Access Journals (Sweden)

    Yoriko Sonoda

    2010-12-01

    Full Text Available [2+2] Photocycloaddition of olefins is a very useful reaction in synthetic organic chemistry to obtain cyclobutane-containing molecules, which are almost inaccessible by other methods. The reaction, when performed in the crystalline state, occurs more efficiently and selectively than in homogeneous solution due to tight and regular molecular arrangement in the crystal state. Despite numerous examples for the solid-state [2+2] photodimerization of monoenes, however, it is still a challenge to prepare not only dimers but also higher oligomers and polymers from conjugated polyenes, which have multiple reactive double bonds in a molecule. In our recent studies of the solid-state photoreactions of α,ω-diarylpolyenes, noncovalent intermolecular interactions in crystals were effectively utilized to prealign molecules in stacking arrangements, suitable for the [2+2] reaction. With appropriate ring-substituents, [2+2] photodimerization and photopolymerization of the polyenes took place, although the degree of polymerization was relatively low. This review will describe the details of these reactions.

  4. A theoretical-experimental proposal, in teaching sequences about intermolecular interactions on teaching chemistry using varations of the test of adulteration in gasline and urucum dyes

    Directory of Open Access Journals (Sweden)

    Ademir de Souza Pereira

    2012-09-01

    Full Text Available This paper reports presents the results of a research developed with students of the high school in the Dourados, Mato Grosso do Sul, with the objective of proposing a theoretical-experimental teaching sequences, potentially significant, approaching the theme Intermolecular Interactions. The teaching sequence was developed with 44 students of the last year of the high school, with the duration of 9 classes of 50 minutes. The methodology presents the characteristics of the qualitative research, being based on David Ausubel's theoretical. We used, as advance organizer, the test determination of the ethanol content in gasoline, adapting, along the experiments, to the use of the natural dyes of the urucum seeds communly used through the region the research was done. The instruments used to collect the information was through the use of questionnaires and observations of the classes. At the end 32 students presented arguments, developing in each stage, as well as in participation, as in classroom discussion, evidencing the evolution conceptual on the process of significant learning.

  5. Anisotropic intermolecular interactions and rotational ordering in hydrogen containing solids. Final report, January 1, 1972--June 30, 1978

    Energy Technology Data Exchange (ETDEWEB)

    White, D.

    1978-01-01

    Thermodynamic properties, order-disorder phenomena, optical, electric and magnetic properties of hydrogen-containing molecular solids have been investigated. A summary of the findings of this 6 year research program is presented here. The approach in these studies was (a) thermodynamic and transport studies extending to very low temperatures, (b) pulsed NMR studies for determination of structural parameters important to spin-lattice relaxation, and (c) pulsed laser studies for the investigation of excitations and energy transfer mechanisms in solids. (GHT)

  6. Competing intramolecular vs. intermolecular hydrogen bonds in solution.

    Science.gov (United States)

    Nagy, Peter I

    2014-01-01

    A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

  7. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    Directory of Open Access Journals (Sweden)

    Peter I. Nagy

    2014-10-01

    Full Text Available A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011 or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic in acid-base complexes have been surveyed.

  8. Energy of the quasi-free electron in H2, D2, and O2: Probing intermolecular potentials within the local Wigner-Seitz model

    International Nuclear Information System (INIS)

    We present for the first time the quasi-free electron energy V0(ρ) for H2, D2, and O2 from gas to liquid densities, on noncritical isotherms and on a near critical isotherm in each fluid. These data illustrate the ability of field enhanced photoemission (FEP) to determine V0(ρ) accurately in strongly absorbing fluids (e.g., O2) and fluids with extremely low critical temperatures (e.g., H2 and D2). We also show that the isotropic local Wigner-Seitz model for V0(ρ) — when coupled with thermodynamic data for the fluid — can yield optimized parameters for intermolecular potentials, as well as zero kinetic energy electron scattering lengths

  9. Disorder and intermolecular interactions in a family of tetranuclear Ni(II) complexes probed by high-frequency electron paramagnetic resonance.

    Science.gov (United States)

    Lawrence, Jon; Yang, En-Che; Edwards, Rachel; Olmstead, Marilyn M; Ramsey, Chris; Dalal, Naresh S; Gantzel, Peter K; Hill, Stephen; Hendrickson, David N

    2008-03-17

    High-frequency electron paramagnetic resonance (HFEPR) data are presented for four closely related tetranuclear Ni(II) complexes, [Ni(hmp)(MeOH)Cl]4.H2O (1a), [Ni(hmp)(MeOH)Br]4.H2O (1b), [Ni(hmp)(EtOH)Cl]4.H2O (2), and [Ni(hmp)(dmb)Cl]4 (3) (where hmp(-) is the anion of 2-hydroxymethylpyridine and dmb is 3,3'-dimethyl-1-butanol), which exhibit magnetic bistability (hysteresis) and fast magnetization tunneling at low temperatures, properties which suggest they are single-molecule magnets (SMMs). The HFEPR spectra confirm spin S = 4 ground states and dominant uniaxial anisotropy (DSz(2), D ZFS) parameters. The broad EPR lines, meanwhile, may be attributed to ligand and solvent disorder, which results in additional distributions of microenvironments. In the case of complex 3, there are no solvate molecules in the structure, and only one distinct Ni 4 molecule in the lattice. Consequently, the HFEPR data for complex 3 are extremely sharp. As the temperature of a crystal of complex 3 is decreased, the HFEPR spectrum splits abruptly at approximately 46 K into two patterns with very slightly different ZFS parameters. Heat capacity data suggest that this is caused by a structural transition at 46.6 K. A single-crystal X-ray structure at 12(2) K indicates large thermal parameters on the terminal methyl groups of the dmb (3,3-dimethyl-1-butanol) ligand. Most likely there exists dynamic disorder of parts of the dmb ligand above 46.6 K; an order-disorder structural phase transition at 46.6 K then removes some of the motion. A further decrease in temperature (<6 K) leads to further fine structure splittings for complex 3. This behavior is thought to be due to the onset of short-range magnetic correlations/coherences between molecules caused by weak intermolecular magnetic exchange interactions. PMID:18284196

  10. Inhomogeneous and interacting vacuum energy

    OpenAIRE

    De-Santiago, Josue; Wands, David; Wang, Yuting

    2012-01-01

    Vacuum energy is a simple model for dark energy driving an accelerated expansion of the universe. If the vacuum energy is inhomogeneous in spacetime then it must be interacting. We present the general equations for a spacetime-dependent vacuum energy in cosmology, including inhomogeneous perturbations. We show how any dark energy cosmology can be described by an interacting vacuum+matter. Different models for the interaction can lead to different behaviour (e.g., sound speed for dark energy p...

  11. Interactions in Dark Energy Models

    OpenAIRE

    ZHANG Yi; Li, Hui; Gong, Yungui; Zhu, Zong-Hong

    2011-01-01

    We perform a full dynamical analysis by considering the interactions between dark energy and radiation, and dark energy and dark matter. We find that the interaction helps alleviate the coincidence problem for the quintessence model.

  12. Accurate non-covalent interaction energies via an efficient MP2 scaling procedure

    CERN Document Server

    Fabiano, E; Grabowski, I

    2015-01-01

    Using the observed proportionality of CCSD(T) and MP2 correlation interaction energies [I. Grabowski, E. Fabiano, F. Della Sala, Phys. Chem. Chem. Phys. 15, 15485 (2013)] we propose a simple scaling procedure to compute accurate interaction energies of non-covalent complexes. Our method makes use of MP2 and CCSD(T) correlation energies, computed in relatively small basis sets, and fitted scaling coefficients to yield interaction energies of almost complete basis set limit CCSD(T) quality. Thanks to the good transferability of the scaling coefficients involved in the calculations, good results can be easily obtained for different intermolecular distances.

  13. Visualizing the orientational dependence of an intermolecular potential.

    Science.gov (United States)

    Sweetman, Adam; Rashid, Mohammad A; Jarvis, Samuel P; Dunn, Janette L; Rahe, Philipp; Moriarty, Philip

    2016-01-01

    Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard-Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation. PMID:26879386

  14. Strong orbital interaction in a weak CH-? hydrogen bonding system

    Science.gov (United States)

    Li, Jianfu; Zhang, Rui-Qin

    2016-01-01

    For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms bonding and antibonding orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-? hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least ?1.51?kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex. PMID:26927609

  15. Characteristics and nature of the intermolecular interactions in boron-bonded complexes with carbene as electron donor: an ab initio, SAPT and QTAIM study.

    Science.gov (United States)

    Esrafili, Mehdi D

    2012-05-01

    We report geometries, stabilization energies, symmetry adapted perturbation theory (SAPT) and quantum theory of atoms in molecules (QTAIM) analyses of a series of carbene-BX(3) complexes, where X = H, OH, NH(2), CH(3), CN, NC, F, Cl, and Br. The stabilization energies were calculated at HF, B3LYP, MP2, MP4 and CCSD(T)/aug-cc-pVDZ levels of theory using optimized geometries of all the complexes obtained from B3LYP/aug-cc-pVTZ. Quantitatively, all the complexes indicate the presence of B-C(carbene) interaction due to the short B-C(carbene) distances. Inspection of stabilization energies reveals that the interaction energies increase in the order NH(2) > OH > CH(3) > F > H > Cl > Br > NC > CN, which is the opposite trend shown in the binding distances. Considering the SAPT results, it is found that electrostatic effects account for about 50% of the overall attraction of the studied complexes. By comparison, the induction components of these interactions represent about 40% of the total attractive forces. Despite falling in a region of charge depletion with nabla(2)ρ(BCP) >0, the B-C(carbene) bond critical points (BCPs) are characterized by a reasonably large value of the electron density (ρ(BCP)) and H(BCP) kinetic energy density at BCP and the B-C(carbene) bond is a polar covalent bond. PMID:21877151

  16. Study of intermolecular interactions in the system of equilibrium catalytic transesterification of esters. 4. Fourier IR studies of the interaction of alcohols with esters

    International Nuclear Information System (INIS)

    Interaction of alcohols ROH with esters PhCOOR (R = Me, n-Bu, n-C7H15) in binary mixtures and in solutions in non-polar solvents was studies over a wide temperature range by means of Fourier IR spectroscopy. Even with alcohol taken in a great excess, two bands are observed in the region of ΝCO vibrations. The low-frequency band, correspond to the ester molecules bonded by hydrogen bonds of the C=O...HO type. The high-frequence band is shifted by 3-5 cm-1 with respect to the ester ΝCO band. The discreteness of the shift, indicates that an H-complex of one more type is formed between the alcohol and the ester. The analysis of data available allows one to conclude that the complex formation involves the alkoxyl oxygen atom of the ester. The formation enthalpies were determined for H-bond of n-BuOH with the esters and with transesterification catalysts B(OBu)3

  17. Intermolecular interactions in nuclear magnetic resonance: medium shifts of the 1H and 13C nuclei in methane in the gas phase and in solution and of gaseous 3He

    International Nuclear Information System (INIS)

    An analysis has been carried out of the continuum and the binary collision models used in the description of NMR solvent shifts caused by Van der Waals intermolecular interactions. The basic assumption underlying the models, i.e. ? sub(w)= -BE2 (I) is examined. The possible effects on I of such phenomena as B anisotropy and field gradients are discussed, as well as the inadequacy of I in representing the true intermolecular shielding. A new expression for E2 is proposed, which in connection with I forms the bais of a modified binary collision model. The new E2 expression takes into account the dynamic character of the interaction. The major obstacle to the binary collision model, the requirement for accurate parameters for the intermolecular potential employed in the statistical-mechanical averaging, is alleviated by the establishment of priority rules to be used in the selection of these paramters. The proposed binary collision model and a collision model are used to interpret the 1H and 13C medium shifts of methane in the gas phase and in solution. The proton shift data conform equally well to either model; the 13C data indicate that a large solvent-dependent term contributes to the observed medium shifts in addition to I. Proton and 13C B parameters of methane in the gas phase and in solution are discussed. Preliminary results of 3He medium shifts as a function of gas density are presented. An extracted B parameter based on the proposed binary collision model appears to agree well with the result of a quantum-mechanical calculation of B for a 3He atom in a uniform static electric field. (LL)

  18. Desensitization of metastable intermolecular composites

    Energy Technology Data Exchange (ETDEWEB)

    Busse, James R. (South Fork, CO); Dye, Robert C. (Los Alamos, NM); Foley, Timothy J. (Los Alamos, NM); Higa, Kelvin T. (Ridgecrest, CA); Jorgensen, Betty S. (Jemez Springs, NM); Sanders, Victor E. (White Rock, NM); Son, Steven F. (Los Alamos, NM)

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  19. Ab initio Intermolecular Potential Energy Surface and Calculation of Second Virial Coefficients for the Cl2–Cl2 Dimer

    Directory of Open Access Journals (Sweden)

    Nguyen Thanh Duoc

    2015-12-01

    Full Text Available The results presented in this paper are the ab initio intermolecular potentials and the second virial coefficient, B2 (T of the dimer Cl2-Cl2. These ab initio potentials were proposed by the quantum chemical calculations at high level of theory CCSD (T with basis sets of Dunning’s valence correlation-consistent aug-cc-pVmZ (m = 2, 3; these results were extrapolated to complete basis set limit aug-cc-pV23Z. The ab initio energies of complete basis set limit aug-cc-pV23Z resulted from the exponential extrapolation were used to construct the 5-site pair potential functions. The second virial coefficients for this dimer were predicted from those with four-dimensional integration. The second virial coefficients were also corrected to first-order quantum effects. The results turn out to be in good agreement with experimental data, if available, or with those from empirical correlation. The quality of ab initio 5-site potentials proved the reliability for prediction of molecular thermodynamic properties.

  20. Asymptotic limits of the retarded interaction energy between two hyperpolarizable molecules

    International Nuclear Information System (INIS)

    The asymptotic limits of the leading term of the energy shift between a pair of molecules due to exchange of three virtual photons are calculated using nonrelativistic quantum electrodynamics. In the electric dipole approximation, this discriminatory interaction depending on the handedness of each species, corresponds to the near- and far-zone energy shifts between two hyperpolarizable molecules. The far-zone result, exhibiting an R-11 dependence on intermolecular separation is compared with far-zone limits of higher multipole polarizable interaction energies arising from a two-photon exchange. copyright 1997 The American Physical Society

  1. Mapping intermolecular bonding in C60

    Science.gov (United States)

    Sundqvist, Bertil

    2014-08-01

    The formation of intermolecular bonds in C60 has been investigated in detail at pressures below 2.2 GPa and up to 750 K. Fullerene samples were heated in a temperature gradient to obtain data on the formation of dimers and low-dimensional polymers along isobars. Intermolecular bonding was analyzed ex situ by Raman scattering, using both intramolecular modes and intermolecular stretching modes. Semi-quantitative reaction maps are given for the formation of dimers and chains. The activation energy for dimer formation decreases by 0.2 meV pm-1 when intermolecular distances decrease and dimer formation is noticeably affected by the rotational state of molecules. Above 400-450 K larger oligomers are formed; below 1.4 GPa most of these are disordered, with small domains of linear chains, but above this the appearance of stretching modes indicates the existence of ordered one-dimensional polymers. At the highest pressures and temperatures two-dimensional polymers are also observed.

  2. Electronic Mechanisms of Intra and Intermolecular J Couplings in Systems with C-H···O Interactions

    Directory of Open Access Journals (Sweden)

    Claudio N. Cavasotto

    2003-04-01

    Full Text Available Abstract: Correlation effects on the change of 1J(CH couplings in model systems I:NCH...H2O and II:CH4...H2O as a function of the H...O distance are discussed. RPA and SOPPA results follow a similar trend in system II. In system I RPA values decrease monotonously as the H...O distance decreases, while SOPPA ones exhibit flat maximum near equilibrium. Such different behavior is ascribed to the π-transmitted component. Intermolecular couplings at the equilibrium geometry of I are analyzed by means of the CLOPPA approach. The larger absolute value of 2hJ(CO compared to 1hJ(HO is found to arise from contributions involving a vacant LMO localized in the C-H...O moiety.

  3. Strong orbital interaction in a weak CH-π hydrogen bonding system.

    Science.gov (United States)

    Li, Jianfu; Zhang, Rui-Qin

    2016-01-01

    For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms "bonding" and "antibonding" orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least -1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex. PMID:26927609

  4. Intermolecular and Intramolecular Excited State Charge Transfer

    OpenAIRE

    Eisenthal, Kenneth B.

    1983-01-01

    A primary mechanism of energy relaxation and chemical change in organic molecules in excited electronic states is charge transfer. 1 The charge transfer process can be intermolecular, involving an excited molecule and a neighboring molecule, one serving as an acceptor and the other as a donor molecule, or intramolecular, involving a charge redistribution in the excited molecule which produces a very large excited state dipole moment.In our investigations of the dynamics of these various charg...

  5. Transport properties and intermolecular forces (1) viscosity

    International Nuclear Information System (INIS)

    A semi-empirical procedure is introduced by means of which the like and unlike interaction parameters of an intermolecular potential of the form L.J. (n-6) can be obtained from the temperature dependence of the viscosity of pure gases and their binary mixtures. The potentials with n=7 to 90 are considered. The procedure is tested and proved successful for the Ar - Kr system. It is found that the best potential representing the interaction of this system is the L.J. (11.5-6). It reproduces the experimental results satisfactorily to within 4%

  6. Impact of protein/protein interactions on global intermolecular translocation rates of the transcription factors Sox2 and Oct1 between DNA cognate sites analyzed by z-exchange NMR spectroscopy.

    Science.gov (United States)

    Takayama, Yuki; Clore, G Marius

    2012-08-01

    Oct1 and Sox2 synergistically regulate developmental genes by binding to adjacent sites within promoters. We have investigated the kinetics of global intermolecular translocation of Sox2 and Oct1 between cognate sites located on different DNA molecules by z-exchange NMR spectroscopy. In the Hoxb1 promoter, the Sox2 and Oct1 sites are immediately adjacent to one another, and the intermolecular translocation rates are too slow to be measured by z-exchange spectroscopy. By introducing a 3-bp insertion between the Sox2 and Oct1 sites to mimic the spacing in the FGF4 enhancer, the interprotein contact surface is reduced, and the translocation rates are increased. Interaction between Sox2 and the POU-specific domain (POU(S)) of Oct1 does not affect the translocation mechanism but modulates the rates. Translocation involves only jumping (dissociation and reassociation) for Sox2, but both jumping and direct intersegment transfer (no dissociation into free solution) for Oct1. The dissociation (k(off) ∼1.5 s(-1)) and association (k(on) ∼5.1 × 10(9) m(-1)s(-1)) rate constants for Sox2 are reduced 4-fold and increased 5-fold, respectively, in the presence of Oct1. k(off) (∼3.5 s(-1)) for Oct1 is unaffected by Sox2, whereas k(on) (∼1.3 × 10(9) m(-1)s(-1)) is increased ∼13-fold. The direct intermolecular translocation rate (k(inter) ∼1.8 × 10(4) m(-1)s(-1)) for the POU(S) domain of Oct1 is reduced 2-fold by Sox2, whereas that for the POU homeodomain (POU(HD)) of Oct1 (k(inter) ∼ 1.7 × 10(4) m(-1)s(-1)) remains unaltered, consistent with the absence of contacts between Sox2 and POU(HD). The data suggest a model for the sequence of binding events involved in synergistic gene regulation by Sox2 and Oct1. PMID:22718759

  7. Intermolecular symmetry-adapted perturbation theory study of large organic complexes

    International Nuclear Information System (INIS)

    Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies

  8. Intermolecular symmetry-adapted perturbation theory study of large organic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Heelmann, Andreas, E-mail: andreas.hesselmann@chemie.uni-erlangen.de [Lehrstuhl fr Theoretische Chemie, Universitt Erlangen-Nrnberg, Egerlandstr. 3, D-91058 Erlangen (Germany); Korona, Tatiana, E-mail: tatiana.korona@chem.uw.edu.pl [Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

    2014-09-07

    Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies.

  9. Intermolecular symmetry-adapted perturbation theory study of large organic complexes

    Science.gov (United States)

    Heßelmann, Andreas; Korona, Tatiana

    2014-09-01

    Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies.

  10. How resonance assists hydrogen bonding interactions: an energy decomposition analysis.

    Science.gov (United States)

    Beck, John Frederick; Mo, Yirong

    2007-01-15

    Block-localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance-assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between pi delocalization and hydrogen-bonding interactions. We examined the dimers of formic acid, formamide, 4-pyrimidinone, 2-pyridinone, 2-hydroxpyridine, and 2-hydroxycyclopenta-2,4-dien-1-one. In addition, we studied the interactions in beta-diketone enols with a simplified model, namely the hydrogen bonds of 3-hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of pi resonance, were decomposed into the Hitler-London energy (DeltaEHL), polarization energy (DeltaEpol), charge transfer energy (DeltaECT), and electron correlation energy (DeltaEcor) terms. This allows for the examination of the character of hydrogen bonds and the impact of pi conjugation on hydrogen bonding interactions. Although it has been proposed that resonance-assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipole-dipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term "resonance-assisted binding (RAB)" instead of "resonance-assisted hydrogen bonding (RHAB)" to highlight the electrostatic, which is a long-range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs. PMID:17143867

  11. Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111)

    Science.gov (United States)

    Mller, Moritz; Diller, Katharina; Maurer, Reinhard J.; Reuter, Karsten

    2016-01-01

    We employ dispersion-corrected density-functional theory to study the adsorption of tetrapyrrole 2H-porphine (2H-P) at Cu(111) and Ag(111). Various contributions to adsorbate-substrate and adsorbate-adsorbate interactions are systematically extracted to analyze the self-assembly behavior of this basic building block to porphyrin-based metal-organic nanostructures. This analysis reveals a surprising importance of substrate-mediated van der Waals interactions between 2H-P molecules, in contrast to negligible direct dispersive interactions. The resulting net repulsive interactions rationalize the experimentally observed tendency for single molecule adsorption.

  12. Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111)

    CERN Document Server

    Müller, Moritz; Maurer, Reinhard J; Reuter, Karsten

    2015-01-01

    We employ dispersion-corrected density-functional theory to study the adsorption of tetrapyrrole 2H-porphine (2H-P) at Cu(111) and Ag(111). Various contributions to adsorbate-substrate and adsorbate-adsorbate interactions are systematically extracted to analyze the self-assembly behavior of this basic building block to porphyrin-based metal-organic nanostructures. This analysis reveals a surprising importance of substrate-mediated van der Waals interactions between 2H-P molecules, in contrast to negligible direct dispersive interactions. The resulting net repulsive interactions rationalize the experimentally observed tendency for single molecule adsorption.

  13. Direct measurements of intermolecular forces by chemical force microscopy

    Science.gov (United States)

    Vezenov, Dmitri Vitalievich

    1999-12-01

    Detailed description of intermolecular forces is key to understanding a wide range of phenomena from molecular recognition to materials failure. The unique features of atomic force microscopy (AFM) to make point contact force measurements with ultra high sensitivity and to generate spatial maps of surface topography and forces have been extended to include measurements between well-defined organic molecular groups. Chemical modification of AFM probes with self-assembled monolayers (SAMs) was used to make them sensitive to specific molecular interactions. This novel chemical force microscopy (CFM) technique was used to probe forces between different molecular groups in a range of environments (vacuum, organic liquids and aqueous solutions); measure surface energetics on a nanometer scale; determine pK values of the surface acid and base groups; measure forces to stretch and unbind a short synthetic DNA duplex and map the spatial distribution of specific functional groups and their ionization state. Studies of adhesion forces demonstrated the important contribution of hydrogen bonding to interactions between simple organic functionalities. The chemical identity of the tip and substrate surfaces as well as the medium had a dramatic effect on adhesion between model monolayers. A direct correlation between surface free energy and adhesion forces was established. The adhesion between epoxy polymer and model mixed SAMs varied with the amount of hydrogen bonding component in the monolayers. A consistent interpretation of CFM measurements in polar solvents was provided by contact mechanics models and intermolecular force components theory. Forces between tips and surfaces functionalized with SAMs terminating in acid or base groups depended on their ionization state. A novel method of force titration was introduced for highly local characterization of the pK's of surface functional groups. The pH-dependent changes in friction forces were exploited to map spatially the changes in ionization state on SAM surfaces. The phase contrast in tapping mode AFM between chemically distinct monolayer regions and corresponding adhesion forces were found to be directly correlated. Thus, both friction and intermittent contact CFM images could be interpreted in terms of the strength of intermolecular interactions. CFM was also used to probe biomolecular interactions. Separation forces between complementary oligonucleotide strands were significantly larger than the forces measured between noncomplementary strands and were consistent with the unbinding of a single DNA duplex. CFM data provided a direct measure of the forces required to elastically deform, structurally-transform and separate well-defined, synthetic duplexes into single strand oligonucleotides.

  14. Evidence for Intermolecular Interactions between the Intracellular Domains of the Arabidopsis Receptor-Like Kinase ACR4, Its Homologs and the Wox5 Transcription Factor

    Science.gov (United States)

    Meyer, Matthew R.; Shah, Shweta; Zhang, J.; Rohrs, Henry; Rao, A. Gururaj

    2015-01-01

    Arabidopsis CRINKLY4 (ACR4) is a receptor-like kinase (RLK) involved in the global development of the plant. The Arabidopsis genome encodes four homologs of ACR4 that contain sequence similarity and analogous architectural elements to ACR4, termed Arabidopsis CRINKLY4 Related (AtCRRs) proteins. Additionally, a signaling module has been previously proposed including a postulated peptide ligand, CLE40, the ACR4 RLK, and the WOX5 transcription factor that engage in a possible feedback mechanism controlling stem cell differentiation. However, little biochemical evidence is available to ascertain the molecular aspects of receptor heterodimerization and the role of phosphorylation in these interactions. Therefore, we have undertaken an investigation of the in vitro interactions between the intracellular domains (ICD) of ACR4, the CRRs and WOX5. We demonstrate that interaction can occur between ACR4 and all four CRRs in the unphosphorylated state. However, phosphorylation dependency is observed for the interaction between ACR4 and CRR3. Furthermore, sequence analysis of the ACR4 gene family has revealed a conserved ‘KDSAF’ motif that may be involved in protein-protein interactions among the receptor family. We demonstrate that peptides harboring this conserved motif in CRR3 and CRK1are able to bind to the ACR4 kinase domain. Our investigations also indicate that the ACR4 ICD can interact with and phosphorylate the transcription factor WOX5. PMID:25756623

  15. Interacting Induced Dark Energy Model

    CERN Document Server

    Bahrehbakhsh, Amir F

    2016-01-01

    Similar to the idea of the brane world scenarios, but based on the approach of the induced matter theory, for a non--vacuum five--dimensional version of general relativity, we propose a model in which the conventional matter sources considered as all kind of the matter (the baryonic and dark) and the induced terms emerging from the extra dimension supposed to be as dark energy. Then we investigate the FLRW type cosmological equations and illustrate that the model is capable to explain respectively the deceleration and then acceleration eras of the universe expansion with an interacting term between the matter and dark energy.

  16. Fixed points in interacting dark energy models

    OpenAIRE

    Chen, Xi-Ming; Gong, Yungui

    2008-01-01

    The dynamical behaviors of two interacting dark energy models are considered. In addition to the scaling attractors found in the non-interacting quintessence model with exponential potential, new accelerated scaling attractors are also found in the interacting dark energy models. The coincidence problem is reduced to the choice of parameters in the interacting dark energy models.

  17. Weak interactions at high energies

    International Nuclear Information System (INIS)

    Review lectures are presented on the phenomenological implications of the modern spontaneously broken gauge theories of the weak and electromagnetic interactions, and some observations are made about which high energy experiments probe what aspects of gauge theories. Basic quantum chromodynamics phenomenology is covered including momentum dependent effective quark distributions, the transverse momentum cutoff, search for gluons as sources of hadron jets, the status and prospects for the spectroscopy of fundamental fermions and how fermions may be used to probe aspects of the weak and electromagnetic gauge theory, studies of intermediate vector bosons, and miscellaneous possibilities suggested by gauge theories from the Higgs bosons to speculations about proton decay. 187 references

  18. Metal-Arene Complexes with Indolo[3,2-c]-quinolines: Effects of Ruthenium vs Osmium and Modifications of the Lactam Unit on Intermolecular Interactions, Anticancer Activity, Cell Cycle, and Cellular Accumulation.

    Science.gov (United States)

    Filak, Lukas K; Gschl, Simone; Heffeter, Petra; Ghannadzadeh Samper, Katia; Egger, Alexander E; Jakupec, Michael A; Keppler, Bernhard K; Berger, Walter; Arion, Vladimir B

    2013-02-11

    Six novel ruthenium(II)- and osmium(II)-arene complexes with three modified indolo[3,2-c]quinolines have been synthesized in situ starting from 2-aminoindoloquinolines and 2-pyridinecarboxaldehyde in the presence of [M(p-cymene)Cl(2)](2) (M = Ru, Os) in ethanol. All complexes have been characterized by elemental analysis, spectroscopic techniques ((1)H, (13)C NMR, IR, UV-vis), and ESI mass spectrometry, while four complexes were investigated by X-ray diffraction. The complexes have been tested for antiproliferative activity in vitro in A549 (non-small cell lung), SW480 (colon), and CH1 (ovarian) human cancer cell lines and showed IC(50) values between 1.3 and >80 ?M. The effects of Ru vs Os and modifications of the lactam unit on intermolecular interactions, antiproliferative activity, and cell cycle are reported. One ruthenium complex and its osmium analogue have been studied for anticancer activity in vivo applied both intraperitoneally and orally against the murine colon carcinoma model CT-26. Interestingly, the osmium(II) complex displayed significant growth-inhibitory activity in contrast to its ruthenium counterpart, providing stimuli for further investigation of this class of compounds as potential antitumor drugs. PMID:23431223

  19. MetalArene Complexes with Indolo[3,2-c]-quinolines: Effects of Ruthenium vs Osmium and Modifications of the Lactam Unit on Intermolecular Interactions, Anticancer Activity, Cell Cycle, and Cellular Accumulation

    Science.gov (United States)

    2013-01-01

    Six novel ruthenium(II) and osmium(II)arene complexes with three modified indolo[3,2-c]quinolines have been synthesized in situ starting from 2-aminoindoloquinolines and 2-pyridinecarboxaldehyde in the presence of [M(p-cymene)Cl2]2 (M = Ru, Os) in ethanol. All complexes have been characterized by elemental analysis, spectroscopic techniques (1H, 13C NMR, IR, UVvis), and ESI mass spectrometry, while four complexes were investigated by X-ray diffraction. The complexes have been tested for antiproliferative activity in vitro in A549 (non-small cell lung), SW480 (colon), and CH1 (ovarian) human cancer cell lines and showed IC50 values between 1.3 and >80 ?M. The effects of Ru vs Os and modifications of the lactam unit on intermolecular interactions, antiproliferative activity, and cell cycle are reported. One ruthenium complex and its osmium analogue have been studied for anticancer activity in vivo applied both intraperitoneally and orally against the murine colon carcinoma model CT-26. Interestingly, the osmium(II) complex displayed significant growth-inhibitory activity in contrast to its ruthenium counterpart, providing stimuli for further investigation of this class of compounds as potential antitumor drugs. PMID:23431223

  20. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    International Nuclear Information System (INIS)

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å

  1. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Rintaro; Hamaguchi, Hiro-o, E-mail: hhama@nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan (China)

    2014-05-28

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.

  2. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(1S) + H2(B 1Σ/sub u/+)

    International Nuclear Information System (INIS)

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H2(B 1Σ/sub u/+) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H2(B 1Σ/sub u/+). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H2(E,F 1Σ/sub g/+) and with He + H2(X 1Σ/sub g/+) and cause a local maximum and a deep minimum in the He + H2(B 1Σ/sub u/+) PES, respectively. The crossing with He + H2(X 1Σ/sub g/+) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H2(B 1Σ/sub u/+) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs

  3. High-Energy Neutrino Interactions

    CERN Multimedia

    2002-01-01

    This experiment studies neutrino interactions in iron at the highest available energies using the narrow-band neutrino beam N3 and the wide-band neutrino beam N1. The basis of the detector is a massive target-calorimeter in which the energy deposited by a neutrino (or antineutrino) is measured by electronic techniques and the momentum of outgoing muons is determined by magnetic deflection. The detector is constructed in the form of a 20 m long iron-cored toroidal magnet, composed of modules of length 70~cm and 90~cm, and of 3.75~m diameter. Drift chambers placed in between each module measure the trajectory of muons from the neutrino interactions. The modules are of three types. The first ten modules are constructed of 2.5~cm iron plates with 20~scintillator planes inserted between the plates. The next five modules are constructed of 5~cm plates with 15~planes of scintillator and the last six modules are constructed of 15~cm plates with 5~planes of scintillators. The total mass of the detector is @=~1400 tons...

  4. Intermolecular Interactions of Xe Atoms Confined in One-dimensional Nanochannels of Tris(o-phenylenedioxy)cyclotriphosphazene as Studied by High-pressure 129Xe NMR

    Science.gov (United States)

    Kobayashi, Hirokazu; Ueda, Takahiro; Miyakubo, Keisuke; Eguchi, Taro

    2003-12-01

    The pressure dependence of the 129Xe chemical shift tensor confined in the Tris(o-phenylenedioxy) cyclotriphosphazene (TPP) nanochannel was investigated by high-pressure 129Xe NMR spectroscopy. The observed 129Xe spectrum in the one-dimensional TPP nanochannel (0.45 nm in diameter) exhibits a powder pattern broadened by an axially symmetric chemical shift tensor. As the pressure increases from 0.02 to 7.0 MPa, a deshielding of 90 ppm is observed for the perpendicular component of the chemical shift tensor δ⊥, whereas a deshielding of about 30 ppm is observed for the parallel one, δ‖. This suggests that the components of the chemical shift tensor, δ‖ and δ⊥, are mainly dominated by the Xe-wall and Xe-Xe interaction, respectively. Furthermore, the effect of helium, which is present along with xenon gas, on the 129Xe chemical shift is examined in detail. The average distance between the Xe atoms in the nanochannel is estimated to be 0.54 nm. This was found by using δ⊥ at the saturated pressure of xenon, and comparing the increment of the chemical shift value in δ⊥ to that of a β -phenol/Xe compound.

  5. Vibrational assignments, spectroscopic investigation (FT-IR and FT-Raman), NBO, MEP, HOMO‒LUMO analysis and intermolecular hydrogen bonding interactions of 7-fluoroisatin, 7-bromoisatin and 1-methylisatin ‒ A comparative study

    Science.gov (United States)

    Polat, Turgay; Bulut, Fatih; Arıcan, Ilknur; Kandemirli, Fatma; Yildirim, Gürcan

    2015-12-01

    In this comprehensive study, theoretical and experimental studies were carried out on 7-fluoroisatin, 7-bromoisatin and 1-methylisatin using FT-Raman and FT-IR spectra. The optimized geometrical parameters and theoretical vibrational frequencies were calculated by means of density functional theory (DFT/B3LYP) with 6-311++G(d,p) basis set based on scaled quantum mechanical (SQM) method for the first time. The relative abundances of the possible tautomers or conformers found were calculated with respect to the Boltzmann distribution. Moreover, the harmonic vibrational frequencies including IR and Raman intensities, thermodynamic and electronic parameters were computed in detail. The effects of substituents -F, ‒Br and -CH3 on the crucial characteristics pertaining to the title compound of isatin were investigated, and the obtained data were compared with each other. Natural bond orbital (NBO) analysis was applied to study the stability arising from charge delocalization along with the compound. The chemical reactivity parameters (chemical hardness and softness, electronegativity, chemical potential and electrophilicity index) were discussed clearly. The HOMO and LUMO energies determined showed that the serious charge transfer occurs in the title molecules studied. Furthermore, the size, shape, charge density distributions and chemical reactivity sites belonging to the molecules were obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Additionally, the hydrogen-bonded complexes were simulated to describe the roles of intermolecular hydrogen bonding on the molecular structures and vibrational frequencies.

  6. Neutral CH3Cl and CH3Br clusters studied by X-ray photoelectron spectroscopy and modeling: Insight to intermolecular interactions and structure

    International Nuclear Information System (INIS)

    Single-component clusters of methyl chloride and methyl bromide have been produced by adiabatic expansion and their C 1s, Cl 2p and Br 3d photoelectron spectra recorded using synchrotron radiation and a high-resolution electron analyzer. The experimentally observed cluster-to-monomer shifts in core-level ionization energies are interpreted in terms of theoretical models based on molecular dynamics (MD) in conjunction with polarizable force fields developed and validated in the course of this work. MD simulations have also been used to explore the global and local structure of the clusters, providing evidence for a predominance of anti-parallel, head-to-tail arrangement of neighboring molecules. Whereas the cluster-to-monomer shifts are strongly dominated by polarization effects, the polarization contribution is very similar for ionization of carbon and the halogen, respectively. The difference in cluster shifts between the two ionization sites within the same molecule, C vs. Cl or C vs. Br, is thus determined by permanent electrostatic moments, i.e. the magnitude and direction of the permanent dipole moment and the local alignment of dipoles

  7. The study of intermolecular energy transfers in electronic energy quenching for molecular collisions N{sub 2}-N{sub 2}, N{sub 2}-O{sub 2}, O{sub 2}-O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Kirillov, A.S. [Kola Science Centre RAS, Apatity (Russian Federation). Polar Geophysical Inst.

    2008-07-01

    Contributions of intermolecular electron energy transfers in the electronic quenching are calculated for molecular collisions N{sub 2}(A{sup 3}{sigma}{sub u}{sup +}, W{sup 3}{delta}{sub u})+N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}, v=0), N{sub 2}(A{sup 3}{sigma}{sub u}{sup +})+N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}, v{>=}0), N{sub 2}(A{sup 3}{sigma}{sub u}{sup +})+O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}, v=0-2), O{sub 2}(a{sup 1}{delta}{sub g}, b{sup 1}{sigma}{sub g}{sup +})+O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}, v=0-2). The calculation has allowed one to estimate the product branching ratios. It is shown that there is a dependence of the calculated rate coefficients on the vibrational excitation of N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}) and O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}) molecules. In many cases, the calculated rate coefficients have a good agreement with available experimental data. (orig.)

  8. Interacting agegraphic tachyon model of dark energy

    International Nuclear Information System (INIS)

    Scalar-field dark energy models like tachyon are often regarded as an effective description of an underlying theory of dark energy. In this Letter, we implement the interacting agegraphic dark energy models with tachyon field. We demonstrate that the interacting agegraphic evolution of the universe can be described completely by a single tachyon scalar field. We thus reconstruct the potential as well as the dynamics of the tachyon field according to the evolutionary behavior of interacting agegraphic dark energy.

  9. Topological characterisation of intermolecular lithium bonding

    Energy Technology Data Exchange (ETDEWEB)

    Vila, Antonio [Departamento de Quimica Fisica, Universidade de Vigo, Lagoas-Marcosende, 36310-Vigo, Galicia (Spain); Vila, Esther [Departamento de Quimica Fisica, Universidade de Vigo, Lagoas-Marcosende, 36310-Vigo, Galicia (Spain); Mosquera, Ricardo A. [Departamento de Quimica Fisica, Universidade de Vigo, Lagoas-Marcosende, 36310-Vigo, Galicia (Spain)], E-mail: mosquera@uvigo.es

    2006-08-01

    Bader's atoms in molecules topological theory was employed to analyse the B3LYP/6-311++G(3d2f,3p2d) electron distributions of several adducts that contain LiF. The results indicate significant differences between lithium bonding (LB) and hydrogen bonding (HB): (i) in spite of their larger stability, the charge density at the intermolecular critical points of LB complexes is about half of its value in the corresponding HB complexes, suggesting a dominant role of electrostatic interactions in the former; (ii) the Li atom in LB compounds is more shared between the base atom and the attached fluorine than hydrogen in HB complexes; and (iii) the Li atom gains electron charge from the hydrogens in all the complexes here studied, undergoing energetic stabilisation.

  10. Topological characterisation of intermolecular lithium bonding

    International Nuclear Information System (INIS)

    Bader's atoms in molecules topological theory was employed to analyse the B3LYP/6-311++G(3d2f,3p2d) electron distributions of several adducts that contain LiF. The results indicate significant differences between lithium bonding (LB) and hydrogen bonding (HB): (i) in spite of their larger stability, the charge density at the intermolecular critical points of LB complexes is about half of its value in the corresponding HB complexes, suggesting a dominant role of electrostatic interactions in the former; (ii) the Li atom in LB compounds is more shared between the base atom and the attached fluorine than hydrogen in HB complexes; and (iii) the Li atom gains electron charge from the hydrogens in all the complexes here studied, undergoing energetic stabilisation

  11. Quantum structure of the intermolecular proton bond.

    Science.gov (United States)

    Roscioli, J R; McCunn, L R; Johnson, M A

    2007-04-13

    A proton shared between two closed-shell molecules, [A.H+.B], constitutes a ubiquitous soft binding motif in biological processes. The vibrational transitions associated with the shared proton, which provide a direct probe of this interaction, have been extensively studied in the condensed phase but have yielded only limited detailed information because of their diffuse character. We exploited recent advances in gas-phase ion spectroscopy to identify sharp spectral features that can be assigned to both the shared proton and the two tethered molecules in a survey of 18 cold, isolated [A.H+.B] ions. These data yield a picture of the intermolecular proton bond at a microscopic scale, facilitating analysis of its properties within the context of a floppy polyatomic molecule. PMID:17431174

  12. New type of dual solid-state thermochromism: modulation of intramolecular charge transfer by intermolecular pi-pi interactions, kinetic trapping of the aci-nitro group, and reversible molecular locking.

    Science.gov (United States)

    Naumov, Pance; Lee, Sang Cheol; Ishizawa, Nobuo; Jeong, Young Gyu; Chung, Ihn Hee; Fukuzumi, Shunichi

    2009-10-22

    When heated above room temperature, some crystalline polymorphs of the 1,3-bis(hydroxyalkylamino)-4,6-dinitrobenzenes (BDBn, n = 2-5), bis(hydroxyalkyl) analogues of the intramolecular charge-transfer molecule 1,3-diamino-4,6-dinitrobenzene, exhibit "dual" thermochromism: gradual color change from yellow to orange at lower temperatures, and sharp color change from orange to red at higher temperatures. These two thermochromic changes are related to different solid-state processes. When allowed to cool to room temperature, the yellow color of the thermochromic molecules with different alkyl length (n) is recovered with unexpectedly different kinetics, the order of the respective rate constants ranging from 10(-7)-10(-6) s(-1) for BDB2 to about 0.1 s(-1) in the case of BDB3. The thermochromic mechanism and the reasons behind the different kinetics were clarified on the basis of detailed crystallographic characterization, kinetic thermoanalysis, and spectroscopic study of eight crystalline forms (seven polymorphs and one solvate). It was found that the polymorphism is due to the possibility of "locking" and "unlocking" of the alkyl arms by formation of a strong intramolecular hydrogen bond between the hydroxyl groups at their hydroxyl termini. The locking of BDB2, with shortest alkyl arms, is reversible and it can be controlled thermally; either of the two conformations can be obtained in the solid state by proper thermal treatment. By use of high temperature in situ single crystal X-ray diffraction analysis of BDB3, direct evidence was obtained that the gradual thermochromic change is related to increased distance and weakened pi-pi interactions between the stacked benzene rings: the lattice expands preferably in the stacking direction, causing enhanced oscillator strength and red shift of the absorption edge of the intramolecular charge transfer transition. The second, sharp thermochromic change had been assigned previously to solid-solid phase transition triggered by intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular pi-pi interactions and thermal intramolecular proton transfer to aromatic nitro group. PMID:19780605

  13. New Type of Dual Solid-State Thermochromism: Modulation of Intramolecular Charge Transfer by Intermolecular π-π Interactions, Kinetic Trapping of the Aci-Nitro Group, and Reversible Molecular Locking

    Science.gov (United States)

    Naumov, Panče; Lee, Sang Cheol; Ishizawa, Nobuo; Jeong, Young Gyu; Chung, Ihn Hee; Fukuzumi, Shunichi

    2009-09-01

    When heated above room temperature, some crystalline polymorphs of the 1,3-bis(hydroxyalkylamino)-4,6-dinitrobenzenes (BDBn, n = 2-5), bis(hydroxyalkyl) analogues of the intramolecular charge-transfer molecule 1,3-diamino-4,6-dinitrobenzene, exhibit "dual" thermochromism: gradual color change from yellow to orange at lower temperatures, and sharp color change from orange to red at higher temperatures. These two thermochromic changes are related to different solid-state processes. When allowed to cool to room temperature, the yellow color of the thermochromic molecules with different alkyl length (n) is recovered with unexpectedly different kinetics, the order of the respective rate constants ranging from 10-7-10-6 s-1 for BDB2 to about 0.1 s-1 in the case of BDB3. The thermochromic mechanism and the reasons behind the different kinetics were clarified on the basis of detailed crystallographic characterization, kinetic thermoanalysis, and spectroscopic study of eight crystalline forms (seven polymorphs and one solvate). It was found that the polymorphism is due to the possibility of "locking" and "unlocking" of the alkyl arms by formation of a strong intramolecular hydrogen bond between the hydroxyl groups at their hydroxyl termini. The locking of BDB2, with shortest alkyl arms, is reversible and it can be controlled thermally; either of the two conformations can be obtained in the solid state by proper thermal treatment. By use of high temperature in situ single crystal X-ray diffraction analysis of BDB3, direct evidence was obtained that the gradual thermochromic change is related to increased distance and weakened π-π interactions between the stacked benzene rings: the lattice expands preferably in the stacking direction, causing enhanced oscillator strength and red shift of the absorption edge of the intramolecular charge transfer transition. The second, sharp thermochromic change had been assigned previously to solid-solid phase transition triggered by intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular π-π interactions and thermal intramolecular proton transfer to aromatic nitro group.

  14. Desensitization and recovery of metastable intermolecular composites

    Energy Technology Data Exchange (ETDEWEB)

    Busse, James R. (South Fork, CO); Dye, Robert C. (Los Alamos, NM); Foley, Timothy J. (Los Alamos, NM); Higa, Kelvin T. (Ridgecrest, CA); Jorgensen, Betty S. (Jemez Springs, NM); Sanders, Victor E. (White Rock, NM); Son, Steven F. (Los Alamos, NM)

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  15. Simulated imaging of intermolecular bonds using high throughput real-space density functional calculations

    Science.gov (United States)

    Lee, Alex; Kim, Minjung; Chelikowsky, James

    2015-03-01

    Recent experimental noncontact atomic force microscopy (AFM) studies on 8-hydroxyquinoline (8-hq) assemblies have imaged distinct lines between molecules that are thought to represent intermolecular bonding. To aid the interpretation of these images, we calculate simulated AFM images of an 8-hq dimer with a CO functionalized tip using a real-space pseudopotential formalism. We examine the effects of Pauli repulsion and tip probe relaxation as explanations for the enhanced resolution that resolves these intermolecular force lines. Our study aims to compute ab initio real-space images of intermolecular interactions.

  16. The interaction region of high energy protons

    OpenAIRE

    Dremin, I. M.; White, S. N.

    2016-01-01

    The spatial view of the interaction region of colliding high energy protons (in terms of impact parameter) is considered. It is shown that the region of inelastic collisions has a very peculiar shape. It saturates for central collisions at an energy of 7 TeV. We speculate on the further evolution with energy, which is contrasted to the "black disk" picture.

  17. Low energy light ion interactions

    Science.gov (United States)

    Cerutti, F.; Ballarini, F.; Battistoni, G.; Colleoni, P.; Ferrari, A.; Frtsch, S. V.; Gadioli, E.; Garzelli, M. V.; Mairani, A.; Ottolenghi, A.; Pepe, A.; Pinsky, L. S.; Sala, P. R.; Steyn, G. F.

    2007-02-01

    Light ion reactions are of importance in many trans-disciplinary fields, particularly in cancer therapy and space radiation protection. We show here the results of an analysis of the spectra of intermediate mass fragments produced in the C+Al interaction at 13 MeV/n, both in direct and inverse kinematics, which supplies a very reasonable reproduction of a great number of data providing useful information on the leading reaction mechanisms.

  18. Hadronic Interactions at Cosmic Ray Energies

    OpenAIRE

    Ostapchenko, S.

    2006-01-01

    General physics of very high energy hadronic interactions is discussed. Special attention is payed to the contribution of semihard processes to the interaction dynamics and to the role of parton shadowing and parton density saturation. In particular, the implementation of non-linear interaction effects in the QGSJET-II model is discussed in detail. The predictions of the model are compared to selected accelerator data, including ones of the RHIC collider, and the relation to the calculated ex...

  19. Expectations for ultra-high energy interactions

    International Nuclear Information System (INIS)

    Strong interactions at ultra-high energies are discussed with emphasis on the hadrons produced in high energy collisions. Evidence is considered that quantum chromodynamics might be the right theory, and also some estimates are given of quantum chromodynamics asymptotic-freedom phenomena, the work under discussion being very preliminary. 6 references

  20. Generalized Interacting Holographic Dark Energy Model

    CERN Document Server

    Rashid, Muneer Ahmad; Jamil, Mubasher

    2009-01-01

    In this manuscript, we present a generalization of the interacting holographic dark energy model using two equations of states for the dark energy: the modified variable Chaplygin gas and the viscous generalized Chaplygin gas. The dynamics of the model are expressed by the use of scalar fields and the scalar potentials.

  1. Dark energy interacting with two fluids

    OpenAIRE

    Cruz, Norman; Lepe, Samuel; Pena, Francisco

    2008-01-01

    A cosmological model of dark energy interacting with dark matter and another general component of the universe is investigated. We found general constraints on these models imposing an accelerated expansion. The same is also studied in the case for holographic dark energy.

  2. Dark energy interacting with two fluids

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, Norman [Departamento de Fisica, Facultad de Ciencia, Universidad de Santiago, Casilla 307, Santiago (Chile)], E-mail: ncruz@lauca.usach.cl; Lepe, Samuel [Instituto de Fisica, Facultad de Ciencias Basicas y Matematicas, Universidad Catolica de Valparaiso, Avenida Brasil 2950, Valparaiso (Chile)], E-mail: slepe@ucv.cl; Pena, Francisco [Departamento de Ciencias Fisicas, Facultad de Ingenieria, Ciencias y Administracion, Universidad de La Frontera, Avda. Francisco Salazar 01145, Casilla 54-D Temuco (Chile)], E-mail: fcampos@ufro.cl

    2008-05-29

    A cosmological model of dark energy interacting with dark matter and another general component of the universe is investigated. We found general constraints on these models imposing an accelerated expansion. The same is also studied in the case for holographic dark energy.

  3. Interacting Induced Dark Energy Model

    OpenAIRE

    Bahrehbakhsh, Amir F.

    2016-01-01

    Similar to the idea of the brane world scenarios, but based on the approach of the induced matter theory, for a non--vacuum five--dimensional version of general relativity, we propose a model in which the conventional matter sources considered as all kind of the matter (the baryonic and dark) and the induced terms emerging from the extra dimension supposed to be as dark energy. Then we investigate the FLRW type cosmological equations and illustrate that the model is capable to explain respect...

  4. Electroweak interactions at LEP energies

    International Nuclear Information System (INIS)

    Some of the processes that have been observed at LEP energies, particularly the decay rate for Z0→ff-bar, and the forward-backward asymmetry in the process e+e-→ff-bar are presented. It is also discussed how measurement of Z0 width counts the number of light neutrinos and how one can look for the Higgs particle and for other exotic particles in the decay of the Z0 and calculate some of the expected rates. The important role played by radiative corrections in the analysis of data is emphasised. 33 refs., 5 tabs., 7 figs

  5. JACEE results on very high energy interactions

    International Nuclear Information System (INIS)

    Direct observations of cosmic ray interactions in emulsion chambers of the JACEE experiment at energies above 1 TeV/nucleon are presented. An analysis of two decay of short lived particles produced in cosmic ray interactions is described. The known decay modes of bottom and charged particles do not account satisfactorily for the observations. This could possibly indicate a new decay channel of a heavy particle. The JACEE results support the hypothesis of existence of a long-flying component in cosmic ray showers. An interaction event was observed which may be the first direct observation of (mini)anticentauro interaction. (author)

  6. Origin of the low-viscosity of [emim][(FSO2)2N] ionic liquid and its lithium salt mixture: experimental and theoretical study of self-diffusion coefficients, conductivities, and intermolecular interactions.

    Science.gov (United States)

    Tsuzuki, Seiji; Hayamizu, Kikuko; Seki, Shiro

    2010-12-16

    The temperature-dependent viscosity, ionic conductivity, and self-diffusion coefficients of an ionic liquid, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide ([emim][FSA]), and its Li salt mixture were studied with reference to emim bis(trifluoromethyl-sulfonyl)amide ([emim][TFSA]) systems. The stabilization energies for the formation of the FSA(-) complexes with emim(+) and Li(+) were calculated by the MP2/6-311G** level ab initio method. The stabilization energies calculated for the FSA(-) complexes with emim(+) and Li(+) (-77.0 and -134.3 kcal/mol) were smaller than those for the corresponding TFSA(-) complexes (-78.8 and -137.2 kcal/mol). The weaker electrostatic and induction interactions are the causes of the smaller interaction energies for the FSA(-) complexes. The weaker interaction between the FSA(-) and emim(+) can be one of the causes of the lower viscosity of the [emim][FSA] ionic liquid compared with that of the [emim][TFSA] ionic liquid. The weaker interaction between the FSA(-) and Li(+) compared with that between the TFSA(-) and Li(+) explains the fact that the addition of Li salt to the [emim][FSA] ionic liquid induces a little increase of the viscosity and a little decrease of the ionic conductivity and self-diffusion coefficients of ions. The FSA(-) in the Li[FSA] complex prefers the cis form due to the stronger attraction and smaller deformation energy of the cis-FSA(-) compared with the trans-FSA(-). PMID:21080680

  7. Casimir energy of frequency dependent interactions

    Science.gov (United States)

    Graham, N.; Quandt, M.; Weigel, H.

    2014-10-01

    Vacuum polarization (or Casimir) energies can be straightforwardly computed from scattering data for static field configurations whose interactions with the fluctuating field are frequency independent. In effective theories, however, such interactions are typically frequency dependent. As a consequence, the relationship between scattering data and the Green's function is modified, which may or may not induce additional contributions to the vacuum polarization energy. We discuss several examples that naturally include frequency dependent interactions: (i) scalar electrodynamics with a static background potential, (ii) an effective theory that emerges from integrating out a heavy degree of freedom, and (iii) quantum electrodynamics coupled to a frequency dependent dielectric material. In the latter case, we argue that introducing dissipation as required by the Kramers-Kronig relations requires the consideration of the Casimir energy within a statistical mechanics formalism, while in the absence of dissipation, we can work entirely within field theory, using an alternative formulation of the energy density.

  8. Interacting holographic dark energy with logarithmic correction

    OpenAIRE

    Jamil, Mubasher(School of Natural Sciences (SNS), National University of Science and Technology (NUST), H-12, Islamabad, Pakistan); Farooq, M. Umar

    2010-01-01

    The holographic dark energy (HDE) is considered to be the most promising candidate of dark energy. Its definition is originally motivated from the entropy-area relation which depends on the theory of gravity under consideration. Recently a new definition of HDE is proposed with the help of quantum corrections to the entropy-area relation in the setup of loop quantum cosmology. Using this new definition, we investigate the model of interacting dark energy and derive its effective equation of s...

  9. Interactive Joint Transfer of Energy and Information

    DEFF Research Database (Denmark)

    Popovski, Petar; Fouladgar, A. M.; Simeone, Osvaldo

    2013-01-01

    reception of a “1” signal, the recipient node “harvests”, with some probability, the energy contained in the signal and stores it for future communication tasks. Inner and outer bounds on the achievable rates are derived. Numerical results demonstrate the effectiveness of the proposed strategies and...... illustrate some key design insights. Index Terms— Two-way channel, interactive communication, energy transfer, energy harvesting....

  10. Intermolecular Forces in Introductory Chemistry Studied by Gas Chromatography, Computer Models, and Viscometry

    Science.gov (United States)

    Wedvik, Jonathan C.; McManaman, Charity; Anderson, Janet S.; Carroll, Mary K.

    1998-07-01

    An experiment on intermolecular forces for first-term introductory college chemistry is presented. The experiment integrates traditional viscometry-based measurements with modern chromatographic analysis and use of computer-based molecular models. Students performing gas chromatographic (GC) analyses of mixtures of n-alkanes and samples that simulate crime scene evidence discover that liquid mixtures can be separated rapidly into their components based upon intermolecular forces. Each group of students is given a liquid sample that simulates one collected at an arson scene, and the group is required to determine the identity of the accelerant. Students also examine computer models to better visualize how molecular structure affects intermolecular forces: London forces, dipole-dipole interactions, and hydrogen bonding. The relative viscosities of organic liquids are also measured to relate physical properties to intermolecular forces.

  11. Visualizing coherent intermolecular dipole–dipole coupling in real space

    Science.gov (United States)

    Zhang, Yang; Luo, Yang; Zhang, Yao; Yu, Yun-Jie; Kuang, Yan-Min; Zhang, Li; Meng, Qiu-Shi; Luo, Yi; Yang, Jin-Long; Dong, Zhen-Chao; Hou, J. G.

    2016-03-01

    Many important energy-transfer and optical processes, in both biological and artificial systems, depend crucially on excitonic coupling that spans several chromophores. Such coupling can in principle be described in a straightforward manner by considering the coherent intermolecular dipole–dipole interactions involved. However, in practice, it is challenging to directly observe in real space the coherent dipole coupling and the related exciton delocalizations, owing to the diffraction limit in conventional optics. Here we demonstrate that the highly localized excitations that are produced by electrons tunnelling from the tip of a scanning tunnelling microscope, in conjunction with imaging of the resultant luminescence, can be used to map the spatial distribution of the excitonic coupling in well-defined arrangements of a few zinc-phthalocyanine molecules. The luminescence patterns obtained for excitons in a dimer, which are recorded for different energy states and found to resemble σ and π molecular orbitals, reveal the local optical response of the system and the dependence of the local optical response on the relative orientation and phase of the transition dipoles of the individual molecules in the dimer. We generate an in-line arrangement up to four zinc-phthalocyanine molecules, with a larger total transition dipole, and show that this results in enhanced ‘single-molecule’ superradiance from the oligomer upon site-selective excitation. These findings demonstrate that our experimental approach provides detailed spatial information about coherent dipole–dipole coupling in molecular systems, which should enable a greater understanding and rational engineering of light-harvesting structures and quantum light sources.

  12. Energy transfer dynamics and kinetics of elementary processes (promoted) by gas-phase CO2 -N2 collisions: Selectivity control by the anisotropy of the interaction.

    Science.gov (United States)

    Lombardi, Andrea; Pirani, Fernando; Laganà, Antonio; Bartolomei, Massimiliano

    2016-06-15

    In this work, we exploit a new formulation of the potential energy and of the related computational procedures, which embodies the coupling between the intra and intermolecular components, to characterize possible propensities of the collision dynamics in energy transfer processes of interest for simulation and control of phenomena occurring in a variety of equilibrium and nonequilibrium environments. The investigation reported in the paper focuses on the prototype CO2 -N2 system, whose intramolecular component of the interaction is modeled in terms of a many body expansion while the intermolecular component is modeled in terms of a recently developed bonds-as-interacting-molecular-centers' approach. The main advantage of this formulation of the potential energy surface is that of being (a) truly full dimensional (i.e., all the variations of the coordinates associated with the molecular vibrations and rotations on the geometrical and electronic structure of the monomers, are explicitly taken into account without freezing any bonds or angles), (b) more flexible than other usual formulations of the interaction and (c) well suited for fitting procedures better adhering to accurate ab initio data and sensitive to experimental arrangement dependent information. Specific attention has been given to the fact that a variation of vibrational and rotational energy has a higher (both qualitative and quantitative) impact on the energy transfer when a more accurate formulation of the intermolecular interaction (with respect to that obtained when using rigid monomers) is adopted. This makes the potential energy surface better suited for the kinetic modeling of gaseous mixtures in plasma, combustion and atmospheric chemistry computational applications. © 2016 Wiley Periodicals, Inc. PMID:27031183

  13. High energy photon interactions at the LHC

    OpenAIRE

    2009-01-01

    Experimental prospects for studying high-energy photon-photon and photon-proton interactions at the CERN Large Hadron Collider (LHC) are discussed. Cross sections are calculated for many electroweak and beyond the Standard Model processes. Selection strategies based on photon interaction tagging techniques are studied. Assuming a typical LHC multipurpose detector, various signals and their irreducible backgrounds are presented after applying acceptance cuts. Prospects are discussed for the Hi...

  14. Interacting holographic dark energy with logarithmic correction

    Energy Technology Data Exchange (ETDEWEB)

    Jamil, Mubasher; Farooq, M. Umar, E-mail: mjamil@camp.nust.edu.pk, E-mail: mufarooq@yahoo.com [Center for Advanced Mathematics and Physics, National University of Sciences and Technology, Rawalpindi, 46000 (Pakistan)

    2010-03-01

    The holographic dark energy (HDE) is considered to be the most promising candidate of dark energy. Its definition is motivated from the entropy-area relation which depends on the theory of gravity under consideration. Recently a new definition of HDE is proposed with the help of quantum corrections to the entropy-area relation in the setup of loop quantum cosmology. Employing this new definition, we investigate the model of interacting dark energy and derive its effective equation of state. Finally we establish a correspondence between generalized Chaplygin gas and entropy-corrected holographic dark energy.

  15. Interacting holographic dark energy with logarithmic correction

    International Nuclear Information System (INIS)

    The holographic dark energy (HDE) is considered to be the most promising candidate of dark energy. Its definition is motivated from the entropy-area relation which depends on the theory of gravity under consideration. Recently a new definition of HDE is proposed with the help of quantum corrections to the entropy-area relation in the setup of loop quantum cosmology. Employing this new definition, we investigate the model of interacting dark energy and derive its effective equation of state. Finally we establish a correspondence between generalized Chaplygin gas and entropy-corrected holographic dark energy

  16. Interacting holographic dark energy with entropy corrections

    CERN Document Server

    Jamil, Mubasher

    2010-01-01

    The holographic dark energy (HDE) is considered to be the most promising candidate of dark energy. Its definition is originally motivated from the entropy-area relation which depends on the theory of gravity under consideration. Recently a new definition of HDE is proposed with the help of quantum corrections to the entropy-area relation in the setup of loop quantum cosmology. Using this new definition, we investigate the model of interacting dark energy and derive its effective equation of state. Finally we establish a correspondence between generalized Chaplygin gas and entropy-corrected holographic dark energy.

  17. Gravity and Cosmology with Interacting Dark Energy

    OpenAIRE

    Silbergleit, A. S.

    2016-01-01

    Dark energy (DE) is not necessarily uniform when other sources of gravity are present: interaction with matter leads to its variation in space and time. We study cosmological implications of this fact by analyzing cosmological models in which DE density interacts with matter and thus changes with time. We model the DE--matter interaction by specifying the rate of change of the DE density as an arbitrary function of it and the density of matter, in a single--phase case. In the case of several ...

  18. Gravity and Cosmology with Interacting Dark Energy

    CERN Document Server

    Silbergleit, A S

    2016-01-01

    Dark energy (DE) is not necessarily uniform when other sources of gravity are present: interaction with matter leads to its variation in space and time. We study cosmological implications of this fact by analyzing cosmological models in which DE density interacts with matter and thus changes with time. We model the DE--matter interaction by specifying the rate of change of the DE density as an arbitrary function of it and the density of matter, in a single--phase case. In the case of several matter components interacting with dark energy we assume the rate of every interacting phase density to be an arbitrary function of this density and the DE density. We describe some properties of cosmological solutions valid for a general law of DE--matter interaction, and discuss physical admissibility of the interaction laws. We study numerous families of exact solutions, both singular, non-singular, and mixed. Some of them exhibit interesting properties, such as, for instance, absence of the horizon problem due to the ...

  19. High energy electron beam interaction with tantalum

    International Nuclear Information System (INIS)

    Preliminary studies were performed on the interaction of high energy electron beams (HEEB) with commercially pure tantalum (Ta). Small Ta bars, nominally 2 x 0.5 x 0.1 cm were irradiated with HEEBs of energies ranging from 2.5 to 3 MeV, 1.5 kA, 1 to 2 micros pulse with a beam radius of 0.3 cm and larger. These HEEBs had a gaussian energy distribution. Following exposure in a vacuum, the bars were examined visually, with light optical microscopy and scanning electron microscopy which also provided energy dispersive x-rays (EDX) analysis. Weight and dimensional measurements were made on some of the bars. Based on the results of these examinations, a model for the interaction of HEEBs with Ta was developed and is presented

  20. High energy interactions and extensive air showers

    International Nuclear Information System (INIS)

    We report on papers presented in the high energy sessions of the conference that do not deal with the theory and observations of muons and neutrinos. We concentrate on the development and testing of hadronic interaction models, their extension to ultrahigh energy and their importance for the analysis and interpretation of air shower data. We also summarize data on the cosmic ray spectrum and composition obtained with air showers

  1. Finding a unifying motif of intermolecular cooperativity in protein associations

    CERN Document Server

    Accordino, Sebastin R; Appignanesi, Gustavo A; Fernndez, Ariel

    2011-01-01

    At the molecular level, most biological processes entail protein associations which in turn rely on a small fraction of interfacial residues called hot spots. Here we show that hot spots share a unifying molecular attribute: they provide a third-body contribution to intermolecular cooperativity. Such motif, based on the wrapping of interfacial electrostatic interactions, is essential to maintain the integrity of the interface and can be exploited in rational drug design since such regions may serve as blueprints to engineer small molecules disruptive of protein-protein interfaces.

  2. Nonlinear interaction involving zero energy wave

    International Nuclear Information System (INIS)

    Three-wave interactions involving one or two modes with non-definite sign of wave energy, treated by second order differential equations in time, are studied. The third mode is assumed to suffer heavy linear damping, and is treated by means of Tang's adiabatic approximation. The possibility of negative pump energy and positive decay mode energy is shown to lead to an explosive situation. Self-similar explosive solutions are derived, and it is shown that almost any solution asymptotically approaches, in some sense, these self-similar solutions

  3. Nonlinear interaction involving zero energy waves

    International Nuclear Information System (INIS)

    Three-wave interactions involving one or two modes with non-definite sign of wave energy, treated by second order differential equations in time, are studied. The third mode is assumed to suffer heavy linear damping, and is treated by means of Tang's adiabatic approximation. The possibility of negative pump energy and positive decay mode energy is shown to lead to an explosive situation. Self-similar explosive solutions are derived, and it is shown that almost any solution asymptotically approaches, in some sense, these self-similar solutions. (Auth.)

  4. Calculations on noncovalent interactions and databases of benchmark interaction energies.

    Science.gov (United States)

    Hobza, Pavel

    2012-04-17

    Although covalent interactions determine the primary structure of a molecule, the noncovalent interactions are responsible for the tertiary and quaternary structure of a molecule and create the fascinating world of the 3D architectures of biomacromolecules. For example, the double helical structure of DNA is of fundamental importance for the function of DNA: it allows it to store and transfer genetic information. To fulfill this role, the structure is rigid to maintain the double helix with a proper positioning of the complementary base, and floppy to allow for its opening. Very strong covalent interactions cannot fulfill both of these criteria, but noncovalent interactions, which are about 2 orders of magnitude weaker, can. This Account highlights the recent advances in the field of the design of novel wave function theory (WFT) methods applicable to noncovalent complexes ranging in size from less than 100 atoms, for which highly accurate ab initio methods are available, up to extended ones (several thousands atoms), which are the domain of semiempirical QM (SQM) methods. Accurate interaction energies for noncovalent complexes are generated by the coupled-cluster technique, taking single- and double-electron excitations iteratively and triple-electron excitation perturbatively with a complete basis set description (CCSD(T)/CBS). The procedure provides interaction energies with high accuracy (error less than 1 kcal/mol). Because the method is computationally demanding, its application is limited to complexes smaller than 30 atoms. But researchers would also like to use computational methods to determine these interaction energies accurately for larger biological and nanoscale structures. Standard QM methods such as MP2, MP3, CCSD, or DFT fail to describe various types of noncovalent systems (H-bonded, stacked, dispersion-controlled, etc.) with comparable accuracy. Therefore, novel methods are needed that have been parametrized toward noncovalent interactions, and existing benchmark data sets represent an important tool for the development of new methods providing reliable characteristics of noncovalent clusters. Our laboratory developed the first suitable data set of CCSD(T)/CBS interaction energies and geometries of various noncovalent complexes, called S22. Since its publication in 2006, it has frequently been applied in parametrization and/or verification of various wave function and density functional techniques. During the intense use of this data set, several inconsistencies emerged, such as the insufficient accuracy of the CCSD(T) correction term or its unbalanced character, which has triggered the introduction of a new, broader, and more accurate data set called the S66 data set. It contains not only 66 CCSD(T)/CBS interaction energies determined in the equilibrium geometries but also 1056 interaction energies calculated at the same level for nonequilibrium geometries. The S22 and S66 data sets have been used for the verification of various WFT methods, and the lowest RMSE (S66, in kcal/mol) was found for the recently introduced SCS-MI-CCSD/CBS (0.08), MP2.5/CBS (0.16), MP2.X/6-31G* (0.27), and SCS-MI-MP2/CBS (0.38) methods. Because of their computational economy, the MP2.5 and MP2.X/6-31G* methods can be recommended for highly accurate calculations of large complexes with up to 100 atoms. The evaluation of SQM methods was based only on the S22 data set, and because some of these methods have been parametrized toward the same data set, the respective results should be taken with caution. For really extended complexes such as protein-ligand systems, only the SMQ methods are applicable. After adding the corrections to the dispersion energy and H-bonding, several methods exhibit surprisingly low RMSE (even below 0.5 kcal/mol). Among the various SMQ methods, the PM6-DH2 can be recommended because of its computational efficiency and it can be used for optimization (which is not the case for other SQM methods). The PM6-DH2 is the base of our novel scoring function used in in silico drug design. PMID:22225511

  5. Department of High Energy Nuclear Interactions - Overview

    International Nuclear Information System (INIS)

    Full text: In 1998 the research activities of the Department concentrated on investigations of heavy ion interactions and the study of the primary cosmic rays. In the field of heavy ion physics the EMU13 experiment supplied us with the data on Pb collisions with different targets at the energy of 158 GeV/nucleon. High multiplicity Pb-Ag/Br collisions were studied on event by event basis. It is believed that the investigation of individual high multiplicity events should reveal the onset of new phenomena such as e.g., creation of a quark gluon plasma. The fragmentation process of lead projectiles in Pb-Pb interactions recorded in emulsion chambers specially designed for this purpose was also studied. The measured cross section indicated the important role of electromagnetic processes in the high energy Pb-Pb interactions. We also continued the investigations of Au collisions with the components of nuclear emulsion at 10.6 GeV/nucleon (experiment BNL868). The results on the particle production were compared with predictions of the RQMD model. The fragmentation of the Au projectile as well as the target nuclei were analyzed. PHOBOS experiment at the Relativistic Heavy Ion Collider at BNL will investigate Au-Au interactions at a center of mass energy 200 GeV/nucleon. Such interactions will produce the highest energy density ever reached in a laboratory. It is expected that under these conditions the quark gluon plasma will be discovered. The preparation for PHOBOS experiment have entered the final stage with the first physical run at the accelerator planned for November 1999. The physicists from our Department and the engineers from the High Energy Physics Detector Construction Group have been involved in computer simulations of various physical processes as well as designing, testing and constructing the elements of the PHOBOS detector. In the field of cosmic ray research our Department has started participating in the Pierre Auger Project. The aim of this broad-based international effort is to study cosmic rays at the highest energies (E > 1019 eV) in order to obtain information on the sources and acceleration mechanisms of these high energy particles. I would like to take this opportunity to acknowledge the great effort of all the members of the Department of High Energy Nuclear Interactions in obtaining the significant scientific results in the past year. (author)

  6. Interacting vacuum energy in the dark sector

    International Nuclear Information System (INIS)

    We analyse three cosmological scenarios with interaction in the dark sector, which are particular cases of a general expression for the energy flux from vacuum to matter. In the first case the interaction leads to a transition from an unstable de Sitter phase to a radiation dominated universe, avoiding in this way the initial singularity. In the second case the interaction gives rise to a slow-roll power-law inflation. Finally, the third scenario is a concordance model for the late-time universe, with the vacuum term decaying into cold dark matter. We identify the physics behind these forms of interaction and show that they can be described as particular types of the modified Chaplygin gas

  7. Interacting vacuum energy in the dark sector

    Energy Technology Data Exchange (ETDEWEB)

    Chimento, L. P. [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IFIBA, CONICET, Cuidad Universitaria, Buenos Aires 1428 (Argentina); Carneiro, S. [Instituto de Física, Uníversídade Federal da Bahia, 40210-340, Salvador, BA (Brazil)

    2015-03-26

    We analyse three cosmological scenarios with interaction in the dark sector, which are particular cases of a general expression for the energy flux from vacuum to matter. In the first case the interaction leads to a transition from an unstable de Sitter phase to a radiation dominated universe, avoiding in this way the initial singularity. In the second case the interaction gives rise to a slow-roll power-law inflation. Finally, the third scenario is a concordance model for the late-time universe, with the vacuum term decaying into cold dark matter. We identify the physics behind these forms of interaction and show that they can be described as particular types of the modified Chaplygin gas.

  8. Constraining dark energy interacting models with WMAP

    CERN Document Server

    Olivares, G; Pavón, D; Olivares, German; Atrio-Barandela, Fernando; Pavon, Diego

    2006-01-01

    We determine the range of parameter space of an interacting quintessence (IQ) model that best fits the luminosity distance of type Ia supernovae data and the recent WMAP measurements of Cosmic Microwave Background temperature anisotropies. Models in which quintessence decays into dark matter provide a clean explanation for the coincidence problem. We focus on cosmological models of zero spatial curvature. We show that if the dark energy (DE) decays into cold dark matter (CDM) at a rate that brings the ratio of matter to dark energy constant at late times, the supernovae data are not sufficient to constrain the interaction parameter. On the contrary, WMAP data constrain it to be smaller than $c^2 < 10^{-2}$ at the $3\\sigma$ level. Accurate measurements of the Hubble constant and the dark energy density, independent of the CMB data, would support/disprove this set of models.

  9. Energy security and climate policy. Assessing interactions

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-03-28

    World energy demand is surging. Oil, coal and natural gas still meet most global energy needs, creating serious implications for the environment. One result is that CO2 emissions, the principal cause of global warming, are rising. This new study underlines the close link between efforts to ensure energy security and those to mitigate climate change. Decisions on one side affect the other. To optimise the efficiency of their energy policy, OECD countries must consider energy security and climate change mitigation priorities jointly. The book presents a framework to assess interactions between energy security and climate change policies, combining qualitative and quantitative analyses. The quantitative analysis is based on the development of energy security indicators, tracking the evolution of policy concerns linked to energy resource concentration. The 'indicators' are applied to a reference scenario and CO2 policy cases for five case-study countries: The Czech Republic, France, Italy, the Netherlands, and the United Kingdom. Simultaneously resolving energy security and environmental concerns is a key challenge for policy makers today. This study helps chart the course.

  10. Interactions between dark energy and dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Baldi, Marco

    2009-03-20

    We have investigated interacting dark energy cosmologies both concerning their impact on the background evolution of the Universe and their effects on cosmological structure growth. For the former aspect, we have developed a cosmological model featuring a matter species consisting of particles with a mass that increases with time. In such model the appearance of a Growing Matter component, which is negligible in early cosmology, dramatically slows down the evolution of the dark energy scalar field at a redshift around six, and triggers the onset of the accelerated expansion of the Universe, therefore addressing the Coincidence Problem. We propose to identify this Growing Matter component with cosmic neutrinos, in which case the present dark energy density can be related to the measured average mass of neutrinos. For the latter aspect, we have implemented the new physical features of interacting dark energy models into the cosmological N-body code GADGET-2, and we present the results of a series of high-resolution simulations for a simple realization of dark energy interaction. As a consequence of the new physics, cold dark matter and baryon distributions evolve differently both in the linear and in the non-linear regime of structure formation. Already on large scales, a linear bias develops between these two components, which is further enhanced by the non-linear evolution. We also find, in contrast with previous work, that the density profiles of cold dark matter halos are less concentrated in coupled dark energy cosmologies compared with {lambda}{sub CDM}. Also, the baryon fraction in halos in the coupled models is significantly reduced below the universal baryon fraction. These features alleviate tensions between observations and the {lambda}{sub CDM} model on small scales. Our methodology is ideally suited to explore the predictions of coupled dark energy models in the fully non-linear regime, which can provide powerful constraints for the viable parameter space of such scenarios. (orig.)

  11. Interactions between dark energy and dark matter

    International Nuclear Information System (INIS)

    We have investigated interacting dark energy cosmologies both concerning their impact on the background evolution of the Universe and their effects on cosmological structure growth. For the former aspect, we have developed a cosmological model featuring a matter species consisting of particles with a mass that increases with time. In such model the appearance of a Growing Matter component, which is negligible in early cosmology, dramatically slows down the evolution of the dark energy scalar field at a redshift around six, and triggers the onset of the accelerated expansion of the Universe, therefore addressing the Coincidence Problem. We propose to identify this Growing Matter component with cosmic neutrinos, in which case the present dark energy density can be related to the measured average mass of neutrinos. For the latter aspect, we have implemented the new physical features of interacting dark energy models into the cosmological N-body code GADGET-2, and we present the results of a series of high-resolution simulations for a simple realization of dark energy interaction. As a consequence of the new physics, cold dark matter and baryon distributions evolve differently both in the linear and in the non-linear regime of structure formation. Already on large scales, a linear bias develops between these two components, which is further enhanced by the non-linear evolution. We also find, in contrast with previous work, that the density profiles of cold dark matter halos are less concentrated in coupled dark energy cosmologies compared with ΛCDM. Also, the baryon fraction in halos in the coupled models is significantly reduced below the universal baryon fraction. These features alleviate tensions between observations and the ΛCDM model on small scales. Our methodology is ideally suited to explore the predictions of coupled dark energy models in the fully non-linear regime, which can provide powerful constraints for the viable parameter space of such scenarios. (orig.)

  12. Correlated ab initio investigations on the intermolecular and intramolecular potential energy surfaces in the ground electronic state of the O2(-)(X2?g)-HF(X1?+) complex.

    Science.gov (United States)

    Fawzy, Wafaa M; Elsayed, Mahmoud; Zhang, Yuchen

    2013-01-01

    This work reports the first highly correlated ab initio study of the intermolecular and intramolecular potential energy surfaces in the ground electronic state of the O(2)(-)(X(2)?(g))-HF(X(1)?(+)) complex. Accurate electronic structure calculations were performed using the coupled cluster method including single and double excitations with addition of the perturbative triples correction [CCSD(T)] with the Dunning's correlation consistent basis sets aug-cc-pVnZ, n = 2-5. Also, the explicitly correlated CCSD(T)-F12a level of theory was employed with the AVnZ basis as well as the Peterson and co-workers VnZ-F12 basis sets with n = 2 and 3. Results of all levels of calculations predicted two equivalent minimum energy structures of planar geometry and C(s) symmetry along the A" surface of the complex, whereas the A' surface is repulsive. Values of the geometrical parameters and the counterpoise corrected dissociation energies (Cp-D(e)) that were calculated using the CCSD(T)-F12a/VnZ-F12 level of theory are in excellent agreement with those obtained from the CCSD(T)/aug-cc-pV5Z calculations. The minimum energy structure is characterized by a very short hydrogen bond of length of 1.328 , with elongation of the HF bond distance in the complex by 0.133 , and D(e) value of 32.313 Kcal/mol. Mulliken atomic charges showed that 65% of the negative charge is localized on the hydrogen bonded end of the superoxide radical and the HF unit becomes considerably polarized in the complex. These results suggest that the hydrogen bond is an incipient ionic bond. Exploration of the potential energy surface confirmed the identified minimum and provided support for vibrationally induced intramolecular proton transfer within the complex. The T-shaped geometry that possesses C(2v) symmetry presents a saddle point on the top of the barrier to the in-plane bending of the hydrogen above and below the axis that connects centers of masses of the monomers. The height of this barrier is 7.257 Kcal/mol, which is higher in energy than the hydrogen bending frequency by 909.2 cm(-1). The calculated harmonic oscillator vibrational frequencies showed that the H-F stretch vibrational transition in the complex is redshifted by 2564 cm(-1) and gained significant intensity (by at least a factor of 30) with respect to the transition in the HF monomer. These results make the O(2)(-)-HF complex an excellent prototype for infrared spectroscopic investigations on open-shell complexes with vibrationally induced proton transfer. PMID:23298038

  13. Thermodynamic curvature for attractive and repulsive intermolecular forces.

    Science.gov (United States)

    May, Helge-Otmar; Mausbach, Peter; Ruppeiner, George

    2013-09-01

    The thermodynamic curvature scalar R for the Lennard-Jones system is evaluated in phase space, including vapor, liquid, and solid state. We paid special attention to the investigation of R along vapor-liquid, liquid-solid, and vapor-solid equilibria. Because R is a measure of interaction strength, we traced out the line R=0 dividing the phase space into regions with effectively attractive (R0) interactions. Furthermore, we analyzed the dependence of R on the strength of attraction applying a perturbation ansatz proposed by Weeks-Chandler-Anderson. Our results show clearly a transition from R>0 (for poorly repulsive interaction) to R<0 when loading attraction in the intermolecular potential. PMID:24125229

  14. Low Energy Pion-Hyperon Interaction

    OpenAIRE

    Junior, Celso de Camargo Barros; Hama, Yogiro

    2000-01-01

    We study the low energy pion-hyperon interaction considering effective non-linear chiral invariant Lagrangians including pions, rho mesons, hyperons and corresponding resonances. Then we calculate the S- and P-wave phase-shifts, total cross sections, angular distributions and polarizations for the momentum in the center-of-mass frame up to k=400 MeV. With these results we discuss the CP violation in the csi-> pi-lambda and omega-> pi-csi weak decays.

  15. Redshift drift exploration for interacting dark energy

    CERN Document Server

    Geng, Jia-Jia; Zhang, Jing-Fei; Zhang, Xin

    2015-01-01

    By detecting redshift drift in the spectra of Lyman-$\\alpha$ forest of distant quasars, Sandage-Loeb (SL) test directly measures the expansion of the universe, covering the "redshift desert" of $2 \\lesssim z \\lesssim5$. Thus this method is definitely an important supplement to the other geometric measurements and will play a crucial role in cosmological constraints. In this paper, we quantify the ability of SL test signal by a CODEX-like spectrograph for constraining interacting dark energy. Four typical interacting dark energy models are considered: (\\romannumeral1) $Q=\\gamma H\\rho_c$, (\\romannumeral2) $Q=\\gamma H\\rho_{de}$, (\\romannumeral3) $Q=\\gamma H_0\\rho_c$, and (\\romannumeral4) $Q=\\gamma H_0\\rho_{de}$. The results show that for all the considered interacting dark energy models, relative to the current joint SN+BAO+CMB+$H_0$ observations, the constraints on $\\Omega_m$ and $H_0$ would be improved by about 60\\% and 30--40\\%, while the constraints on $w$ and $\\gamma$ would be slightly improved, with a 30-y...

  16. Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

    Science.gov (United States)

    Parrish, Robert M.; Sherrill, C. David

    2014-07-01

    We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work through the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-? interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.

  17. Monomer spectroscopic analysis and dimer interaction energies on N-(4-methoxybenzoyl)-2-methylbenzenesulfonamide by experimental and theoretical approaches

    Science.gov (United States)

    Karakaya, Mustafa; Sert, Yusuf; Sreenivasa, Swamy; Suchetan, Parameshwar Adimoole; ?rak, a?r?

    2015-05-01

    In this study, theoretical harmonic vibrational frequencies and geometric parameters of N-(4-methoxybenzoyl)-2-methylbenzenesulfonamide have been investigated by Hartree-Fock (HF), density functional theory (B3LYP hybrid functional) methods with 6-311++G (d,p) basis set, for the first time. Experimental FT-IR (400-4000 cm-1) and Laser-Raman spectra (100-4000 cm-1) of title compound in solid phase have been recorded. Interaction energies, N-H⋯O hydrogen bonds, C-H⋯O and aromatic ?⋯? stacking interactions in dimer structures of the title compound have been evaluated by the calculation methods. The dimer calculations have aimed to present the efficacy and performance of M06-2X hybrid functional on the intermolecular interactions and more strongly bound systems for the corrected and interaction energy by the counterpoise correction procedure. The interaction energies by M06-2X approach give more stable results than HF and B3LYP, extremely. The more strongly bonds, especially, on N-H⋯O hydrogen bonds and ?⋯? interaction for the both dimer structure have also supported that the M06-2X functional of density functional is more effective.

  18. Four-body long-range interactions between ultracold weakly-bound diatomic molecules

    CERN Document Server

    Lepers, Maxence; Luc-Koenig, Eliane; Dulieu, Olivier

    2015-01-01

    Using the multipolar expansion of electrostatic and magnetostatic potential energies, we characterize the long-range interactions between two weakly-bound diatomic molecules, taking as an example the paramagnetic Er$_2$ Feshbach molecules which were produced recently. Since inside each molecule, individual atoms conserve their identity, the intermolecular potential energy can be expanded as the sum of pairwise atomic potential energies. In the case of Er$_2$ Feshbach molecules, we show that the interaction between atomic magnetic dipoles gives rise to the usual $R^{-3}$ term of the multipolar expansion, with $R$ the intermolecular distance, but also to additional terms scaling as $R^{-5}$, $R^{-7}$, and so on. Those terms are due to the interaction between effective molecular multipole moments, and are strongly anisotropic with respect to the orientation of the molecules. Similarly the atomic pairwise van der Waals interaction results in $R^{-6}$, $R^{-8}$, ... terms in the intermolecular potential energy. By...

  19. New models for intermolecular repulsion and their application to Van Der Waals complexes and crystals of organic molecules

    International Nuclear Information System (INIS)

    Model intermolecular potentials are required for simulations of molecules in the gas, liquid, or solid phase. The widely used isotropic atom-atom model potentials are empirically fitted and based on the assumptions of transferability, combining rules and that atoms in molecules are spherical. This thesis develops a non-empirical method of modelling repulsion by applying the overlap model, which we show as a general non-empirical method of deriving repulsion potentials for a specific molecule. In this thesis, the repulsion parameters for an exponential atom-atom model potential are obtained from the ab initio charge density of a small organic molecule by making the assumption that the repulsion is proportional to the overlap of a pair of molecules. The proportionality constant is fixed by a limited number of intermolecular perturbation theory (IMPT) calculations. To complete the model potential, the electrostatic interaction is represented by a distributed multipole analysis, and the Slater-Kirkwood formula is used for the dispersion. These non-empirical potentials can reproduce experimental crystal structure when applied to crystal structure prediction of an oxyboryl derivative. A detailed study on further improving the overlap model was carried out for phenol-water, by including other minor intermolecular contributions of charge-transfer and penetration. High quality ab initio calculations on the complex were performed for use in comparison. To compare with experimental data, diffusion Monte Carlo simulations were performed with the potential, so that the effects of anharmonic zero-point motion on structure and energy of the system are included. When the system is too large for an IMPT calculation, the proportionality constant can be determined empirically by fitting the cell volume as shown in our study of crystal structures of chlorothalonil. This is used with an anisotropic repulsion model that has been derived for Cl and N atoms in chlorothalonil. This model potential reproduces the crystal structure well, and is used to predict other polymorphs by a search for minima in the lattice energy. (author)

  20. Ground state analytical ab initio intermolecular potential for the Cl{sub 2}-water system

    Energy Technology Data Exchange (ETDEWEB)

    Hormain, Laureline; Monnerville, Maurice, E-mail: maurice.monnerville@univ-lille1.fr; Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane [Laboratoire de Physique des Lasers Atomes et Molécules, Unité Mixte de Recherche (UMR) 8523, Université Lille I, Bât. P5, 59655 Villeneuve d’Ascq Cedex (France); Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón [Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Cuernavaca 62209, México (Mexico)

    2015-04-14

    The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl{sub 2} molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl{sub 2} − H{sub 2}O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl{sub 2} interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl{sub 2} on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results.

  1. Ground state analytical ab initio intermolecular potential for the Cl2-water system

    Science.gov (United States)

    Hormain, Laureline; Monnerville, Maurice; Toubin, Cline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stphane; Bernal-Uruchurtu, Margarita I.; Hernndez-Lamoneda, Ramn

    2015-04-01

    The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl2 molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl2 - H2O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl2 interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl2 on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results.

  2. Ground state analytical ab initio intermolecular potential for the Cl2-water system

    International Nuclear Information System (INIS)

    The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl2 molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl2 ? H2O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl2 interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl2 on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results

  3. Calculation of intermolecular potentials for H2−H2 and H2−O2 dimers ab initio and prediction of second virial coefficients

    International Nuclear Information System (INIS)

    Highlights: • We construct the angular orientations of dimers H2−H2 and H2−O2. • We calculate the ab initio intermolecular interaction energies for all built orientations. • Extrapolating the interaction energies to the complete basis set limit aug-cc-pV23Z. • We develop two 5-site ab initio intermolecular potentials of dimers H2−H2, H2−O2. • Calculating the virial coefficients of dimer H2−H2 and H2−O2. - Abstract: The intermolecular interaction potentials of the dimers H2−H2 and H2−O2 were calculated from quantum mechanics, using coupled-cluster theory CCSD(T) and correlation-consistent basis sets aug-cc-pVmZ (m = 2, 3); the results were extrapolated to the basis set limit aug-cc-pV23Z. The interaction energies were corrected for the basis set superposition error with the counterpoise scheme. For comparison also Møller–Plesset perturbation theory (at levels 2–4) with the basis sets aug-cc-pVTZ were considered, but the results proved inferior. The quantum mechanical results were used to construct analytical pair potential functions. From these functions the second virial coefficients of hydrogen and the cross virial coefficients of the hydrogen–oxygen system were obtained by integration; in both cases corrections for quantum effects were included. The results agree well with experimental data, if available, or with empirical correlations

  4. Detection of complex formation and determination of intermolecular geometry through electrical anharmonic coupling of molecular vibrations using electron-vibration-vibration two-dimensional infrared spectroscopy.

    Science.gov (United States)

    Guo, Rui; Fournier, Frederic; Donaldson, Paul M; Gardner, Elizabeth M; Gould, Ian R; Klug, David R

    2009-10-14

    Electrical interactions between molecular vibrations can be non-linear and thereby produce intermolecular coupling even in the absence of a chemical bond. We use this fact to detect the formation of an intermolecular complex using electron-vibration-vibration two-dimensional infrared spectroscopy (EVV 2DIR) and also to determine the distance and angle between the two molecular species. PMID:19774270

  5. Isotopic effects on non-linearity, molecular radius and intermolecular free length

    Indian Academy of Sciences (India)

    Ranjan Dey; Arvind K Singh; N K Soni; B S Bisht; J D Pandey

    2006-08-01

    Computation of non-linearity parameter (/), molecular radius (rm) and intermolecular free length (f) for H2O, C6H6, C6H12, CH3OH, C2H5OH and their deuterium-substituted compounds have been carried out at four different temperatures, viz., 293.15, 303.15, 313.15 and 323.15 K. The aim of the investigation is an attempt to study the isotopic effects on the non-linearity parameter and the physicochemical properties of the liquids, which in turn has been used to study their effect on the intermolecular interactions produced thereof.

  6. [High-energy electron-positron interactions

    International Nuclear Information System (INIS)

    The purpose of the research was the study of electron-positron interactions at high energies using the Time Projection Chamber (TPC) at the Positron Electron Project (PEP) at SLAC. The TPC detector had an initial data gathering from 1982 until 1986 and accumulated a data sample with an integrated luminosity of -150 pb-1 at an electron-positron energy of 29 GeV. The data runs in the 1988--1990 time period (yielding ∼ pb-1) were abbreviated, due to the need of the laboratory to give highest priority to the new Stanford Linear Collider (SLC). The TPC collaboration decided in 1991 to discontinue data taking, but has continued the collaboration for the purpose of completing the analysis of the data. When UMass joined the SLD project, it was being designed as a new state-of-the-art detector for studying electron-positron interactions at energies in the vicinity of 91 GeV, the Z0 mass. The detector was completed and installed at the interaction point of the SLC in 1991, at which time an initial, ''engineering run'' allowed the debugging of detector components and provided a data sample of ∼1,000 events with hadronic Z0 decays. In 1992 the SLC provided beams of polarized electrons and the SLD collected a data sample in excess of 11,000 hadronic Z0 events produced by polarized electrons, allowing unique measurements of some of the parameters of the standard model. This project is continuing to take data in 1993 with increased polarization and higher luminosity. This report reviews the research work performed under the contract, and survey's the physics results

  7. Redshift drift exploration for interacting dark energy

    Energy Technology Data Exchange (ETDEWEB)

    Geng, Jia-Jia; Li, Yun-He; Zhang, Jing-Fei [Northeastern University, Department of Physics, College of Sciences, Shenyang (China); Zhang, Xin [Northeastern University, Department of Physics, College of Sciences, Shenyang (China); Peking University, Center for High Energy Physics, Beijing (China)

    2015-08-15

    By detecting redshift drift in the spectra of the Lyman-α forest of distant quasars, the Sandage-Loeb (SL) test directly measures the expansion of the universe, covering the ''redshift desert'' of 2 interacting dark energy. Four typical interacting dark energy models are considered: (i) Q = γHρ{sub c}, (ii) Q = γHρ{sub de}, (iii) Q = γH{sub 0}ρ{sub c}, and (iv) Q = γH{sub 0}ρ{sub de}. The results show that for all the considered interacting dark energy models, relative to the current joint SN + BAO + CMB + H{sub 0} observations, the constraints on Ω{sub m} and H{sub 0} would be improved by about 60 and 30-40 %, while the constraints on w and γ would be slightly improved, with a 30-year observation of the SL test. We also explore the impact of the SL test on future joint geometric observations. In this analysis, we take the model with Q = γHρ{sub c} as an example, and we simulate future SN and BAO data based on the space-based project WFIRST. We find that with the future geometric constraints, the redshift drift observations would help break the geometric degeneracies in a meaningful way, thus the measurement precisions of Ω{sub m}, H{sub 0}, w, and γ could be substantially improved using future probes. (orig.)

  8. Redshift drift exploration for interacting dark energy

    International Nuclear Information System (INIS)

    By detecting redshift drift in the spectra of the Lyman-α forest of distant quasars, the Sandage-Loeb (SL) test directly measures the expansion of the universe, covering the ''redshift desert'' of 2 interacting dark energy. Four typical interacting dark energy models are considered: (i) Q = γHρc, (ii) Q = γHρde, (iii) Q = γH0ρc, and (iv) Q = γH0ρde. The results show that for all the considered interacting dark energy models, relative to the current joint SN + BAO + CMB + H0 observations, the constraints on Ωm and H0 would be improved by about 60 and 30-40 %, while the constraints on w and γ would be slightly improved, with a 30-year observation of the SL test. We also explore the impact of the SL test on future joint geometric observations. In this analysis, we take the model with Q = γHρc as an example, and we simulate future SN and BAO data based on the space-based project WFIRST. We find that with the future geometric constraints, the redshift drift observations would help break the geometric degeneracies in a meaningful way, thus the measurement precisions of Ωm, H0, w, and γ could be substantially improved using future probes. (orig.)

  9. Weak interactions at high energies. [Lectures, review

    Energy Technology Data Exchange (ETDEWEB)

    Ellis, J.

    1978-08-01

    Review lectures are presented on the phenomenological implications of the modern spontaneously broken gauge theories of the weak and electromagnetic interactions, and some observations are made about which high energy experiments probe what aspects of gauge theories. Basic quantum chromodynamics phenomenology is covered including momentum dependent effective quark distributions, the transverse momentum cutoff, search for gluons as sources of hadron jets, the status and prospects for the spectroscopy of fundamental fermions and how fermions may be used to probe aspects of the weak and electromagnetic gauge theory, studies of intermediate vector bosons, and miscellaneous possibilities suggested by gauge theories from the Higgs bosons to speculations about proton decay. 187 references. (JFP)

  10. Correlations in high-energy interactions

    International Nuclear Information System (INIS)

    The short-range correlations in rapidity whose existence has been firmly established in high-energy interactions are used to explain chaotic multiplicity behavior in proton-nucleon collisions at 800 GeV. In order to determine the values of higher-order moments from the second-order moment, we have used the pure birth approximation which is in agreement with the ''linked pair'' approximation of Carruthers. The calculated values of the normalized factorial moments for a given bin size show a good agreement with our data

  11. Lipid intermolecular hydrogen bonding: influence on structural organization and membrane function.

    Science.gov (United States)

    Boggs, J M

    1987-10-01

    The great variety of different lipids in membranes, with modifications to the hydrocarbon chains, polar groups and backbone structure suggests that many of these lipids may have unique roles in membrane structure and function. Acidic groups on lipids are clearly important, since they allow interaction with basic groups on proteins and with divalent cations. Another important property of certain lipids is their ability to interact intermolecularly with other lipids via hydrogen bonds. This interaction occurs through acidic and basic moieties in the polar head groups of phospholipids, and the amide moiety and hydroxyl groups on the acyl chain, sphingosine base and sugar groups of sphingo- and glycolipids. The putative ability of different classes of lipids to interact by intermolecular hydrogen bonding, the molecular groups which may participate and the effect of these interactions on some of their physical properties are summarized in Table IX. It is frequently questioned whether intermolecular hydrogen bonding could occur between lipids in the presence of water. Correlations of their properties with their molecular structures, however, suggest that it can. Participation in intermolecular hydrogen bonding increases the lipid phase transition temperature by approx. 8-16 Cdeg relative to the electrostatically shielded state and by 20-30 Cdeg relative to the repulsively charged state, while having variable effects on the enthalpy. It increases the packing density in monolayers, possibly also in the liquid-crystalline phase in bilayers, and decreases the lipid hydration. These effects can probably be accounted for by transient, fluctuating hydrogen bonds involving only a small percentage of the lipid at any one time. Thus, rotational and lateral diffusion of the lipids may take place but at a slower rate, and the lateral expansion is limited. Intermolecular hydrogen bonding between lipids in bilayers may be significantly stabilized, despite the presence of water, by the fact that the lipids are already intermolecularly associated as a result of the hydrophobic effect and the Van der Waals' interactions between their chains. The tendency of certain lipids to self-associate, their asymmetric distribution in SUVs, their preferential association with cholesterol in non-cocrystallizing mixtures, their temperature-induced transitions to the hexagonal phase and their inhibitory effect on penetration of hydrophobic residues of proteins partway into the bilayer can all be explained by their participation in intermolecular hydrogen bonding interactions.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:3307919

  12. Novel Heterogeneous Catalysts for Intermolecular Hydroamination Reactions

    OpenAIRE

    Jiménez Silva, Oriol

    2007-01-01

    In this thesis, intermolecular hydroamination reactions were studied on a new type of heterogeneous catalysts in both a slurry reactor and a fixed bed reactor. In the first part of the thesis, catalysts with a high concentration of strong Brønsted acid sites and a high ratio of Brønsted to Lewis acid sites exhibited an especially high catalytic activitity for the addition of aniline to 1,3-cyclohexadiene. In the second part, palladium complexes immobilized in a thin film of supported ionic li...

  13. A new intermolecular mechanism to selectively drive photoinduced damages

    CERN Document Server

    Gokhberg, Kirill; Kuleff, Alexander I; Cederbaum, Lorenz S

    2014-01-01

    Low-energy electrons (LEEs) are known to be effective in causing strand breaks in DNA. Recent experiments show that an important direct source of LEEs is the intermolecular Coulombic decay (ICD) process. Here we propose a new cascade mechanism initiated by core excitation and terminated by ICD and demonstrate its properties. Explicit calculations show that the energies of the emitted ICD-electrons can be controlled by selecting the initial atomic excitation. The properties of the cascade may have interesting applications in the fields of electron spectroscopy and radiation damage. Initiating such a cascade by resonant X-ray absorption from a high-Z element embedded in a cancerous cell nucleus, ICD will deliver genotoxic particles \\textit{locally} at the absorption site, increasing in that way the controllability of the induced damage.

  14. Calculation of the absolute thermodynamic properties of association of host-guest systems from the intermolecular potential of mean force

    Science.gov (United States)

    Ghoufi, Aziz; Malfreyt, Patrice

    2006-12-01

    The authors report calculations of the intermolecular potential of mean force (PMF) in the case of the host-guest interaction. The host-guest system is defined by a water soluble calixarene and a cation. With an organic cation such as the tetramethylammonium cation, the calixarene forms an insertion complex, whereas with the Lanthane cation, the supramolecular assembly is an outer-sphere complex. The authors apply a modified free energy perturbation method and the force constraint technique to establish the PMF profiles as a function of the separation distance between the host and guest. They use the PMF profile for the calculation of the absolute thermodynamic properties of association that they compare to the experimental values previously determined. They finish by giving some structural features of the insertion and outer-sphere complexes at the Gibbs free energy minimum.

  15. Low-energy electron interactions with biomolecules

    Science.gov (United States)

    Winstead, Carl

    2012-06-01

    Low-energy electron interactions with biomolecules have been the focus of sustained attention over the past decade. The demonstration by Sanche and coworkers that even subexcitation and subionization electrons can induce strand breaks in DNA opened a new frontier in understanding radiation damage to living systems. Many studies of DNA subunits and their analogues, both experimental and theoretical, have elucidated likely mechanisms by which slow electrons attach to and disrupt DNA, although the full picture is far from clear and some elements of it remain controversial. Increasing attention is also being given to low-energy electron collisions with amino acids in order to explore possible mechanisms of electron-mediated radiation damage to proteins. In a completely different context, electron-biomolecule collisions are fundamental to spark ignition and cumbustion of biofuels such as methanol and ethanol. Not to be overlooked, either, is the simplest but most ubiquitous biomolecule of all, water, whose low-energy electron cross sections remain surprisingly ill-characterized. This talk will survery recent ab initio computational studies using the Schwinger multichannel method of DNA- and protein-related molecules, alcohols, and water. Much of the work to be presented was carried out in collaboration with experimentalists who undertook complementary measurements, allowing for useful comparisons to be made. Although the primary focus will be on electronically elastic collisions relevant to dissociative attachment and electron transport, electron-impact excitation cross sections for water will be presented and discussed.

  16. Nano-spectroscopic imaging of intermolecular structure, coupling and dynamics

    CERN Document Server

    Pollard, Benjamin; Hinrichs, Karsten; Raschke, Markus B

    2013-01-01

    Molecular self-assembly, the function of biomembranes, and the performance of organic solar cells rely on molecular interactions on the nanoscale. The understanding and design of such intrinsic or engineered heterogeneous functional soft matter has long been impeded by a lack of spectroscopic tools with sufficient nanometer spatial resolution, attomolar sensitivity, and intermolecular spectroscopic specificity. We implement vibrational scattering-scanning near-field optical microscopy ($s$-SNOM) in a multi-spectral modality with unprecedented spectral precision to investigate the structure-function relationship in nano-phase separated block-copolymers. We use a vibrational resonance as a sensitive reporter of the local chemical environment and resolve, with few nanometer spatial resolution and 0.2 cm$^{-1}$ spectral precision, spectral Stark shifts and line broadening correlated with molecular-scale morphologies. By creating images of solvatochromic vibrational shifts we discriminate local variations in elect...

  17. The growth of structure in interacting dark energy models

    OpenAIRE

    Calderacabral, Gaby; Maartens, Roy; Schafer, B.

    2009-01-01

    If dark energy interacts with dark matter, there is a change in the background evolution of the universe, since the dark matter density no longer evolves as a^{-3}. In addition, the non-gravitational interaction affects the growth of structure. In principle, these changes allow us to detect and constrain an interaction in the dark sector. Here we investigate the growth factor and the weak lensing signal for a new class of interacting dark energy models. In these models, the interaction genera...

  18. K--4He interaction at low energies

    International Nuclear Information System (INIS)

    An isobar model of the anti KN-?? coupled-channels system is constructed for the total isospin I = 0 channel, which has an s-wave resonance, Y0*(1405) or ?(1405), about 30 MeV below the anti KN threshold. Low-energy K--4He elastic scattering is analyzed using the isobar-hole formalism, which can cope with the complexity of the anti KN-?? coupled-channels system and the singular behaviour of the scattering amplitude at the anti KN threshold. Various medium corrections to the ? propagation through the nucleus are properly taken into account and the ?-(residual) nucleus interaction is treated by introducing a phenomenological potential VY. The experimental scattering data can be well reproduced with an appropriate choice of the potential VY. A simple calculation using the isobar-hole model, however, fails to explain the kaonic helium atom data. (orig.)

  19. Exchange interaction energy in magnetic recording simulation

    Energy Technology Data Exchange (ETDEWEB)

    Igarashi, Masukazu, E-mail: masukazu.igarashi@xmail.plala.or.jp; Tonooka, Shun; Katada, Hiroyuki; Maeda, Maki; Hara, Miki [HGST, A Western Digital Company, 2880 Kohzu, Odawara, Kanagawa 256-8510 (Japan); Wood, Roger [HGST, A Western Digital Company, San Jose, California 95119 (United States)

    2015-05-07

    Based on a phenomenological theory, micromagnetic simulations and experiments are used to evaluate an improved function for the exchange interaction between magnetic particles in perpendicular recording media. Assuming diluted spin layers in the particle boundary and a gradual rather than abrupt rotation of magnetization between grain cores, the exchange energy is better described by an even power series of θ, rather than a cosine function. The conventional cosine function does not have a restoring torque near θ = π and adjacent grains tend to align strictly antiparallel. In contrast, using a power series of θ, adjacent grains tend to align at a small angle away from θ = π. This gives rise to a small in-plane magnetization component and therefore a distinct peak in in-plane susceptibility is observed around H = 0. From magnetization measurements of a real medium, a peak is observed around H = 0, which matches with an assumption of 2 or 3 spin layers. In some situations, the exchange interaction between discretized cells for numerical calculation is better described by a power series rather than a cosine function.

  20. Interacting Dark Energy with Inhomogeneous Equation of State

    OpenAIRE

    Jamil, Mubasher(School of Natural Sciences (SNS), National University of Sciences and Technology (NUST), H-12, Islamabad 44000, Pakistan); Rashid, Muneer Ahmad

    2008-01-01

    We have investigated the model of dark energy interacting with dark matter by choosing inhomogeneous equations of state for dark energy and a non-linear interaction term for the underlying interaction. The equation of state have dependencies either on the energy densities, redshift, Hubble parameter and its derivatives or the bulk viscosity. We have considered these possibilities and have derived the effective equations of state for the dark energy in each case.

  1. Cosmological Evolution With Interaction Between Dark Energy And Dark Matter

    OpenAIRE

    Bolotin, Yu. L.; Kostenko, A.; Lemets, O. A.; Yerokhin, D. A.

    2013-01-01

    In this review we consider in detail different theoretical topics associated with interaction in the dark sector. We study linear and nonlinear interactions which depend on the dark matter and dark energy densities. We consider a number of different models (including the holographic dark energy and dark energy in a fractal universe) with interacting dark energy (DE) and dark matter (DM), have done a thorough analysis of these models. The main task of this review was not only to give an idea a...

  2. Allowance for intermolecular forces of attraction in the derivation of kinetic equations

    International Nuclear Information System (INIS)

    This paper proposes a method for solving the Bogolyubov hierarchy for dense gases with real interaction potentials. The idea of the method is to decouple each equation of the hierarchy with respect to scales that characterize the strength of the intermolecular repulsion and attraction. Kinetic equations for moderately dense and dense gases are derived and some model equations of the kinetic theory of dense gases with real interaction potentials are constructed

  3. Stacked and H-Bonded Cytosine Dimers. Analysis of the Intermolecular Interaction Energies by Parallel Quantum Chemistry and Polarizable Molecular Mechanics.

    Czech Academy of Sciences Publication Activity Database

    Gresh, N.; Šponer, Judit E.; Devereux, M.; Gkionis, Konstantinos; de Courcy, B.; Piquemal, J.P.; Šponer, Jiří

    2015-01-01

    Roč. 119, č. 30 (2015), s. 9477-9495. ISSN 1520-6106 R&D Projects: GA ČR(CZ) GAP208/11/1822 Institutional support: RVO:68081707 Keywords : DENSITY-FUNCTIONAL THEORY * DISTRIBUTED MULTIPOLE ANALYSIS * PERTURBATION-THEORY APPROACH Subject RIV: BO - Biophysics Impact factor: 3.302, year: 2014

  4. Nucleon structure and high energy interactions

    CERN Document Server

    Selyugin, O V

    2015-01-01

    On the basis of the representation of the generalized structure of nucleons a new model of the hadron interaction at high energies is presented. The new t-dependence of the generalized parton distributions (GPDs) is obtained from the comparative analysis of different sets of the parton distribution functions (PDFs), based on the description of the whole sets of experimental data of electromagnetic form factors of the proton and neutron. Taking into account the different moments of GPDs of the hadron the quantitative descriptions of all existing experimental data of the proton-proton and proton-antiproton elastic scattering from $\\sqrt{s} = 9.8$ GeV to $8$ TeV, including the Coulomb range and large momentum transfers up to $-t=15$ GeV$^2$, are obtained with a few free fitting high energy parameters. The real part of the hadronic elastic scattering amplitude is determined only through complex $s$ satisfying the dispersion relations. The negligible contributions of the hard Pomeron and the presence of the non-sm...

  5. Calculations on Noncovalent Interactions and Databases of Benchmark Interaction Energies

    Czech Academy of Sciences Publication Activity Database

    Hobza, Pavel

    2012-01-01

    Roč. 45, č. 4 (2012), s. 663-672. ISSN 0001-4842 R&D Projects: GA ČR GBP208/12/G016 Grant ostatní: European Social Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : non-covalent interaction s * covalent interaction s * quantum chemical approach Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 20.833, year: 2012

  6. Understanding the interaction between dark energy and dark matter

    International Nuclear Information System (INIS)

    We have studied the interaction between dark energy and dark matter from the thermodynamical consideration. Assuming the interaction as stable fluctuations around equilibrium and using the logarithmic correction to entropy caused by the fluctuation, we have derived the physical expression of the interaction. We have tested the viability of our scenario on the interaction by confronting with cosmological observations. (authors)

  7. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(/sup 1/S) + H/sub 2/(B /sup 1/. sigma. /sub u//sup +/). [Solution for coupled channel equations

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, R.M.

    1986-11-01

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H/sub 2/(B /sup 1/..sigma../sub u//sup +/). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H/sub 2/(E,F /sup 1/..sigma../sub g//sup +/) and with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) and cause a local maximum and a deep minimum in the He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) PES, respectively. The crossing with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H/sub 2/(B /sup 1/..sigma../sub u//sup +/) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs.

  8. Importance of Intermolecular Hydrogen Bonding for the Stereochemical Control of Allene-Enone (3+2) Annulations Catalyzed by a Bifunctional, Amino Acid Derived Phosphine Catalyst.

    Science.gov (United States)

    Holland, Mareike C; Gilmour, Ryan; Houk, K N

    2016-02-01

    The origin of stereoselectivity in the (3+2) annulation of allenes and enones catalyzed by an amino acid derived phosphine catalyst has been investigated by the use of dispersion-corrected density functional theory. An intermolecular hydrogen bond between the intermediate zwitterion and the enone was found to be the key interaction in the two enantiomeric transition states. Additional stabilization is provided by intermolecular hydrogen-bonding interactions between acidic positions on the catalyst backbone and the substrate. Enantioselectivity occurs because the intermolecular hydrogen bond in the transition state leading to the minor enantiomer is only possible at the expense of reactant distortion. PMID:26732907

  9. Virtual photon interactions in high energy QCD

    International Nuclear Information System (INIS)

    We study the interactions of virtual photons in the high energy limit of quantum chromodynamics (QCD). The subject is discussed in terms of two closely linked applications: the calculation of the total cross section for γ*γ*-scattering and the description of DIS in the colour dipole model. We calculate virtual corrections in αs to the process γ* q → (qq)q and the tree level process γ* q → (qqg)q in the high energy limit. From this calculation we obtain one-loop corrections to the effective γ*-reggeon-qq-vertex in the helicity basis of the virtual photon and the qq-pair. The loop integrals for the virtual corrections have been performed and expressed in dimensional regularization in terms of logarithms and dilogarithms. We have convoluted the virtual one-loop matrix elements with tree level matrix elements and expressed the integrals over the phase space of the qq-pair explicitly in terms of a set of standard integrals. The real corrections have been calculated and, in case of the longitudinal polarization, expressed in factorized form. From these calculations, the impact factor of virtual photons will be determined, allowing for a first prediction of the total cross section for γ*γ*-scattering in the next-to-leading-log s approximation. The calculations in this thesis extend the photon wave function picture in the colour dipole model to next-to-leading order. For this purpose, the real corrections with a qqg final state are analyzed in transverse configuration space and interpreted as a first higher Fock component of the photon wave function. In addition, the matrix elements that have been calculated in this thesis are needed for the calculation of jet cross sections. (orig.)

  10. Lepton and photon interactions at high energies

    International Nuclear Information System (INIS)

    The 1989 International Symposium on Lepton and Photon Interactions at High Energies was held at Stanford from August 7 through August 12. This was the fourteenth meeting in this series, which dates back to 1963, and the third time the Symposium has been hosted by the Stanford Linear Accelerator Center. The earlier meetings coincided with major physics accomplishments at SLAC; the first results from the two-mile accelerator were presented at the 1967 meeting, and the 1975 meeting followed closely the discoveries of the ψ and τ particles at SPEAR. In keeping with this tradition, the latest meeting included the first results from e+e- → Z0 events observed at the SLC. A report to the symposium indicated that LEP results on the same reaction were close at hand, and subsequent developments have shown that claim to be amply justified. Other advances of great interest reported to the symposium included new limits on the top mass from the p bar p colliders, the ε'/ε results from experiments at CERN and Fermilab, and evidence for b → u quark transitions at CESR and DESY. The Standard Model continues to accommodate virtually all measurements in the field, including the wealth of new data presented to this conference. Let us hope that future experiments will soon modify that situation

  11. IMPROPER HYDROGEN BONDS - A THEORETICAL STUDY ABOUT THE MOLECULAR STRUCTURE OF INTERMOLECULAR SYSTEMS FORMED BY H3C-H+Δ...X AND H3C+Δ...H-Y WITH X = CL- OR F- AND Y = CL OR F

    Directory of Open Access Journals (Sweden)

    B.G OLIVEIRA

    2009-01-01

    Full Text Available In this work is presented a theoretical study of the molecular properties of the H3C-H...X and H3C+δ...H-Y intermolecular systems with X = CL- or F- and Y = Cl or F. In the H3C-H...X complex, it is formed a traditional hydrogen bond between the CL- or F- anions and the hydrogen atom of the methyl. About the H3C+δ...H-Y complex, it was observed an improper hydrogen bond because the carbon atom of the methyl cation function as a proton acceptor. In this insight, the capacity of methane to interact with halogen anions (CL- or F- and molecular acids (HCl or HF was examined at the B3LYP/6-311++G(3df,3dp level of calculation. Moreover, the interaction strengths of the H3C-H...X and H3C+δ...H-Y complexes was evaluated by computing their intermolecular distances and binding energies. Finally, QTAIM calculations also were executed with the purpose to examine the intermolecular interactions through the quantification of their electronic densities (p as well as by the interpretation of the Laplacian operators (.

  12. Interacting holographic dark energy model in non-flat universe

    International Nuclear Information System (INIS)

    We employ the holographic model of interacting dark energy to obtain the equation of state for the holographic energy density in non-flat (closed) universe enclosed by the event horizon measured from the sphere of horizon named L

  13. Statefinder diagnosis for the interacting model of holographic dark energy

    International Nuclear Information System (INIS)

    In this Letter, we investigate the holographic dark energy model with interaction between dark energy and dark matter, from the statefinder viewpoint. We plot the trajectories of the interacting holographic dark energy model for different interaction cases as well as for different values of the parameter c in the statefinder-plane. The statefinder diagrams characterize the properties of the holographic dark energy and show the discrimination between the two cases with and without interaction. As a result, we show the influence of the interaction on the evolution of the universe in the statefinder diagrams. Moreover, as a complement to the statefinder diagnosis, we study the interacting holographic dark energy model in the w-w' plane, which can provide us with a dynamical diagnosis

  14. THz absorption spectrum of the CO2–H2O complex: Observation and assignment of intermolecular van der Waals vibrations

    DEFF Research Database (Denmark)

    Andersen, Jonas; Heimdal, J.; Wallin Mahler Andersen, Denise; Nelander, B.; Larsen, René Wugt

    2014-01-01

    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...

  15. Structure, vibrational spectra and DFT characterization of the intra- and inter-molecular interactions in 2-hydroxy-5-methylpyridine-3-carboxylic acid--normal modes of the eight-membered HB ring.

    Science.gov (United States)

    Godlewska, P; Ja?czak, J; Kucharska, E; Hanuza, J; Lorenc, J; Michalski, J; Dymi?ska, L; W?gli?ski, Z

    2014-01-01

    Fourier transform IR and Raman spectra, XRD studies and DFT quantum chemical calculations have been used to characterize the structural and vibrational properties of 2-hydroxy-5-methylpyridine-3-carboxylic acid. In the unit-cell of this compound two molecules related by the inversion center interact via OH?N hydrogen bonds. The double hydrogen bridge system is spaced parallel to the (102) crystallographic plane forming eight-membered arrangement characteristic for pyridine derivatives. The six-membered ring is the second characteristic unit formed via the intramolecular OH?O hydrogen bond. The geometry optimization of the monomer and dimer have been performed applying the Gaussian03 program package. All calculations were performed in the B3LYP/6-31G(d,p) basis set using the XRD data as input parameters. The relation between the molecular and crystal structures has been discussed in terms of the hydrogen bonds formed in the unit cell. The vibrations of the dimer have been discussed in terms of the resonance inside the system built of five rings coupled via hydrogen bonds. PMID:24184924

  16. Comparison of the local binding motifs in the imidazolium-based ionic liquids [EMIM][BF{sub 4}] and [EMMIM][BF{sub 4}] through cryogenic ion vibrational predissociation spectroscopy: Unraveling the roles of anharmonicity and intermolecular interactions

    Energy Technology Data Exchange (ETDEWEB)

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; Johnson, Mark A., E-mail: mark.johnson@yale.edu, E-mail: mccoy@chemistry.ohio-state.edu [Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06520 (United States); McCoy, Anne B., E-mail: mark.johnson@yale.edu, E-mail: mccoy@chemistry.ohio-state.edu [Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210 (United States)

    2015-02-14

    We clarify the role of the critical imidazolium C{sub (2)}H position (the central C between N atoms in the heterocycle) in the assembly motif of the [EMIM][BF{sub 4}] ionic liquid by analyzing the vibrational spectra of the bare EMIM{sup +} ion as well as that of the cationic [EMIM]{sub 2}[BF{sub 4}]{sup +} (EMIM{sup +} = 1-ethyl-3-methylimidazolium, C{sub 6}H{sub 11}N{sub 2}{sup +}) cluster. Vibrational spectra of the cold, mass-selected ions are obtained using cryogenic ion vibrational predissociation of weakly bound D{sub 2} molecules formed in a 10 K ion trap. The C{sub (2)}H behavior is isolated by following the evolution of key vibrational features when the C{sub (2)} hydrogen, the proposed binding location of the anion to the imidazolium ring, is replaced by either deuterium or a methyl group (i.e., in the EMMIM{sup +} analogue). Strong features in the ring CH stretching region of the bare ion are traced to Fermi resonances with overtones of lower frequency modes. Upon incorporation into the EMIM{sup +} ? ? ? BF{sub 4}{sup ?} ? ? ? EMIM{sup +} ternary complex, the C{sub (2)}H oscillator strength is dramatically increased, accounting for the much more complicated patterns derived from the EMIM{sup +} ring CH stretches in the light isotopomer, which are strongly suppressed in the deuterated analogue. Further changes in the spectra that occur when the C{sub (2)}H is replaced by a methyl group are consistent with BF{sub 4}{sup ?} attachment directly to the imidazolium ring in an arrangement that maximizes the electrostatic interaction between the molecular ions.

  17. Dark Mass Creation During EWPT Via Dark Energy Interaction

    OpenAIRE

    Kisslinger, Leonard S.; Casper, Steven

    2013-01-01

    We add Dark Matter Dark Energy terms with a quintessence field interacting with a Dark Matter field to a MSSM EW Lagrangian previously used to calculate the magnetic field created during the EWPT. From the expectation value of the quintessence field we estimate the Dark Matter mass for parameters used in previous work on Dark Matter-Dark Energy interactions.

  18. Supramolecular methods for controlling intermolecular [2+2] photocycloaddition reactions of unsaturated compounds in solutions

    Science.gov (United States)

    Ushakov, E. N.; Gromov, S. P.

    2015-08-01

    This review deals with the methods of supramolecular chemistry used for controlling the efficiency and stereoselectivity of intermolecular [2+2] photocycloaddition of olefins and other unsaturated compounds in homogeneous solutions. The best-studied methods are self-assembly through cation-macrocycle interactions, complexation with molecular templates through hydrogen bonding, and confinement of the reactants in supramolecular containers. The possibilities of using anionic templates and combined supramolecular approaches are discussed. The bibliography includes 107 references.

  19. Cosmological constraints on a dark matter -- dark energy interaction

    OpenAIRE

    Hoffman, Mark B.

    2003-01-01

    It is generally assumed that the two dark components of the energy density of the universe, a smooth component called dark energy and a fluid of nonrelativistic weakly interacting particles called dark matter, are independent of each other and interact only through gravity. In this paper, we consider a class of models in which the dark matter and dark energy interact directly. The dark matter particle mass is proportional to the value of a scalar field, and the energy density of this scalar f...

  20. Intermolecularly-induced conformational disorder in ferrocene, 1-bromoferrocene and 1,1‧-dibromoferrocene

    Science.gov (United States)

    Silva, Patrícia A.; Maria, Teresa M. R.; Nunes, Cláudio M.; Eusébio, Maria Ermelinda S.; Fausto, Rui

    2014-12-01

    Conformational preferences for isolated molecules of ferrocene, 1-bromoferrocene and 1,1‧-dibromoferrocene were obtained by combined use of matrix-isolation infrared spectroscopy and quantum chemical calculations. Monomeric ferrocene and 1-dibromoferrocene were found to exist in a low temperature argon matrix (T = 15 K) exclusively in the eclipsed configuration, which corresponds to their most stable conformation in gas phase. On the other hand, for the neat compounds in crystalline phase, intermolecular interactions induce conformational disorder, leading to presence in the room temperature polymorphic forms of monomeric units with the staggered (or nearly staggered) conformation. 1,1‧-Dibromoferrocene exists in both gas phase and low temperature argon matrix in two conformers of C2 symmetry (C2-I and C2-II), with eclipsed cyclopentadienyl moieties and Br atoms opposed to H atoms. The populations of the two conformers trapped in the as-deposited matrix were found to correspond to those estimated from theory for the room temperature equilibrium gas phase. By increasing the temperature of the matrix (up to 35 K), the gas phase lower energy form (C2-I) converted to the C2-II form. Besides allowing the precise structural and spectroscopic characterization of the two forms, these studies also revealed that the C2-II conformer (having a largest dipole moment) is stabilized in the matrix media, thus becoming more stable than the C2-I form under these conditions. Very interestingly, the room temperature stable polymorph of the compound (Tfus = 325.4 ± 0.1 K) is composed by 1,1‧-dibromoferrocene units exhibiting the C2v symmetry eclipsed conformation with opposed bromine atoms, which for the isolated molecule corresponds to the highest energy conformation along the ring torsional coordinate and is the transition state structure between the two symmetry equivalent C2-II minima. Differential scanning calorimetry, polarized light thermomicroscopy and infrared measurements on 1,1‧-dibromoferrocene allowed to identify a new polymorph of the compound, with Tfus = 320.2 ± 0.1 K. On the whole, the results presented in this article represent illuminating examples of intermolecularly-induced conformational disorder in solid phase and of its relevance to polymorphism.

  1. Fluorescence photoactivation by intermolecular proton transfer.

    Science.gov (United States)

    Swaminathan, Subramani; Petriella, Marco; Deniz, Erhan; Cusido, Janet; Baker, James D; Bossi, Mariano L; Raymo, Françisco M

    2012-10-11

    We designed a strategy to activate fluorescence under the influence of optical stimulations based on the intermolecular transfer of protons. Specifically, the illumination of a 2-nitrobenzyl derivative at an activating wavelength is accompanied by the release of hydrogen bromide. In turn, the photogenerated acid encourages the opening of an oxazine ring embedded within a halochromic compound. This structural transformation extends the conjugation of an adjacent coumarin fluorophore and enables its absorption at an appropriate excitation wavelength. Indeed, this bimolecular system offers the opportunity to activate fluorescence in liquid solutions, within rigid matrixes and inside micellar assemblies, relying on the interplay of activating and exciting beams. Furthermore, this strategy permits the permanent imprinting of fluorescent patterns on polymer films, the monitoring of proton diffusion within such materials in real time on a millisecond time scale, and the acquisition of images with spatial resolution at the nanometer level. Thus, our operating principles for fluorescence activation can eventually lead to the development of valuable photoswitchable probes for imaging applications and versatile mechanisms for the investigation of proton transport. PMID:22994311

  2. Magnon energies and exchange interactions in terbium

    DEFF Research Database (Denmark)

    Houmann, Jens Christian Gylden

    1968-01-01

    The magnon density of states, and hence the magnetic contribution to the specific heat, and also the exchange interaction between ions in the same sublattice have been calculated for Tb at 90K, using experimental results obtained by inelastic neutron scattering.......The magnon density of states, and hence the magnetic contribution to the specific heat, and also the exchange interaction between ions in the same sublattice have been calculated for Tb at 90K, using experimental results obtained by inelastic neutron scattering....

  3. Buildings Interaction with Urban Energy Systems

    DEFF Research Database (Denmark)

    Heller, Alfred; Wyckmans, Annemie; Zucker, Gerhard; Petersen, Steffen; Haider, Catrin

    2015-01-01

    to demonstrate that they can become not only smart fossil-free energy cities but sustainable in a wider sense, including water, waste, transportation and more. In the current paper, the research agenda to support such goals through smart city efforts is presented for a few European cases as examples......The goal towards a fossil free energy system is expressed in amongst others European and national targets, and puts pressure on the application of renewable energy sources combined with energy efficiency. Many cities are even more ambitious than their national targets and want to be among the first...

  4. Exactly solved models of interacting dark matter and dark energy

    CERN Document Server

    Chimento, Luis P

    2012-01-01

    We introduce an effective one-fluid description of the interacting dark sector in a spatially flat Friedmann-Robertson-Walker space-time and investigate the stability of the power-law solutions. We find the "source equation" for the total energy density and determine the energy density of each dark component. We study linear and nonlinear interactions which depend on the dark matter and dark energy densities, their first derivatives, the total energy density with its derivatives up to second order and the scale factor. We solve the evolution equations of the dark components for both interactions, examine exhaustively several examples and show cases where the problem of the coincidence is alleviated. We show that a generic nonlinear interaction gives rise to the "relaxed Chaplygin gas model" whose effective equation of state includes the variable modified Chaplygin gas model while some others nonlinear interactions yield de Sitter and power-law scenarios.

  5. Hadron-nucleus interactions at high energy

    International Nuclear Information System (INIS)

    Properties of energetic secondaries produced at large angles using 800 GeV incident protons are presented. H2, Be, C, Al, Cu and Pb targets were used for the study. The yields for producing such secondaries vary as A/sup ?/ where A is the atomic mass number of the target and ? attains values as large as 1.6. There is evidence that jet-like events have ? values approaching unity, indicating a hard scattering mechanism may be occurring. Events with large values of target-fragmentation energy have, on average, large values of energy in the central region and small values of forward-going energy. Energy flows and number of secondaries are independent of the target when events with similar amounts of energy in the central region are studied

  6. Hadron-nucleus interactions at high energy

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, R.; Dauwe, L.; Haggerty, H.; Malamud, E.; Nikolic, M.; Lannutti, J.; Hagopian, S.; Pifer, B.; Abrams, R.; Ares, J.

    1986-05-01

    Properties of energetic secondaries produced at large angles using 800 GeV incident protons are presented. H/sub 2/, Be, C, Al, Cu and Pb targets were used for the study. The yields for producing such secondaries vary as A/sup ..cap alpha../ where A is the atomic mass number of the target and ..cap alpha.. attains values as large as 1.6. There is evidence that jet-like events have ..cap alpha.. values approaching unity, indicating a hard scattering mechanism may be occurring. Events with large values of target-fragmentation energy have, on average, large values of energy in the central region and small values of forward-going energy. Energy flows and number of secondaries are independent of the target when events with similar amounts of energy in the central region are studied.

  7. Cosmological Evolution With Interaction Between Dark Energy And Dark Matter

    CERN Document Server

    Bolotin, Yu L; Lemets, O A; Yerokhin, D A

    2013-01-01

    In this review we consider in detail different theoretical topics associated with interaction in the dark sector. We study linear and nonlinear interactions which depend on the dark matter and dark energy densities. We consider a number of different models (including the holographic dark energy and dark energy in a fractal universe) with interacting dark energy (DE) and dark matter (DM), have done a thorough analysis of these models. The main task of this review was not only to give an idea about the modern set of different models of dark energy, but to show how much can be diverse dynamics of the universe in these models. We find that the dynamics of a Universe that contains interaction in the dark sector can differ significantly from the Standard Cosmological Model (SCM).

  8. Load Matching and Grid Interaction of Net Zero Energy Buildings

    DEFF Research Database (Denmark)

    Voss, Karsten; Sartori, Igor; Napolitano, Assunta; Geier, Sonja; Gonzalves, Helder; Hall, Monika; Heiselberg, Per; Widén, Joakim; Candanedo, José A.; Musall, Eike; Karlsson, Björn; Torcellini, Paul

    2010-01-01

    “Net Zero Energy Building” has become a prominent wording to describe the synergy of energy efficient building and renewable energy utilization to reach a balanced energy budget over a yearly cycle. Taking into account the energy exchange with a grid infrastructure overcomes the limitations of...... seasonal energy storage on-site. Even though the wording “Net Zero Energy Building” focuses on the annual energy balance, large differences may occur between solution sets in the amount of grid interaction needed to reach the goal. The paper reports on the analysis of example buildings concerning the load...... matching and grid interaction. Indices to describe both issues are proposed and foreseen as part of a harmonized definition framework. The work is part of subtask A of the IEA SHCP Task40/ECBCS Annex 52: “Towards Net Zero Energy Solar Buildings”....

  9. Instability in interacting dark energy and dark matter fluids

    International Nuclear Information System (INIS)

    We consider a model of dark energy interacting with dark matter. An interaction may be interesting for the solution of the coincidence problem. We model dark energy as a fluid with constant equation of state parameter w and study background and linear perturbations. While non-interacting models with constant w are well behaved, a simple interaction leads to an instability in the dark sector perturbations at early times. The instability is severe, non-adiabatic and independent of how weak the coupling is.

  10. Intermolecular Interactions in Ternary Glycerol–Sample–H2O

    DEFF Research Database (Denmark)

    Westh, Peter; Rasmussen, Erik Lumby; Koga, Yoshikata

    2011-01-01

    ranking of these ions, the kosmotropes are hydration centers and the more kosmotropic the higher the hydration number, consistent with the original Hofmeister’s concept of “H2O withdrawing power.” Br−, I− and SCN−, on the other hand, acted as hydrophiles and the more chaotropic they are the more...... hydrophilic. These observations hint that whatever effect each individual ion has on H2O, it is sensitive only to hydrophobes (such as 1P) but not to hydrophiles (such as Gly). This may have an important bearing towards understanding the Hofmeister series, since biopolymers are amphiphilic and their surfaces...

  11. Study of intermolecular interactions in hetero-organic thin films

    OpenAIRE

    Stadtmüller, Benjamin

    2013-01-01

    The interest in organic semiconductors is based on their great potential to serve as active materials in electronic devices such as organic light-emitting diodes or organic photovoltaic cells. The performance of these molecular assemblies does not only depend on the properties of the organic bulk materials but also on the interfaces formed by the contact between different materials. Therefore, the physical properties of interfaces between metal contacts and organic materials have been studied...

  12. High energy e+e- interactions

    International Nuclear Information System (INIS)

    A review is given about the experimental studies of e+e- interactions. After a description of the PETRA and PEP storage rings the structure of leptons and the weak neutral current contributions to lepton pair production are discussed. Then experiments for the search for new particles, the jet formation in e+e- annihilation, and the quark and gluon fragmentation are described. (HSI)

  13. Effective dark energy equation of state in interacting dark energy models

    OpenAIRE

    Avelino, P. P.; da Silva, H. M. R.

    2012-01-01

    In models where dark matter and dark energy interact non-minimally, the total amount of matter in a fixed comoving volume may vary from the time of recombination to the present time due to energy transfer between the two components. This implies that, in interacting dark energy models, the fractional matter density estimated using the cosmic microwave background assuming no interaction between dark matter and dark energy will in general be shifted with respect to its true value. This may resu...

  14. An Interacting Dark Energy Model with Nonminimal Derivative Coupling

    CERN Document Server

    Nozari, Kourosh

    2016-01-01

    We study cosmological dynamics of an extended gravitational theory that gravity is coupled non-minimally with derivatives of a dark energy component and there is also a phenomenological interaction between the dark energy and dark matter. Depending on the direction of energy flow between the dark sectors, the phenomenological interaction gets two different signs. We show that this feature affects the existence of attractor solution, the rate of growth of perturbations and stability of the solutions. By considering an exponential potential as a self-interaction potential of the scalar field, we obtain accelerated scaling solutions that are attractors and have the potential to alleviate the coincidence problem. While in the absence of the nonminimal derivative coupling there is no attractor solution for phantom field when energy transfers from dark matter to dark energy, we show an attractor solution exists if one considers an explicit nonminimal derivative coupling for phantom field in this case of energy tran...

  15. Interacting new agegraphic viscous dark energy with varying $G$

    OpenAIRE

    Sheykhi, A.; Setare, M. R.

    2010-01-01

    We consider the new agegraphic model of dark energy with a varying gravitational constant, $G$, in a non-flat universe. We obtain the equation of state and the deceleration parameters for both interacting and noninteracting new agegraphic dark energy. We also present the equation of motion determining the evolution behavior of the dark energy density with a time variable gravitational constant. Finally, we generalize our study to the case of viscous new agegraphic dark energy in the presence ...

  16. Non-flat universe and interacting dark energy model

    International Nuclear Information System (INIS)

    For non-flat universe of k0, we investigate a model of the interacting holographic dark energy with cold dark matter (CDM). There exists a mixture of two components arisen from decaying of the holographic dark energy into CDM. In this case we use the effective equations of state (ωΛeff,ωmeff) instead of the native equations of state (ωΛ,ωm). Consequently, we show that interacting holographic energy models in non-flat universe cannot accommodate a transition from the dark energy to the phantom regime

  17. Photons from Jet - Plasma Interaction in collisional energy loss scenario

    OpenAIRE

    Bhattacharya, Lusaka; Roy, Pradip K

    2008-01-01

    We calculate photons from jet plasma interaction in a collisional energy loss scenario. It is shown that the PHENIX photon data is well reproduced when photons from initial hard collisions are taken into account.

  18. Evolution of interacting viscous dark energy model in Einstein cosmology

    International Nuclear Information System (INIS)

    We investigate the evolution of the viscous dark energy (DE) interacting with the dark matter (DM) in the Einstein cosmology model. By using the linearizing theory of the dynamical system, we find that, in our model, there exists a stable late time scaling solution which corresponds to the accelerating universe. We also find the unstable solution under some appropriate parameters. In order to alleviate the coincidence problem, some authors considered the effect of quantum correction due to the conform anomaly and the interacting dark energy with the dark matter. However, if we take into account the bulk viscosity of the cosmic fluid, the coincidence problem will be softened just like the interacting dark energy cosmology model. That is to say, both the non-perfect fluid model and the interacting the dark energy cosmic model can alleviate or soften the singularity of the universe. (authors)

  19. Chirality of weakly bound complexes: The potential energy surfaces for the hydrogen-peroxide−noble-gas interactions

    Energy Technology Data Exchange (ETDEWEB)

    Roncaratti, L. F., E-mail: lz@fis.unb.br; Leal, L. A.; Silva, G. M. de [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Pirani, F. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, V. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Instituto de Física, Universidade Federal da Bahia, 40210 Salvador (Brazil); Gargano, R. [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Departments of Chemistry and Physics, University of Florida, Quantum Theory Project, Gainesville, Florida 32611 (United States)

    2014-10-07

    We consider the analytical representation of the potential energy surfaces of relevance for the intermolecular dynamics of weakly bound complexes of chiral molecules. In this paper we study the H{sub 2}O{sub 2}−Ng (Ng=He, Ne, Ar, Kr, and Xe) systems providing the radial and the angular dependence of the potential energy surface on the relative position of the Ng atom. We accomplish this by introducing an analytical representation which is able to fit the ab initio energies of these complexes in a wide range of geometries. Our analysis sheds light on the role that the enantiomeric forms and the symmetry of the H{sub 2}O{sub 2} molecule play on the resulting barriers and equilibrium geometries. The proposed theoretical framework is useful to study the dynamics of the H{sub 2}O{sub 2} molecule, or other systems involving O–O and S–S bonds, interacting by non-covalent forces with atoms or molecules and to understand how the relative orientation of the O–H bonds changes along collisional events that may lead to a hydrogen bond formation or even to selectivity in chemical reactions.

  20. Effective theory of interacting dark energy

    Science.gov (United States)

    Gleyzes, Jrme; Langlois, David; Mancarella, Michele; Vernizzi, Filippo

    2015-08-01

    We present a unifying treatment of dark energy and modified gravity that allows distinct conformal-disformal couplings of matter species to the gravitational sector. In this very general approach, we derive the conditions to avoid ghost and gradient instabilities. We compute the equations of motion for background quantities and linear perturbations. We illustrate our formalism with two simple scenarios, where either cold dark matter or a relativistic fluid is nonminimally coupled. This extends previous studies of coupled dark energy to a much broader spectrum of gravitational theories.

  1. Effective Theory of Interacting Dark Energy

    CERN Document Server

    Gleyzes, Jrme; Mancarella, Michele; Vernizzi, Filippo

    2015-01-01

    We present a unifying treatment of dark energy and modified gravity that allows distinct conformal-disformal couplings of matter species to the gravitational sector. In this very general approach, we derive the conditions to avoid ghost and gradient instabilities. We compute the equations of motion for background quantities and linear perturbations. We illustrate our formalism with two simple scenarios, where either cold dark matter or a relativistic fluid is nonminimally coupled. This extends previous studies of coupled dark energy to a much broader spectrum of gravitational theories.

  2. Dynamical behavior of interacting dark energy in loop quantum cosmology

    OpenAIRE

    Xiao, Kui; Zhu, Jian-Yang

    2010-01-01

    The dynamical behaviors of interacting dark energy in loop quantum cosmology are discussed in this paper. Based on defining three dimensionless variables, we simplify the equations of the fixed points. The fixed points for interacting dark energy can be determined by the Friedmann equation coupled with the dynamical equations {in Einstein cosmology}. But in loop quantum cosmology, besides the Friedmann equation, the conversation equation also give a constrain on the fixed points. The differen...

  3. On effect of strong interaction on binding energies of mesomolecules

    International Nuclear Information System (INIS)

    An effect of nuclear interaction on the binding energy of mesomolecular ions is considered. The nuclear dd potential has been reconstructed from phase shifts of the deuteron-deuteron scattering, so it has been possible to estimate reliably a contribution from the nuclear interaction to the binding energies for all five discrete levels of the dd? mesomolecule. The results obtained can be of interest in problem of the mesomolecular physics and, in particular, for mesonic catalysis of nuclear reactions

  4. The growth of structure in interacting dark energy models

    International Nuclear Information System (INIS)

    If dark energy interacts with dark matter, there is a change in the background evolution of the universe, since the dark matter density no longer evolves as a−3. In addition, the non-gravitational interaction affects the growth of structure. In principle, these changes allow us to detect and constrain an interaction in the dark sector. Here we investigate the growth factor and the weak lensing signal for a new class of interacting dark energy models. In these models, the interaction generalises the simple cases where one dark fluid decays into the other. In order to calculate the effect on structure formation, we perform a careful analysis of the perturbed interaction and its effect on peculiar velocities. Assuming a normalization to today's values of dark matter density and overdensity, the signal of the interaction is an enhancement (suppression) of both the growth factor and the lensing power, when the energy transfer in the background is from dark matter to dark energy (dark energy to dark matter)

  5. Strong interactions studies with medium energy probes

    International Nuclear Information System (INIS)

    This report discusses work on: charmonium spectroscopy; proton form- factor in the time-like region; proton-antiproton forward scattering; QCD scaling laws; light quark spectroscopy; high resolutions electron scattering; quasi-free electron scattering; and low energy pion double charge exchange

  6. Nuclear interactions and the highest energy air showers

    International Nuclear Information System (INIS)

    Based on the energy distribution of particles produced in multiple particle production, which is formulated phenomenologically by the data of direct observation, it was calculated the air shower development at E0=1020 eV. The calculation shows that the formula, extrapolated into the higher energy region, does not describe the highest energy air showers. It was also argued that the energy estimation of the highest energy air showers may have an ambiguity of a factor ∼ 2, due to the incomplete knowledge on high energy interactions

  7. Interacting agegraphic dark energy models in non-flat universe

    OpenAIRE

    Sheykhi, Ahmad

    2009-01-01

    A so-called "agegraphic dark energy" was recently proposed to explain the dark energy-dominated universe. In this Letter, we generalize the agegraphic dark energy models to the universe with spatial curvature in the presence of interaction between dark matter and dark energy. We show that these models can accommodate $w_D = -1 $ crossing for the equation of state of dark energy. In the limiting case of a flat universe, i.e. $k = 0$, all previous results of agegraphic dark energy in flat unive...

  8. Explosives sensing by using electron-rich supramolecular polymers: role of intermolecular hydrogen bonding in significant enhancement of sensitivity.

    Science.gov (United States)

    Gole, Bappaditya; Song, Wentao; Lackinger, Markus; Mukherjee, Partha Sarathi

    2014-10-13

    We demonstrate here that supramolecular interactions enhance the sensitivity towards detection of electron-deficient nitro-aromatic compounds (NACs) over discrete analogues. NACs are the most commonly used explosive ingredients and are common constituents of many unexploded landmines used during World War II. In this study, we have synthesised a series of pyrene-based polycarboxylic acids along with their corresponding discrete esters. Due to the electron richness and the fluorescent behaviour of the pyrene moiety, all the compounds act as sensors for electron-deficient NACs through a fluorescence quenching mechanism. A Stern-Volmer quenching constant determination revealed that the carboxylic acids are more sensitive than the corresponding esters towards NACs in solution. The high sensitivity of the acids was attributed to supramolecular polymer formation through hydrogen bonding in the case of the acids, and the enhancement mechanism is based on an exciton energy migration upon excitation along the hydrogen-bond backbone. The presence of intermolecular hydrogen bonding in the acids in solution was established by solvent-dependent fluorescence studies and dynamic light scattering (DLS) experiments. In addition, the importance of intermolecular hydrogen bonds in solid-state sensing was further explored by scanning tunnelling microscopy (STM) experiments at the liquid-solid interface, in which structures of self-assembled monolayer of the acids and the corresponding esters were compared. The sensitivity tests revealed that these supramolecular sensors can even detect picric acid and trinitrotoluene in solution at levels as low as parts per trillion (ppt), which is much below the recommended permissible level of these constituents in drinking water. PMID:25187022

  9. Effective Theory of Interacting Dark Energy

    OpenAIRE

    Gleyzes, Jérôme; Langlois, David; Mancarella, Michele; Vernizzi, Filippo

    2015-01-01

    We present a unifying treatment of dark energy and modified gravity that allows distinct conformal-disformal couplings of matter species to the gravitational sector. In this very general approach, we derive the conditions to avoid ghost and gradient instabilities. We compute the equations of motion for background quantities and linear perturbations. We illustrate our formalism with two simple scenarios, where either cold dark matter or a relativistic fluid is nonminimally coupled. This extend...

  10. Low-energy weak-interaction studies

    International Nuclear Information System (INIS)

    An overview is given of the present status of low-energy tests of the Standard Model in nuclear beta-decay and neutron decay, covering the unitarity problem, searches for right-handed currents, scalar- and tensor-type currents, tests of time-reversal violation, as well as experiments to set the neutrino mass scale. In view of the large amount of ongoing and planned experiments in this sector, many new results can be expected in the coming decade. (orig.)

  11. Dynamics of interacting phantom and quintessence dark energies

    CERN Document Server

    Farooq, M Umar; Debnath, Ujjal

    2011-01-01

    We present models, in which phantom energy interacts with two different types of dark energies including variable modified Chaplygin gas (VMCG) and new modified Chaplygin gas (NMCG). We then construct potentials for these cases. It has been shown that the potential of the phantom field decreases from a higher value with the evolution of the Universe.

  12. Constraints on the interacting holographic dark energy model

    International Nuclear Information System (INIS)

    We examined the interacting holographic dark energy model in a universe with spatial curvature. Using the near-flatness condition and requiring that the universe is experiencing an accelerated expansion, we have constrained the parameter space of the model and found that the model can accommodate a transition of the dark energy from ωD>-1 to ωD<-1

  13. The Energy of a Trapped Interacting Bose Gas

    OpenAIRE

    Shi, Hualin; Zheng, Wei-Mou

    1996-01-01

    A Bose gas in an external potential is studied by means of the semi-classical approximation. Analytical results are derived for the energy of an interacting Bose gas in a generic power-law trapping potential. An expression for the chemical potential below the critical temperature is also obtained. The theoretical results are in qualitative agreement with a recent energy measurement.

  14. Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis

    Directory of Open Access Journals (Sweden)

    Feng Wang

    2015-11-01

    Full Text Available Two very different quantum mechanically based energy decomposition analyses (EDA schemes are employed to study the dominant energy differences between the eclipsed and staggered ferrocene conformers. One is the extended transition state (ETS based on the Amsterdam Density Functional (ADF package and the other is natural EDA (NEDA based in the General Atomic and Molecular Electronic Structure System (GAMESS package. It reveals that in addition to the model (theory and basis set, the fragmentation channels more significantly affect the interaction energy terms (ΔE between the conformers. It is discovered that such an interaction energy can be absorbed into the pre-partitioned fragment channels so that to affect the interaction energies in a particular conformer of Fc. To avoid this, the present study employs a complete fragment channel—the fragments of ferrocene are individual neutral atoms. It therefore discovers that the major difference between the ferrocene conformers is due to the quantum mechanical Pauli repulsive energy and orbital attractive energy, leading to the eclipsed ferrocene the energy preferred structure. The NEDA scheme further indicates that the sum of attractive (negative polarization (POL and charge transfer (CL energies prefers the eclipsed ferrocene. The repulsive (positive deformation (DEF energy, which is dominated by the cyclopentadienyle (Cp rings, prefers the staggered ferrocene. Again, the cancellation results in a small energy residue in favour of the eclipsed ferrocene, in agreement with the ETS scheme. Further Natural Bond Orbital (NBO analysis indicates that all NBO energies, total Lewis (no Fe and lone pair (LP deletion all prefer the eclipsed Fc conformer. The most significant energy preferring the eclipsed ferrocene without cancellation is the interactions between the donor lone pairs (LP of the Fe atom and the acceptor antibond (BD* NBOs of all C–C and C–H bonds in the ligand, LP(Fe-BD*(C–C & C–H, which strongly stabilizes the eclipsed (D5h conformation by −457.6 kcal·mol−1.

  15. High-energy interactions at the Pierre Auger Observatory

    CERN Document Server

    ,

    2015-01-01

    The interaction of Ultra High Energy Cosmic Rays (UHECRs) with the atoms of the atmosphere can occur at center-of-mass energies that surpass 100 TeV, while present human-made accelerators go up to 13 TeV. Therefore it provides a unique opportunity to explore hadronic interactions at the highest energies. However, the extraction of hadronic interaction properties from the Extensive Air Showers (EAS) characteristics, which are induced by the UHECR, is intrinsically related to the nature of the primary cosmic ray. As such, to break the degeneracy between hadronic interactions and primary mass composition, a consistent description of the shower observables must be achieved. Such detailed studies have been conducted in the last years at the Pierre Auger Observatory, the largest UHECRs detector in the world. It combines two complementary techniques to measure the EAS characteristics. In this talk, we will present the latest measurements on shower observables, both on the electromagnetic and muonic shower components...

  16. Calculations of Potential Energy Surfaces Using Monte Carlo Configuration Interaction

    CERN Document Server

    Coe, J P; Paterson, M J; 10.1063/1.4767052

    2012-01-01

    We apply the method of Monte Carlo configuration interaction (MCCI) to calculate ground-state potential energy curves for a range of small molecules and compare the results with full configuration interaction. We show that the MCCI potential energy curve can be calculated to relatively good accuracy, as quantified using the non-parallelity error, using only a very small fraction of the FCI space. In most cases the potential curve is of better accuracy than its constituent single-point energies. We finally test the MCCI program on systems with basis sets beyond full configuration interaction: a lattice of fifty hydrogen atoms and ethylene. The results for ethylene agree fairly well with other computational work while for the lattice of fifty hydrogens we find that the fraction of the full configuration interaction space we were able to consider appears to be too small as, although some qualitative features are reproduced, the potential curve is less accurate.

  17. Meson-nuclear interactions at medium energies

    International Nuclear Information System (INIS)

    A brief review of selected directions in medium energy physics is given. Special attention is paid to the propagation of hadrons in the nuclear medium which results in a modification of the free properties of the probe hadron and the nucleus. Such modifications are germane to our understanding of both particles and nuclei. Examples are given involving pion and kaon scattering, absorption and production from nuclei. Some of what has been learned is summarized and some of the hopes for the future are outlined

  18. Meson-nuclear interactions at medium energies

    Energy Technology Data Exchange (ETDEWEB)

    Eisenstein, R A

    1981-01-01

    A brief review of selected directions in medium energy physics is given. Special attention is paid to the propagation of hadrons in the nuclear medium which results in a modification of the free properties of the probe hadron and the nucleus. Such modifications are germane to our understanding of both particles and nuclei. Examples are given involving pion and kaon scattering, absorption and production from nuclei. Some of what has been learned is summarized and some of the hopes for the future are outlined.

  19. Energy exchange in systems of particles with nonreciprocal interaction

    International Nuclear Information System (INIS)

    A model is proposed to describe the sources of additional kinetic energy and its redistribution in systems of particles with a nonreciprocal interaction. The proposed model is shown to explain the qualitative specific features of the dust particle dynamics in the sheath region of an RF discharge. Prominence is given to the systems of particles with a quasi-dipole–dipole interaction, which is similar to the interaction induced by the ion focusing effects that occur in experiments on a laboratory dusty plasma, and with the shadow interaction caused by thermophoretic forces and Le Sage’s forces

  20. Energy exchange in systems of particles with nonreciprocal interaction

    Energy Technology Data Exchange (ETDEWEB)

    Vaulina, O. S.; Lisina, I. I., E-mail: Irina.Lisina@mail.ru; Lisin, E. A. [Russian Academy of Sciences, Joint Institute for High Temperatures (Russian Federation)

    2015-10-15

    A model is proposed to describe the sources of additional kinetic energy and its redistribution in systems of particles with a nonreciprocal interaction. The proposed model is shown to explain the qualitative specific features of the dust particle dynamics in the sheath region of an RF discharge. Prominence is given to the systems of particles with a quasi-dipole–dipole interaction, which is similar to the interaction induced by the ion focusing effects that occur in experiments on a laboratory dusty plasma, and with the shadow interaction caused by thermophoretic forces and Le Sage’s forces.

  1. Interacting Ghost Dark Energy Model: Dynamical System Analysis

    CERN Document Server

    Golchin, Hanif; Ebrahimi, Esmaeil

    2016-01-01

    We study the impacts of interaction between dark matter and dark energy in the context of ghost dark energy model. Using the dynamical system analysis, we obtain the fixed points of the system for different types of interactions while the universe is filled with radiation, matter (including dark matter and luminous matter) and dark energy components. We consider the stability of the fixed points in details for different cases. In all cases there is an unstable matter dominated epoch and a stable late time dark energy dominated phase. However, we find that adding the linear interaction, the evolution of ghost dark energy model does not contain the radiation dominated epoch in the early times which is a necessary point in any cosmic model. This failure resolved when we add the non-linear interaction to the model. We also find an upper bound for the value of the coupling constant of the interaction between dark matter and dark energy as b < 0.57 . This bound is necessary to have a decelerating and unstable ma...

  2. Ultra-high energy neutrino interactions and compositeness

    International Nuclear Information System (INIS)

    This paper reviews the arguments leading to the suggestion that muon-rich extensive air showers (EAS) and underground muon bursts associated with point sources in the sky may be caused by neutrinos rather than photons. If quarks and leptons possess a substructure with a characteristic energy scale Λ, neutrinos are capable of interacting with cross sections much larger than predicted by the standard model, once the CMS energy exceeds Λ. The authors give estimates of the energy and angular distributions of hard anomalous neutrino interactions. Experiments are suggested in order to distinguish between photon and neutrino primaries

  3. Computation of ab initio energy savings due to magnetic interactions

    Science.gov (United States)

    Munoz, Alexander; Wagner, Lucas

    The double-exchange mechanism is the traditional explanation for antiferromagnetic coupling between magnetic ions. In this theory, the energy savings within the context of a hopping model is derived from kinetic energy terms. However, the connection to ab initio energy savings to our knowledge has not been studied using an explicitly correlated theory that can obtain quantitative accuracy. Our study focuses on determining, from ab initio calculations, whether the origin of interactions in magnetic systems is explainable through conventional arguments. To this end, we investigate the contributions (kinetic, ionic, electron-electron) to the total energy of the (Mn-O-Mn)+2system using quantum Monte Carlo techniques. We will report on progress in elucidating the connection between the ab initio energy savings and the effective model energy savings that result in an antiferromagnetic interaction in this system. L.K. Wagner was supported by NSF DMR 1206242.

  4. Experimentally based contact energies decode interactions responsible for protein-DNA affinity and the role of molecular waters at the binding interface.

    Science.gov (United States)

    Temiz, N Alpay; Camacho, Carlos J

    2009-07-01

    A major obstacle towards understanding the molecular basis of transcriptional regulation is the lack of a recognition code for protein-DNA interactions. Using high-quality crystal structures and binding data on the promiscuous family of C(2)H(2) zinc fingers (ZF), we decode 10 fundamental specific interactions responsible for protein-DNA recognition. The interactions include five hydrogen bond types, three atomic desolvation penalties, a favorable non-polar energy, and a novel water accessibility factor. We apply this code to three large datasets containing a total of 89 C(2)H(2) transcription factor (TF) mutants on the three ZFs of EGR. Guided by molecular dynamics simulations of individual ZFs, we map the interactions into homology models that embody all feasible intra- and intermolecular bonds, selecting for each sequence the structure with the lowest free energy. These interactions reproduce the change in affinity of 35 mutants of finger I (R(2) = 0.998), 23 mutants of finger II (R(2) = 0.96) and 31 finger III human domains (R(2) = 0.94). Our findings reveal recognition rules that depend on DNA sequence/structure, molecular water at the interface and induced fit of the C(2)H(2) TFs. Collectively, our method provides the first robust framework to decode the molecular basis of TFs binding to DNA. PMID:19429892

  5. Very low-energy neutrino interactions

    International Nuclear Information System (INIS)

    Neutrino-nucleus reaction cross sections are now evaluated rather accurately by shell-model (SM) or SM+RPA calculations based on recent advances in nuclear structure studies. Due to these achievements, reliable constraints on super-nova neutrino temperatures as well as neutrino oscillation parameters become possible. Supernova neutrino tempeatures are constrained from abundances of elements obtained by using new ν-nucleus reaction cross sections. A possibility of constructing supernova neutrino spectrum from beta-beam measurements is pointed out. Neutrino mass hierarchy and mixing angle θ13 can be determined from abundance ratio of 7Li/11B, which is sensitive to the MSW matter oscillation effects in supernova explosions. Inverted mass hierarchy is shown to be statistically more favored based on a recent analysis of presolar grains. Effects of neutrino-neutrino interactions are also shown to play important roles in r-process nucleosynthesis. Importance and possibilities of direct measurements of ν-induced cross sections on 40Ar and 208Pb are discussed for future supernova neutrino detections. Recent calculations of the cross sections for ν-40Ar are presented. The need for new theoretical evaluations of the cross sections for ν-208Pb is pointed out. Challenges to experiments on coherent elastic scattering are presented

  6. Very low-energy neutrino interactions

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Toshio [Department of Physics and Graduate School of Integrated Basic Sciences, College of Humanities and Sciences, Nihon University, Sakurajosui 3-25-40, Setagaya-ku, Tokyo 156-8550 (Japan); Department of Physics and Graduate School of Integrated Basic Sciences, College of Humanities and Sciences, National Astronomical Observatory of Japan, Mitaka, Tokyo 181-8588 (Japan)

    2015-05-15

    Neutrino-nucleus reaction cross sections are now evaluated rather accurately by shell-model (SM) or SM+RPA calculations based on recent advances in nuclear structure studies. Due to these achievements, reliable constraints on super-nova neutrino temperatures as well as neutrino oscillation parameters become possible. Supernova neutrino tempeatures are constrained from abundances of elements obtained by using new ν-nucleus reaction cross sections. A possibility of constructing supernova neutrino spectrum from beta-beam measurements is pointed out. Neutrino mass hierarchy and mixing angle θ{sub 13} can be determined from abundance ratio of {sup 7}Li/{sup 11}B, which is sensitive to the MSW matter oscillation effects in supernova explosions. Inverted mass hierarchy is shown to be statistically more favored based on a recent analysis of presolar grains. Effects of neutrino-neutrino interactions are also shown to play important roles in r-process nucleosynthesis. Importance and possibilities of direct measurements of ν-induced cross sections on {sup 40}Ar and {sup 208}Pb are discussed for future supernova neutrino detections. Recent calculations of the cross sections for ν-{sup 40}Ar are presented. The need for new theoretical evaluations of the cross sections for ν-{sup 208}Pb is pointed out. Challenges to experiments on coherent elastic scattering are presented.

  7. Breaking parameter degeneracy in interacting dark energy models from observations

    OpenAIRE

    Xu, Xiao-Dong; He, Jian-Hua; Wang, Bin

    2011-01-01

    We study the interacting dark energy model with time varying dark energy equation of state. We examine the stability in the perturbation formalism and the degeneracy among the coupling between dark sectors, the time-dependent dark energy equation of state and dark matter abundance in the cosmic microwave background radiation. Further we discuss the possible ways to break such degeneracy by doing global fitting using the latest observational data and we get a tight constraint on the interactio...

  8. Early dark energy and its interaction with dark matter

    OpenAIRE

    Pu, Bo-Yu; Xu, Xiao-Dong; Wang, Bin; Abdalla, Elcio

    2014-01-01

    We study a class of early dark energy models which has substantial amount of dark energy in the early epoch of the universe. We examine the impact of the early dark energy fluctuations on the growth of structure and the CMB power spectrum in the linear approximation. Furthermore we investigate the influence of the interaction between the early dark energy and the dark matter and its effect on the structure growth and CMB. We finally constrain the early dark energy model parameters and the cou...

  9. Generalized dark energy interactions with multiple fluids

    CERN Document Server

    van de Bruck, Carsten; Mimoso, José P; Nunes, Nelson J

    2016-01-01

    In the search for an explanation for the current acceleration of the Universe, scalar fields are the most simple and useful tools to build models of dark energy. This field, however, must in principle couple with the rest of the world and not necessarily in the same way to different particles or fluids. We provide the most complete dynamical system analysis to date, consisting of a canonical scalar field conformally and disformally coupled to both dust and radiation. We perform a detailed study of the existence and stability conditions of the systems and comment on constraints imposed on the disformal coupling from Big-Bang Nucleosynthesis and given current limits on the variation of the fine-structure constant.

  10. Device interactions in reducing the cost of tidal stream energy

    International Nuclear Information System (INIS)

    Highlights: • Numerical modelling is used to estimate the levelised cost of tidal stream energy. • As a case study, a model of Lynmouth (UK) is implemented and successfully validated. • The resolution of the model allows the demarcation of individual devices on the model grid. • Device interactions reduce the available tidal resource and the cost increases significantly. - Abstract: The levelised cost of energy takes into account the lifetime generated energy and the costs associated with a project. The objective of this work is to investigate the effects of device interactions on the energy output and, therefore, on the levelised cost of energy of a tidal stream project, by means of numerical modelling. For this purpose, a case study is considered: Lynmouth (North Devon, UK), an area in the Bristol Channel in which the first tidal stream turbine was installed − a testimony of its potential as a tidal energy site. A state-of-the-art hydrodynamics model is implemented on a high-resolution computational grid, which allows the demarcation of the individual devices. The modification to the energy output resulting from interaction between turbines within the tidal farm is thus resolved for each individual turbine. The results indicate that significant changes in the levelised cost of energy values, of up to £0.221 kW h−1, occur due to the aforementioned modifications, which should not be disregarded if the cost of tidal stream energy is to be minimised

  11. Simulating two-dimensional infrared-Raman and Raman spectroscopies for intermolecular and intramolecular modes of liquid water

    Science.gov (United States)

    Ito, Hironobu; Tanimura, Yoshitaka

    2016-02-01

    Full classical molecular dynamics (MD) simulations of two-dimensional (2D) infrared-Raman and 2D Raman spectroscopies of liquid water were carried out to elucidate a mode-mode coupling mechanism using a polarizable water model for intermolecular and intramolecular vibrational spectroscopy (POLI2VS). This model is capable of describing both infrared and Raman spectra. Second-order response functions, which consist of one molecular polarizability and two molecular dipole moments for 2D IR-Raman and three molecular polarizabilities for 2D Raman spectroscopies, were calculated using an equilibrium-non-equilibrium hybrid MD approach. The obtained signals were analyzed using a multi-mode Brownian oscillator (BO) model with nonlinear system-bath interactions representing the intramolecular OH stretching, intramolecular HOH bending, hydrogen bonded (HB)-intermolecular librational motion and HB-intermolecular vibrational (translational) motion of liquid water. This model was applied through use of hierarchal Fokker-Planck equations. The qualitative features of the peak profiles in the 2D spectra obtained from the MD simulations are accurately reproduced with the BO model. This indicates that this model captures the essential features of the intermolecular and intramolecular motion. We elucidate the mechanisms governing the 2D signal profiles involving anharmonic mode-mode coupling, the nonlinearities of the polarizability and dipole moment, and the vibrational dephasing processes of liquid water even in the case that the 2D spectral peaks obtained from the MD simulation overlap or are unclear. The mode coupling peaks caused by electrical anharmonic coupling (EAHC) and mechanical anharmonic coupling (MAHC) are observed in all of the 2D spectra. We find that the strength of the MAHC between the OH-stretching and HB-intermolecular vibrational modes is comparable to that between the OH-stretching and HOH bending modes. Moreover, we find that this OH-stretching and HB-intermolecular vibrational coupling should be observed as off-diagonal cross peaks in the 2D spectra.

  12. Simulating two-dimensional infrared-Raman and Raman spectroscopies for intermolecular and intramolecular modes of liquid water.

    Science.gov (United States)

    Ito, Hironobu; Tanimura, Yoshitaka

    2016-02-21

    Full classical molecular dynamics (MD) simulations of two-dimensional (2D) infrared-Raman and 2D Raman spectroscopies of liquid water were carried out to elucidate a mode-mode coupling mechanism using a polarizable water model for intermolecular and intramolecular vibrational spectroscopy (POLI2VS). This model is capable of describing both infrared and Raman spectra. Second-order response functions, which consist of one molecular polarizability and two molecular dipole moments for 2D IR-Raman and three molecular polarizabilities for 2D Raman spectroscopies, were calculated using an equilibrium-non-equilibrium hybrid MD approach. The obtained signals were analyzed using a multi-mode Brownian oscillator (BO) model with nonlinear system-bath interactions representing the intramolecular OH stretching, intramolecular HOH bending, hydrogen bonded (HB)-intermolecular librational motion and HB-intermolecular vibrational (translational) motion of liquid water. This model was applied through use of hierarchal Fokker-Planck equations. The qualitative features of the peak profiles in the 2D spectra obtained from the MD simulations are accurately reproduced with the BO model. This indicates that this model captures the essential features of the intermolecular and intramolecular motion. We elucidate the mechanisms governing the 2D signal profiles involving anharmonic mode-mode coupling, the nonlinearities of the polarizability and dipole moment, and the vibrational dephasing processes of liquid water even in the case that the 2D spectral peaks obtained from the MD simulation overlap or are unclear. The mode coupling peaks caused by electrical anharmonic coupling (EAHC) and mechanical anharmonic coupling (MAHC) are observed in all of the 2D spectra. We find that the strength of the MAHC between the OH-stretching and HB-intermolecular vibrational modes is comparable to that between the OH-stretching and HOH bending modes. Moreover, we find that this OH-stretching and HB-intermolecular vibrational coupling should be observed as off-diagonal cross peaks in the 2D spectra. PMID:26896979

  13. Vibrational Spectra of β″-Type BEDT-TTF Salts: Relationship between Conducting Property, Time-Averaged Site Charge and Inter-Molecular Distance

    Directory of Open Access Journals (Sweden)

    Takashi Yamamoto

    2012-07-01

    Full Text Available The relationship between the conducting behavior and the degree of charge fluctuation in the β″-type BEDT-TTF salts is reviewed from the standpoints of vibrational spectroscopy and crystal structure. A group of β″-type ET salts demonstrates the best model compounds for achieving the above relationship because the two-dimensional structure is simple and great diversity in conducting behavior is realized under ambient pressure. After describing the requirement for the model compound, the methodology for analyzing the results of the vibrational spectra is presented. Vibrational spectroscopy provides the time-averaged molecular charge, the charge distribution in the two-dimensional layer, and the inter-molecular interactions, etc. The experimental results applied to 2/3-filled and 3/4-filled β″-type ET salts are reported. These experimental results suggest that the conducting property, the difference in the time-averaged molecular charges between the ionic and neutral-like sites, the alternation in the inter-molecular distances and the energy levels in the charge distributions are relevant to one another. The difference in the time-averaged molecular charges, ∆ρ, is a useful criterion for indicating conducting behavior. All superconductors presented in this review are characterized as small but finite ∆ρ.

  14. Strong interactions studies with medium energy probes

    International Nuclear Information System (INIS)

    This progress report refers to the period August 1992 to August 1993, which includes the first year of the three-year period December 1, 1992--November 30, 1995 of the existing research contract. As anticipated in the 1992--1995 proposal the major preoccupation during 1992--1993 was with Fermilab experiment E760. This experiment, whose primary objective is to make very high-resolution study of Charmonium Spectroscopy via proton-antiproton annihilations, has turned out to be a veritable gold-mine of exciting hadronic physics in other areas as well. These include the proton from factor in the time-life region, proton-antiproton forward scattering, QCD scaling laws, and light quark spectroscopy. A large fraction of the data from E760 have been analyzed during this year, and several papers have been published. In addition to the E760 experiment at Fermilab continued progress was made earlier nuclear physics-related experiments at LAMPF, MIT, and NIKHEF, and their results for publication. Topics include high- resolution electron scattering, quasi-free electron scattering and low-energy pion double charge exchange

  15. Interacting holographic dark energy in Brans-Dicke theory

    International Nuclear Information System (INIS)

    We study cosmological application of interacting holographic energy density in the framework of Brans-Dicke cosmology. We obtain the equation of state and the deceleration parameter of the holographic dark energy in a non-flat universe. As system's IR cutoff we choose the radius of the event horizon measured on the sphere of the horizon, defined as L=ar(t). We find that the combination of Brans-Dicke field and holographic dark energy can accommodate wD=-1 crossing for the equation of state of noninteracting holographic dark energy. When an interaction between dark energy and dark matter is taken into account, the transition of wD to phantom regime can be more easily accounted for than when resort to the Einstein field equations is made.

  16. Bulk-brane interaction and holographic dark energy

    International Nuclear Information System (INIS)

    In this Letter we consider the bulk-brane interaction to obtain the equation of state for the holographic energy density in non-flat universe enclosed by the event horizon measured from the sphere of horizon named L. We assume that the cold dark matter energy density on the brane is conserved, but the holographic dark energy density on the brane is not conserved due to brane-bulk energy exchange. Our calculation shows, taking ΩΛ=0.73 for the present time, the lower bound of wΛeff is -0.9. This implies that one cannot generate phantom-like equation of state from an interacting holographic dark energy model in non-flat universe

  17. Four-body long-range interactions between ultracold weakly-bound diatomic molecules

    Science.gov (United States)

    Lepers, M.; Qumner, G.; Luc-Koenig, E.; Dulieu, O.

    2016-01-01

    Using the multipolar expansion of electrostatic and magnetostatic potential energies, we characterize the long-range interactions between two weakly-bound diatomic molecules, taking as an example the paramagnetic Er2 Feshbach molecules which were produced recently. Since inside each molecule individual atoms conserve their identity, the intermolecular potential energy can be expanded as the sum of pairwise atomic potential energies. In the case of Er2 Feshbach molecules, we show that the interaction between atomic magnetic dipoles gives rise to the usual {R}-3 term of the multipolar expansion, where R is the intermolecular distance, but also to additional terms scaling as {R}-5, {R}-7, and so on. Those terms are due to the interaction between effective molecular multipole moments, and are strongly anisotropic with respect to the orientation of the molecules. Similarly, the atomic pairwise van der Waals interaction results in {R}-6, {R}-8, ... terms in the intermolecular potential energy. By calculating the reduced electric-quadrupole moment of erbium ground level =-1.305 a.u., we also demonstrate that the electricquadrupole interaction energy is negligible with respect to the magnetic dipole and van der Waals interaction energies. The general formalism presented in this article can be applied to calculate the long-range potential energy between arbitrary charge distributions composed of almost free subsystems.

  18. Does the Dark Energy Interact with the Ordinary Baryonic Matter?

    Science.gov (United States)

    Harutyunian, Haik

    2015-08-01

    The possible consequences resulted due to the interaction and energy exchange between the dark energy carrier and the ordinary baryonic matter is considered. We act on the premise that the acceleration of the Universe would be impossible if no such interaction did occur. Second point to be taken into account is the structural features of baryonic matter which consist of atoms with the most mass concentrated in their nuclei. On the other hand all the objects started with the atomic nuclei and up to planets and stars exist owing to their negative binding (nuclear or gravitational) energy. Then one should expect the objects made of baryonic matter to gain energy in average if the mentioned two substances really interact. Therefore the absolute value of binding energy seems to go down both for gravitationally bound objects and atomic nuclei, thus increasing their internal excessive energy and the probability of the spontaneous decay. Any self-consistent consideration based on the common physical concepts leads one to arrive at a conclusion that the gradual decrease of nuclear binding energy makes the mass of nucleons and nuclei should grow up. Moreover, due to the decrease of the nuclear binding energy the limit of instability or radioactivity gradually shifts towards the lighter nuclei. The cosmological consequences of such a possibility are considered in this report.

  19. Hadron diffractive scattering at ultrahigh energies and Coulomb interaction

    Science.gov (United States)

    Anisovich, V. V.; Nikonov, V. A.

    2016-03-01

    We study the interplay of hadronic and Coulomb interactions for pp scattering at LHC energies on the basis of the previous determination of the real part of the amplitude [V. V. Anisovich, V. A. Nikonov and J. Nyiri, Int. J. Mod. Phys. A 30, 1550188 (2015)]. The interference of hadron and Coulomb interactions is discussed in terms of the K-matrix function technique. Supposing the black disk mode for the asymptotic interaction of hadrons, we calculate interference effects for the energies right up to s = 106 TeV. It turns out that the real part of the amplitude is concentrated in the impact parameter space at the border of the black disk that results in a growth of interplay effects with the energy increase.

  20. Hadron diffractive scattering at ultrahigh energies and coulomb interaction

    CERN Document Server

    Anisovich, V V

    2016-01-01

    We study the interplay of hadronic and Coulomb interactions for $pp$ scattering at LHC energies on the basis of the previous determination of the real part of the amplitude [{\\it V.V. Anisovich, V.A. Nikonov, J. Nyiri}, Int. J. Mod. Phys. A{\\bf 30}, 1550188 (2015)]. The interference of hadron and Coulomb interactions is discussed in terms of the $K$-matrix function technique. Supposing the black disk mode for the asymptotic interaction of hadrons, we calculate interference effects for the energies right up to $\\sqrt{s}= 10^6$ TeV. It turns out that the real part of the amplitude is concentrated in the impact parameter space at the border of the black disk that results in a growth of interplay effects with the energy increase.

  1. New constraints on interacting dark energy from cosmic chronometers

    CERN Document Server

    Nunes, Rafael C; Saridakis, Emmanuel N

    2016-01-01

    We use the latest compilation of observational Hubble parameter measurements estimated with the differential evolution of cosmic chronometers, in combination with the local value of the Hubble constant recently measured with 2.4% precision, to constrain the cosmological scenario where dark energy interacts directly with the dark matter sector. To diminish the degeneracy between the parameters we additionally consider standard probes, such as Supernovae Type Ia from joint light curves (JLA) sample and Baryon Acoustic Oscillation distance measurements (BAO). Our analysis shows that the direct interaction between dark energy and dark matter is mildly favored. This result is in qualitative agreement with the results of other observational works, and the fact that it has been extracted using novel observational data acts as an additional argument in favor of interacting dark energy.

  2. On the Casimir Energy of Frequency Dependent Interactions

    CERN Document Server

    Graham, N; Weigel, H

    2014-01-01

    Vacuum polarization (or Casimir) energies can be straightforwardly computed from scattering data for static field configurations whose interactions with the fluctuating field are frequency independent. In effective theories, however,such interactions are typically frequency dependent. As a consequence, the relationship between scattering data and the Green's function is modified, which may or may not induce additional contributions to the vacuum polarization energy. We discuss several examples that naturally include frequency dependent interactions: (i) scalar electrodynamics with a static background potential, (ii) an effective theory that emerges from integrating out a heavy degree of freedom, and (iii) quantum electrodynamics coupled to a frequency dependent dielectric material. In the latter case, we argue that introducing dissipation as required by the Kramers-Kronig relations requires the consideration of the Casimir energy within a statistical mechanics formalism, while in the absence of dissipation we...

  3. Systematic Uncertainties in High-Energy Hadronic Interaction Models

    Science.gov (United States)

    Zha, M.; Knapp, J.; Ostapchenko, S.

    2003-07-01

    Hadronic interaction models for cosmic ray energies are uncertain since our knowledge of hadronic interactions is extrap olated from accelerator experiments at much lower energies. At present most high-energy models are based on Grib ov-Regge theory of multi-Pomeron exchange, which provides a theoretical framework to evaluate cross-sections and particle production. While experimental data constrain some of the model parameters, others are not well determined and are therefore a source of systematic uncertainties. In this paper we evaluate the variation of results obtained with the QGSJET model, when modifying parameters relating to three ma jor sources of uncertainty: the form of the parton structure function, the role of diffractive interactions, and the string hadronisation. Results on inelastic cross sections, on secondary particle production and on the air shower development are discussed.

  4. The Nuclear Tensor Interaction in Covariant Energy Density Functional

    OpenAIRE

    Jiang, Li Juan; Yang, Shen; Sun, Bao Yuan; Long, Wen Hui; Gu, Huai Qiang

    2014-01-01

    The origin of the nuclear tensor interaction in the covariant energy density functional (EDF) is presented in this work, associated with the Fock diagrams of Lorentz scalar and vector couplings. With this newly obtained relativistic formalism of the nuclear tensor interaction, more distinct tensor effects are found in the Fock diagrams of the Lorentz scalar and vector couplings, as compared to the Lorentz pseudo-vector and tensor channels. A unified and self-consistent treatment on both the n...

  5. Post-$Planck$ constraints on interacting vacuum energy

    OpenAIRE

    Wang, Yuting; Wands, David; Zhao, Gong-bo; Xu, Lixin(Institute of Theoretical Physics, School of Physics and Optoelectronic Technology, Dalian University of Technology, 116024, Dalian , People’s Republic of China)

    2014-01-01

    We present improved constraints on an interacting vacuum model using updated astronomical observations including the first data release from Planck. We consider a model with one dimensionless parameter, $\\alpha$, describing the interaction between dark matter and vacuum energy (with fixed equation of state $w=-1$). The background dynamics correspond to a generalised Chaplygin gas cosmology, but the perturbations have a zero sound speed. The tension between the value of the Hubble constant, $H...

  6. ?? production and multiple parton interactions at supercollider energies

    International Nuclear Information System (INIS)

    We extend previous calculations of direct charmonium production at large pT to SSC energies and then calculate the cross-section for ?? production due to multiple parton interactions in a single hadronic collision. We compare these results to standard ?? production considering such processes as qanti q/gg??? and discuss the possible utility of such events as a gauge of multiple parton interactions. (orig.)

  7. Interactions of Policies for Renewable Energy and Climate

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2011-07-01

    This paper explores the relationships between climate policy and renewable energy policy instruments. It shows that, even where CO2 emissions are duly priced, specific incentives for supporting the early deployment of renewable energy technologies are justified by the steep learning curves of nascent technologies. This early investment reduces costs in the longer term and makes renewable energy affordable when it needs to be deployed on a very large scale to fully contribute to climate change mitigation and energy security. The paper also reveals other noteworthy interaction effects of climate policy and renewable policy instruments on the wholesale electricity prices in deregulated markets, which open new areas for future research.

  8. Modelling transient energy release from molten fuel coolant interaction debris

    International Nuclear Information System (INIS)

    A simple model of transient energy release in a Molten Fuel Coolant Interaction is presented. A distributed heat transfer model is used to examine the effect of heat transfer coefficient, time available for rapid energy heat transfer and particle size on transient energy release. The debris is assumed to have an Upper Limit Lognormal distribution. Model predictions are compared with results from the SUW series of experiments which used thermite-generated uranium dioxide molybdenum melts released below the surface of a pool of water. Uncertainties in the physical principles involved in the calculation of energy transfer rates are discussed. (author)

  9. Wormhole solutions supported by interacting dark matter and dark energy

    OpenAIRE

    Folomeev, Vladimir; Dzhunushaliev, Vladimir

    2013-01-01

    We show that the presence of a nonminimal interaction between dark matter and dark energy may lead to a violation of the null energy condition and to the formation of a configuration with nontrivial topology (a wormhole). In this it is assumed that both dark matter and dark energy satisfy the null energy condition, a violation of which takes place only in the inner high-density regions of the configuration. This is achieved by assuming that, in a high-density environment, a nonminimal couplin...

  10. Bulk-Brane Interaction and Holographic Dark Energy

    OpenAIRE

    Setare, M.R.

    2006-01-01

    In this paper we consider the bulk-brane interaction to obtain the equation of state for the holographic energy density in non-flat universe enclosed by the event horizon measured from the sphere of horizon named $L$. We assumes that the cold dark matter energy density on the brane is conserved, but the holographic dark energy density on the brane is not conserved due to brane-bulk energy exchange. Our calculation show, taking $\\Omega_{\\Lambda}=0.73$ for the present time, the lower bound of $...

  11. Simulated galaxy interactions as probes of merger spectral energy distributions

    Energy Technology Data Exchange (ETDEWEB)

    Lanz, Lauranne; Zezas, Andreas; Smith, Howard A.; Ashby, Matthew L. N.; Fazio, Giovanni G.; Hernquist, Lars [Harvard-Smithsonian Center for Astrophysics, 60 Garden St., Cambridge, MA 02138 (United States); Hayward, Christopher C. [Heidelberger Institut für Theoretische Studien, Schloss-Wolfsbrunnenweg 35, D-69118 Heidelberg (Germany); Brassington, Nicola, E-mail: llanz@ipac.caltech.edu [School of Physics, Astronomy and Mathematics, University of Hertfordshire, College Lane, Hatfield, AL10 9AB (United Kingdom)

    2014-04-10

    We present the first systematic comparison of ultraviolet-millimeter spectral energy distributions (SEDs) of observed and simulated interacting galaxies. Our sample is drawn from the Spitzer Interacting Galaxy Survey and probes a range of galaxy interaction parameters. We use 31 galaxies in 14 systems which have been observed with Herschel, Spitzer, GALEX, and 2MASS. We create a suite of GADGET-3 hydrodynamic simulations of isolated and interacting galaxies with stellar masses comparable to those in our sample of interacting galaxies. Photometry for the simulated systems is then calculated with the SUNRISE radiative transfer code for comparison with the observed systems. For most of the observed systems, one or more of the simulated SEDs match reasonably well. The best matches recover the infrared luminosity and the star formation rate of the observed systems, and the more massive systems preferentially match SEDs from simulations of more massive galaxies. The most morphologically distorted systems in our sample are best matched to the simulated SEDs that are close to coalescence, while less evolved systems match well with the SEDs over a wide range of interaction stages, suggesting that an SED alone is insufficient for identifying the interaction stage except during the most active phases in strongly interacting systems. This result is supported by our finding that the SEDs calculated for simulated systems vary little over the interaction sequence.

  12. Reconstruction of interacting dark energy models from parametrizations

    International Nuclear Information System (INIS)

    Models with interacting dark energy can alleviate the cosmic coincidence problem by allowing dark matter and dark energy to evolve in a similar fashion. At a fundamental level, these models are specified by choosing a functional form for the scalar potential and for the interaction term. However, in order to compare to observational data it is usually more convenient to use parametrizations of the dark energy equation of state and the evolution of the dark matter energy density. Once the relevant parameters are fitted, it is important to obtain the shape of the fundamental functions. In this paper I show how to reconstruct the scalar potential and the scalar interaction with dark matter from general parametrizations. I give a few examples and show that it is possible for the effective equation of state for the scalar field to cross the phantom barrier when interactions are allowed. I analyze the uncertainties in the reconstructed potential arising from foreseen errors in the estimation of fit parameters and point out that a Yukawa-like linear interaction results from a simple parametrization of the coupling

  13. Partonic description of soft high energy pp interactions

    CERN Document Server

    Martin, A D; Ryskin, M G

    2012-01-01

    We discuss how the main features of high-energy `soft' and `semihard' pp collisions may be described in terms of parton cascades and multi-Pomeron exchange. The interaction between Pomerons produces an effective infrared cutoff, k_sat, by the absorption of low k_t partons. This provides the possibility of extending the parton approach, used for `hard' processes, to also describe high-energy soft and semihard interactions. We outline a model which incorporates these features. Finally, we discuss what the most recent LHC measurements in the soft domain imply for the model.

  14. Soft Interactions at High Energies: Amplitudes and Cross-Sections

    Science.gov (United States)

    Gotsman, Errol

    2015-05-01

    I briefly specify elements of the GLM model that successfully describes soft hadronic interactions at energies from ISR to LHC. The model is based on a single Pomeron with a large intercept ΔIP = 0.23 and slope α'IP= 0.028, and so provides a natural matching with perturbative QCD. I analyze the elastic, single diffractive and double diffractive amplitudes, and compare the behaviour of the GLM amplitudes to those of other parameterizations. I then summarize the main features and results of the GLM model and compare with those of the Kaidalov-Poghosyan and other models for soft interactions at high energies.

  15. Constraints on interacting Dark Energy models from galaxy rotation curves

    International Nuclear Information System (INIS)

    Interacting Dark Energy models have been introduced as a possible alternative to the standard ?CDM concordance cosmological scenario in order to ease the fine-tuning problems of the cosmological constant. However, the interaction of the Dark Energy field with other massive particles in the universe induces also an effective modification of structure formation processes, leading to a different dynamical behavior of density perturbations with respect to the standard scenario. In particular, high-resolution N-body simulations have recently shown that also the structural properties of highly nonlinear objects, as e.g. their average concentration at a given mass, could be significantly modified in the presence of an interaction between Dark Energy and Dark Matter. While a constant interaction strength leads to less concentrated density profiles, a steep growth in time of the coupling function has been shown to determine a large increase of halo concentrations over a wide range of masses, including the typical halos hosting luminous spiral galaxies. This determines a substantial worsening of the 'cusp-core' tension arising in the standard ?CDM model and provides a direct way to constrain the form of the Dark Energy interaction. In the present paper we make use of the outcomes of some high-resolution N-body simulations of a specific class of interacting Dark Energy models to compare the predicted rotation curves of luminous spiral galaxies forming in these cosmologies against real observational data. Our results show how some specific interacting Dark Energy scenarios featuring a steep growth in time of the coupling function which are virtually indistinguishable from ?CDM in the background cannot fit the observed rotation curves of luminous spiral galaxies and can therefore be ruled out only on the basis of dynamical properties of small-scale structures. Our study is a pilot investigation of the effects of a Dark Energy interaction at small scales, and demonstrates how the dynamical properties of visible galaxies can in some cases provide direct constraints on the nature of Dark Energy

  16. Correlation energies in the random phase approximation using realistic interactions

    CERN Document Server

    Barbieri, C; Papakonstantinou, P; Roth, R

    2006-01-01

    The self-consistent random phase approximation (RPA) based on a correlated realistic nucleon-nucleon interaction is used to evaluate correlation energies in closed-shell nuclei beyond the Hartree-Fock level. The relevance of contributions associated with charge exchange excitations as well as the necessity to correct for the double counting of the second order contribution to the RPA ring summation are emphasized. Once these effects are properly accounted for, the RPA ring summation provides an efficient tool to assess the impact of long-range correlations on binding energies throughout the whole nuclear chart, which is of particular importance when starting from realistic interactions.

  17. Elastic energy of the flux lines in the matter. The interaction energy

    International Nuclear Information System (INIS)

    A theoretical treatment of the interaction between the bodies, by using the elastic coupling through the flux lines, is presented. We show that the elastic coupling through the flux lines gives an interaction energy between two superconductor or magnetic pieces, which is inversely proportional to the distance between the two bodies. We extend this concept to the gravitational and electrical interaction. For the electrical interaction one obtains that the statics interaction energy is inversely proportional to the distance between the charges, as in the Coulomb's law, while the oscillatory interaction is inversely proportional to the third power of the distance between the charged particles. This means that at shorter distance an attraction between the two charged particles of the same sign, may appear if the oscillatory energy of interaction is larger than the statics energy of interaction. In addition, the oscillatory interaction appears only as a virtual process. We apply these results to the deuteron and to the electron pairs in superconductors. Also, for the gravitation one obtains that the interaction energy is inversely proportional to the distance between the centers of the two bodies as in Newton's law. (author)

  18. Intermolecular Casimir-Polder Forces in Water and near Surfaces

    CERN Document Server

    Thiyam, Priyadarshini; Sernelius, Bo E; Parsons, Drew F; Malthe-Sørenssen, Anders; Boström, Mathias

    2014-01-01

    The Casimir-Polder force is an important long range interaction involved in adsorption and desorption of molecules in fluids. We explore Casimir-Polder interactions between methane molecules in water, and between a molecule in water near SiO2 and hexane surfaces. Inclusion of the finite molecular size in the expression for the Casimir-Polder energy leads to estimates of the dispersion contribution to the binding energies between molecules and between one molecule and a planar surface.

  19. Intermolecular Casimir-Polder forces in water and near surfaces

    OpenAIRE

    Thiyam, Priyadarshini; Persson, Clas; Sernelius, Bo; Parsons, Drew F.; Malthe-Sorenssen, Anders; Bostrom, Mathias

    2014-01-01

    The Casimir-Polder force is an important long-range interaction involved in adsorption and desorption of molecules in fluids. We explore Casimir-Polder interactions between methane molecules in water, and between a molecule in water near SiO2 and hexane surfaces. Inclusion of the finite molecular size in the expression for the Casimir-Polder energy leads to estimates of the dispersion contribution to the binding energies between molecules and between one molecule and a planar surface.

  20. Electron-gas plus damped-dispersion model for intermolecular forces: the rare-gas and H2-He, H2-Ne, and H2-Ar potentials

    International Nuclear Information System (INIS)

    The modified Gordon-Kim (MGK) electron-gas model for the calculation of the short-range repulsive interactions between closed-shell atoms and molecules is used with a damped-dispersion term of a form suggested by Hepburn et al. to calculate the intermolecular potentials between the rare-gas atoms and H2-He, H2-Ne, and H2-Ar. The damping function for the dispersion energies is found by comparison with the experimental Ar-Ar potential and is then used without change for all other interactions. Except for interactions involving Ne atoms, the results for the atom-atom interactions are uniformly quite good, with an average deviation from experiment in the position of the minimum (neglecting those involving Ne atoms) of only 0.7%. Both the radical V0(r) and anisotropic V2(r) terms of the atom-molecule results are compared with experiment. The calculated V0(r) potentials for He-H2 and Ar-H2 show close agreement with experiment, though the V2 terms are less well determined. All interactions involving Ne atoms are too repulsive. The errors in the potentials involving Ne atoms are attributed to errors in the treatment of the exchange energy in the MGK model. 29 references, 11 figures, 5 tables

  1. Transition of the dark energy equation of state in an interacting holographic dark energy model

    International Nuclear Information System (INIS)

    A model of holographic dark energy with an interaction with matter fields has been investigated. Choosing the future event horizon as an IR cutoff, we have shown that the ratio of energy densities can vary with time. With the interaction between the two different constituents of the universe, we observed the evolution of the universe, from early deceleration to late time acceleration. In addition, we have found that such an interacting dark energy model can accommodate a transition of the dark energy from a normal state where wD>-1 to wD<-1 phantom regimes. Implications of interacting dark energy model for the observation of dark energy transition has been discussed

  2. Making Energy Interventions more Effective : Situation, Interaction, and Precondition

    OpenAIRE

    Henning, Annette

    2015-01-01

    A main purpose of this paper is to propose to policy makers, building professionals, and other non-social scientists a way to make energy interventions more culturally informed and, thereby, more effective. The case study on house purchasers gives an ample illustration of the richer results that can be achieved by paying attention to three aspects of energy efficiency initiatives: the contexts and situations of choice in each particular case, the interaction among relevant social actors, and ...

  3. The Interaction of Emissions Trading and Renewable Energy Promotion

    OpenAIRE

    Abrell, Jan; Weigt, Hannes

    2008-01-01

    Given the ambitious goal of the European Union to achieve CO2 emission reduction, support to renewable energies, and increased energy efficiency a portfolio of different policies is going to be implemented or is already in place in the member states. These instruments have at least partly overlapping objectives; thus, a high degree of interaction is to be expected. In this paper we analyze how the EU ETS and renewable support mechanisms influence one another. We apply a static open economy co...

  4. Reconstruction of the dark matter-vacuum energy interaction

    OpenAIRE

    Wang, Yuting; Zhao, Gong Bo; Wands, David; Pogosian, Levon; Crittenden, Robert G.

    2015-01-01

    An interaction between the vacuum energy and dark matter is an intriguing possibility which may offer a way of solving the cosmological constant problem. Adopting a general prescription for momentum exchange between the two dark components, we reconstruct $\\alpha(a)$, the temporal evolution of the coupling strength between dark matter and vacuum energy, in a nonparametric Bayesian approach using combined observational data sets from the cosmic microwave background, supernovae and large scale ...

  5. Hadron spectra from high energy proton proton interactions

    Energy Technology Data Exchange (ETDEWEB)

    Diebold, R.; /Argonne; Guerriero, L.; /Bari U.; Lanou, R.; /Brown U.; Cocconi, G.; /CERN; Gittelman, B.; Loh, E.; /Cornell U., Phys. Dept.; Friedman, J.; Kendall, H.; Rosenson, L.; /MIT; Awschalom, M.; Billinge, R.; Brenner, A.E.; Juhala, R.; Peters, R.; Read, A.L.; Reardon, P.J.; Schievell, J.F.; Shafer, R.; White, T.O.; /Fermilab

    1970-06-01

    It is proposed to measure the hadron spectra resulting from high energy proton-proton collisions using a single arm focusing spectrometer. These measurements will provide elastic and inelastic P-P cross sections for incident beam energies up to 200 GeV/c and for momentum transfers |t| from 0.01 up to about 10 to 15 (BeV/c){sup 2}. In addition, they will obtain yields of pions and kaons produced in the interactions.

  6. Self-interaction errors in nuclear energy density functionals

    OpenAIRE

    Chamel, N.

    2010-01-01

    When applied to a single nucleon, nuclear energy density functionals may yield a non-vanishing internal energy thus implying that the nucleon is interacting with itself. It is shown how to avoid this unphysical feature for semi-local phenomenological functionals containing all possible bilinear combinations of local densities and currents up to second order in the derivatives. The method outlined in this Rapid Communication could be easily extended to functionals containing higher order terms...

  7. Interactions between renewable energy policy and renewable energy industrial policy: A critical analysis of China's policy approach to renewable energies

    International Nuclear Information System (INIS)

    This paper analyzes China's policy approach to renewable energies and assesses how effectively China has met the ideal of appropriate interactions between renewable energy policy and renewable energy industrial policy. First we briefly discuss the interactions between these two policies. Then we outline China's key renewable energy and renewable industrial policies and find that China's government has well recognized the need for this policy interaction. After that, we study the achievements and problems in China's wind and solar PV sector during 2005–2012 and argue that China's policy approach to renewable energies has placed priority first on developing a renewable energy manufacturing industry and only second on renewable energy itself, and it has not effectively met the ideal of appropriate interactions between renewable energy policy and renewable energy industrial policy. Lastly, we make an in-depth analysis of the three ideas underlying this policy approach, that is, the green development idea, the low-carbon leadership idea and indigenous innovation idea. We conclude that Chinas' policy approach to renewable energies needs to enhance the interactions between renewable energy policy and renewable energy industrial policy. The paper contributes to a deeper understanding of China's policy strategy toward renewable energies. -- Highlights: •Interactions between renewable energy policy and renewable energy industrial policy are discussed. •China's key renewable energy and renewable energy industrial policies are outlined. •Two empirical cases illustrate China's policy approach to renewable energies. •We argue that China needs to enhance the interactions between the two policies. •Three ideas underlie China's policy approach to renewable energies

  8. Experimental studies of pion-nucleus interactions at intermediate energies

    International Nuclear Information System (INIS)

    This report summarizes the work on experimental research in intermediate energy nuclear physics carried out at New Mexico State University in 1991 under a great from the US Department of Energy. Most of these studies have involved investigations of various pion-nucleus interactions. The work has been carried out both with the LAMPF accelerator at the Los Alamos National Laboratory and with the cyclotron at the Paul Scherrer Institute (PSI) near Zurich, Switzerland. Part of the experimental work involves measurements of new data on double-charge-exchange scattering, using facilities at LAMPF which we helped modify, and on pion absorption, using a new detector system at PSI that covers nearly the full solid-angle region which we helped construct. Other work involved preparation for future experiments using polarized nuclear targets and a new high-resolution spectrometer system for detecting π0 mesons. We also presented several proposals for works to be done in future years, involving studies related to pi-mesonic atoms, fundamental pion-nucleon interactions, studies of the difference between charged and neutral pion interactions with the nucleon, studies of the isospin structure of pion-nucleus interactions, and pion scattering from polarized 3He targets. This work is aimed at improving our understanding of the pion-nucleon interaction, of the pion-nucleus interaction mechanism, and of nuclear structure

  9. Colloid interaction energies for physically and chemically heterogeneous porous media

    Science.gov (United States)

    The mean and variance of the colloid interaction energy (phi*) as a function of separation distance (h) were calculated on physically and/or chemically heterogeneous solid surfaces at the representative elementary area (REA) scale. Nanoscale roughness was demonstrated to have a significant influence...

  10. Reconstruction of interacting dark energy models from parameterizations

    CERN Document Server

    Rosenfeld, Rogerio

    2008-01-01

    Models with interacting dark energy can alleviate the cosmic coincidence problem by allowing dark matter and dark energy to evolve in a similar fashion. At a fundamental level, these models are specified by choosing a functional form for the scalar potential and for the interaction term. However, in order to compare to observational data it is usually more convenient to use parameterizations of the dark energy equation of state and the evolution of the dark matter energy density. Once the relevant parameters are fitted it is important to obtain the shape of the fundamental functions. In this paper I show how to reconstruct the scalar potential and the scalar interaction with dark matter from general parameterizations. I give a few examples and show that it is possible for the effective equation of state for the scalar field to cross the phantom barrier when interactions are allowed. I analyze the uncertainties in the reconstructed potential arising from foreseen errors in the estimation of fit parameters and ...

  11. MINT - A Simple Model for Low Energy Hadronic Interactions

    CERN Document Server

    Schmelling, M

    2005-01-01

    The bulk of inelastic hadronic interactions is characterized by longitudinal phase space and exponentially damped transverse momentum spectra. A simple model with only a single adjustable parameter is presented, making it a very convenient tool for systematic studies, which gives a surprisingly good description of pA-collisions at 920 GeV beam energy.

  12. Polarization phenomena in electromagnetic interactions at intermediate energies

    Energy Technology Data Exchange (ETDEWEB)

    Burkert, V.

    1990-01-01

    Recent results of polarization measurements in electromagnetic interactions at intermediate energies are discussed. Prospects of polarization experiments at the new CW electron accelerators, as well as on upgraded older machines are outlined. It is concluded that polarization experiments will play a very important role in the study of the structure of the nucleon and of light nuclei. 72 refs.

  13. Dimensionality of Local Minimizers of the Interaction Energy

    KAUST Repository

    Balagué, D.

    2013-05-22

    In this work we consider local minimizers (in the topology of transport distances) of the interaction energy associated with a repulsive-attractive potential. We show how the dimensionality of the support of local minimizers is related to the repulsive strength of the potential at the origin. © 2013 Springer-Verlag Berlin Heidelberg.

  14. Dancing Crystals: A Dramatic Illustration of Intermolecular Forces

    Science.gov (United States)

    Mundell, Donald W.

    2007-01-01

    Crystals of naphthalene form on the surface of an acetone solution and dance about in an animated fashion illustrating surface tension, crystallization, and intermolecular forces. Additional experiments reveal the properties of the solution. Flows within the solutions can be visualized by various means. Previous demonstrations of surface motion

  15. Intermolecular Silacarbonyl Ylide Cycloadditions: A Direct Pathway to Oxasilacyclopentenes

    Science.gov (United States)

    Bourque, Laura E.; Woerpel, K. A.

    2009-01-01

    Silacarbonyl ylides, generated by metal-catalyzed silylene transfer to carbonyls, participate in formal intermolecular 1,3-dipolar cycloaddition reactions with carbonyl compounds and alkynes to form dioxasilacyclopentane acetals and oxasilacyclopentenes in an efficient, one-step process. PMID:18922005

  16. A single model of interacting dark energy: generalized phantom energy or generalized Chaplygin gas

    OpenAIRE

    Jamil, Mubasher

    2009-01-01

    I present a model in which dark energy interacts with matter. The former is represented by a variable equation of state. It is shown that the phantom crossing takes place at zero redshift, moreover, stable scaling solution of the Friedmann equations is obtained. I show that dark energy is most probably be either generalized phantom energy or the generalized Chaplygin gas.

  17. Interactions of quarks and gluons with nuclei at intermediate energies

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, A.H. [Columbia Univ., New York, NY (United States)

    1994-04-01

    Some processes involving the interaction of medium energy quarks and gluons with nuclear matter are described. Possible mechanisms for the A-dependence of the energy loss of leading protons produced in proton-nucleus collisions are given, and an experiment which may help to distinguish these mechanisms is described. A possible color transparency experiment at CEBAF is described. Experiments to measure energy loss of quarks in nuclear matter and the formation time of hadrons are discussed along with the possibilities of measuring {sigma}{sub J}/{psi} and {sigma}{sub {psi}{prime}} at CEBAF.

  18. Schematic potential energy for interaction between isobutene and zeolite mordenite

    International Nuclear Information System (INIS)

    A schematic representation of the potential energy for the interaction between isobutene and H mordenite was presented by using eight different positions (P1-P8) of C1 or C2 atoms located in front of the acid hydrogen (H+). In all cases a π complex was formed yielding different values of the adsorption energy. In some cases of the adsorption point in P1-P8 the frontier orbitals are shown. The P8 position exhibits the highest value obtained for the adsorption energy, where the C1 atom is in front of the H+. Calculations were of all electron type employing HF/6-31G**

  19. Energies and pressures in viruses: contribution of nonspecific electrostatic interactions

    CERN Document Server

    Šiber, Antonio; Podgornik, Rudolf

    2011-01-01

    We summarize some aspects of electrostatic interactions in the context of viruses. A simplified but, within well defined limitations, reliable approach is used to derive expressions for electrostatic energies and the corresponding osmotic pressures in single-stranded RNA viruses and double-stranded DNA bacteriophages. The two types of viruses differ crucially in the spatial distribution of their genome charge which leads to essential differences in their free energies, depending on the capsid size and total charge in a quite different fashion. Differences in the free energies are trailed by the corresponding characteristics and variations in the osmotic pressure between the inside of the virus and the external bathing solution.

  20. The interaction between dark energy and dark matter

    International Nuclear Information System (INIS)

    In this review we first present a general formalism to study the growth of dark matter perturbations in the presence of interactions between dark matter(DM) and dark energy(DE). We also study the signature of such interaction on the temperature anisotropies of the large scale cosmic microwave background (CMB). We find that the effect of such interaction has significant signature on both the growth of dark matter structure and the late Integrated Sachs Wolfe effect(ISW). We further discuss the potential possibility to detect the coupling by cross-correlating CMB maps with tracers of the large scale structure. We finally confront this interacting model with WMAP 5-year data as well as other data sets. We find that in the 1? range, the constrained coupling between dark sectors can solve the coincidence problem.

  1. Interacting Generalized Ghost Dark Energy in Non-isotropic Background

    Science.gov (United States)

    Barati, F.

    2016-04-01

    In this work, the generalized Quantum Chromodynamics (QCD) ghost model of dark energy in the framework of Einstein gravity is investigated. At first, the non-interacting generalized ghost dark energy in a Bianchi type I (BI) background is discussed. Then the equation of state parameter, ω D = p D / ρ D , the deceleration parameter, and the evolution equation of the generalized ghost dark energy are obtained. It was found that, in this case, ω D cannot cross the phantom line (ω D >-1) and eventually the universe approaches a de-Sitter phase of expansion (ω D →-1). Then, this investigation was extended to the interacting ghost dark energy in a non-isotropic universe. It was found that the equation of state parameter of the interacting generalized ghost dark energy can cross the phantom line (ω D <-1) provided the parameters of the model are chosen suitably. It was considered a specific model which permits the standard continuity equation in this theory. Besides ΩΛ and Ω m in standard Einstein cosmology, another density parameter, Ω σ , is expected by the anisotropy. The anisotropy of the universe decreases and the universe transits to an isotropic flat FRW universe accommodating the present acceleration.

  2. Effective low-energy Hamiltonians for interacting nanostructures

    Science.gov (United States)

    Kinza, Michael; Ortloff, Jutta; Honerkamp, Carsten

    2010-10-01

    We present a functional renormalization group (fRG) treatment of trigonal graphene nanodisks and composites thereof, modeled by finite-size Hubbard-like Hamiltonians with honeycomb lattice structure. At half filling, the noninteracting spectrum of these structures contains a certain number of half-filled states at the Fermi level. For the case of trigonal nanodisks, including interactions between these degenerate states was argued to lead to a large ground state spin with potential spintronics applications [M. Ezawa, Eur. Phys. J. B 67, 543 (2009)10.1140/epjb/e2009-00041-7]. Here we perform a systematic fRG flow where the excited single-particle states are integrated out with a decreasing energy cutoff, yielding a renormalized low-energy Hamiltonian for the zero-energy states that includes effects of the excited levels. The numerical implementation corroborates the results obtained with a simpler Hartree-Fock treatment of the interaction effects within the zero-energy states only. In particular, for trigonal nanodisks the degeneracy of the one-particle-states with zero energy turns out to be protected against influences of the higher levels. As an explanation, we give a general argument that within this fRG scheme the zero-energy degeneracy remains unsplit under quite general conditions and for any size of the trigonal nanodisk. We also discuss a second class of nanostructures, bow-tie-shaped systems, where the zero-energy states are not protected.

  3. Reconstruction of the dark matter-vacuum energy interaction

    CERN Document Server

    Wang, Yuting; Wands, David; Pogosian, Levon; Crittenden, Robert G

    2015-01-01

    An interaction between the vacuum energy and dark matter is an intriguing possibility which may offer a way of solving the cosmological constant problem. Adopting a general prescription for momentum exchange between the two dark components, we reconstruct the temporal evolution of the coupling strength between dark matter and vacuum energy, $\\alpha(a)$ in a non-parametric Bayesian approach using the combined observational datasets from the cosmic microwave background, supernovae and large scale structure. An evolving interaction between the vacuum energy and dark matter removes some of the tensions between different types of datasets, and is favoured at $\\sim95\\%$ CL if we include the baryon acoustic oscillations measurements of the BOSS Lyman-$\\alpha$ forest sample.

  4. Equilibrium surface tension and the interaction energy of DMSO with tert-butyl alcohol or iso-amyl alcohol at various temperatures

    International Nuclear Information System (INIS)

    Highlights: • Surface tension of non-ideal binary systems of alcohol/DMSO determined. • The surface tension data of binary mixtures were correlated with five equations. • The interaction energy values were calculated by using LWW model. • The U12 value shows different behavior for two systems with increasing temperature. - Abstract: Surface tension of binary mixtures of tert-butyl alcohol (TBA) and iso-amyl alcohol (IAA) with DMSO (dimethyl sulfoxide) were measured over the entire concentration range at pressure of 82.5 kPa at temperatures between (298.15 and 328.15) K. Correlating the surface tension and surface tension deviation of the above mentioned binary systems was performed with empirical and thermodynamic based models. The average relative error obtained from the comparison of experimental and calculated surface tension values for the two binary systems with five models at various temperatures is less than 2%. The effect of temperature on the interaction energy values in binary mixtures has been used to obtain information about solute structural effects on DMSO. Also, the experimental data were used to evaluate the nature and type of intermolecular interactions in binary mixtures

  5. Inelastic interactions of high energy particles with nuclei

    International Nuclear Information System (INIS)

    Problems of inelastic interaction of high energy particles (protons, pions etc.) with nuclei: are discussed in the lecture. Main attention is paid to phenomena related to the growth of lengths of secondary particle production at high energies. Multiperipheral parton model data are used. Three models of hadron multiple production on nuclei are considered and compared: dominance model of fan-shaped diagrams (DMED) eikonal model (EM), based on the Glanber multiple scattering theory and additive quark model (AQM), which to some extent is a synthesis of the first two models. The above models differ in describing spacetime picture of interaction process. In DMED the absence of leading particle rescattering and presence of cascade of secondary particles of moderate energy are noted. Successive rescattering of leading particles at complete absence of the cascade of secondary particles is investigated in the framework of the EM. Both types of rescattering exist in the AQM determined by quark state of initial and secondary particles. Two-part correlations are studied in particle production on nuclei, correlations in jets etc. It is shown that all known experimental data can be described in the framework of multiperipheral parton model of strong interactions. The AQM complemented by the conception of production lengths provides a perfect quantitative description of inclusive spectra in hadron-nuclei as well as in lepton-nuclei interactions

  6. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  7. Six-dimensional calculation of intermolecular states in molecule-large molecule complexes by filter diagonalization: Benzene - H2O

    International Nuclear Information System (INIS)

    We present an approach toward the dynamically exact calculation of intermolecular states in molecule-large molecule complexes. The approach employs an intermolecular Hamiltonian specifically formulated with the case of molecule-large molecule complexes in mind. In addition, it makes use of filter diagonalization techniques to diagonalize that Hamiltonian. The approach is applied to the calculation of J=0 intermolecular states below about 110 cm-1 in the benzene -H2O complex. The results of the calculation are interpreted in terms of five internal rotation states, a doubly degenerate bending mode and a singly degenerate stretching mode, the latter two modes involving the relative translation of the monomer moieties in the complex. The internal rotation states are discussed in the context of the two-dimensional, free internal rotation/water in-plane torsion model of Pribble et al. [J. Chem. Phys. 103, 531 (1995)]. It is shown that that model is largely successful in identifying the important features of the low-energy benzene - H2O states that involve rotation and/or libration of water. It is also shown, though, that multimode couplings can have major effects on the detailed nature of the intermolecular level structure of the species. copyright 1999 American Institute of Physics

  8. Mutually interacting tachyon dark energy with variable G and Λ

    Science.gov (United States)

    Sadeghi, Jafar; Khurshudyan, Martiros; Hakobyan, Margarit; Farahani, Hoda

    2015-02-01

    We consider a tachyonic scalar field as a model of dark energy with interaction between components in the case of variable G and Λ. We assume a flat Universe with a specific form of scale factor and study cosmological parameters numerically and graphically. Statefinder analysis is also performed. For a particular choice of interaction parameters we succeed in obtaining an analytical expression of densities. We find that our model will be stable at the late stage but there is an instability in the early Universe, so we propose this model as a realistic model of our Universe.

  9. Contemporary models of high energy interactions: present status and perspectives

    Science.gov (United States)

    Ostapchenko, S. S.

    2003-05-01

    Modern approaches to the description of high energy hadronic and nuclear collisions are reviewed in connection with extensive air shower (EAS) physics. Special attention is devoted to the so-called semihard partonic processes which appear to dominate the interactions at very high energies. It is shown that a corresponding treatment can be developed in the framework of the Gribov-Regge approach, introducing a concept of 'semihard Pomeron', the latter being a t-channel iteration of the phenomenological 'soft' Pomeron and QCD parton ladder. A comparison is made with the QCD eikonal (mini-jet) scheme and essential differences as well as observable consequences for EAS development are analysed in detail. The role of nonlinear interaction contributions described by enhanced Pomeron diagrams is also investigated. It is demonstrated that such diagrams provide important screening corrections to the interaction mechanism and allow us to resolve a seeming contradiction between realistic parton momentum distributions and observed energy dependence of hadron-hadron cross sections. A modification of the standard scheme by correct treatment of energy-momentum sharing mechanism in hadronic collisions is also considered. Finally, we discuss possible ways to discriminate between the alternative approaches.

  10. Proton tunnelling in intermolecular hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Horsewill, A.J. [Nottingham Univ. (United Kingdom); Johnson, M.R. [Institut Max von Laue - Paul Langevin (ILL), 38 - Grenoble (France); Trommsdorff, H.P. [Grenoble-1 Univ., 38 (France)

    1997-04-01

    The wavefunctions of particles extend beyond the classically accessible regions of potential energy-surfaces (PES). A manifestation of this partial delocalization is the quantum-mechanical tunneling effect which enables a particle to escape from a metastable potential-well. Tunnelling is most important for the lightest atoms, so that the determination of its contribution to proton transfer, one of the most fundamental chemical reactions, is an important issue. QENS and NMR techniques have been employed to study the motion of protons in the hydrogen bond of benzoic-acid crystals, a system which has emerged as a particularly suitable model since proton transfer occurs in a near symmetric double-well potential. The influence of quantum tunnelling was revealed and investigated in these experiments. This work provides an experimental benchmark for theoretical descriptions of translational proton-tunnelling. (author). 7 refs.

  11. Accurate nuclear radii and binding energies from a chiral interaction

    CERN Document Server

    Ekstrom, A; Wendt, K A; Hagen, G; Papenbrock, T; Carlsson, B D; Forssen, C; Hjorth-Jensen, M; Navratil, P; Nazarewicz, W

    2015-01-01

    The accurate reproduction of nuclear radii and binding energies is a long-standing challenge in nuclear theory. To address this problem two-nucleon and three-nucleon forces from chiral effective field theory are optimized simultaneously to low-energy nucleon-nucleon scattering data, as well as binding energies and radii of few-nucleon systems and selected isotopes of carbon and oxygen. Coupled-cluster calculations based on this interaction, named NNLOsat, yield accurate binding energies and radii of nuclei up to 40Ca, and are consistent with the empirical saturation point of symmetric nuclear matter. In addition, the low-lying collective 3- states in 16O and 40Ca are described accurately, while spectra for selected p- and sd-shell nuclei are in reasonable agreement with experiment.

  12. New holographic dark energy model with non-linear interaction

    Science.gov (United States)

    Oliveros, A.; Acero, Mario A.

    2015-05-01

    In this paper the cosmological evolution of a holographic dark energy model with a non-linear interaction between the dark energy and dark matter components in a FRW type flat universe is analysed. In this context, the deceleration parameter q and the equation state w Λ are obtained. We found that, as the square of the speed of sound remains positive, the model is stable under perturbations since early times; it also shows that the evolution of the matter and dark energy densities are of the same order for a long period of time, avoiding the so-called coincidence problem. We have also made the correspondence of the model with the dark energy densities and pressures for the quintessence and tachyon fields. From this correspondence we have reconstructed the potential of scalar fields and their dynamics.

  13. New holographic dark energy model with non-linear interaction

    CERN Document Server

    Oliveros, A

    2014-01-01

    In this paper the cosmological evolution of a holographic dark energy model with a non-linear interaction between the dark energy and dark matter components in a FRW type flat universe is analysed. In this context, the deceleration parameter $q$ and the equation state $w_{\\Lambda}$ are obtained. We found that, as the square of the speed of sound remains positive, the model is stable under perturbations since early times; it also shows that the evolution of the matter and dark energy densities are of the same order for a long period of time, avoiding the so--called coincidence problem. We have also made the correspondence of the model with the dark energy densities and pressures for the quintessence and tachyon fields. From this correspondence we have reconstructed the potential of scalar fields and their dynamics.

  14. Finite-size Energy of Non-interacting Fermi Gases

    Energy Technology Data Exchange (ETDEWEB)

    Gebert, Martin, E-mail: gebert@math.lmu.de [ETH Zürich , Theoretische Physik (Switzerland)

    2015-12-15

    We study the asymptotics of the difference of the ground-state energies of two non-interacting N-particle Fermi gases in a finite volume of length L in the thermodynamic limit up to order 1/L. We are particularly interested in subdominant terms proportional to 1/L, called finite-size energy. In the nineties (Affleck, Nuc. Phys. B 58, 35–41 1997; Zagoskin and Affleck, J. Phys. A 30, 5743–5765 1997) claimed that the finite-size energy is related to the decay exponent occurring in Anderson’s orthogonality. We prove that the finite-size energy depends on the details of the thermodynamic limit and is therefore non-universal. Typically, it includes an additional linear term in the scattering phase shift.

  15. Finite-size Energy of Non-interacting Fermi Gases

    International Nuclear Information System (INIS)

    We study the asymptotics of the difference of the ground-state energies of two non-interacting N-particle Fermi gases in a finite volume of length L in the thermodynamic limit up to order 1/L. We are particularly interested in subdominant terms proportional to 1/L, called finite-size energy. In the nineties (Affleck, Nuc. Phys. B 58, 35–41 1997; Zagoskin and Affleck, J. Phys. A 30, 5743–5765 1997) claimed that the finite-size energy is related to the decay exponent occurring in Anderson’s orthogonality. We prove that the finite-size energy depends on the details of the thermodynamic limit and is therefore non-universal. Typically, it includes an additional linear term in the scattering phase shift

  16. Balancing Local Order and Long-Ranged Interactions in the Molecular Theory of Liquid Water

    CERN Document Server

    Shah, J K; Pratt, L R; Paulaitis, M E

    2007-01-01

    A molecular theory of liquid water is identified and studied on the basis of computer simulation of the TIP3P model of liquid water. This theory would be exact for models of liquid water in which the intermolecular interactions vanish outside a finite spatial range, and therefore provides a precise analysis tool for investigating the effects of longer-ranged intermolecular interactions. We show how local order can be introduced through quasi-chemical theory. Long-ranged interactions are characterized generally by a conditional distribution of binding energies, and this formulation is interpreted as a regularization of the primitive statistical thermodynamic problem. These binding-energy distributions for liquid water are observed to be unimodal. The gaussian approximation proposed is remarkably successful in predicting the Gibbs free energy and the molar entropy of liquid water, as judged by comparison with numerically exact results. The remaining discrepancies are subtle quantitative problems that do have si...

  17. Regional Analysis of Energy, Water, Land and Climate Interactions

    Science.gov (United States)

    Tidwell, V. C.; Averyt, K.; Harriss, R. C.; Hibbard, K. A.; Newmark, R. L.; Rose, S. K.; Shevliakova, E.; Wilson, T.

    2014-12-01

    Energy, water, and land systems interact in many ways and are impacted by management and climate change. These systems and their interactions often differ in significant ways from region-to-region. To explore the coupled energy-water-land system and its relation to climate change and management a simple conceptual model of demand, endowment and technology (DET) is proposed. A consistent and comparable analysis framework is needed as climate change and resource management practices have the potential to impact each DET element, resource, and region differently. These linkages are further complicated by policy and trade agreements where endowments of one region are used to meet demands in another. This paper reviews the unique DET characteristics of land, energy and water resources across the United States. Analyses are conducted according to the eight geographic regions defined in the 2014 National Climate Assessment. Evident from the analyses are regional differences in resources endowments in land (strong East-West gradient in forest, cropland and desert), water (similar East-West gradient), and energy. Demands likewise vary regionally reflecting differences in population density and endowment (e.g., higher water use in West reflecting insufficient precipitation to support dryland farming). The effect of technology and policy are particularly evident in differences in the energy portfolios across the eight regions. Integrated analyses that account for the various spatial and temporal differences in regional energy, water and land systems are critical to informing effective policy requirements for future energy, climate and resource management. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  18. Exploring the properties of valence electron based potential functions for the nonbonded interactions in atomistic force fields

    CERN Document Server

    Plattner, Nuria

    2016-01-01

    The possibility to construct and parametrize the nonbonded interactions in atomistic force fields based on the valence electron structure of molecules is explored in this paper. Three different charge distribution models using simple valence electron based potential functions are introduced and compared. It is shown that the three models can be constructed such that they only require one adjustable parameter for the electrostatic potential of a molecule. The accuracy of the electrostatic potential is evaluated for the three models and compared to population-derived charges and higher order multipole moments for a set of 12 small molecules. Furthermore the accuracy and parametrization of the interaction energies of the three models is evaluated based on {\\it ab initio} intermolecular interaction energies. It is shown that the valence electron potential models provide systematic advantages over conventional point charge models for the calculation of intermolecular interaction energies even with the very simple ...

  19. Analytic energy gradients for constrained DFT-configuration interaction

    Science.gov (United States)

    Kaduk, Benjamin; Tsuchimochi, Takashi; Van Voorhis, Troy

    2014-05-01

    The constrained density functional theory-configuration interaction (CDFT-CI) method has previously been used to calculate ground-state energies and barrier heights, and to describe electronic excited states, in particular conical intersections. However, the method has been limited to evaluating the electronic energy at just a single nuclear configuration, with the gradient of the energy being available only via finite difference. In this paper, we present analytic gradients of the CDFT-CI energy with respect to nuclear coordinates, which gives the potential for accurate geometry optimization and molecular dynamics on both the ground and excited electronic states, a realm which is currently quite challenging for electronic structure theory. We report the performance of CDFT-CI geometry optimization for representative reaction transition states as well as molecules in an excited state. The overall accuracy of CDFT-CI for computing barrier heights is essentially unchanged whether the energies are evaluated at geometries obtained from quadratic configuration-interaction singles and doubles (QCISD) or CDFT-CI, indicating that CDFT-CI produces very good reaction transition states. These results open up tantalizing possibilities for future work on excited states.

  20. Interaction of the intermediate energy neutrino with nuclei

    Science.gov (United States)

    Bugayev, E. V.; Rudzskiy, M. A.; Bisnovatyy-Kogan, G. S.; Seidov, Z. F.

    1980-01-01

    The interaction of the electronic neutrino with nuclei C-12, O-16, Ci-37, Fe-56, Ga-71, and Br81 is considered for neutrino energy up to 300 MeV. The nuclei are described by single-particle shell-model with Woods-Saxon potential. The parameters of the potential are specially chosen for each nuclei in order to describe correctly the upper occupied single particle levels of the nuclei. The cross sections for inelastic and elastic interactions of neutrino with nuclei are calculated within this model, taking into account charged and neutral current of weak interaction. The neutral currents are described by Weinberg theory. The results of the cross section calculations are presented and the comparisons with the results of the other authors are given. The possibilities of improvement of the exactness of obtained results are discussed. Some details of the calculations are included.

  1. Self-interaction errors in nuclear energy density functionals

    CERN Document Server

    Chamel, N

    2010-01-01

    When applied to a single nucleon, nuclear energy density functionals may yield a non-vanishing internal energy thus implying that the nucleon is interacting with itself. It is shown how to avoid this unphysical feature for semi-local phenomenological functionals containing all possible bilinear combinations of local densities and currents up to second order in the derivatives. The method outlined in this Rapid Communication could be easily extended to functionals containing higher order terms, and could serve as a guide for constraining the time-odd part of the functional.

  2. Interaction of Compliance and Voluntary Renewable Energy Markets

    Energy Technology Data Exchange (ETDEWEB)

    Bird, Lori [National Renewable Energy Lab. (NREL), Golden, CO (United States); Lokey, Elizabeth [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2007-10-01

    In recent years, both compliance and voluntary markets have emerged to help support the development of renewable energy resources. Both of these markets are growing rapidly and today about half of U.S. states have RPS policies in place, with a number of these policies adopted in the last several years. In addition, many states have recently increased the stringency of their RPS policies. This paper examines key market interaction issues between compliance and voluntary renewable energy markets. It provides an overview of both the compliance and voluntary markets, addressing each market's history, purpose, size, scope, and benefits while addressing issues, including double counting.

  3. T asymmetry in the strong interaction at medium energies

    International Nuclear Information System (INIS)

    We examine current intermediate-energy nucleon-nucleon data sensitive to T asymmetry and conclude that of these data, some np polarization and asymmetry measurements give the best evidence that T is good, despite the fact that these data have the largest errors of any of the data considered. This conclusion is reached using a one-boson-exchange potential due to Bryan and Gersten, wherein T is violated at short distances. We argue that any short-range T-asymmetric model would probably lead to the same conculsion. We show that the current N-N data admit the possibility of strong-interaction T asymmetry, so long as it be of short range. For experimentalists who may search for strong-interaction T violation in intermediate energy N-N scattering, we suggest maximum errors for several measurements so that any such T violation may not be missed

  4. Interacting new agegraphic version of pilgrim dark energy

    Science.gov (United States)

    Jawad, Abdul; Abbas, G.

    2015-05-01

    We discuss the cosmological evolution of the interacting pilgrim dark energy (DE) with conformal age of the universe in flat FRW universe. We evaluate the equation of state (EoS) parameter for three different values of interacting parameter which evolutes the universe from matter dominated to phantom-like eras by evolving quintessence as well as vacuum DE eras. We also give the correspondence of the present DE model with quintessence, tachyon, k-essence, dilaton and DBI-essence scalar field models. We discuss the dynamics of scalar field and corresponding potentials. We find that the behavior of scalar field, corresponding potentials and kinetic energy terms (in k-essence and dilaton field) consistent with the present day observations. Also, cosmological planes such as ω ǎrtheta-ω ǎrtheta' and r - s planes corresponds to ΛCDM limit.

  5. Accuracy of Several Wave Function and Density Functional Theory Methods for Description of Noncovalent Interaction of Saturated and Unsaturated Hydrocarbon Dimers

    Czech Academy of Sciences Publication Activity Database

    Granatier, Jaroslav; Pitoňák, M.; Hobza, Pavel

    2012-01-01

    Roč. 8, č. 7 (2012), s. 2282-2292. ISSN 1549-9618 Grant ostatní: APVV(SK) APVV-0059-10 Institutional research plan: CEZ:AV0Z40550506 Keywords : intermolecular interaction energies * Plesset perturbation- theory * molecular-orbital methods * protein rubredoxin Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

  6. Interaction of low-energy neutrons with tellurium isotopes

    International Nuclear Information System (INIS)

    Total neutron cross sections of sup(122,124,126,128,130)Te isotopes are obtained for 0.41-2.16 MeV energy range. These data are analyzed on the basis of different variants of the generalized optical model. The optical potential real part had the radial Woods-Saxon dependence. The potential imaginary part was taken in the form of the Woods-Saxon form-factor derivative and spinorbit interaction - in the Thomas form

  7. On phenomenological models of dark energy interacting with dark matter

    OpenAIRE

    Tamanini, Nicola

    2015-01-01

    An interaction between dark matter and dark energy is usually introduced by a phenomenological modification of the matter conservation equations, while the Einstein equations are left unchanged. Starting from some general and fundamental considerations, in this work it is shown that a coupling in the dark sector is likely to introduce new terms also in the gravitational dynamics. Specifically in the cosmological background equations a bulk dissipative pressure, characterizing viscous effects ...

  8. Energy-dependent interactions in few-body systems

    International Nuclear Information System (INIS)

    Energy-dependent interactions in few-body systems are discussed. A class of multichannel few-body scattering models which are characterized by the simultaneous presence of and communication between two different types of channels. First, usual two- and three-particle scattering channels (external ones), hamiltonians for which have ordinary spectral properties. Second, the internal channels, hamiltonians for which have only a point spectrum. Faddeev equations for external and internal channels are discussed

  9. Nucleus-nucleus interactions in the transition energy regime

    International Nuclear Information System (INIS)

    There are at least two ways for studying large interactions in nucleus-nucleus collisions. One way is to use the method of angular correlations between fission fragments. The aim of the experiments presented here was to make a survey on the role of the various experimental parameters. In that respect three targets have been studied and different projectiles and bombarding energies have been used. Results are presented and discussed

  10. Intermolecular Casimir-Polder forces in water and near surfaces.

    Science.gov (United States)

    Thiyam, Priyadarshini; Persson, Clas; Sernelius, Bo E; Parsons, Drew F; Malthe-Sørenssen, Anders; Boström, Mathias

    2014-09-01

    The Casimir-Polder force is an important long-range interaction involved in adsorption and desorption of molecules in fluids. We explore Casimir-Polder interactions between methane molecules in water, and between a molecule in water near SiO(2) and hexane surfaces. Inclusion of the finite molecular size in the expression for the Casimir-Polder energy leads to estimates of the dispersion contribution to the binding energies between molecules and between one molecule and a planar surface. PMID:25314410

  11. Post-Planck constraints on interacting vacuum energy

    Science.gov (United States)

    Wang, Yuting; Wands, David; Zhao, Gong-Bo; Xu, Lixin

    2014-07-01

    We present improved constraints on an interacting vacuum model using updated astronomical observations including the first data release from Planck. We consider a model with one dimensionless parameter, α, describing the interaction between dark matter and vacuum energy (with fixed equation of state w=-1). The background dynamics correspond to a generalized Chaplygin gas cosmology, but the perturbations have a zero sound speed. The tension between the value of the Hubble constant, H0, determined by Planck data plus WMAP polarization (Planck +WP) and that determined by the Hubble Space Telescope (HST) can be alleviated by energy transfer from dark matter to vacuum (α>0). A positive α increases the allowed values of H0 due to parameter degeneracy within the model using only cosmic microwave background data. Combining with additional data sets of including supernova type Ia (SN Ia) and baryon acoustic oscillation (BAO), we can significantly tighten the bounds on α. Redshift-space distortions (RSD), which constrain the linear growth of structure, provide the tightest constraints on vacuum interaction when combined with Planck+WP, and prefer energy transfer from vacuum to dark matter (α0, but not both at the same time.

  12. Scattered energy spectra from the interaction of multi-energy photons with single layer shields

    International Nuclear Information System (INIS)

    Scattered energy spectra produced from the interaction of multi-energy photons, emitted from an N-16 radioactive source, with concrete, steel and lead single layer shields will be examined. The influence of the material atomic number and the bremsstrahlung contribution to the examined spectra are also considered

  13. INTERMOLECULAR ENERGY AND SURFACE TENSION IN PURE NON AUTOASSOCIATED LIQUIDS

    Directory of Open Access Journals (Sweden)

    Gabriel Hernández de la Torre

    2010-08-01

    Full Text Available Se deduce una ecuación para calcular la energía libre en la superficie de un líquido, como una función de las densidades ortobáricas. Se considera la contribución molecular al área de la superficie de moléculas globulares, moléculas planas y parafinas normales y se calcula la tensión superficial para las especies anteriores. Los valores calculados de la tensión superficial presentan excelente concordancia con los valores experimentales.

  14. Microscopic positive-energy potential based on Gogny interaction

    CERN Document Server

    Blanchon, G; Arellano, H F; Mau, N Vinh

    2014-01-01

    We present nucleon elastic scattering calculation based on Green's function formalism in the Random-Phase Approximation. For the first time, the Gogny effective interaction is used consistently throughout the whole calculation to account for the complex, non-local and energy-dependent optical potential. Effects of intermediate single-particle resonances are included and found to play a crucial role in the account for measured reaction cross section. Double counting of the particle-hole second-order contribution is carefully addressed. The resulting integro-differential Schr\\"odinger equation for the scattering process is solved without localization procedures. The method is applied to neutron and proton elastic scattering from $^{40}$Ca. A successful account for differential and integral cross sections, including analyzing powers, is obtained for incident energies up to 30 MeV. Discrepancies at higher energies are related to much too high volume integral of the real potential for large partial waves. Moreover...

  15. Photoinduced tautomerism of 2,6-dicarbomethoxyphenol in DMFwater mixtures: Perturbation from intermolecular processes

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Abhijit, E-mail: pcam2008@gmail.com [Department of Chemistry and Environment, Heritage Institute of Technology, Chowbaga Road, Anandapur, Kolkata 700107 (India); Misra, Ramprasad [Department of Physical Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2014-06-01

    In this paper, we report the spectral signatures of photoinduced tautomerism of 4-methyl-2,6-dicarbomethoxyphenol (CMOH) in DMFwater mixtures with varying compositions. Excited state intramolecular proton transfer (ESIPT) reaction of CMOH has been observed in bulk DMF, indicated by dual fluorescence from its normal and tautomeric forms while only a single emission peak is observed in water from its anionic species. Binary mixture of a polar aprotic (DMF) and a polar protic (water) solvent gives rise to a competition between intramolecular and intermolecular hydrogen bonding (with media) processes of the probe. This competition is found to be largely dependent on the proton affinity of the media and also on the excitation energy. Solvent separated ion pair and intermolecularly H-bonded CMOHSolvent complex have been detected in the excited state at specific solvent compositions that are converted to the anionic form due to the change in excitation wavelengths. The formation of hydrogen bonded 1:1 molecular clusters of different rotamers of CMOH with DMF and water in the ground state has been investigated using quantum chemical calculations. A combined experimental and theoretical analysis indicates that the HOMO to LUMO transitions dictate the electronic absorption profiles of the CMOHDMF and CMOHwater clusters. These findings are expected to shed light on the mechanism of acidbase reactions of several hydrogen bonded systems that are part of many biologically relevant processes. -- Highlights: Photoinduced tautomerization of CMOH has been studied in DMFwater mixture. CMOH forms 1:1 molecular clusters with DMF and water. The competition between intra- and intermolecular hydrogen bonding is revealed. HOMO to LUMO transition dictates the absorption spectra of CMOH in DMF and water.

  16. Analysis of Intermolecular Coordinate Contributions to Third-order Ultrafast Spectroscopy of Liquids in the Harmonic Oscillator

    Energy Technology Data Exchange (ETDEWEB)

    Thantu, Napoleon; McMorrow, D.; Melinger, J. S.; Kleiman, V.; Lotshaw, W. T.

    2001-07-01

    The apparently-multicomponent subpicosecond intermolecular dynamics of carbon disulfide liquid are addressed in a unified manner in terms of an inhomogeneously broadened quantum mechanical harmonic oscillator model for a single vibrational coordinate. For an inhomogeneously broadened (Gaussian) distribution of oscillators, the model predicts naturally the bimodal character of the subpicosecond intermolecular dynamics of carbon disulfide liquid, and also the spectral evolution effects (spectral narrowing and saturation) that are observed for solutions of carbon disulfide in weakly interacting alkane solvents. The unique dynamical signature of these low-frequency vibrational coordinates is determined largely by the physical constraints on the coordinates (near equality of oscillator frequency, dephasing frequency, and inhomogeneous bandwidth), such that constructive and destructive interference effects play a dominant role in shaping the experimental observable.

  17. Rovibrational matrix elements of the multipole moments and of the polarizability of the H2 molecule in the solid phase: Effect of intermolecular potential

    Indian Academy of Sciences (India)

    Adya Prasad Mishra; T K Balasubramanian

    2001-10-01

    Rovibrational matrix elements of the multipole moments ℓ up to rank 10 and of the linear polarizability of the H2 molecule in the condensed phase have been computed taking into account the effect of the intermolecular potential. Comparison with gas phase matrix elements shows that the effect of solid state interactions is marginal.

  18. Intermolecular complexation and phase separation in aqueous solutions of oppositely charged biopolymers.

    Science.gov (United States)

    Singh, S Santinath; Siddhanta, A K; Meena, Ramavatar; Prasad, Kamalesh; Bandyopadhyay, S; Bohidar, H B

    2007-07-01

    Turbidity measurements performed at 450nm were used to follow the process of complex formation, and phase separation in gelatin-agar aqueous solutions. Acid (Type-A) and alkali (Type-B) processed gelatin (polyampholyte) and agar (anionic polyelectrolyte) solutions, both having concentration of 0.1% (w/v) were mixed in various proportions, and the mixture was titrated (with 0.01 M HCl or NaOH) to initiate associative complexation that led to coacervation. The titration profiles clearly established observable transitions in terms of the solution pH corresponding to the first occurrence of turbidity (pH(C), formation of soluble complexes), and a point of turbidity maximum (pH(phi), formation of insoluble complexes). Decreasing the pH beyond pH(phi) drove the system towards precipitation. The values of pH(C) and pH(phi) characterized the initiation of the formation of intermolecular charge neutralized soluble aggregates, and the subsequent formation of microscopic coacervate droplets. These aggregates were characterized by dynamic light scattering. It was found that Type-A and -B gelatin samples formed soluble intermolecular complexes (and coacervates) with agar molecules through electrostatic and patch-binding interactions, respectively. PMID:17367849

  19. Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs.

    Science.gov (United States)

    Metters, Owen J; Forrest, Sebastian J K; Sparkes, Hazel A; Manners, Ian; Wass, Duncan F

    2016-02-17

    We report intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene aryloxide and phosphine moieties that exhibit a broad range of small molecule activation chemistry that has previously been the preserve of only intramolecular pairs. Reactions with D2, CO2, THF, and PhCCH are reported. By contrast with previous intramolecular examples, these systems allow facile access to a variety of steric and electronic characteristics at the Lewis acidic and Lewis basic components, with the three-step syntheses of 10 new intermolecular transition metal FLPs being reported. Systematic variation to the phosphine Lewis base is used to unravel steric considerations, with the surprising conclusion that phosphines with relatively small Tolman steric parameters not only give highly reactive FLPs but are often seen to have the highest selectivity for the desired product. DOSY NMR spectroscopic studies on these systems reveal for the first time the nature of the Lewis acid/Lewis base interactions in transition metal FLPs of this type. PMID:26788963

  20. Intra- and intermolecular electron transfer reactions in covalently linked donor-acceptor molecules

    International Nuclear Information System (INIS)

    We synthesized a homologous series of molecules (MVnn'Q) where a methylviologen (MV2+) and an amino-chloronaphthoquinone (Q) are linked to each other via a flexible chain. Using the electron pulse radiolysis technique, we have measured time-resolved spectra and determined rate constants for intra- and intermolecular electron transfer (ET) between donor and acceptor site of the MVnn'Q molecules in water and in sodium dodecyl sulfate (SDS) micellar solution. For comparison, we also irradiated a solution containing a 1:1 mixture of methylviologen and amino-chloronaphthoquinone and measured spectra and intermolecular ET reactions between the separated electron donor and acceptor molecules. We found a remarkably slow intramolecular electron transfer from the reduced methylviologen moiety to the quinone site of all MVnn'Q molecules both in water and in aqueous SDS micellar suspensions. The intramolecular rate constants measured in water increase with the number of intervening bonds, leading to the conclusion that electron transfer occurs by a through-space rather than through-bond mechanism. The intramolecular rate constants virtually lose their chain length dependence in SDS suspensions where, because of an extended configuration of the micellized MVnn'Q molecules, through-space interaction is not favored. (orig.)

  1. Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties.

    Science.gov (United States)

    Garino, Claudio; Gobetto, Roberto; Nervi, Carlo; Salassa, Luca; Rosenberg, Edward; Ross, J B Alexander; Chu, Xi; Hardcastle, Kenneth I; Sabatini, Cristiana

    2007-10-15

    The complex [Ru(tpy)(CO)(2)TFA]+[PF(6)]- (where tpy = 2,2':6',2' '-terpyridine and TFA = CF(3)CO(2)-) (1) has been synthesized and fully characterized spectroscopically. The X-ray structure of the complex has been determined. The photopysical properties of the ruthenium complex and the free ligand tpy have been investigated at room temperature and at 77 K in acetonitrile solution and in the solid state. Their electronic spectra are highly influenced by intermolecular stacking interactions, both in solution and in the solid state. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed to characterize the electronic structure and the excited states of [Ru(tpy)(CO)(2)TFA]+[PF(6)]- and tpy. TDDFT calculations on three different conformations of free ligand have been performed as well. Absorption and emission spectra of tpy have been studied at different temperatures and concentrations in order to have a better understanding of this ruthenium derivative's properties. The absorption spectrum of 1 is characterized by metal-perturbed ligand-centered (LC) bands in the UV region. No metal-to-ligand charge transfer (MLCT) bands are observed in the visible for the complex. Only at high concentrations (10(-4) M) does a very weak band appear at 470 nm. At 77 K and low concentrations, solutions of 1 exhibit a major 3LC emission band centered at 468 nm (21.4 x 10(-3) cm(-1)). When the concentration of the complex is increased, an unstructured narrow emission at 603 nm (16.6 x 10(-3) cm(-1)), with a lifetime of 10 micros, dominates the emission spectrum in glassy acetonitrile. This emission originates from a pi-pi stacked dimeric (or oligomeric) species. TDDFT calculations performed on a tail-to-tail dimer structure, similar to that seen in the solid state, ascribe the transition to a triplet excited state, where intermolecular metal (d) --> ligand (pi*, polypyridine) charge transfer occurs. A good estimate of the transition energy is also obtained (623 nm, 1.94 eV). PMID:17845034

  2. AIC, BIC, Bayesian evidence against the interacting dark energy model

    International Nuclear Information System (INIS)

    Recent astronomical observations have indicated that the Universe is in a phase of accelerated expansion. While there are many cosmological models which try to explain this phenomenon, we focus on the interacting ΛCDM model where an interaction between the dark energy and dark matter sectors takes place. This model is compared to its simpler alternative—the ΛCDM model. To choose between these models the likelihood ratio test was applied as well as the model comparison methods (employing Occam’s principle): the Akaike information criterion (AIC), the Bayesian information criterion (BIC) and the Bayesian evidence. Using the current astronomical data: type Ia supernova (Union2.1), h(z), baryon acoustic oscillation, the Alcock–Paczynski test, and the cosmic microwave background data, we evaluated both models. The analyses based on the AIC indicated that there is less support for the interacting ΛCDM model when compared to the ΛCDM model, while those based on the BIC indicated that there is strong evidence against it in favor of the ΛCDM model. Given the weak or almost non-existing support for the interacting ΛCDM model and bearing in mind Occam’s razor we are inclined to reject this model

  3. AIC, BIC, Bayesian evidence against the interacting dark energy model

    Energy Technology Data Exchange (ETDEWEB)

    Szydlowski, Marek [Jagiellonian University, Astronomical Observatory, Krakow (Poland); Jagiellonian University, Mark Kac Complex Systems Research Centre, Krakow (Poland); Krawiec, Adam [Jagiellonian University, Institute of Economics, Finance and Management, Krakow (Poland); Jagiellonian University, Mark Kac Complex Systems Research Centre, Krakow (Poland); Kurek, Aleksandra [Jagiellonian University, Astronomical Observatory, Krakow (Poland); Kamionka, Michal [University of Wroclaw, Astronomical Institute, Wroclaw (Poland)

    2015-01-01

    Recent astronomical observations have indicated that the Universe is in a phase of accelerated expansion. While there are many cosmological models which try to explain this phenomenon, we focus on the interacting ?CDM model where an interaction between the dark energy and dark matter sectors takes place. This model is compared to its simpler alternative - the ?CDM model. To choose between these models the likelihood ratio test was applied as well as the model comparison methods (employing Occam's principle): the Akaike information criterion (AIC), the Bayesian information criterion (BIC) and the Bayesian evidence. Using the current astronomical data: type Ia supernova (Union2.1), h(z), baryon acoustic oscillation, the Alcock- Paczynski test, and the cosmic microwave background data, we evaluated both models. The analyses based on the AIC indicated that there is less support for the interacting ?CDM model when compared to the ?CDM model, while those based on the BIC indicated that there is strong evidence against it in favor of the ?CDM model. Given the weak or almost non-existing support for the interacting ?CDM model and bearing in mind Occam's razor we are inclined to reject this model. (orig.)

  4. Impurity formation energies and effective interactions in DMS

    International Nuclear Information System (INIS)

    We use a recently developed method (Phil. Mag. 88 (2008), 2777) based on the TB-LMTO scheme to calculate the electronic structure of atomic clusters embedded in an ideal crystal or in an effective medium that represents a random alloy. We determine from the first principles impurity formation energies and effective interatomic interactions (i.e. the parameters of the alloy Ising Hamiltonian that governs structural stability of materials) and exchange interactions (i.e. parameters of the Heisenberg Hamiltonian that determines the magnetic structure). We present the results for impurities in (Ga,Mn)As alloys and for vacancies and alkali metal impurities in zirconia that can induce the the so-called d0-magnetism.

  5. Emergent dark energy via decoherence in quantum interactions

    CERN Document Server

    Altamirano, Natacha; Khosla, Kiran; Mann, Robert B; Milburn, Gerard

    2016-01-01

    Much effort has been devoted into understanding the quantum mechanical properties of gravitational interactions. Here we explore the recent suggestion that gravitational interactions are a fundamental classical channel that is described by continuous quantum measurements and feedforward (CQMF). Specifically, we investigate the possibility that some properties of our universe, modeled using a Friedman-Robertson-Walker metric, can emerge from CQMF by introducing an underlying quantum system for the dynamical variables, avoiding well known difficulties in trying to quantize the spacetime itself. We show that the quantum decoherence necessary in such a measurement model manifests itself as a dark energy fluid that fills the spacetime and whose equation of state asymptotically oscillates around the value $w=-1/3$, regardless of the spatial curvature, which provides the bound between accelerating and decelerating expanding FRW cosmologies.

  6. Experimental Summary: Very High Energy Cosmic Rays and their Interactions

    Directory of Open Access Journals (Sweden)

    Kampert Karl-Heinz

    2013-06-01

    Full Text Available The XVII International Symposium on Very High Energy Cosmic Ray Interactions, held in August of 2012 in Berlin, was the first one in the history of the Symposium,where a plethora of high precision LHC data with relevance for cosmic ray physics was presented. This report aims at giving a brief summary of those measurements andit discusses their relevance for observations of high energy cosmic rays. Enormous progress has been made also in air shower observations and in direct measurements of cosmic rays, exhibiting many more structure in the cosmic ray energy spectrum than just a simple power law with a knee and an ankle. At the highest energy, the flux suppression may not be dominated by the GZK-effect but by the limiting energy of a nearby source or source population. New projects and application of new technologies promise further advances also in the near future. We shall discuss the experimental and theoretical progress in the field and its prospects for coming years.

  7. Elastic diffraction interactions of hadrons at high energies

    International Nuclear Information System (INIS)

    Full text: 1. The diffraction theory of elastic and inelastic scattering of hadron-hadron and hadron-nucleus processes is developed. The description of experimental data on differential cross section of elastic scattering p p, p-bar p in wide range of transferred momentum is made in the frames of the developed inelastic overlap function model. The investigation of nuclei elastic scattering at the low, middle and high energies is carried out, that allowed to execute quantitative control of efficiency or quantum-field and phenomenological theories and make critical analysis of their utility. The principle of construction of realistic amplitudes of the elastic scattering is confirmed on the basic of the s- and t-channel approaches both conditions stationary of amplitudes. For a wide range of models the comparative analysis of amplitude of inelastic scattering in representation of impact parameter is executed. The expression for effective radius of interaction, effective trajectory Regge and slope of inelastic function of overlapping are analysed. In diffraction approximation the satisfactory description of the data on hadrons interaction at the energy of tens GeV with proton and deuterons is received. The features of spectra of fast particles are analysed. The theory of collective variables S, T, P which characterize a deviation degree of angular distribution of particles from spherical symmetry, the general formula for dispersion of any density of obtained, the particles decays are investigated [1-2]. 2. The solution of Lippmann-Schwinger equation investigated within the frameworks of frameworks of high -energy approximation satisfies the generalized Huygens principle used in the diffraction theory nuclear processes. The diffraction emission is considered at the interaction of charged hadrons one with another and the nuclei [3]. 3. Study of elastic interactions of hadrons at high energies is of great interest due to the fact that the amplitude of this process is the simplest, and at the same time, it is a fundamental object for theoretical and experimental researches. Study of this process allows one to have a quantitative check of various theories and experimental researches. Study of this process allows one to have a quantitative check of various theories and models, and to make a critical selection. By using of fundamental property of theory-unitarity condition of scattering matrix- elastic scattering can be connected with inelastic reaction. Based on S-channel unitarity condition expressing elastic amplitude via inelastic overlapping function, it is important to study the latter, as well as to describe the experimentally measured characteristics of hadron-nucleon interaction at high-energies and to have results prediction. By using experimental data on differential cross section elastic scattering of hadrons at various energies and by theoretical information on ratio of a real part and an imaginary part of scattering amplitude δ(t) the t- dependence of inelastic and elastic overlapping functions is studied. Influence of a zigzag from differential cross-section of elastic p p( p-bar) scattering on profile function and inelastic overlapping function to violation of geometric scaling was studied. In frames of scaling the general expressions for s- and t- dependences of inelastic and elastic overlapping function are derived. Comparison of this function in three elastic scattering models was carried out. It was demonstrated that one would need to assume that hadrons become blacker at central part in order to correctly describe experimental angular distribution data. Dependence of differential cross-section on transfer momentum square for elastic hadron scattering at energies of ISR and SPS in the model of inelastic overlapping function is studied [1-2]. (author)

  8. Interacting ghost dark energy models with variable G and Λ

    International Nuclear Information System (INIS)

    In this paper we consider several phenomenological models of variable Λ. Model of a flat Universe with variable Λ and G is accepted. It is well known, that varying G and Λ gives rise to modified field equations and modified conservation laws, which gives rise to many different manipulations and assumptions in literature. We will consider two component fluid, which parameters will enter to Λ. Interaction between fluids with energy densities ρ1 and ρ2 assumed as Q = 3Hb(ρ1+ρ2). We have numerical analyze of important cosmological parameters like EoS parameter of the composed fluid and deceleration parameter q of the model

  9. Study of high energy cosmic ray interactions at Chacaltaya laboratory

    International Nuclear Information System (INIS)

    Cosmic rays physics is currently studied with rather sophisticated detectors operating in a variety of either experimental conditions or atmospheric depths in the world. In this paper we present the main properties of the observed features of high-energy nuclear interaction phenomena of cosmic rays, with particular emphasis on some experimental observations made by the emulsion chamber technique at Chacaltaya Laboratory (Bolivia, 5230 m a.s.l.). A discussion on the past and present achievements as well as the future prospects of high altitude mountain laboratories for cosmic ray physics is presented

  10. Observational constraints on a holographic, interacting dark energy model

    International Nuclear Information System (INIS)

    We constrain an interacting, holographic dark energy model, first proposed by two of us in [1], with observational data from supernovae, CMB shift, baryon acoustic oscillations, x-rays, and the Hubble rate. The growth function for this model is also studied. The model fits the data reasonably well but still the conventional ?CDM model fares better. Nevertheless, the holographic model greatly alleviates the coincidence problem and shows compatibility at 1? confidence level with the age of the old quasar APM 08279+5255

  11. Low-Energy Antinucleon-Nucleus Interaction Revisited

    CERN Document Server

    Friedman, E

    2015-01-01

    Annihilation cross sections of antiprotons and antineutrons on the proton between 50 and 400 MeV/c show Coulomb focusing below 200 MeV/c and almost no charge-dependence above 200 MeV/c. Similar comparisons for heavier targets are not possible for lack of overlap between nuclear targets studied with $\\bar p$ and $\\bar n$ beams. Interpolating between $\\bar p$-nucleus annihilation cross sections with the help of an optical potential to compare with $\\bar n$-nucleus annihilation cross sections reveal unexpected features of Coulomb interactions in the latter. Direct comparisons between $\\bar n$-nucleus and $\\bar p$-nucleus annihilations at very low energies could be possible if $\\bar p$ cross sections are measured on the same targets and at the same energies as the available cross sections for $\\bar n$. Such measurements may be feasible in the foreseeable future.

  12. Screening effects in the ultra-high energy neutrino interactions

    International Nuclear Information System (INIS)

    We study possible saturation effects in the total crosssections describing the interaction of ultra-high energy neutrinos with nucleons. This analysis is performed within two approaches, i.e., within the Golec-Biernat-Wuesthoff saturation model and within the scheme unifying the DGLAP and BFKL dynamics incorporating non-linear screening effects which follow from the Balitzki-Kovchegov equation. The structure functions in both approaches are constrained by HERA data. It is found that screening effects affect the extrapolation of the neutrino-nucleon total cross-sections to ultra-high neutrino energies E? and reduce their magnitude by a factor equal to about 2 at E??1012 GeV. This reduction becomes amplified by nuclear shadowing in the case of the neutrino-nucleus cross-sections and an approximate estimate of this effect is performed. (orig.)

  13. High-energy interactions in the region of extreme multiplicities

    International Nuclear Information System (INIS)

    Hadron and nuclear interactions at high energies in the region of extreme multiplicities (much higher than mean multiplicities) are reviewed. Collective phenomena such as Bose-Einstein condensation, Cherenkov gluon radiation, clustering, and an excess yield of soft photons may manifest themselves in this region. The phenomenological gluon-dominance model developed for describing extreme multiplicities predicts the restrictions on their values and the type of hadronization mechanism and makes it possible to estimate thee size of the hadronization region. The status of the research within the Thermalization project at the U-70 accelerator of the Institute for High Energy Physics (IHEP, Protvino) is reported, and information about searches for new collective phenomena and about studies of known ones in the region of extreme multiplicities is given.

  14. Importance of the Donor:Fullerene intermolecular arrangement for high-efficiency organic photovoltaics

    KAUST Repository

    Graham, Kenneth

    2014-07-09

    The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b]dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) 13C{1H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems. © 2014 American Chemical Society.

  15. On intermolecular dipolar coupling in two strongly polar liquids: dimethyl sulfoxide and acetonitrile.

    Science.gov (United States)

    Jadzyn, Jan; Swiergiel, Jolanta

    2011-05-26

    The paper presents the results of studies of the electric and dielectric properties of dimethyl sulfoxide (DMSO) and acetonitrile (ACN), two strongly polar liquids composed of the molecules of the same dipole moment value (? ? 4 D) but of a quite different static dielectric permittivity (?(S)(DMSO) > ?(S)(ACN)). It was shown that the activation energies for both the dc ionic conductivity (?(DC)) and the viscosity (?) are two times higher for DMSO than for ACN; however, for both of the liquids, the temperature dependence of the product ?(DC)? is quite close to the prediction of the Stokes-Einstein relation. The dielectric results are interpreted in terms of the intermolecular dipole-dipole coupling. An exceptional behavior of DMSO most certainly results from its "monomolecularity", i.e., from the lack of the dipolar coupling in that strongly polar liquid. The effect is a consequence of a very specific structure of the DMSO molecule where its rotational dynamics makes the intermolecular dipole-dipole coupling very unfavorable, in contrast to the ACN molecules. PMID:21528869

  16. Multiple scattering of low energy ions in matter: Influence of energy loss and interaction potential

    International Nuclear Information System (INIS)

    In this paper, the effect of inelastic energy loss and interaction potential on transmitted ions at low energy is studied. For this purpose, angular distributions of slow He+ ions transmitted through thin Ag films are calculated using the theory of multiple scattering. Thin films (20–50 Å at 2 keV and 50–200 Å at 10 keV) are considered so that the total path length of transmitted ions can be approximated by the value of the target thickness in this calculation. The corresponding values of the relative energy loss ΔE/E are comprised between 0.04 and 0.17. We show that even if low values of the thickness are considered, the total energy loss of ions in the target should be included in the calculation. These calculated angular distributions are also influenced by the potential used to describe the interaction between the incident ion and the target atom

  17. Multiple scattering of low energy ions in matter: Influence of energy loss and interaction potential

    Energy Technology Data Exchange (ETDEWEB)

    Mekhtiche, A. [Laboratoire SNIRM, Faculté de Physique, Université des Sciences et de la Technologie Houari Boumediene (USTHB), BP 32 El Alia, Bab Ezzouar, Algiers (Algeria); Faculté des Sciences et de la Technologie, Université Yahia Farès de Médéa (Algeria); Khalal-Kouache, K., E-mail: kkouache@yahoo.fr [Laboratoire SNIRM, Faculté de Physique, Université des Sciences et de la Technologie Houari Boumediene (USTHB), BP 32 El Alia, Bab Ezzouar, Algiers (Algeria)

    2015-07-01

    In this paper, the effect of inelastic energy loss and interaction potential on transmitted ions at low energy is studied. For this purpose, angular distributions of slow He{sup +} ions transmitted through thin Ag films are calculated using the theory of multiple scattering. Thin films (20–50 Å at 2 keV and 50–200 Å at 10 keV) are considered so that the total path length of transmitted ions can be approximated by the value of the target thickness in this calculation. The corresponding values of the relative energy loss ΔE/E are comprised between 0.04 and 0.17. We show that even if low values of the thickness are considered, the total energy loss of ions in the target should be included in the calculation. These calculated angular distributions are also influenced by the potential used to describe the interaction between the incident ion and the target atom.

  18. A Field Theory Model for Dark Matter and Dark Energy in Interaction

    OpenAIRE

    Micheletti, Sandro; Abdalla, Elcio; Wang, Bin

    2009-01-01

    We propose a field theory model for dark energy and dark matter in interaction. Comparing the classical solutions of the field equations with the observations of the CMB shift parameter, BAO, lookback time and Gold supernovae sample, we observe a possible interaction between dark sectors with energy decay from dark energy into dark matter. The observed interaction provides an alleviation to the coincidence problem.

  19. Resonant Electromagnetic Interaction in Low Energy Nuclear Reactions

    Science.gov (United States)

    Chubb, Scott

    2008-03-01

    Basic ideas about how resonant electromagnetic interaction (EMI) can take place in finite solids are reviewed. These ideas not only provide a basis for conventional, electron energy band theory (which explains charge and heat transport in solids), but they also explain how through finite size effects, it is possible to create many of the kinds of effects envisioned by Giuliano Preparata. The underlying formalism predicts that the orientation of the external fields in the SPAWAR protocolootnotetextKrivit, Steven B., New Energy Times, 2007, issue 21, item 10. http://newenergytimes.com/news/2007/NET21.htm^,ootnotetextSzpak, S.; Mosier-Boss, P.A.; Gordon, F.E. Further evidence of nuclear reactions in the Pd lattice: emission of charged particles. Naturwissenschaften 94,511(2007)..has direct bearing on the emission of high-energy particles. Resonant EMI also implies that nano-scale solids, of a particular size, provide an optimal environment for initiating Low Energy Nuclear Reactions (LENR) in the PdD system.

  20. Search for Quarks in High-Energy Neutrino Interactions

    CERN Multimedia

    2002-01-01

    This experiment is a search for quarks produced in high energy neutrino interactions. Neutrino interactions take place in a 23-ton lead target and are recognized by one or more particles crossing the counter hodoscopes S1 and S2, together with the absence of an incident particle signal in the initial veto counter V^0.\\\\ \\\\ The lead is viewed by an avalanche chamber to measure the specific ionization of the charged secondaries produced in the @n-interaction with high accuracy even in jet-like events, and by a series of two pairs of scintillation counter hodoscopes (ST1, ST2). The latter provide time-of-flight measurements and dE/dx measurements for a fast analysis in low and medium multiplicity provide a trigger for the chamber. \\\\ \\\\ In order to reduce the background in the set-up, very low momentum particles (mainly due to cascading processes in the target) are separated out by a @= 1 T.m magnet placed behind the target. \\\\ \\\\ A system of wire chambers W1, W2, which register both the position and the time at...

  1. Saturation model for two-photon interactions at high energies

    CERN Document Server

    Timneanu, N; Motyka, L; 10.1007/s100520200893

    2002-01-01

    We formulate and analyse a saturation model for the total gamma gamma and gamma* gamma* cross-sections and for the real photon structure function F_2^gamma(x,Q^2). The model is based on a picture in which the gamma* gamma* total cross-section for arbitrary photon virtualities is driven by the interaction of colour dipoles, into which the virtual photons fluctuate. The cross-section describing this interaction is assumed to satisfy the saturation property with the saturation radius taken from the Golec-Biernat and Wusthoff analysis of the gamma* p interaction at HERA. The model is supplemented by the QPM and non-pomeron reggeon contributions. The model gives a very good description of the data on the gamma gamma total cross-section, on the photon structure function F_2^gamma(x,Q^2) at low x and on the gamma* gamma* cross-section extracted from LEP double tagged events. Production of heavy flavours in gamma gamma collisions is also studied. Predictions of the model for the very high energy range which will be p...

  2. Saturation model for two-photon interactions at high energies

    International Nuclear Information System (INIS)

    We formulate and analyse a saturation model for the total ?? and ?* ?* cross-sections and for the real photon structure function F2?(x,Q2). The model is based on a picture in which the ?* ?* total cross-section for arbitrary photon virtualities is driven by the interaction of colour dipoles into which the virtual photons fluctuate. The cross-section describing this interaction is assumed to satisfy the saturation property with the saturation radius taken from the Golec-Biernat and Wuesthoff analysis of the ?*p interaction at HERA. The model is supplemented by the QPM and non-pomeron reggeon contributions. The model gives a very good description of the data on the ?? total cross-section, on the photon structure function F2?(x,Q2) at low x and on the ?* ?* cross-section extracted from LEP double tagged events. The production of heavy flavours in ?? collisions is also studied. Predictions of the model for the very high energy range which will be probed at future linear colliders are given. (orig.)

  3. Inhomogeneous models of interacting dark matter and dark energy

    CERN Document Server

    Sussman, R A; Gonzalez, O M; Sussman, Roberto A; Quiros, Israel; Gonzalez, Osmel Martin

    2005-01-01

    We derive and analyze a class of spherically symmetric cosmological models whose source is an interactive mixture of inhomogeneous cold dark matter (DM) and a generic homogeneous dark energy (DE) fluid. If the DE fluid corresponds to a quintessense scalar field, the interaction term can be associated with a well motivated non--minimal coupling to the DM component. By constructing a suitable volume average of the DM component we obtain a Friedman evolution equation relating this average density with an average Hubble scalar, with the DE component playing the role of a repulsive and time-dependent $\\Lambda$ term. Once we select an ``equation of state'' linking the energy density ($\\mu$) and pressure ($p$) of the DE fluid, as well as a free function governing the radial dependence, the models become fully determinate and can be applied to known specific DE sources, such as quintessense scalar fields or tachyonic fluids. Considering the simple equation of state $p= (\\gamma-1) \\mu$ with $0\\leq\\gamma <2/3$, we s...

  4. High-energy strong interactions: from `hard' to `soft'

    CERN Document Server

    Ryskin, M G; Khoze, V A

    2011-01-01

    We discuss the qualitative features of the recent data on multiparticle production observed at the LHC. The tolerable agreement with Monte Carlos based on LO DGLAP evolution indicates that there is no qualitative difference between `hard' and `soft' interactions; and that a perturbative QCD approach may be extended into the soft domain. However, in order to describe the data, these Monte Carlos need an additional infrared cutoff k_min with a value k_min ~ 2-3 GeV which is not small, and which increases with collider energy. Here we explain the physical origin of the large k_min. Using an alternative model which matches the `soft' high-energy hadron interactions smoothly on to perturbative QCD at small x, we demonstrate that this effective cutoff k_min is actually due to the strong absorption of low k_t partons. The model embodies the main features of the BFKL approach, including the diffusion in transverse momenta, lnk_t, and an intercept consistent with resummed next-to-leading log corrections. Moreover, the...

  5. Strong interactions and electromagnetism in low-energy hadron physics

    International Nuclear Information System (INIS)

    In the present work, we study various aspects of the entanglement of the strong and electromagnetic interactions as it is manifest in low-energy hadron physics. In the framework of chiral perturbation theory, two aspects are investigated: the test of the structure of baryons as probed by external electromagnetic currents, and the modification of reactions mediated by the strong interactions in the presence of internal (virtual) photons. In the first part of this work, we study the electromagnetic form factors of nucleons and the ground state baryon octet, as well as strangeness form factors of the nucleon. Emphasis is put on the comparison of a new relativistic scheme for the calculation of loop diagrams to the heavy-baryon formalism, and on the convergence of higher-order corrections in both schemes. The new scheme is shown to yield both a phenomenologically more successful description of the data and better convergence behaviour. In the second part, we study isospin violation in pion-kaon scattering as mediated by virtual photon effects and the light quark mass difference. This investigation is of particular importance for the extraction of scattering lengths from measurements of lifetime and energy levels in pion-kaon atoms. The isospin breaking corrections are shown to be small and sufficiently well under control. (orig.)

  6. Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions.

    Science.gov (United States)

    Haubenreisser, Stefan; Wste, Thorsten H; Martnez, Claudio; Ishihara, Kazuaki; Muiz, Kilian

    2016-01-01

    Molecular structures of the most prominent chiral non-racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen-bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis. PMID:26596513

  7. Dissecting Anion Effects in Gold(I)-Catalyzed Intermolecular Cycloadditions

    OpenAIRE

    Homs, Anna; Obradors, Carla; Lebœuf, David; Echavarren, Antonio M.

    2014-01-01

    From a series of gold complexes of the type [t-BuXPhosAu(MeCN)]X (X=anion), the best results in intermolecular gold(I)-catalyzed reactions are obtained with the complex with the bulky and soft anion BAr4 F− [BAr4 F−=3,5-bis(trifluoromethyl)phenylborate] improving the original protocols by 10–30% yield. A kinetic study on the [2+2] cycloaddition reaction of alkynes with alkenes is consistent with an scenario in which the rate-determining step is the ligand exchange to generate the (η2-phenylac...

  8. Combining climate and energy policies: synergies or antagonism? Modeling interactions with energy efficiency instruments

    Energy Technology Data Exchange (ETDEWEB)

    Lecuyer, Oskar [EDF R and D - Efese, 1 av du General de Gaulle, 92141 Clamart (France)] [CIRED, 45 bis av de la Belle-Gabrielle, 94736 Nogent-sur-Marne (France); Bibas, Ruben [CIRED, 45 bis av de la Belle-Gabrielle, 94736 Nogent-sur-Marne (France)

    2012-01-15

    In addition to the already present Climate and Energy package, the European Union (EU) plans to include a binding target to reduce energy consumption. We analyze the rationales the EU invokes to justify such an overlapping and develop a minimal common framework to study interactions arising from the combination of instruments reducing emissions, promoting renewable energy (RE) production and reducing energy demand through energy efficiency (EE) investments. We find that although all instruments tend to reduce GHG emissions and although a price on carbon tends also to give the right incentives for RE and EE, the combination of more than one instrument leads to significant antagonisms regarding major objectives of the policy package. The model allows to show in a single framework and to quantify the antagonistic effects of the joint promotion of RE and EE. We also show and quantify the effects of this joint promotion on ETS permit price, on wholesale market price and on energy production levels. (authors)

  9. Combining climate and energy policies: synergies or antagonism? Modeling interactions with energy efficiency instruments

    International Nuclear Information System (INIS)

    In addition to the already present Climate and Energy package, the European Union (EU) plans to include a binding target to reduce energy consumption. We analyze the rationales the EU invokes to justify such an overlapping and develop a minimal common framework to study interactions arising from the combination of instruments reducing emissions, promoting renewable energy (RE) production and reducing energy demand through energy efficiency (EE) investments. We find that although all instruments tend to reduce GHG emissions and although a price on carbon tends also to give the right incentives for RE and EE, the combination of more than one instrument leads to significant antagonisms regarding major objectives of the policy package. The model allows to show in a single framework and to quantify the antagonistic effects of the joint promotion of RE and EE. We also show and quantify the effects of this joint promotion on ETS permit price, on wholesale market price and on energy production levels. (authors)

  10. A chemical approach for site-specific identification of NMR signals from protein side-chain NH3+ groups forming intermolecular ion pairs in protein–nucleic acid complexes

    International Nuclear Information System (INIS)

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH3+ groups forming the intermolecular ion pairs. A characteristic change in their 1H and 15N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain 15N and DNA phosphorodithiaote 31P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well

  11. A chemical approach for site-specific identification of NMR signals from protein side-chain NH{sub 3}{sup +} groups forming intermolecular ion pairs in protein–nucleic acid complexes

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kurtis M. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States); Gorenstein, David G. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Iwahara, Junji, E-mail: juiwahar@utmb.edu, E-mail: j.iwahara@utmb.edu [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States)

    2015-05-15

    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH{sub 3}{sup +} groups forming the intermolecular ion pairs. A characteristic change in their {sup 1}H and {sup 15}N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain {sup 15}N and DNA phosphorodithiaote {sup 31}P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well.

  12. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    OpenAIRE

    Nagy, Peter I.

    2014-01-01

    A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with int...

  13. Resonant Interaction, Approximate Symmetry, and Electromagnetic Interaction (EMI) in Low Energy Nuclear Reactions (LENR)

    Science.gov (United States)

    Chubb, Scott

    2007-03-01

    Only recently (talk by P.A. Mosier-Boss et al, in this session) has it become possible to trigger high energy particle emission and Excess Heat, on demand, in LENR involving PdD. Also, most nuclear physicists are bothered by the fact that the dominant reaction appears to be related to the least common deuteron(d) fusion reaction,d+d ->α+γ. A clear consensus about the underlying effect has also been illusive. One reason for this involves confusion about the approximate (SU2) symmetry: The fact that all d-d fusion reactions conserve isospin has been widely assumed to mean the dynamics is driven by the strong force interaction (SFI), NOT EMI. Thus, most nuclear physicists assume: 1. EMI is static; 2. Dominant reactions have smallest changes in incident kinetic energy (T); and (because of 2), d+d ->α+γ is suppressed. But this assumes a stronger form of SU2 symmetry than is present; d+d ->α+γ reactions are suppressed not because of large changes in T but because the interaction potential involves EMI, is dynamic (not static), the SFI is static, and because the two incident deuterons must have approximate Bose Exchange symmetry and vanishing spin. A generalization of this idea involves a resonant form of reaction, similar to the de-excitation of an atom. These and related (broken gauge) symmetry EMI effects on LENR are discussed.

  14. [Noncovalent cation-? interactions--their role in nature].

    Science.gov (United States)

    Fink, Krzysztof; Boraty?ski, Janusz

    2014-01-01

    Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-? interactions--is gaining increasing attention. These interactions occur between a cation and a ? system. The main contributors to cation-? interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-? interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-? interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-? interactions occur in environments with lower accessibility to a polar solvent. Cation-? interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-? interactions are abundant and play an important role in many biological processes. PMID:25380210

  15. Interaction of low-energy highly charged ions with matter

    International Nuclear Information System (INIS)

    The thesis presented herein deals with experimental studies of the interaction between highly charged ions and neutral matter at low collision energies. The energy range investigated is of great interest for the understanding of both charge exchange reactions between ions comprising the solar wind and various astrophysical gases, as well as the creation of near-surface nanostructures. Over the course of this thesis an experimental setup was constructed, capable of reducing the kinetic energy of incoming ions by two orders of magnitude and finally focussing the decelerated ion beam onto a solid or gaseous target. A coincidence method was employed for the simultaneous detection of photons emitted during the charge exchange process together with the corresponding projectile ions. In this manner, it was possible to separate reaction channels, whose superposition presumably propagated large uncertainties and systematic errors in previous measurements. This work has unveiled unexpectedly strong contributions of slow radiative decay channels and clear evidence of previously only postulated decay processes in charge exchange-induced X-ray spectra. (orig.)

  16. Low energy charged particles interacting with amorphous solid water layers

    International Nuclear Information System (INIS)

    The interaction of charged particles with condensed water films has been studied extensively in recent years due to its importance in biological systems, ecology as well as interstellar processes. We have studied low energy electrons (3-25 eV) and positive argon ions (55 eV) charging effects on amorphous solid water (ASW) and ice films, 120-1080 ML thick, deposited on ruthenium single crystal under ultrahigh vacuum conditions. Charging the ASW films by both electrons and positive argon ions has been measured using a Kelvin probe for contact potential difference (CPD) detection and found to obey plate capacitor physics. The incoming electrons kinetic energy has defined the maximum measurable CPD values by retarding further impinging electrons. L-defects (shallow traps) are suggested to be populated by the penetrating electrons and stabilize them. Low energy electron transmission measurements (currents of 0.4-1.5 μA) have shown that the maximal and stable CPD values were obtained only after a relatively slow change has been completed within the ASW structure. Once the film has been stabilized, the spontaneous discharge was measured over a period of several hours at 103 ± 2 K. Finally, UV laser photo-emission study of the charged films has suggested that the negative charges tend to reside primarily at the ASW-vacuum interface, in good agreement with the known behavior of charged water clusters.

  17. Heavy ion interactions in the TeV energy domain

    International Nuclear Information System (INIS)

    Heavy-ion interactions at 60 and 200 A GeV have been studied at the CERN SPS. The energy flow in the pseudo-rapidity region >2.4 is studied with two sampling calorimeters in the WA80 experiment. It is concluded that the nuclear geometry plays an important role for energy flow in nucleus-nucleus collisions at these energies. The laser system for the gain control of the sampling calorimeters is described as well. A new emulsion technique for accurate angular measurements in the pseudo-rapidity region >1.3 used in the EMU01 experiment is described. With this technique the pseudo-rapidity distributions of relativistic singly charged particles are studied. The conclusion is that the geometry together with the fluctuations in participating nucleons, break-up of strings and decay of resonances can describe the obtained results. The standard emulsion technique is used to study the target fragmentation in nucleus-nucleus collisions at 200 A GeV. It is found that a first order cascade correction alone is unable to explain the observed emulsion results on target related fragments. (author)

  18. High energy neutral atoms from high intensity laser plasma interaction

    International Nuclear Information System (INIS)

    Interaction of a high intensity laser with solid targets leads to acceleration of ions from the surface of the target. Ion acceleration is governed by electron dynamics at the target vacuum interface setting up a charge separation. This electron cloud near the target interface can also provide a neutralizing background for ions that have been accelerated. The accelerated ions are thus detected as a high energy neutral atom on a detector. Further, due to the inherent contrast profile of high intensity lasers a pre-plasma is almost always formed and neutral atoms can be detected. The ion and neutral atom energies are measured by a Thomson parabola spectrometer coupled with a 'time of flight' measurement. The neutral atom energies are obtained from the time of flight. The TIFR 20TW laser with an intensity contrast 10-5 was used to carry out the experiment. Defocusing the target led to a 2 fold increase in the neutral atom yield suggesting the role of the pre-plasma. Using a high contrast laser we attempt to tune the recombination dynamics for efficient neutralization of ions by using a controlled pre-plasma. (author)

  19. Probing molecular interaction in ionic liquids by low frequency spectroscopy: Coulomb energy, hydrogen bonding and dispersion forces.

    Science.gov (United States)

    Fumino, Koichi; Reimann, Sebastian; Ludwig, Ralf

    2014-10-28

    Ionic liquids are defined as salts composed solely of ions with melting points below 100 °C. These remarkable liquids have unique and fascinating properties and offer new opportunities for science and technology. New combinations of ions provide changing physical properties and thus novel potential applications for this class of liquid materials. To a large extent, the structure and properties of ionic liquids are determined by the intermolecular interaction between anions and cations. In this perspective we show that far infrared and terahertz spectroscopy are suitable methods for studying the cation-anion interaction in these Coulomb fluids. The interpretation of the measured low frequency spectra is supported by density functional theory calculations and molecular dynamics simulations. We present results for selected aprotic and protic ionic liquids and their mixtures with molecular solvents. In particular, we focus on the strength and type of intermolecular interaction and how both parameters are influenced by the character of the ions and their combinations. We show that the total interaction between cations and anions is a result of a subtle balance between Coulomb forces, hydrogen bonds and dispersion forces. For protic ionic liquids we could measure distinct vibrational modes in the low frequency spectra indicating clearly the cation-anion interaction characterized by linear and medium to strong hydrogen bonds. Using isotopic substitution we have been able to dissect frequency shifts related to pure interaction strength between cations and anions and to different reduced masses only. In this context we also show how these different types of interaction may influence the physical properties of ionic liquids such as the melting point, viscosity or enthalpy of vaporization. Furthermore we demonstrate that low frequency spectroscopy can also be used for studying ion speciation. Low vibrational features can be assigned to contact ion pairs and solvent separated ion pairs. In conclusion we showed how detailed knowledge of the low frequency spectra can be used to understand the change in interaction strength and structure by variation of temperature, solvent polarity and solvent concentration in ionic liquids and their mixtures with molecular solvents. In principle the used combination of methods is suitable for studying intermolecular interaction in pure molecular liquids and their solutions including additive materials such as nanoparticles. PMID:24898478

  20. Intra- and intermolecular reaction selectivities of γ-substituted adamantanylidenes.

    Science.gov (United States)

    Knoll, Wolfgang; Kaneno, Daisuke; Bobek, Michael M; Brecker, Lothar; Rosenberg, Murray G; Tomoda, Shuji; Brinker, Udo H

    2012-02-01

    A study of adamantanylidenes having a γ-substituent (R) was undertaken to gauge how inductive and steric effects of remotely positioned functional groups influence intra- and intermolecular product selectivity. 3H-Diazirines were thermolyzed or photolyzed to generate the corresponding carbenes. On rapid heating, the resulting carbenes isomerized to 2,4-didehydroadamantanes by intramolecular 1,3-CH insertions. When R was an electron donor (R(D)) mostly asymmetric 1-substituted derivatives were produced but when it was an electron acceptor (R(A)) the symmetric 7-substituted ones were formed. When solutions were exposed to UV-A light, intermolecular adducts from the carbenes and solvent predominated with lesser amounts of intramolecular product being formed. Valence isomerization of 3H-diazirines also afforded diazo compounds. In methanol, protonation of diazo compounds to give the corresponding 2-adamantyl cations exceeds their coupling. This diversion was controlled with fumaronitrile by trapping the diazo compounds. The adducts possessed mostly anti configurations with R = R(D) and syn arrangements with R = R(A). The connection between as- and anti-product formation and that of s- and syn-products was deemed to be the consequence of a rapid equilibrium between two distinct carbene conformations. This was qualified and quantified using ab initio calculations and NBO analyses. PMID:22168480