WorldWideScience

Sample records for polarizable transferable intermolecular

  1. Molecular dynamics simulations of nonpolarizable inorganic salt solution interfaces: NaCl, NaBr, and NaI in transferable intermolecular potential 4-point with charge dependent polarizability (TIP4P-QDP) water

    Science.gov (United States)

    Bauer, Brad A.; Patel, Sandeep

    2010-01-01

    We present molecular dynamics simulations of the liquid-vapor interface of 1M salt solutions of nonpolarizable NaCl, NaBr, and NaI in polarizable transferable intermolecular potential 4-point with charge dependent polarizability water [B. A. Bauer et al., J. Chem. Theory Comput. 5, 359 (2009)]; this water model accommodates increased solvent polarizability (relative to the condensed phase) in the interfacial and vapor regions. We employ fixed-charge ion models developed in conjunction with the TIP4P-QDP water model to reproduce ab initio ion-water binding energies and ion-water distances for isolated ion-water pairs. The transferability of these ion models to the condensed phase was validated with hydration free energies computed using thermodynamic integration (TI) and appropriate energy corrections. Density profiles of Cl-, Br-, and I- exhibit charge layering in the interfacial region; anions and cation interfacial probabilities show marked localization, with the anions penetrating further toward the vapor than the cations. Importantly, in none of the cases studied do anions favor the outermost regions of the interface; there is always an aqueous region between the anions and vapor phase. Observed interfacial charge layering is independent of the strength of anion-cation interactions as manifest in anion-cation contact ion pair peaks and solvent separated ion pair peaks; by artificially modulating the strength of anion-cation interactions (independent of their interactions with solvent), we find little dependence on charge layering particularly for the larger iodide anion. The present results reiterate the widely held view of the importance of solvent and ion polarizability in mediating specific anion surface segregation effects. Moreover, due to the higher parametrized polarizability of the TIP4P-QDP condensed phase {1.31 Å3 for TIP4P-QDP versus 1.1 Å3 (TIP4P-FQ) and 0.87 Å3 (POL3) [Ponder and Case, Adv. Protein Chem. 66, 27 (2003)]} based on ab initio

  2. Transferability of polarizable models for ion-water electrostatic interaction

    International Nuclear Information System (INIS)

    Masia, Marco

    2009-01-01

    Studies of ion-water systems at condensed phase and at interfaces have pointed out that molecular and ionic polarization plays an important role for many phenomena ranging from hydrogen bond dynamics to water interfaces' structure. Classical and ab initio Molecular Dynamics simulations reveal that induced dipole moments at interfaces (e.g. air-water and water-protein) are usually high, hinting that polarizable models to be implemented in classical force fields should be very accurate in reproducing the electrostatic properties of the system. In this paper the electrostatic properties of three classical polarizable models for ion-water interaction are compared with ab initio results both at gas and condensed phase. For Li + - water and Cl - -water dimers the reproducibility of total dipole moments obtained with high level quantum chemical calculations is studied; for the same ions in liquid water, Car-Parrinello Molecular Dynamics simulations are used to compute the time evolution of ionic and molecular dipole moments, which are compared with the classical models. The PD2-H2O model developed by the author and coworkers [Masia et al. J. Chem. Phys. 2004, 121, 7362] together with the gaussian intermolecular damping for ion-water interaction [Masia et al. J. Chem. Phys. 2005, 123, 164505] showed to be the fittest in reproducing the ab initio results from gas to condensed phase, allowing for force field transferability.

  3. A Polarizable and Transferable PHAST CO 2 Potential for Materials Simulation

    KAUST Repository

    Mullen, Ashley L.

    2013-12-10

    Reliable PHAST (Potentials with High Accuracy Speed and Transferability) intermolecular potential energy functions for CO2 have been developed from first principles for use in heterogeneous systems, including one with explicit polarization. The intermolecular potentials have been expressed in a transferable form and parametrized from nearly exact electronic structure calculations. Models with and without explicit many-body polarization effects, known to be important in simulation of interfacial processes, are constructed. The models have been validated on pressure-density isotherms of bulk CO 2 and adsorption in three metal-organic framework (MOF) materials. The present models appear to offer advantages over high quality fluid/liquid state potentials in describing CO2 interactions in interfacial environments where sorbates adopt orientations not commonly explored in bulk fluids. Thus, the nonpolar CO2-PHAST and polarizable CO 2-PHAST* potentials are recommended for materials/interfacial simulations. © 2013 American Chemical Society.

  4. Electronic Energy Transfer in Polarizable Heterogeneous Environments

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Kongsted, Jacob

    2015-01-01

    such couplings provide important insight into the strength of interaction between photo-active pigments in protein-pigment complexes. Recently, attention has been payed to how the environment modifies or even controls the electronic couplings. To enable such theoretical predictions, a fully polarizable embedding......-order multipole moments. We use this extended model to systematically examine three different ways of obtaining EET couplings in a heterogeneous medium ranging from use of the exact transition density to a point-dipole approximation. Several interesting observations are made including that explicit use...... of transition densities in the calculation of the electronic couplings - also when including the explicit environment contribution - can be replaced by a much simpler transition point charge description without comprising the quality of the model predictions....

  5. Ultrafast intermolecular energy transfer in heavy water

    NARCIS (Netherlands)

    Piatkowski, L.; Eisenthal, K.B.; Bakker, H.J.

    2009-01-01

    We report on a study of the vibrational energy relaxation and resonant vibrational (Forster) energy transfer of the OD vibrations of D2O and mixtures of D2O and H2O using femtosecond mid-infrared spectroscopy. We observe the lifetime of the OD vibrations of bulk D2O to be 400 +/- 30 fs. The rate of

  6. Intermolecular polarizabilities in H{sub 2}-rare-gas mixtures (H{sub 2}–He, Ne, Ar, Kr, Xe): Insight from collisional isotropic spectral properties

    Energy Technology Data Exchange (ETDEWEB)

    Głaz, Waldemar, E-mail: glaz@kielich.amu.edu.pl; Bancewicz, Tadeusz [Nonlinear Optics Division, Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Godet, Jean-Luc [Laboratoire de photonique d’Angers, Université d’Angers, 2 boulevard Lavoisier, 49045 Angers (France); Gustafsson, Magnus [Department of Chemistry and Molecular Biology, University of Gothenburg, SE 412 96 Gothenburg (Sweden); Maroulis, George; Haskopoulos, Anastasios [Department of Chemistry, University of Patras, GR-26500 Patras (Greece)

    2014-08-21

    The report presents results of theoretical and numerical analysis of the electrical properties related to the isotropic part of the polarizability induced by interactions within compounds built up of a hydrogen H{sub 2} molecule and a set of noble gas atoms, Rg, ranging from the least massive helium up to the heaviest xenon perturber. The Cartesian components of the collisional polarizabilities of the H{sub 2}–Rg systems are found by means of the quantum chemistry methods and their dependence on the intermolecular distance is determined. On the basis of these data, the spherical, symmetry adapted components of the trace polarizability are derived in order to provide data sets that are convenient for evaluating collisional spectral profiles of the isotropic polarized part of light scattered by the H{sub 2}–Rg mixtures. Three independent methods of numerical computing of the spectral intensities are applied at room temperature (295 K). The properties of the roto-translational profiles obtained are discussed in order to determine the role played by contributions corresponding to each of the symmetry adapted parts of the trace polarizability. By spreading the analysis over the collection of the H{sub 2}–Rg systems, evolution of the spectral properties with the growing masses of the supermolecular compounds can be observed.

  7. Intermolecular polarizabilities in H2-rare-gas mixtures (H2-He, Ne, Ar, Kr, Xe): insight from collisional isotropic spectral properties.

    Science.gov (United States)

    Głaz, Waldemar; Bancewicz, Tadeusz; Godet, Jean-Luc; Gustafsson, Magnus; Maroulis, George; Haskopoulos, Anastasios

    2014-08-21

    The report presents results of theoretical and numerical analysis of the electrical properties related to the isotropic part of the polarizability induced by interactions within compounds built up of a hydrogen H2 molecule and a set of noble gas atoms, Rg, ranging from the least massive helium up to the heaviest xenon perturber. The Cartesian components of the collisional polarizabilities of the H2-Rg systems are found by means of the quantum chemistry methods and their dependence on the intermolecular distance is determined. On the basis of these data, the spherical, symmetry adapted components of the trace polarizability are derived in order to provide data sets that are convenient for evaluating collisional spectral profiles of the isotropic polarized part of light scattered by the H2-Rg mixtures. Three independent methods of numerical computing of the spectral intensities are applied at room temperature (295 K). The properties of the roto-translational profiles obtained are discussed in order to determine the role played by contributions corresponding to each of the symmetry adapted parts of the trace polarizability. By spreading the analysis over the collection of the H2-Rg systems, evolution of the spectral properties with the growing masses of the supermolecular compounds can be observed.

  8. Ion Transfer Voltammetry Associated with Two Polarizable Interfaces Within Water and Moderately Hydrophobic Ionic Liquid Systems

    DEFF Research Database (Denmark)

    Gan, Shiyu; Zhou, Min; Zhang, Jingdong

    2013-01-01

    An electrochemical system composed of two polarizable interfaces (the metallic electrode|water and water|ionic liquid interfaces), namely two‐polarized‐interface (TPI) technique, has been proposed to explore the ion transfer processes between water and moderately hydrophobic ionic liquids (W|mIL)...

  9. Intermolecular proton transfer in anionic complexes of uracil with alcohols

    International Nuclear Information System (INIS)

    Haranczyk, Maciej; Rak, Janusz; Gutowski, Maciej S.; Radisic, Dunja; Stokes, Sarah T.; Bowen, Kit H.

    2005-01-01

    A series of eighteen alcohols (ROH) has been designed with an enthalpy of deprotonation (H DP ) in a range of 13.8-16.3 eV. The effects of excess electron attachment to the binary alcohol-uracil (ROH...U) complexes have been studied at the density functional level with a B3LYP exchange-correlation functional and at the second order Moeller-Plesset perturbation theory level. The photoelectron spectra of anionic complexes of uracil with three alcohols (ethanol, 2,2,3,3,3-pentafluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol) have been measured with 2.54 eV photons. For ROHs with deprotonation enthalpies larger than 14.8 eV only the ROH...U - minimum exists on the potential energy surface of the anionic complex. For alcohols with deprotonation enthalpies in a range of 14.3-14.8 eV two minima might exist on the anionic potential energy surface, which correspond to the RO - ...HU . and ROH...U - structures. For ROHs with deprotonation enthalpies smaller than 14.3 eV, the excess electron attachment to the ROH...U complex always induces a barrier-free proton transfer from the hydroxyl group of ROH to the O8 atom of U, with the product being RO - ...HU . . A driving force for the intermolecular proton transfer is to stabilize the excess negative charge localized on a orbital of uracil. Therefore, these complexes with proton transferred to the anionic uracil are characterized by larger values of electron vertical detachment energy (VDE). The values of VDE for anionic complexes span a range from 1.0 to 2.3 eV and roughly correlate with the acidity of alcohols. However, there is a gap of ∼0.5 eV in the values of VDE, which separates the two families, ROH...U - and RO - ...HU . , of anionic complexes. The energy of stabilization for the anionic complexes spans a range from 0.6 to 1.7 eV and roughly correlates with the acidity of alcohols. The measured photoelectron spectra are in good agreement with the theoretical predictions

  10. Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies.

    Science.gov (United States)

    Dolan, Nicholas S; Scamp, Ryan J; Yang, Tzuhsiung; Berry, John F; Schomaker, Jennifer M

    2016-11-09

    The development of new catalysts for selective nitrene transfer is a continuing area of interest. In particular, the ability to control the chemoselectivity of intermolecular reactions in the presence of multiple reactive sites has been a long-standing challenge in the field. In this paper, we demonstrate examples of silver-catalyzed, nondirected, intermolecular nitrene transfer reactions that are both chemoselective and flexible for aziridination or C-H insertion, depending on the choice of ligand. Experimental probes present a puzzling picture of the mechanistic details of the pathways mediated by [( t Bu 3 tpy)AgOTf] 2 and (tpa)AgOTf. Computational studies elucidate these subtleties and provide guidance for the future development of new catalysts exhibiting improved tunability in group transfer reactions.

  11. Organic narrowband near-infrared photodetectors based on intermolecular charge-transfer absorption

    Science.gov (United States)

    Siegmund, Bernhard; Mischok, Andreas; Benduhn, Johannes; Zeika, Olaf; Ullbrich, Sascha; Nehm, Frederik; Böhm, Matthias; Spoltore, Donato; Fröb, Hartmut; Körner, Christian; Leo, Karl; Vandewal, Koen

    2017-06-01

    Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection.

  12. Formation of an intermolecular charge-transfer compound in UHV codeposited tetramethoxypyrene and tetracyanoquinodimethane

    DEFF Research Database (Denmark)

    Medjanik, K.; Perkert, S.; Naghavi, S.

    2010-01-01

    Ultrahigh vacuum (UHV)-deposited films of the mixed phase of tetramethoxypyrene and tetracyanoquinodimethane (TMP -TCNQ ) on gold have been studied using ultraviolet photoelectron spectroscopy (UPS), x-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning tunneling spectroscopy (STS......). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d =0.894nm and d =0.677nm). A softening of the CN stretching vibration (redshift by 7 cm⊃-1) of TCNQ is visible in the IR spectra, being indicative of a CT on the order of 0.3e from TMP...

  13. Altering intra- to inter-molecular hydrogen bonding by dimethylsulfoxide: A TDDFT study of charge transfer for coumarin 343

    Science.gov (United States)

    Liu, Xiaochun; Yin, Hang; Li, Hui; Shi, Ying

    2017-04-01

    DFT and TDDFT methods were carried out to investigate the influences of intramolecular and intermolecular hydrogen bonding on excited state charge transfer for coumarin 343 (C343). Intramolecular hydrogen bonding is formed between carboxylic acid group and carbonyl group in C343 monomer. However, in dimethylsulfoxide (DMSO) solution, DMSO 'opens up' the intramolecular hydrogen bonding and forms solute-solvent intermolecular hydrogen bonded C343-DMSO complex. Analysis of frontier molecular orbitals reveals that intramolecular charge transfer (ICT) occurs in the first excited state both for C343 monomer and complex. The results of optimized geometric structures indicate that the intramolecular hydrogen bonding interaction is strengthened while the intermolecular hydrogen bonding is weakened in excited state, which is confirmed again by monitoring the shifts of characteristic peaks of infrared spectra. We demonstrated that DMSO solvent can not only break the intramolecular hydrogen bonding to form intermolecular hydrogen bonding with C343 but also alter the mechanism of excited state hydrogen bonding strengthening.

  14. Intermolecular Singlet and Triplet Exciton Transfer Integrals from Many-Body Green's Functions Theory.

    Science.gov (United States)

    Wehner, Jens; Baumeier, Björn

    2017-04-11

    A general approach to determine orientation and distance-dependent effective intermolecular exciton transfer integrals from many-body Green's functions theory is presented. On the basis of the GW approximation and the Bethe-Salpeter equation (BSE), a projection technique is employed to obtain the excitonic coupling by forming the expectation value of a supramolecular BSE Hamiltonian with electron-hole wave functions for excitations localized on two separated chromophores. Within this approach, accounting for the effects of coupling mediated by intermolecular charge transfer (CT) excitations is possible via perturbation theory or a reduction technique. Application to model configurations of pyrene dimers shows an accurate description of short-range exchange and long-range Coulomb interactions for the coupling of singlet and triplet excitons. Computational parameters, such as the choice of the exchange-correlation functional in the density-functional theory (DFT) calculations that underly the GW-BSE steps and the convergence with the number of included CT excitations, are scrutinized. Finally, an optimal strategy is derived for simulations of full large-scale morphologies by benchmarking various approximations using pairs of dicyanovinyl end-capped oligothiophenes (DCV5T), which are used as donor material in state-of-the-art organic solar cells.

  15. 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

    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...

  16. Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N2 Collisions.

    Science.gov (United States)

    Kim, Hyunsik; Paul, Amit K; Pratihar, Subha; Hase, William L

    2016-07-14

    Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N2 bath. The intermolecular potential between Az and N2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum microcanonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N2 bath density. Using the N2 bath density and Lennard-Jones collision number, the average energy transfer per collision ⟨ΔEc⟩ was obtained for Az* as it is collisionally relaxed. By comparing ⟨ΔEc⟩ versus the bath density, the single collision limiting density was found for energy transfer. The resulting ⟨ΔEc⟩, for an 87.5 kcal/mol excitation energy, is 0.30 ± 0.01 and 0.32 ± 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 ± 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N2 bath.

  17. Keto-enol tautomerization and intermolecular proton transfer in photoionized cyclopentanone dimer in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Arup K.; Chatterjee, Piyali; Chakraborty, Tapas, E-mail: pctc@iacs.res.in [Department of Physical Chemistry, Indian Association for the Cultivation of Science, 2A Raja S. C. Mullick Road, Jadavpur, Kolkata 700032 (India)

    2014-07-28

    Time-of-flight mass spectra of cyclopentanone and its clusters cooled in a supersonic jet expansion have been measured following 4-, 3-, and 2-photon ionizations by the 2nd, 3rd, and 4th harmonic wavelengths, respectively, of a Q-switched Nd:YAG laser. The mass spectra reveal signatures of energetically favored keto to enol tautomerization of the molecular ion leading to intermolecular proton transfer, and this observation is found sharply dependent on the ionization wavelengths used. Electronic structure calculation predicts that in spite of the energetic preference, keto-enol conversion barrier of isolated molecular ion is high. However, the barrier is significantly reduced in a CH⋯O hydrogen-bonded dimer of the molecule. The transition states associated with tautomeric conversion of both cyclopentanone monomer and dimer cations have been identified by means of intrinsic reaction co-ordinate calculation. In a supersonic jet expansion, although a weakly bound dimer is readily generated, the corresponding cation and also the protonated counterpart are observed only for ionization by 532 nm. For other two ionization wavelengths, these species do not register in the mass spectra, where the competing reaction channels via α-cleavage of the ring become dominant. In contrast to the report of a recent study, we notice that the intact molecular ion largely survives fragmentations when ionized from the 2-photon resonant 3p Rydberg state as intermediate using nanosecond laser pulses, and the corresponding resonant 3-photon ionization spectrum has been recorded probing the intact molecular ion.

  18. Intermolecular hydrogen transfer catalyzed by a flavodehydrogenase, bakers' yeast flavocytochrome b2

    International Nuclear Information System (INIS)

    Urban, P.; Lederer, F.

    1985-01-01

    Bakers yeast flavocytochrome b2 is a flavin-dependent L-2-hydroxy acid dehydrogenase which also exhibits transhydrogenase activity. When a reaction takes place between [2- 3 H]lactate and a halogenopyruvate, tritium is found in water and at the halogenolactate C2 position. When the halogenopyruvate undergoes halide ion elimination, tritium is also found at the C3 position of the resulting pyruvate. The amount tau of this intermolecular tritium transfer depends on the initial keto acid-acceptor concentration. At infinite acceptor concentration, extrapolation yields a maximal transfer of 97 +/- 11%. This indicates that the hydroxy acid-derived hydrogen resides transiently on enzyme monoprotic heteroatoms and that exchange with bulk solvent occurs only at the level of free reduced enzyme. Using a minimal kinetic scheme, the rate constant for hydrogen exchange between Ered and solvent is calculated to be on the order of 10(2) M-1 S-1, which leads to an estimated pK approximately equal to 15 for the ionization of the substrate-derived proton while on the enzyme. It is suggested that this hydrogen could be shared between the active site base and Flred N5 anion. It is furthermore shown that some tritium is incorporated into the products when the transhydrogenation is carried out in tritiated water. Finally, with [2-2H]lactate-reduced enzyme, a deuterium isotope effect is observed on the rate of bromopyruvate disappearance. Extrapolation to infinite bromopyruvate concentration yields DV = 4.4. An apparent inverse isotope effect is determined for bromide ion elimination. These results strengthen the idea that oxidoreduction and elimination pathways involve a common carbanionic intermediate

  19. Observation of aggregation triggered by Resonance Energy Transfer (RET) induced intermolecular pairing force.

    Science.gov (United States)

    Pan, Xiaoyong; Wang, Weizhi; Ke, Lin; Zhang, Nan

    2017-07-20

    In this report, we showed the existence of RET induced intermolecular pairing force by comparing their fluorescence behaviors under room illumination vs standing in dark area for either PFluAnt solution or PFluAnt&PFOBT mixture. Their prominent emission attenuation under room illumination brought out the critical role of photo, i.e. RET induced intermolecular pairing force in induction of polymer aggregation. Constant UV-Vis absorption and fluorescence spectra in terms of both peak shapes and maximum wavelengths implied no chemical decomposition was involved. Recoverable fluorescence intensity, fluorescence lifetime as well as NMR spectra further exclude photo induced decomposition. The controllable on/off state of RET induced intermolecular pairing force was verified by the masking effect of outside PFluAnt solution which function as filter to block the excitation of inside PFluAnt and thus off the RET induced intermolecular pairing force. Theoretical calculation suggest that magnitude of RET induced intermolecular pairing force is on the same scale as that of van der Waals interaction. Although the absolute magnitude of RET induced intermolecular pairing force was not tunable, its effect can be magnified by intentionally turn it "on", which was achieved by irradiance with 5 W desk lamp in this report.

  20. Atomic polarizabilities

    International Nuclear Information System (INIS)

    Safronova, M. S.; Mitroy, J.; Clark, Charles W.; Kozlov, M. G.

    2015-01-01

    The atomic dipole polarizability governs the first-order response of an atom to an applied electric field. Atomic polarization phenomena impinge upon a number of areas and processes in physics and have been the subject of considerable interest and heightened importance in recent years. In this paper, we will summarize some of the recent applications of atomic polarizability studies. A summary of results for polarizabilities of noble gases, monovalent, and divalent atoms is given. The development of the CI+all-order method that combines configuration interaction and linearized coupled-cluster approaches is discussed

  1. Atomic polarizabilities

    Energy Technology Data Exchange (ETDEWEB)

    Safronova, M. S. [Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 (United States); Mitroy, J. [School of Engineering, Charles Darwin University, Darwin NT 0909 (Australia); Clark, Charles W. [Joint Quantum Institute, National Institute of Standards and Technology and the University of Maryland, Gaithersburg, Maryland 20899-8410 (United States); Kozlov, M. G. [Petersburg Nuclear Physics Institute, Gatchina 188300 (Russian Federation)

    2015-01-22

    The atomic dipole polarizability governs the first-order response of an atom to an applied electric field. Atomic polarization phenomena impinge upon a number of areas and processes in physics and have been the subject of considerable interest and heightened importance in recent years. In this paper, we will summarize some of the recent applications of atomic polarizability studies. A summary of results for polarizabilities of noble gases, monovalent, and divalent atoms is given. The development of the CI+all-order method that combines configuration interaction and linearized coupled-cluster approaches is discussed.

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

    International Nuclear Information System (INIS)

    Tardy, D.C.

    1988-05-01

    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

  3. Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Zhu, Qilei; Graff, David E; Knowles, Robert R

    2018-01-17

    Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N-H bond. Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented.

  4. Evaluating excited state atomic polarizabilities of chromophores.

    Science.gov (United States)

    Heid, Esther; Hunt, Patricia A; Schröder, Christian

    2018-03-28

    Ground and excited state dipoles and polarizabilities of the chromophores N-methyl-6-oxyquinolinium betaine (MQ) and coumarin 153 (C153) in solution have been evaluated using time-dependent density functional theory (TD-DFT). A method for determining the atomic polarizabilities has been developed; the molecular dipole has been decomposed into atomic charge transfer and polarizability terms, and variation in the presence of an electric field has been used to evaluate atomic polarizabilities. On excitation, MQ undergoes very site-specific changes in polarizability while C153 shows significantly less variation. We also conclude that MQ cannot be adequately described by standard atomic polarizabilities based on atomic number and hybridization state. Changes in the molecular polarizability of MQ (on excitation) are not representative of the local site-specific changes in atomic polarizability, thus the overall molecular polarizability ratio does not provide a good approximation for local atom-specific polarizability changes on excitation. Accurate excited state force fields are needed for computer simulation of solvation dynamics. The chromophores considered in this study are often used as molecular probes. The methods and data reported here can be used for the construction of polarizable ground and excited state force fields. Atomic and molecular polarizabilities (ground and excited states) have been evaluated over a range of functionals and basis sets. Different mechanisms for including solvation effects have been examined; using a polarizable continuum model, explicit solvation and via sampling of clusters extracted from a MD simulation. A range of different solvents have also been considered.

  5. 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

    2002-01-01

    The calcium-sensing receptor (CaR) belongs to family C of the G-protein coupled receptor superfamily. The receptor is believed to exist as a homodimer due to covalent and non-covalent interactions between the two amino terminal domains (ATDs). It is well established that agonist binding to family C...... receptors takes place at the ATD and that this causes the ATD dimer to twist. However, very little is known about the translation of the ATD dimer twist into G-protein coupling to the 7 transmembrane moieties (7TMs) of these receptor dimers. In this study we have attempted to delineate the agonist......-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...

  6. Transfer of Frequency-Dependent Polarizabilities: A Tool To Simulate Absorption and Circular Dichroism Molecular Spectra

    Czech Academy of Sciences Publication Activity Database

    Kessler, Jiří; Bouř, Petr

    2015-01-01

    Roč. 11, č. 5 (2015), s. 2210-2220 ISSN 1549-9618 R&D Projects: GA ČR GAP208/11/0105; GA ČR GA13-03978S; GA ČR GA15-09072S Grant - others:GA AV ČR(CZ) M200551205; GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : Raman optical activity * density functional theory * charge-transfer transitions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

  7. The first strand transfer during HIV-1 reverse transcription can occur either intramolecularly or intermolecularly

    NARCIS (Netherlands)

    van Wamel, J. L.; Berkhout, B.

    1998-01-01

    Reverse transcription is a complicated process that involves at least two cDNA transfer reactions to produce a full-length copy DNA of the retroviral RNA genome. Because one retrovirus particle contains two identical genomic RNA molecules, the transfers can occur in an intramolecular or

  8. TOWARDS PHASE TRANSFERABLE POTENTIAL FUNCTIONS - METHODOLOGY AND APPLICATION TO NITROGEN

    NARCIS (Netherlands)

    JORDAN, PC; VAN MAAREN, PJ; MAVRI, J; VAN DER SPOEL, D; BERENDSEN, HJC

    1995-01-01

    We describe a generalizable approach to the development of phase transferable effective intermolecular potentials and apply the method to the study of N-2 The method is based on a polarizable shell model description of the isolated molecule and uses experimental data to establish the parameters.

  9. Intermolecular photoinduced electron-transfer processes between C60 and aniline derivatives in benzonitrile

    International Nuclear Information System (INIS)

    Pan Yang; Tang Wenjian; Yu Tangqin; Wang Jinting; Fu Yao; Wang Guanwu; Yu Shuqin

    2007-01-01

    The quenching behavior of the triplets of C 60 by various aniline derivatives (1a-d and 2a-e) was investigated by means of laser flash photolysis in benzonitrile at 293K. Electron transfer process was proposed to be the main mechanism because of the direct detection of radical ions of aniline derivatives and C 60 in time-resolved transient absorption spectra. The quenching rate constants (k q ) of 3 C 60 * by different substrates determined at 740nm approach or reach the diffusion-controlled limit. DFT method was employed to calculate the unknown oxidation potentials of substrates in solution. With these E ox values, free energy changes (ΔG) were obtained through Rehm-Weller equation. Dependence of observed quenching rate constants on the free energy changes further indicates the photoinduced reactions between 3 C 60 * and substrates proceed through an electron transfer mechanism. Obtained k q values for the aniline derivatives are impacted obviously by ground-state configurations and the kinds substituents quantified by Hammett σ constant. Good correlation between logk q and σ values conforms to the empirical Hammett equation. A more negative ρ value (-3.356) was gained for anilines (2a-e) than that of N,N-dimethylanilines (1a-d) (-1.382), which suggests a more susceptible reactivity for the former substrates. Charge density distribution of reaction center ''N'' originated from quantum calculation supports this suggestion. In addition, a relationship between quenching rate constants and solvent viscosity was gained from C 60 /dimethyl-p-toluidine system in altered mixtures of acetonitrile and toluene

  10. CORCEMA evaluation of the potential role of intermolecular transferred NOESY in the characterization of ligand-receptor complexes

    Science.gov (United States)

    Curto, Ernest V.; Moseley, Hunter N. B.; Krishna, N. Rama

    1996-10-01

    We report a theoretical characterization of the intermolecular transferred NOESY (inter-TrNOESY) between ligands and receptor macromolecules that bind reversibly, using a COmplete Relaxation and Conformational Exchange MAtrix (CORCEMA) theory developed in our laboratory. We examine the dependence of inter-TrNOESY on the dissociation constant, off-rate, ligand-to-receptor ratio, and distance variations between protons of interacting species within the complex. These factors are analyzed from simulations on two model systems: (i) neuraminidase complexed to a transition-state analogue; and (ii) thermolysin complexed to a leucine-based inhibitor. The latter case utilizes a three-state model of interaction to simulate the effect of hinge-bending motions on the inter-TrNOESY. Our calculations suggest a potential role for inter-TrNOESY (when observable) and CORCEMA analysis in properly docking the ligand within the active site, and in refining the conformation of the ligand-receptor (active-site) complex. These findings have implications on the structure-based design of ligands (e.g., inhibitors) reversibly binding to receptors (e.g., enzymes).

  11. Estimating and modeling charge transfer from the SAPT induction energy.

    Science.gov (United States)

    Deng, Shi; Wang, Qiantao; Ren, Pengyu

    2017-10-05

    Recent studies using quantum mechanics energy decomposition methods, for example, SAPT and ALMO, have revealed that the charge transfer energy may play an important role in short ranged inter-molecular interactions, and have a different distance dependence comparing with the polarization energy. However, the charge transfer energy component has been ignored in most current polarizable or non-polarizable force fields. In this work, first, we proposed an empirical decomposition of SAPT induction energy into charge transfer and polarization energy that mimics the regularized SAPT method (ED-SAPT). This empirical decomposition is free of the divergence issue, hence providing a good reference for force field development. Then, we further extended this concept in the context of AMOEBA polarizable force field, proposed a consistent approach to treat the charge transfer phenomenon. Current results show a promising application of this charge transfer model in future force field development. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  12. Electromagnetic polarizabilities of hadrons

    International Nuclear Information System (INIS)

    Friar, J.L.

    1988-01-01

    Electromagnetic polarizabilities of hadrons are reviewed, after a discussion of classical analogues. Differences between relativistic and non-relativistic approaches can lead to conflicts with conventional nuclear physics sum rules and calculational techniques. The nucleon polarizabilities are discussed in the context of the non-relativistic valence quark model, which provides a good qualitative description. The recently measured pion polarizabilities are discussed in the context of chiral symmetry and quark-loop models. 58 refs., 5 figs

  13. Description of the Charge Transfer States at the Pentacene/C60 Interface: Combining Range-Separated Hybrid Functionals with the Polarizable Continuum Model

    KAUST Repository

    Zheng, Zilong

    2016-06-24

    Density functional theory (DFT) approaches based on range-separated hybrid functionals are currently methods of choice for the description of the charge-transfer (CT) states in organic donor/acceptor solar cells. However, these calculations are usually performed on small-size donor/acceptor complexes and as result do not account for electronic polarization effects. Here, using a pentacene/C60 complex as a model system, we discuss the ability of long-range corrected (LCR) hybrid functionals in combination with the polarizable continuum model (PCM) to determine the impact of the solid-state environment on the CT states. The CT energies are found to be insensitive to the interactions with the dielectric medium when a conventional time-dependent DFT/PCM (TDDFT/PCM) approach is used. However, a decrease in the energy of the CT state in the framework of LRC functionals can be obtained by using a smaller range-separated parameter when going from an isolated donor/acceptor complex to the solid-state case.

  14. The nonadditive intermolecular potential for water revised

    International Nuclear Information System (INIS)

    Dang, L.X.

    1992-01-01

    The results of an improved version of a nonadditive intermolecular model for water that explicitly includes the nonadditive polarization energy are reported. The original polarizable water potential model (POL1), upon which the improved version is based, was developed by Caldwell, Dang, and Kollman [J. Am. Soc. Chem. 112, 9144 (1990)]. To improve the POL1 model, we developed a new set of atomic polarizabilities that reproduce the experimental molecular polarizability for water using the atom--dipole interaction model (Applequist, Carl, and Fung [J. Am. Soc. Chem. 94, 2952 (1972)]). Using the new atomic polarizabilities, we optimized the Lennard-Jones parameters for O--O interactions to improve the model. As expected, the new model has improved the radial distribution functions and the average potential energy for liquid water as well as the density and the average total dipole moment. The model is then used to compute the binding energies of Cs + --water clusters. Without the need for three-body forces (ion--water--water interaction), the agreement between the results of molecular-dynamics simulations and experimental energies of cluster formation is very good

  15. Computational insight into relations between electronic and vibrational polarizabilities within the two-state valence-bond charge-transfer model

    Czech Academy of Sciences Publication Activity Database

    Zalesny, R.; Bartkowiak, W.; Toman, Petr; Leszczynski, J.

    2007-01-01

    Roč. 337, 1-3 (2007), s. 77-80 ISSN 0301-0104 Grant - others:Polish Committee for Scientific Research and the Ministry of Education, Youth, and Sports of the Czech Republic(PL) CZ25 Institutional research plan: CEZ:AV0Z40500505 Keywords : polarizability * first hyperpolarizability * second hyperpolarizability * nonlinear optical properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.805, year: 2007

  16. Characterizing the Polymer:Fullerene Intermolecular Interactions

    KAUST Repository

    Sweetnam, Sean

    2016-02-02

    Polymer:fullerene solar cells depend heavily on the electronic coupling of the polymer and fullerene molecular species from which they are composed. The intermolecular interaction between the polymer and fullerene tends to be strong in efficient photovoltaic systems, as evidenced by efficient charge transfer processes and by large changes in the energetics of the polymer and fullerene when they are molecularly mixed. Despite the clear presence of these strong intermolecular interactions between the polymer and fullerene, there is not a consensus on the nature of these interactions. In this work, we use a combination of Raman spectroscopy, charge transfer state absorption, and density functional theory calculations to show that the intermolecular interactions do not appear to be caused by ground state charge transfer between the polymer and fullerene. We conclude that these intermolecular interactions are primarily van der Waals in nature. © 2016 American Chemical Society.

  17. Polarizable protein packing

    KAUST Repository

    Ng, Albert H.

    2011-01-24

    To incorporate protein polarization effects within a protein combinatorial optimization framework, we decompose the polarizable force field AMOEBA into low order terms. Including terms up to the third-order provides a fair approximation to the full energy while maintaining tractability. We represent the polarizable packing problem for protein G as a hypergraph and solve for optimal rotamers with the FASTER combinatorial optimization algorithm. These approximate energy models can be improved to high accuracy [root mean square deviation (rmsd) < 1 kJ mol -1] via ridge regression. The resulting trained approximations are used to efficiently identify new, low-energy solutions. The approach is general and should allow combinatorial optimization of other many-body problems. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011 Copyright © 2011 Wiley Periodicals, Inc.

  18. Gaussian-Charge Polarizable and Nonpolarizable Models for CO2.

    Science.gov (United States)

    Jiang, Hao; Moultos, Othonas A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2016-02-11

    A polarizable intermolecular potential model using three classical Drude oscillators on the atomic sites has been developed for CO2. The model is rigid with bond lengths and molecular geometries set to their experimental values. Electrostatic interactions are represented by three Gaussian charges connected to the molecular frame by harmonic springs. Nonelectrostatic interactions are represented by the Buckingham exponential-6 potential, with potential parameters optimized to vapor-liquid equilibria (VLE) data. A nonpolarizable CO2 model that shares the other ingredients of the polarizable model was also developed and optimized to VLE data. Gibbs ensemble Monte Carlo and molecular dynamics simulations were used to evaluate the two models with respect to a variety of thermodynamic and transport properties, including the enthalpy of vaporization, second virial coefficient, density in the one-phase fluid region, isobaric and isochoric heat capacities, radial distribution functions, self-diffusion coefficient, and shear viscosity. Excellent agreement between model predictions and experimental data was found for all properties studied. The polarizable and nonpolarizable models provide a similar representation of CO2 properties, which indicates that the properties of pure CO2 fluid are not strongly affected by polarization. The polarizable model, which has an order of magnitude higher computational cost than the nonpolarizable model, will likely be useful for the study of a mixture of CO2 and polar components for which polarization is important.

  19. Parity nonconservation and nuclear polarizabilities

    International Nuclear Information System (INIS)

    Haxton, W.

    1990-01-01

    The hadronic weak interaction contributes to parity nonconserving observables in semileptonic interactions. Weak nuclear polarizabilities are frequently important in such interactions. Some of the interesting physics is illustrated by 18 F, a nucleus that provides an important constraint on the neutral weak hadronic current. One observable where the nuclear polarizability is expected to dominate is the nuclear anapole moment. The long-range pion contribution to this weak radiative correction is explored for both nucleons and nuclei. Similar polarizabilities that arise for time-reversal-odd hadronic interactions that conserve or violate parity are discussed in connection with atomic electric dipole moments. 20 refs., 4 figs

  20. The Raman and vibronic activity of intermolecular vibrations in aromatic-containing complexes and clusters

    International Nuclear Information System (INIS)

    Maxton, P.M.; Schaeffer, M.W.; Ohline, S.M.; Kim, W.; Venturo, V.A.; Felker, P.M.

    1994-01-01

    Theoretical and experimental results pertaining to the excitation of intermolecular vibrations in the Raman and vibronic spectra of aromatic-containing, weakly bound complexes and clusters are reported. The theoretical analysis of intermolecular Raman activity is based on the assumption that the polarizability tensor of a weakly bound species is given by the sum of the polarizability tensors of its constituent monomers. The analysis shows that the van der Waals bending fundamentals in aromatic--rare gas complexes may be expected to be strongly Raman active. More generally, it predicts strong Raman activity for intermolecular vibrations that involve the libration or internal rotation of monomer moieties having appreciable permanent polarizability anisotropies. The vibronic activity of intermolecular vibrations in aromatic-rare gas complexes is analyzed under the assumption that every vibronic band gains its strength from an aromatic-localized transition. It is found that intermolecular vibrational excitations can accompany aromatic-localized vibronic excitations by the usual Franck--Condon mechanism or by a mechanism dependent on the librational amplitude of the aromatic moiety during the course of the pertinent intermolecular vibration. The latter mechanism can impart appreciable intensity to bands that are forbidden by rigid-molecule symmetry selection rules. The applicability of such rules is therefore called into question. Finally, experimental spectra of intermolecular transitions, obtained by mass-selective, ionization-detected stimulated Raman spectroscopies, are reported for benzene--X (X=Ar, --Ar 2 , N 2 , HCl, CO 2 , and --fluorene), fluorobenzene--Ar and --Kr, aniline--Ar, and fluorene--Ar and --Ar 2 . The results support the conclusions of the theoretical analyses and provide further evidence for the value of Raman methods in characterizing intermolecular vibrational level structures

  1. Intermolecular and surface forces

    CERN Document Server

    Israelachvili, Jacob N

    2011-01-01

    This reference describes the role of various intermolecular and interparticle forces in determining the properties of simple systems such as gases, liquids and solids, with a special focus on more complex colloidal, polymeric and biological systems. The book provides a thorough foundation in theories and concepts of intermolecular forces, allowing researchers and students to recognize which forces are important in any particular system, as well as how to control these forces. This third edition is expanded into three sections and contains five new chapters over the previous edition.· starts fr

  2. Pion polarizabilities measurement at COMPASS

    CERN Document Server

    Guskov, Alexey

    2008-01-01

    The electromagnetic structure of pions is probed in $\\pi^{−}+(A,Z) \\rightarrow\\pi^{−}+(A,Z)+\\gamma$ Compton scattering in inverse kinematics (Primakoff reaction) and described by the electric ($\\bar{\\alpha_{\\pi}}$) and the magnetic ($\\bar{\\beta_{\\pi}}$) polarizabilities that depend on the rigidity of pion’s internal structure as a composite particle. Values for pion polarizabilities can be extracted from the comparison of the differential cross section for scattering of pointlike pions with the measured cross section. The pion polarizability measurement was performed with a $\\pi^{-}$ beam of 190 GeV. The high beam intensity, the good spectrometer resolution, the high rate capability, the high acceptance and the possibility to use pion and muon beams, unique to the COMPASS experiment, provide the tools to measure precisely the pion polarizabilities in the Primakoff reaction.

  3. Molecular Properties through Polarizable Embedding

    DEFF Research Database (Denmark)

    Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob

    2011-01-01

    We review the theory related to the calculation of electric and magnetic molecular properties through polarizable embedding. In particular, we derive the expressions for the response functions up to the level of cubic response within the density functional theory-based polarizable embedding (PE......-DFT) formalism. In addition, we discuss some illustrative applications related to the calculation of nuclear magnetic resonance parameters, nonlinear optical properties, and electronic excited states in solution....

  4. Neutral pion electroproduction and virtual Compton scattering on proton with four-momentum transfer squared Q2 = 1 GeV2. Measurement of cross-sections and of generalized polarizabilities

    International Nuclear Information System (INIS)

    Laveissiere, G.

    2001-11-01

    In hadronic physics, the nucleon structure and the quarks confinement are still topical issues. The neutral pion electroproduction and virtual Compton scattering (VCS) reactions allow us to access new observables that describe this structure. This work is focussed on the VCS experiment performed at Jefferson Lab in 1998. The 4 GeV electron beam is scattered off a cryogenic hydrogen target, and the scattered electron and recoiled proton are detected in coincidence in the twin hall A spectrometers. The photon (pion) is reconstructed using a missing particle technique. The data analysis allowed to extract the cross sections relative to both process at four-momentum transfer squared Q 2 = 1 GeV 2 . The VCS cross section has been extracted for the first time in the proton resonance region (W between 1.O and 2.0 GeV) through the photon electroproduction reaction. Around the pion-production threshold up to the Delta(1232) resonance region, these results lead to the measurement of the generalized polarizabilities, that describe the proton structure in the same way as the elastic form factors. Moreover, the neutral pion electroproduction cross section measurement in the resonance region has brought new constraints on the existing phenomenological models. (author)

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

    International Nuclear Information System (INIS)

    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 2 (B 1 Σ/sub u/ + ) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H 2 (B 1 Σ/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 + H 2 (E,F 1 Σ/sub g/ + ) and with He + H 2 (X 1 Σ/sub g/ + ) and cause a local maximum and a deep minimum in the He + H 2 (B 1 Σ/sub u/ + ) PES, respectively. The crossing with He + H 2 (X 1 Σ/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 H 2 (B 1 Σ/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

  6. Pion polarizabilities measurement at COMPASS

    CERN Document Server

    Guskov, Alexey

    2008-01-01

    The electromagnetic structure of pions is probed in $\\pi^{−} + (A,Z)\\rightarrow\\pi^{−} + (A,Z) +\\gamma$ Compton scattering in inverse kinematics (Primakoff reaction) and described by the electric $(\\bar{\\alpha_{\\pi}})$ and the magnetic $(\\bar{\\beta_{\\pi}})$ polarizabilities that depend on the rigidity of pion’s internal structure as a composite particle. Values for pion polarizabilities can be extracted from the comparison of the differential cross section for scattering of pointlike pions with the measured cross section. The pion polarizability measurement was performed with $a \\pi^{−}$ beam of 190 GeV. The high beam intensity, the good spectrometer resolution, the high rate capability, the high acceptance and the possibility to use pion and muon beams, unique to the COMPASS experiment, provide the tools to measure precisely the pion polarizabilities in the Primakoff reaction. The preliminary result for pion polarizabilities under the assumption of $\\bar{\\alpha_{\\pi}} + \\bar{\\beta_{\\pi}} =$ 0 is $\\ba...

  7. Thole's interacting polarizability model in computational chemistry practice

    NARCIS (Netherlands)

    deVries, AH; vanDuijnen, PT; Zijlstra, RWJ; Swart, M

    Thole's interacting polarizability model to calculate molecular polarizabilities from interacting atomic polarizabilities is reviewed and its major applications in computational chemistry are illustrated. The applications include prediction of molecular polarizabilities, use in classical expressions

  8. Gravitational polarizability of black holes

    International Nuclear Information System (INIS)

    Damour, Thibault; Lecian, Orchidea Maria

    2009-01-01

    The gravitational polarizability properties of black holes are compared and contrasted with their electromagnetic polarizability properties. The 'shape' or 'height' multipolar Love numbers h l of a black hole are defined and computed. They are then compared to their electromagnetic analogs h l EM . The Love numbers h l give the height of the lth multipolar 'tidal bulge' raised on the horizon of a black hole by faraway masses. We also discuss the shape of the tidal bulge raised by a test-mass m, in the limit where m gets very close to the horizon.

  9. Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives and thermodynamic study on intermolecular charge transfer for developing efficient organic solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chao-Zhi, E-mail: zhangchaozhi@nuist.edu.cn [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Shen, Dan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Yuan, Yang [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Song, Ming-Xia; Li, Shi-Juan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Cao, Hui, E-mail: yccaoh@hotmail.com [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China)

    2016-07-01

    A series of planar 1,5,2,4,6,8-dithiotetrazocine derivatives were synthesized for study on charge transfer at donor/acceptor interface. The fluorescence quenching spectra, and the highest occupied molecular orbital (−6.10 ∼ −6.25 eV) and the lowest unoccupied molecular orbital (−3.45 ∼ −3.58 eV) energy levels of these 1,5,2,4,6,8-dithiotetrazocine derivatives show that they would be potential acceptor materials. Based on theoretical calculations, thermodynamic study on charge transfer at donor/acceptor interface was carried out. The results of experiments and theoretical calculations show that the electrons could transfer spontaneously from poly(3-hexylthiophene) to these acceptors. The percentages of fluorescence quenching increase with negative Gibbs free energy values increasing in the charge transfer procedures. Therefore, short circuit current values of organic solar cells would increase with the Gibbs free energy values increasing. This paper suggests a useful way for developing efficient organic solar cells. - Highlights: • Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives for develop effective acceptor. • Electrons at excited state in P3HT could transfer spontaneously to these acceptors. • Thermodynamic study on charge transfer at donor/acceptor interface. • Short circuit currents would be predicted by Gibbs free energy in procedure of charge transfer.

  10. Pion Polarizability Status Report (2017)

    OpenAIRE

    Moinester, Murray

    2017-01-01

    The electric ${\\alpha}_{\\pi}$ and magnetic $\\beta_{\\pi}$ charged pion Compton polarizabilities are of fundamental interest in the low-energy sector of quantum chromodynamics (QCD).They are directly linked to the phenomenon of spontaneously broken chiral symmetry within QCD and to the dynamics of the pion-photon interaction.The combination (${\\alpha}_{\\pi}-\\beta_{\\pi}$) was measured by:(1) CERN COMPASS via radiative pion Primakoff scattering (Bremsstrahlung) in the nuclear Coulomb field, ${\\pi...

  11. Conformational analysis of a Chlamydia-specific disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl in aqueous solution and bound to a monoclonal antibody: Observation of intermolecular transfer NOEs

    Energy Technology Data Exchange (ETDEWEB)

    Sokolowski, Tobias; Haselhorst, Thomas; Scheffler, Karoline [Medizinische Universitaet, Institut fuer Chemie (Germany); Weisemann, Ruediger [Bruker Analytik GmbH, Silberstreifen (Germany); Kosma, Paul [Institut fuer Chemie der Universitaet fuer Bodenkultur Wien (Austria); Brade, Helmut; Brade, Lore [Forschungszentrum Borstel, Zentrum fuer Medizin und Biowissenschaften Parkallee 22 (Germany); Peters, Thomas [Medizinische Universitaet, Institut fuer Chemie (Germany)

    1998-07-15

    The disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo (Kdo: 3-deoxy-d-manno-oct-2-ulosonic acid) represents a genus-specific epitope of the lipopolysaccharide of the obligate intracellular human pathogen Chlamydia. The conformation of the synthetically derived disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl was studied in aqueous solution, and complexed to a monoclonal antibody S25-2. Various NMR experiments based on the detection of NOEs (or transfer NOEs) and ROEs (or transfer ROEs) were performed. A major problem was the extensive overlap of almost all {sup 1}H NMR signals of {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl. To overcome this difficulty, HMQC-NOESY and HMQC-trNOESY experiments were employed. Spin diffusion effects were identified using trROESY experiments, QUIET-trNOESY experiments and MINSY experiments. It was found that protein protons contribute to the observed spin diffusion effects. At 800 MHz, intermolecular trNOEs were observed between ligand protons and aromatic protons in the antibody binding site. From NMR experiments and Metropolis Monte Carlo simulations, it was concluded that {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl in aqueous solution exists as a complex conformational mixture. Upon binding to the monoclonal antibody S25-2, only a limited range of conformations is available to {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl. These possible bound conformations were derived from a distance geometry analysis using transfer NOEs as experimental constraints. It is clear that a conformation is selected which lies within a part of the conformational space that is highly populated in solution. This conformational space also includes the conformation found in the crystal structure. Our results provide a basis for modeling studies of the antibody-disaccharide complex.

  12. Real and virtual Compton scattering: The nucleon polarizabilities

    International Nuclear Information System (INIS)

    Downie, E.J.; Fonvieille, H.

    2011-01-01

    We give an overview of low-energy Compton scattering γ (*) p → γp with a real or virtual incoming photon. These processes allow the investigation of one of the fundamental properties of the nucleon, i.e. how its internal structure deforms under an applied static electromagnetic field. Our knowledge of nucleon polarizabilities and their generalization to non-zero four-momentum transfer will be reviewed, including the presently ongoing experiments and future perspectives. (authors)

  13. Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

    International Nuclear Information System (INIS)

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2004-01-01

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (ΔG 0 ) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-ΔG 0 ) of ∼0.7-0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (V el ) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor-acceptor separation in the micellar ET reactions is substantially larger than for the donor-acceptor contact distance. Comparison of the V el values in the micellar solution and in the donor

  14. Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

    Science.gov (United States)

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2004-02-01

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (ΔG0) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-ΔG0) of ~0.7-0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (Vel) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor-acceptor separation in the micellar ET reactions is substantially larger than for the donor-acceptor contact distance. Comparison of the Vel values in the micellar solution and in the donor-acceptor close

  15. The Roles of Structural Order and Intermolecular Interactions in Determining Ionization Energies and Charge-Transfer State Energies in Organic Semiconductors

    KAUST Repository

    Graham, Kenneth

    2016-08-17

    The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases of material present, including pure phases of one molecule or polymer and mixed phases exhibiting different degrees of order and composition. In this work, ultraviolet photoelectron spectroscopy measurements of ionization energies (IEs) and external quantum efficiency measurements of charge-transfer (CT) state energies (ECT) are applied to molecular photovoltaic material systems to characterize energy landscapes. The results show that IEs and ECT values are highly dependent on structural order and phase composition. In the sexithiophene:C60 system both the IEs of sexithiophene and C60 shift by over 0.4 eV while ECT shifts by 0.5 eV depending on molecular composition. By contrast, in the rubrene:C60 system the IE of rubrene and C60 vary by ≤0.11 eV and ECT varies by ≤0.04 eV as the material composition varies. These results suggest that energy landscapes can exist whereby the binding energies of the CT states are overcome by energy offsets between charges in CT states in mixed regions and free charges in pure phases. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Measurement of the charged pion polarizability at COMPASS

    International Nuclear Information System (INIS)

    Nagel, Thiemo Christian Ingo

    2012-01-01

    The reaction π - +Z→π - +γ+Z in which a photon is produced by a beam pion scattering off a quasi-real photon of the Coulomb field of the target nucleus is identified experimentally by the tiny magnitude of the momentum transfer to the nucleus. This process gives access to the charged pion polarizabilities α π and β π whose experimental determination constitutes an important test of Chiral Perturbation Theory. In this work, the pion polarizability is obtained as α π =(1.9±0.7 stat. ±0.8 syst. ) x 10 -4 fm 3 from data taken with 190 GeV/c hadron beam provided by SPS to the COMPASS experiment at CERN in November 2009 and under the assumption of α π +β π =0.

  17. Measurement of the charged pion polarizability at COMPASS

    Energy Technology Data Exchange (ETDEWEB)

    Nagel, Thiemo Christian Ingo

    2012-09-26

    The reaction {pi}{sup -}+Z{yields}{pi}{sup -}+{gamma}+Z in which a photon is produced by a beam pion scattering off a quasi-real photon of the Coulomb field of the target nucleus is identified experimentally by the tiny magnitude of the momentum transfer to the nucleus. This process gives access to the charged pion polarizabilities {alpha}{sub {pi}} and {beta}{sub {pi}} whose experimental determination constitutes an important test of Chiral Perturbation Theory. In this work, the pion polarizability is obtained as {alpha}{sub {pi}}=(1.9{+-}0.7{sub stat.}{+-}0.8{sub syst.}) x 10{sup -4} fm{sup 3} from data taken with 190 GeV/c hadron beam provided by SPS to the COMPASS experiment at CERN in November 2009 and under the assumption of {alpha}{sub {pi}}+{beta}{sub {pi}}=0.

  18. Computational analysis of electronic polarizabilities in Thomas ...

    African Journals Online (AJOL)

    The electric polarizability,α, of a molecule is a measure of its ability to respond to an electric field and acquire an electric dipole moment, μ. The electric polarizability, α has been calculated for several ions and atoms by obtaining the perturbation of wave functions by an external field from a numerical solution of differential ...

  19. Influence of an intermolecular charge-transfer state on excited-state relaxation dynamics: solvent effect on the methylnaphthalene-oxygen system and its significance for singlet oxygen production.

    Science.gov (United States)

    Jensen, Poul-Gudmund; Arnbjerg, Jacob; Tolbod, Lars Poulsen; Toftegaard, Rasmus; Ogilby, Peter R

    2009-09-17

    The extent to which an intermolecular charge-transfer (CT) state can influence excited-state relaxation dynamics is examined for the system wherein 1-methylnaphthalene (MN) interacts with molecular oxygen. The MN-O2 system is ideally suited for such a study because excited states can be independently accessed by (i) irradiation into the discrete MN-O2 CT absorption band, (ii) direct irradiation of MN, and (iii) the photosensitized production of triplet state MN. Changing the solvent in which the MN-O2 system is dissolved influences the MN-dependent photoinduced production of singlet oxygen, O2(a1Delta(g)), which, in turn, yields information about fundamental concepts of state mixing. Results of experiments conducted in the polar solvent acetonitrile differ substantially from those obtained from the nonpolar solvent cyclohexane. The data reflect differences in the energy and behavior of the solvent-equilibrated MN-O2 CT state, CT(SE), and the extent to which this state couples to other states of the MN-O2 system. In particular, the data are consistent with a model where both the MN triplet state and the MN-O2 CT(SE) state are immediate precursors of O2(a1Delta(g)). Although the work reported herein is of direct and practical significance for the wide variety of systems in which O2(a1Delta(g)) can be produced upon irradiation, it also serves as an accessible model for a study of general issues pertinent to state mixing and the solvent-dependent dynamics of CT-mediated excited-state relaxation.

  20. Development of polarizable models for molecular mechanical calculations I: parameterization of atomic polarizability.

    Science.gov (United States)

    Wang, Junmei; Cieplak, Piotr; Li, Jie; Hou, Tingjun; Luo, Ray; Duan, Yong

    2011-03-31

    In this work, four types of polarizable models have been developed for calculating interactions between atomic charges and induced point dipoles. These include the Applequist, Thole linear, Thole exponential model, and the Thole Tinker-like. The polarizability models have been optimized to reproduce the experimental static molecular polarizabilities obtained from the molecular refraction measurements on a set of 420 molecules reported by Bosque and Sales. We grouped the models into five sets depending on the interaction types, that is, whether the interactions of two atoms that form the bond, bond angle, and dihedral angle are turned off or scaled down. When 1-2 (bonded) and 1-3 (separated by two bonds) interactions are turned off, 1-4 (separated by three bonds) interactions are scaled down, or both, all models including the Applequist model achieved similar performance: the average percentage error (APE) ranges from 1.15 to 1.23%, and the average unsigned error (AUE) ranges from 0.143 to 0.158 Å(3). When the short-range 1-2, 1-3, and full 1-4 terms are taken into account (set D models), the APE ranges from 1.30 to 1.58% for the three Thole models, whereas the Applequist model (DA) has a significantly larger APE (3.82%). The AUE ranges from 0.166 to 0.196 Å(3) for the three Thole models, compared with 0.446 Å(3) for the Applequist model. Further assessment using the 70-molecule van Duijnen and Swart data set clearly showed that the developed models are both accurate and highly transferable and are in fact have smaller errors than the models developed using this particular data set (set E models). The fact that A, B, and C model sets are notably more accurate than both D and E model sets strongly suggests that the inclusion of 1-2 and 1-3 interactions reduces the transferability and accuracy.

  1. 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.

  2. Classification of Simple Oxides: A Polarizability Approach

    Science.gov (United States)

    Dimitrov, Vesselin; Komatsu, Takayuki

    2002-01-01

    A simple oxide classification has been proposed on the basis of correlation between electronic polarizabilities of the ions and their binding energies determined by XPS. Three groups of oxides have been considered taking into account the values obtained on refractive-index- or energy-gap-based oxide ion polarizability, cation polarizability, optical basicity, O 1s binding energy, metal (or nonmetal) binding energy, and Yamashita-Kurosawa's interaction parameter of the oxides. The group of semicovalent predominantly acidic oxides includes BeO, B2O3, P2O5, SiO2, Al2O3, GeO2, and Ga2O3 with low oxide ion polarizability, high O 1s binding energy, low cation polarizability, high metal (or nonmetal) outermost binding energy, comparatively low optical basicity, and strong interionic interaction, leading to the formation of strong covalent bonds. Some main group oxides so-called ionic or basic such as CaO, In2O3, SnO2, and TeO2 and most transition metal oxides show relatively high oxide ion polarizability, O 1s binding energy in a very narrow medium range, high cation polarizability, and low metal (or nonmetal) binding energy. Their optical basicity varies in a narrow range and it is close to that of CaO. The group of very ionic or very basic oxides includes CdO, SrO, and BaO as well as PbO, Sb2O3, and Bi2O3, which possess very high oxide ion polarizability, low O 1s binding energy, very high cation polarizability, and very low metal (or nonmetal) binding energy. Their optical basicity is higher than that of CaO and the interionic interaction is very weak, giving rise to the formation of very ionic chemical bonds.

  3. Excited States in Solution through Polarizable Embedding

    DEFF Research Database (Denmark)

    Olsen, Jógvan Magnus; Aidas, Kestutis; Kongsted, Jacob

    2010-01-01

    We present theory and implementation of an advanced quantum mechanics/molecular mechanics (QM/MM) approach using a fully self-consistent polarizable embedding (PE) scheme. It is a polarizable layered model designed for effective yet accurate inclusion of an anisotropic medium in a quantum...... a nonequilibrium formulation of the environmental response. In our formulation of polarizable embedding we explicitly take into account the full self-consistent many-body environmental response from both ground and excited states. The PE-DFT method can be applied to any molecular system, e.g., proteins...

  4. United polarizable multipole water model for molecular mechanics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Rui; Wang, Qiantao; Ren, Pengyu, E-mail: pren@mail.utexas.edu [Department of Biomedical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Wang, Lee-Ping; Pande, Vijay S. [Department of Chemistry, Stanford University, Stanford, California 94305 (United States)

    2015-07-07

    We report the development of a united AMOEBA (uAMOEBA) polarizable water model, which is computationally 3–5 times more efficient than the three-site AMOEBA03 model in molecular dynamics simulations while providing comparable accuracy for gas-phase and liquid properties. In this coarse-grained polarizable water model, both electrostatic (permanent and induced) and van der Waals representations have been reduced to a single site located at the oxygen atom. The permanent charge distribution is described via the molecular dipole and quadrupole moments and the many-body polarization via an isotropic molecular polarizability, all located at the oxygen center. Similarly, a single van der Waals interaction site is used for each water molecule. Hydrogen atoms are retained only for the purpose of defining local frames for the molecular multipole moments and intramolecular vibrational modes. The parameters have been derived based on a combination of ab initio quantum mechanical and experimental data set containing gas-phase cluster structures and energies, and liquid thermodynamic properties. For validation, additional properties including dimer interaction energy, liquid structures, self-diffusion coefficient, and shear viscosity have been evaluated. The results demonstrate good transferability from the gas to the liquid phase over a wide range of temperatures, and from nonpolar to polar environments, due to the presence of molecular polarizability. The water coordination, hydrogen-bonding structure, and dynamic properties given by uAMOEBA are similar to those derived from the all-atom AMOEBA03 model and experiments. Thus, the current model is an accurate and efficient alternative for modeling water.

  5. Electronic transitions and intermolecular forces

    International Nuclear Information System (INIS)

    Hemert, M.C. van.

    1981-01-01

    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.)

  6. Intermolecular Interactions at high pressure

    DEFF Research Database (Denmark)

    Eikeland, Espen Zink

    2016-01-01

    transmitting medium. Through careful structural analysis combined with theoretical calculations, the structures of all the new high-pressure phases identified herein were determined. In the hydroquinone - methanol and hydroquinone - acetonitrile clathrate structures the phase transitions break the host...... illustrates how important it is to quantify all intermolecular interactions in structures. This enables researchers to see a more complete picture and not focus only on a few interactions deemed particularly important....

  7. Molecule-specific determination of atomic polarizabilities with the polarizable atomic multipole model.

    Science.gov (United States)

    Woo Kim, Hyun; Rhee, Young Min

    2012-07-30

    Recently, many polarizable force fields have been devised to describe induction effects between molecules. In popular polarizable models based on induced dipole moments, atomic polarizabilities are the essential parameters and should be derived carefully. Here, we present a parameterization scheme for atomic polarizabilities using a minimization target function containing both molecular and atomic information. The main idea is to adopt reference data only from quantum chemical calculations, to perform atomic polarizability parameterizations even when relevant experimental data are scarce as in the case of electronically excited molecules. Specifically, our scheme assigns the atomic polarizabilities of any given molecule in such a way that its molecular polarizability tensor is well reproduced. We show that our scheme successfully works for various molecules in mimicking dipole responses not only in ground states but also in valence excited states. The electrostatic potential around a molecule with an externally perturbing nearby charge also exhibits a near-quantitative agreement with the reference data from quantum chemical calculations. The limitation of the model with isotropic atoms is also discussed to examine the scope of its applicability. Copyright © 2012 Wiley Periodicals, Inc.

  8. Charged pions polarizability measurement at COMPASS

    CERN Document Server

    Guskov, A

    2010-01-01

    The pion electromagnetic structure can be probed in $\\pi^{−}+(A,Z)\\rightarrow\\pi^{-}+(A,Z)+\\gamma$ Compton scattering in inverse kinematics (Primakoff reaction) and described by the electric $(\\alpha_{\\pi})$ and the magnetic $(\\beta_{\\pi})$ polarizabilities that depend on the rigidity of pion’s internal structure as a composite particle. Values for pion polarizabilities can be extracted from the comparison of the differential cross section for scattering of point-like pions with the measured cross section. The opportunity to measure pion polarizability via the Primakoff reaction at the COMPASS experiment was studied with $a$ $\\pi^{-}$ beam of 190 GeV during pilot run 2004. The obtained results were used for preparation of the new data taking which was performed in 2009.

  9. Measurement of the pion polarizabilities at COMPASS

    CERN Document Server

    Guskov, A V

    2006-01-01

    The electromagnetic structure of pions is probed in $\\pi\\gamma$ Compton scattering in inverse kinematics (Primakoff effect) and described by the electric ($\\alpha_{\\pi}$) and magnetic ($\\beta_{\\pi}$) polarizabilities, that depend on the rigidity of pion’s internal structure as a composite particle. Values for pion polarizabilities can be extracted from the comparison of the theoretically predicted (under approximation of unstructured pion) cross section of Primakoff scattering and the measured cross section. The high beam intensity, good spectrometer resolution, the high rate capability, the high acceptance and possibility to use pion and muon beams, that are unique to the COMPASS experiment provide the tools to measure precisely the pion polarizabilities in the $\\pi^{-} + (A,Z)\\rightarrow\\pi^{-} + (A,Z) + \\gamma$ Primakoff reaction. This cross section is related to the cross section of Compton scattering on pion. A precise tracking system, electromagnetic and hadron calorimeters provide good conditions for...

  10. Polarizable Density Embedding Coupled Cluster Method

    DEFF Research Database (Denmark)

    Hršak, Dalibor; Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob

    2018-01-01

    by an embedding potential consisting of a set of fragment densities obtained from calculations on isolated fragments with a quantum-chemistry method such as Hartree-Fock (HF) or Kohn-Sham density functional theory (KS-DFT) and dressed with a set of atom-centered anisotropic dipole-dipole polarizabilities......). In the PDE-CC method, the smaller, but chemically important core region is described with a high-level CC method. The environment surrounding the core region can be separated into two levels of description: an inner and an outer region. The effect of the inner region on the core region is described......We present the theory and implementation of the polarizable density embedding (PDE) model in combination with coupled cluster (CC) theory (PDE-CC). This model has been implemented in the Dalton quantum chemistry program by adapting the CC code to the polarizable embedding library (PElib...

  11. Empirical intermolecular potential from depolarized interaction-induced light scattering spectra for tetrafluoromethane

    Science.gov (United States)

    Kader, Mohamed Sayed Abdel

    2002-07-01

    Depolarized interaction-induced light scattering spectra of tetrafluoromethane in the frequency range 2-150 cm-1 at 294.5 K and 0.91 mol/l with the interaction pressure virial coefficient and viscosity have been used for deriving the empirical multiparameter Morse-Morse-Morse-Spline-van der Waals (M3SV), Lennard-Jones, Kihara, and exp-6 intermolecular potentials. The line shape at relatively low frequencies is determined largely by the effect of bound and free transitions. At intermediate frequencies it is sensitive to both the attractive part of the potential and the short-range part of the polarizability anisotropy. The high frequency wings are discussed in terms of the collision-induced rotational Raman effect and estimates for the dipole-quadrupole and dipole-octopole polarizabilities A and E, respectively, are obtained. Absolute zeroth and second moments have been measured and compared with theoretical calculations using these models of the intermolecular potentials. The results show that M3SV is the most accurate potential yet reported for this system.

  12. K$_{-}$ and K$_{-}$ polarizability from kaonic atoms

    CERN Document Server

    Backenstoss, Gerhard; Bergström, I; Bunaciu, T; Egger, J; Hagelberg, R; Hultberg, S; Koch, H; Lynen, Y; Ritter, H G; Schwitter, A; Tauscher, L

    1973-01-01

    The K/sup -/ mass was determined from kaonic atomic X-rays from Au and Ba to be 493.691+or-0.040 MeV. An upper limit for the polarizability of the K/sup -/ was found to be 0.020 fm/sup 3/ at 90% confidence. (18 refs).

  13. The axial polarizability of nucleons and nuclei

    International Nuclear Information System (INIS)

    Ericson, M.; Figureau, A.

    1981-02-01

    The part of the static nuclear axial polarizability arising from the nucleonic excitations is derived from the low energy expansion of the πN amplitude. It is shown that the contribution of the Δ intermediate state, though dominant, does not saturate the nucleonic response. A similar effect, though more pronounced, is known to occur for the magnetic susceptibility

  14. Polarizabilities of the beryllium clock transition

    International Nuclear Information System (INIS)

    Mitroy, J.

    2010-01-01

    The polarizabilities of the three lowest states of the beryllium atom are determined from a large basis configuration interaction calculation. The polarizabilities of the 2s 2 1 S e ground state (37.73a 0 3 ) and the 2s2p 3 P 0 o metastable state (39.04a 0 3 ) are found to be very similar in size and magnitude. This leads to an anomalously small blackbody radiation shift at 300 K of -0.018(4) Hz for the 2s 2 1 S e -2s2p 3 P 0 o clock transition. Magic wavelengths for simultaneous trapping of the ground and metastable states are also computed.

  15. Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard-Jones potential.

    Science.gov (United States)

    Geada, Isidro Lorenzo; Ramezani-Dakhel, Hadi; Jamil, Tariq; Sulpizi, Marialore; Heinz, Hendrik

    2018-02-19

    Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

  16. Quantum Gravitational Force Between Polarizable Objects

    Science.gov (United States)

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

    2016-04-01

    Since general relativity is a consistent low energy effective field theory, it is possible to compute quantum corrections to classical forces. Here we compute a quantum correction to the gravitational potential between a pair of polarizable objects. We study two distant bodies and compute a quantum force from their induced quadrupole moments due to two-graviton exchange. The effect is in close analogy to the Casimir-Polder and London-van der Waals forces between a pair of atoms from their induced dipole moments due to two photon exchange. The new effect is computed from the shift in vacuum energy of metric fluctuations due to the polarizability of the objects. We compute the potential energy at arbitrary distances compared to the wavelengths in the system, including the far and near regimes. In the far distance, or retarded, regime, the potential energy takes on a particularly simple form: V (r )=-3987 ℏc G2α1 Sα2 S/(4 π r11) , where α1 S , α2 S are the static gravitational quadrupole polarizabilities of each object. We provide estimates of this effect.

  17. Axial polarizability and weak currents in nuclei

    International Nuclear Information System (INIS)

    Ericson, M.

    1977-01-01

    The weak interaction nucleonic coupling constants in nuclei are modified by the presence of the neighbouring nucleons. One type of modification is due to the virtual excitation of the isobars through meson exchange. The influence of the isobars is described by means of the nuclear axial polarizability coefficient. This polarizability is known; it is linked to the p-wave πN scattering volume. A relation is derived between the axial nuclear current and the pion field which incorporates the polarizability effects. This relation has an electromagnetic analogue. It is then possible to derive the axial and pseudoscalar coupling constants from a knowledge of the pion field. This field in turn obeys a Klein-Gordon equation which has to include the isobaric excitations. The propagation of the pion field is similar to that of an electromagnetic wave in a dielectric medium. The strong interaction coupling constant is shown to be renormalized in nuclei by the effect of the various types of correlations. (author)

  18. Multi-property isotropic intermolecular potentials and predicted spectral lineshapes of collision-induced absorption (CIA), collision-induced light scattering (CILS) and collision-induced hyper-Rayleigh scattering (CIHR) for H2sbnd Ne, -Kr and -Xe

    Science.gov (United States)

    El-Kader, M. S. A.; Godet, J.-L.; Gustafsson, M.; Maroulis, G.

    2018-04-01

    Quantum mechanical lineshapes of collision-induced absorption (CIA), collision-induced light scattering (CILS) and collision-induced hyper-Rayleigh scattering (CIHR) at room temperature (295 K) are computed for gaseous mixtures of molecular hydrogen with neon, krypton and xenon. The induced spectra are detected using theoretical values for induced dipole moment, pair-polarizability trace and anisotropy, hyper-polarizability and updated intermolecular potentials. Good agreement is observed for all spectra when the literature and the present potentials which are constructed from the transport and thermo-physical properties are used.

  19. Size-scaling behaviour of the electronic polarizability of one-dimensional interacting systems

    Science.gov (United States)

    Chiappe, G.; Louis, E.; Vergés, J. A.

    2018-05-01

    Electronic polarizability of finite chains is accurately calculated from the total energy variation of the system produced by small but finite static electric fields applied along the chain direction. Normalized polarizability, that is, polarizability divided by chain length, diverges as the second power of length for metallic systems but approaches a constant value for insulating systems. This behaviour provides a very convenient way to characterize the wave-function malleability of finite systems as it avoids the need of attaching infinite contacts to the chain ends. Hubbard model calculations at half filling show that the method works for a small U  =  1 interaction value that corresponds to a really small spectral gap of 0.005 (hopping t  =  ‑1 is assumed). Once successfully checked, the method has been applied to the long-range hopping model of Gebhard and Ruckenstein showing 1/r hopping decay (Gebhard and Ruckenstein 1992 Phys. Rev. Lett. 68 244; Gebhard et al 1994 Phys. Rev. B 49 10926). Metallicity for U values below the reported metal-insulator transition is obtained but the surprise comes for U values larger than the critical one (when a gap appears in the spectral density of states) because a steady increase of the normalized polarizability with size is obtained. This critical size-scaling behaviour can be understood as corresponding to a molecule which polarizability is unbounded. We have checked that a real transfer of charge from one chain end to the opposite occurs as a response to very small electric fields in spite of the existence of a large gap of the order of U for one-particle excitations. Finally, ab initio quantum chemistry calculations of realistic poly-acetylene chains prove that the occurrence of such critical behaviour in real systems is unlikely.

  20. Off-planar geometry and structural instability of EDO-TTF explained by using the extended debye polarizability model for bond angles.

    Science.gov (United States)

    Linker, Gerrit-Jan; van Duijnen, Piet Th; van Loosdrecht, Paul H M; Broer, Ria

    2012-07-05

    The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF(6). The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model for the bond angle. The geometrical structure of EDO-TTF is dictated by its four sulfur bond angles and these are, in turn, determined by the polarizability of the sulfur atoms. With Hartree-Fock and second-order Møller-Plesset perturbation theory calculations on EDO-TTF, TTF, H(2)S, and their oxygen and selenium substituted counterparts we confirm this hypothesis. The Debye polarizability model for bond angles relates directly the optimum bond angle with the polarizability of the center atom. Considering the (EDO-TTF)(2)PF(6) material in this light proves to be very fruitful.

  1. Pion polarizability in nonlocal quark model

    International Nuclear Information System (INIS)

    Efimov, G.V.; Okhlopkova, V.A.

    1978-01-01

    The γγ→ππ amplitude was calculated in nonlocal quark model in the fourth order on the perturbation theory. The coefficients of electric[a) and magnetic polarizability (β) determined are equal in magnitude and opposite in sign αsub(π+-)=βsub(π+-)=+0.014α/msub(π)sup(3), αsub(πsup(0))=-βsub(πsup(0))=-0.07α/msub(π)sup(3). The results have been compared with calculations in other models

  2. Radiation damping of a polarizable particle

    Science.gov (United States)

    Novotny, Lukas

    2017-09-01

    A polarizable body moving in an external electromagnetic field will slow down. This effect is referred to as radiation damping and is analogous to Doppler cooling in atomic physics. Using the principles of special relativity we derive an expression for the radiation damping force and find that it solely depends on the scattered power. The cooling of the particle's center-of-mass motion is balanced by heating due to radiation pressure shot noise, giving rise to an equilibrium that depends on the ratio of the field's frequency and the particle's mass. While damping is of relativistic nature, heating has its roots in quantum mechanics.

  3. Radiative corrections for pion polarizability experiments

    International Nuclear Information System (INIS)

    Akhundov, A.A.; Gerzon, S.; Kananov, S.; Moinester, M.A.

    1994-08-01

    We use the semi-analytical program RCFORGV to evaluate radiative corrections to one-photon radiative emission in the high-energy scattering of pions in the Coulomb field of a nucleus with atomic number Z. It is shown that radiative corrections can simulate a pion polarizability effect. The average effect is α rc π =-β rc π =(0.20±0.05) x 10 -43 cm 3 , for pion energies 40-600 GeV. We also study the range of applicability of the equivalent photon approximation in describing one-photon radiative emission. (author). 21 refs, 6 figs, 1 tab

  4. Relativistic corrections to molecular dynamic dipole polarizabilities

    DEFF Research Database (Denmark)

    Kirpekar, Sheela; Oddershede, Jens; Jensen, Hans Jørgen Aagaard

    1995-01-01

    in the correlated calculations, as has also been observed for other properties. For SnH4 the correlation contribution and the pure relativistic correction are of the same order of magnitude, whereas for PbH 4 the relativistic correction becomes more important than the correlation contribution. We report estimated...... Cauchy moments, obtained from fitting the dispersion of the calculated corrections as a function of ω2. The frequency dependence of the nonrelativistic polarizability is most pronounced at the correlated level, mainly due to lower excitation energies in the multiconfigurational calculations than those...

  5. The polarizable embedding coupled cluster method

    DEFF Research Database (Denmark)

    Sneskov, Kristian; Schwabe, Tobias; Kongsted, Jacob

    2011-01-01

    We formulate a new combined quantum mechanics/molecular mechanics (QM/MM) method based on a self-consistent polarizable embedding (PE) scheme. For the description of the QM region, we apply the popular coupled cluster (CC) method detailing the inclusion of electrostatic and polarization effects......-called PE-CCSDR(3) model. Finally, we utilize the presented method in the description of a full protein by investigating the shift of the intense electronic excitation energy of the photoactive yellow protein due to the surrounding amino acids....

  6. Nuclear magnetic resonance J coupling constant polarizabilities of hydrogen peroxide

    DEFF Research Database (Denmark)

    Kjær, Hanna; Nielsen, Monia R.; Pagola, Gabriel I.

    2012-01-01

    In this paper we present the so far most extended investigation of the calculation of the coupling constant polarizability of a molecule. The components of the coupling constant polarizability are derivatives of the NMR indirect nuclear spin-spin coupling constant with respect to an external elec...

  7. An averaged polarizable potential for multiscale modeling in phospholipid membranes

    DEFF Research Database (Denmark)

    Witzke, Sarah; List, Nanna Holmgaard; Olsen, Jógvan Magnus Haugaard

    2017-01-01

    is underlined for the description of larger assemblies of lipids, that is, membranes. In conclusion, we find that specially developed polarizable parameters are needed for embedding calculations in membranes, while common non-polarizable point-charge force fields usually perform well enough for structural...

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

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, Anders S., E-mail: andersx@chem.wisc.edu, E-mail: cui@chem.wisc.edu; Cui, Qiang, E-mail: andersx@chem.wisc.edu, E-mail: cui@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave., Madison, Wisconsin 53706 (United States); Elstner, Marcus [Theoretische Chemische Biologie, Universität Karlsruhe, Kaiserstr. 12, 76131 Karlsruhe (Germany)

    2015-08-28

    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.

  9. Model-independent effects of Δ excitation in nucleon polarizabilities

    International Nuclear Information System (INIS)

    Pascalutsa, Vladimir; Phillips, Daniel R.

    2003-01-01

    Model-independent effects of Δ(1232) excitation on nucleon polarizabilities are computed in a Lorentz-invariant fashion. We find a large effect of relative order (M Δ -M)/M in some of the spin polarizabilities, with the backward spin polarizability receiving the largest contribution. Similar subleading effects are found to be important in the fourth-order spin-independent polarizabilities α Eν , α E2 , β Mν , and β M2 . Combining our results with those for the model-independent effects of pion loops we obtain predictions for spin and fourth-order polarizabilities which compare favorably with the results of a recent dispersion-relation analysis of data

  10. The role of molecular conformation and polarizable embedding for one- and two-photon absorption of disperse orange 3 in solution.

    Science.gov (United States)

    Silva, Daniel L; Murugan, N Arul; Kongsted, Jacob; Rinkevicius, Zilvinas; Canuto, Sylvio; Ågren, Hans

    2012-07-19

    Solvent effects on the one- and two-photon absorption (1PA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.

  11. Density and polarizability of liquid 4He

    International Nuclear Information System (INIS)

    Kempin'ski, V.; Zhuk, T.; Stankovski, Ya.; Sitarzh, S.

    1988-01-01

    The temperature changes in the density of liquid helium are measured in the temperature range of 1.63 to 4.2 K.; Unlike the conventional pycnometric technique, the changes in the hydrostatic displacement of the liquid were determined. The cirrectness of the method chosen and the appropriate equipment for its realization are substantiated. The results obtained are in good agreement with those of other authors. On the basis of temperature measurements of the dependence of density ρ and permittivity ε, the dependence of polarizability A of liquid 4 He on temperature and density was calculated. The results obtained show an alternating character of the dependences A(T) and A(ρ). These dependences are found to correlate

  12. Cohesion: a scientific history of intermolecular forces

    National Research Council Canada - National Science Library

    Rowlinson, J. S

    2002-01-01

    .... The final section gives an account of the successful use in the 20th century of quantum mechanics and statistical mechanics to resolve most of the remaining problems. Throughout the last 300 years there have been periods of tremendous growth in our understanding of intermolecular forces but such interest proved to be unsustainable, and long periods of...

  13. Quantitative investigation of intermolecular interactions in dimorphs ...

    Indian Academy of Sciences (India)

    RAHUL SHUKLA

    2018-03-23

    Mar 23, 2018 ... molecular interactions in derivatives of 1,2,4-triazoles. CrystEngComm 16 1702. 48. Shukla R, Mohan T P, Vishalakshi B and Chopra D. 2017 Synthesis, crystal structure and theoretical analysis of intermolecular interactions in two biologically active derivatives of 1,2,4-triazoles J. Mol. Struct. 1134 426. 49.

  14. Interfacial Structural Transition in Hydration Shells of a Polarizable Solute.

    Science.gov (United States)

    Dinpajooh, Mohammadhasan; Matyushov, Dmitry V

    2015-05-22

    Electrostatics of polar solvation is typically described by harmonic free energy functionals. Polarizability contributes a negative polarization term that can make the harmonic free energy negative. The harmonic truncation fails in this regime. Simulations of polarizable ideal dipoles in water show that water's susceptibility passes through a maximum in the range of polarizabilities zeroing the harmonic term out. The microscopic origin of the nonmonotonic behavior is an interfacial structural transition involving the density collapse of the first hydration layer and enhanced number of dangling OH bonds.

  15. Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction.

    Science.gov (United States)

    Miyabe, Kanji; Suzuki, Nozomu

    2017-01-01

    New moment equations were developed for size exclusion capillary electrochromatography (SECEC), in which intermolecular chemical reactions simultaneously took place. They explain how the first absolute and second central moments of elution peaks are correlated with some fundamental equilibrium and kinetic parameters of mass transfer and chemical reaction in SECEC column. In order to demonstrate the effectiveness of the moment equations, they were used to predict chromatographic behavior under hypothetical SECEC conditions. It was quantitatively studied how the association and dissociation rate constants of intermolecular interaction affected the position and spreading of elution peaks. It was indicated that both the intermolecular reaction kinetics and axial dispersion of solute molecules in a capillary column had a predominant contribution to the band broadening.

  16. Polarizabilities and hyperpolarizabilities of the alkali metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Fuentealba, P. (Chile Univ., Santiago (Chile). Departamento de Fisica and Centro de Mecanica Cuantica Aplicada (CMCA)); Reyes, O. (Chile Univ., Santiago (Chile). Dept. de Fisica)

    1993-08-14

    The electric static dipole polarizability [alpha], quadrupole polarizability C, dipole-quadrupole polarizability B, and the second dipole hyperpolarizability [gamma] have been calculated for the alkali metal atoms in the ground state. The results are based on a pseudopotential which is able to incorporate the very important core-valence correlation effect through a core polarization potential, and, in an empirical way, the main relativistic effects. The calculated properties compare very well with more elaborated calculations for the Li atom, excepting the second hyperpolarizability [gamma]. For the other atoms, there is neither theoretical nor experimental information about most of the higher polarizabilities. Hence, the results of this paper should be seen as a first attempt to give a complete account of the series expansion of the interaction energy of an alkali metal atom and a static electric field. (author).

  17. Dynamic polarizabilities for the low lying states of Ca+

    International Nuclear Information System (INIS)

    Tang, Yong-Bo; Shi, Ting-Yun; Qiao, Hao-Xue; Mitroy, J

    2014-01-01

    The dynamic polarizabilities of the 4s, 3d and 4p states of Ca + are calculated using a relativistic structure model. The wavelengths at which the Stark shifts between different pairs of transitions are zero are calculated. Experimental determination of the magic wavelengths could prove useful in developing better atomic structure models and in particular lead to improved values of the polarizabilities for the Ca + (3d) states

  18. Electric dipole polarizability: from few- to many-body systems

    Directory of Open Access Journals (Sweden)

    Miorelli Mirko

    2016-01-01

    Full Text Available We review the Lorentz integral transform coupled-cluster method for the calculation of the electric dipole polarizability. We benchmark our results with exact hyperspherical harmonics calculations for 4He and then we move to a heavier nucleus studying 16O. We observe that the implemented chiral nucleon-nucleon interaction at next-to-next-to-next-to-leading order underestimates the electric dipole polarizability.

  19. On the use of pseudostates to calculate molecular polarizabilities

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Marc; Tennyson, Jonathan [Department of Physics and Astronomy, University College London, Gower St, London WC1E 6BT (United Kingdom)

    2010-02-28

    The polarizability of a molecule is an intrinsic property which is important for a large variety of problems. However, determining reliable values for these polarizabilities is not straightforward: for instance the standard sum over states formulation of the problem does not converge because of the need to include not only many excited states but also to allow for contributions from the continuum. Here a formulation of this technique is given which uses pseudostates to allow for physical and continuum states otherwise omitted from the expansion. The pseudostates are represented by even-tempered expansions of Gaussian-type orbitals at the molecular centre-of-mass. The method is tested for LiH, Li{sub 2}, water and CO molecules. For LiH and CO, calculations for the polarizability of low-lying excited states are presented including that for the A {sup 3}PI state of CO, whose polarizability appears not to have been previously determined. It is suggested that the use of pseudostates provides a straightforward method of calculating static polarizabilities of molecules in both ground and excited electronic states. The extension of the method to the calculation of dynamic polarizabilities is discussed.

  20. Event horizons in the Polarizable Vacuum Model

    CERN Document Server

    Desiato, J T

    2003-01-01

    The Polarizable Vacuum (PV) Model representation of General Relativity (GR) is used to show that an in-falling particle of matter will reach the central mass object in a finite amount of proper time, as measured along the world line of the particle, when using the PV Metric. It is shown that the in-falling particle passes through an event horizon, analogous to that found in the Schwarzschild solution of GR. Once it passes through this horizon, any light signal emitted outward by the in-falling particle will be moving slower than the in-falling particle, due to the reduced speed of light in this region. Therefore the signal can never escape this horizon. However, the light emitted by a stationary object below the horizon is exponentially red-shifted and can escape along the null geodesics, as was originally predicted by the PV Model. A static, non-rotating charge distribution is added to the central mass and the PV equivalent to the Reissner-Nordstrom metric is derived. It is illustrated that the dipole moment...

  1. Single-molecule magnets ``without'' intermolecular interactions

    Science.gov (United States)

    Wernsdorfer, W.; Vergnani, L.; Rodriguez-Douton, M. J.; Cornia, A.; Neugebauer, P.; Barra, A. L.; Sorace, L.; Sessoli, R.

    2012-02-01

    Intermolecular magnetic interactions (dipole-dipole and exchange) affect strongly the magnetic relaxation of crystals of single-molecule magnets (SMMs), especially at low temperature, where quantum tunneling of the magnetization (QTM) dominates. This leads to complex many-body problems [l]. Measurements on magnetically diluted samples are desirable to clearly sort out the behaviour of magnetically-isolated SMMs and to reveal, by comparison, the effect of intermolecular interactions. Here, we diluted a Fe4 SMM into a diamagnetic crystal lattice, affording arrays of independent and iso-oriented magnetic units. We found that the resonant tunnel transitions are much sharper, the tunneling efficiency changes significantly, and two-body QTM transitions disappear. These changes have been rationalized on the basis of a dipolar shuffling mechanism and of transverse dipolar fields, whose effect has been analyzed using a multispin model. Our findings directly prove the impact of intermolecular magnetic couplings on the SMM behaviour and disclose the magnetic response of truly-isolated giant spins in a diamagnetic crystalline environment.[4pt] [1] W. Wernsdorfer, at al, PRL 82, 3903 (1999); PRL 89, 197201 (2002); Nature 416, 406 (2002); IS Tupitsyn, PCE Stamp, NV Prokof'ev, PRB 69, 132406 (2004).

  2. Transetherification on Polyols by Intra- and Intermolecular Nucleophilic Substitutions

    Science.gov (United States)

    Muraoka, Takahiro; Adachi, Kota; Chowdhury, Rainy; Kinbara, Kazushi

    2014-01-01

    Transetherification on polyols involving intra- and intermolecular nucleophilic substitutions is reported. Di- or trialkoxide formation of propane-1,3-diol or 2-(hydroxymethyl)propane-1,3-diol derivatives by NaH triggers the reaction via oxetanes formation, where the order to add NaH and a polyol significantly influences the yields of products. It was demonstrated that the protective group on the pentaerythritol skeleton is apparently transferred to the hydrophilic and hydrophobic chain molecules bearing a leaving group in one-step, and a protective group conversion from tosyl to benzyl was successful using a benzyl-appending triol to afford a desired product in 67% yield. PMID:24663293

  3. Off-Planar Geometry and Structural Instability of EDO-TTF Explained by Using the Extended Debye Polarizability Model for Bond Angles

    NARCIS (Netherlands)

    Linker, Gerrit-Jan; van Duijnen, Piet Th.; van Loosdrecht, Paul H. M.; Broer-Braam, Henderika

    2012-01-01

    The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF6. The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model

  4. Neutral pion electroproduction and virtual Compton scattering on proton with four-momentum transfer squared Q{sup 2} = 1 GeV{sup 2}. Measurement of cross-sections and of generalized polarizabilities; Electroproduction de photons et de pions sur le proton au quadrimoment de transfert Q{sup 2} = 1.0 GeV{sup 2}. Mesure des sections efficaces et extraction des polarisabilites generalisees

    Energy Technology Data Exchange (ETDEWEB)

    Laveissiere, G

    2001-11-01

    In hadronic physics, the nucleon structure and the quarks confinement are still topical issues. The neutral pion electroproduction and virtual Compton scattering (VCS) reactions allow us to access new observables that describe this structure. This work is focussed on the VCS experiment performed at Jefferson Lab in 1998. The 4 GeV electron beam is scattered off a cryogenic hydrogen target, and the scattered electron and recoiled proton are detected in coincidence in the twin hall A spectrometers. The photon (pion) is reconstructed using a missing particle technique. The data analysis allowed to extract the cross sections relative to both process at four-momentum transfer squared Q{sup 2} = 1 GeV{sup 2}. The VCS cross section has been extracted for the first time in the proton resonance region (W between 1.O and 2.0 GeV) through the photon electroproduction reaction. Around the pion-production threshold up to the Delta(1232) resonance region, these results lead to the measurement of the generalized polarizabilities, that describe the proton structure in the same way as the elastic form factors. Moreover, the neutral pion electroproduction cross section measurement in the resonance region has brought new constraints on the existing phenomenological models. (author)

  5. Derivation of Distributed Models of Atomic Polarizability for Molecular Simulations.

    Science.gov (United States)

    Soteras, Ignacio; Curutchet, Carles; Bidon-Chanal, Axel; Dehez, François; Ángyán, János G; Orozco, Modesto; Chipot, Christophe; Luque, F Javier

    2007-11-01

    The main thrust of this investigation is the development of models of distributed atomic polarizabilities for the treatment of induction effects in molecular mechanics simulations. The models are obtained within the framework of the induced dipole theory by fitting the induction energies computed via a fast but accurate MP2/Sadlej-adjusted perturbational approach in a grid of points surrounding the molecule. Particular care is paid in the examination of the atomic quantities obtained from models of implicitly and explicitly interacting polarizabilities. Appropriateness and accuracy of the distributed models are assessed by comparing the molecular polarizabilities recovered from the models and those obtained experimentally and from MP2/Sadlej calculations. The behavior of the models is further explored by computing the polarization energy for aromatic compounds in the context of cation-π interactions and for selected neutral compounds in a TIP3P aqueous environment. The present results suggest that the computational strategy described here constitutes a very effective tool for the development of distributed models of atomic polarizabilities and can be used in the generation of new polarizable force fields.

  6. The possibility for a pion polarizability measurement at COMPASS

    CERN Document Server

    Guskov, A

    2010-01-01

    The pion electromagnetic structure can be probed in $\\pi^{−}+(A,Z)\\rightarrow\\pi^{-}+(A,Z) + \\gamma$ Compton scattering in inverse kinematics (Primakoff reaction) and described by the electric $(\\alpha_{\\pi})$ and the magnetic $(\\beta_{\\pi})$ polarizabilities that depend on the rigidity of pion’s internal structure as a composite particle. Values for pion polarizabilities can be extracted from the comparison of the differential cross section for scattering of point-like pions with the measured cross section. The opportunity to measure pion polarizability via the Primakoff reaction at the COMPASS experiment was studied with a $\\pi^{−}$ beam of 190 GeV. The obtained results are used for preparation of the new measurement.

  7. Dipole (hyper)polarizabilities of neutral silver clusters

    Science.gov (United States)

    Jorge, Francisco E.; de Macedo, Luiz G. M.

    2016-12-01

    At the Douglas-Kroll-Hess (DKH) level, the B3PW91 functional along with the all-electron relativistic basis sets of valence triple and quadruple zeta qualities are used to determine the structure, stability, and electronic properties of the small silver clusters (Agn, n ⩽ 7). The results presented in this study are in good agreement with the experimental data and theoretical values obtained at a higher level of theory from the literature. Static polarizability and hyperpolarizability are also reported. It is verified that the mean dipole polarizability per atom exhibits an odd-even oscillation and that the polarizability anisotropy is directly related to the cluster shape. In this article, the first study of hyperpolarizabilities of small silver clusters is presented. Except for the monomer, the second hyperpolarizabilities of the silver clusters are significantly larger than those of the copper clusters. Project supported by CNPq, CAPES, and FAPES (Brazilian Agencies).

  8. Ab initio self-consistent calculations of the Compton profiles and polarizabilities of diamond and cubic boron nitride

    CERN Document Server

    Ayma, D; Lichanot, A

    1998-01-01

    Compton profiles, polarizabilities and related functions of diamond and cubic boron nitride have been investigated within the Hartree-Fock approximation and the density functional theory, calculated within the local density approximation and generalized gradient approximation, but without any explicit correlation correction for the Compton profiles. The correlation part already included in the standard uncorrected density functional theory is deduced from the comparison of the two types of calculation. The Compton profile and reciprocal-form-factor anisotropies, polarizability, dielectric constant and energy loss function of the two compounds are compared at the same level of accuracy. These properties are very close in spite of the rather different chemical bonds due to the charge transfer occurring in cubic boron nitride and gaps. (author)

  9. QM/MM based fitting of atomic polarizabilities for use in condensed-phase biomolecular simulation

    NARCIS (Netherlands)

    Vosmeer, C.R.; Rustenburg, A.S.; Rice, J.E.; Horn, H.W.; Swope, W.C.; Geerke, D.P.

    2012-01-01

    Accounting for electronic polarization effects in biomolecular simulation (by using a polarizable force field) can increase the accuracy of simulation results. However, the use of gas-phase estimates of atomic polarizabilities α

  10. The origins of the directionality of noncovalent intermolecular interactions.

    Science.gov (United States)

    Wang, Changwei; Guan, Liangyu; Danovich, David; Shaik, Sason; Mo, Yirong

    2016-01-05

    The recent σ-hole concept emphasizes the contribution of electrostatic attraction to noncovalent bonds, and implies that the electrostatic force has an angular dependency. Here a set of clusters, which includes hydrogen bonding, halogen bonding, chalcogen bonding, and pnicogen bonding systems, is investigated to probe the magnitude of covalency and its contribution to the directionality in noncovalent bonding. The study is based on the block-localized wavefunction (BLW) method that decomposes the binding energy into the steric and the charge transfer (CT) (hyperconjugation) contributions. One unique feature of the BLW method is its capability to derive optimal geometries with only steric effect taken into account, while excluding the CT interaction. The results reveal that the overall steric energy exhibits angular dependency notably in halogen bonding, chalcogen bonding, and pnicogen bonding systems. Turning on the CT interactions further shortens the intermolecular distances. This bond shortening enhances the Pauli repulsion, which in turn offsets the electrostatic attraction, such that in the final sum, the contribution of the steric effect to bonding is diminished, leaving the CT to dominate the binding energy. In several other systems particularly hydrogen bonding systems, the steric effect nevertheless still plays the major role whereas the CT interaction is minor. However, in all cases, the CT exhibits strong directionality, suggesting that the linearity or near linearity of noncovalent bonds is largely governed by the charge-transfer interaction whose magnitude determines the covalency in noncovalent bonds. © 2015 Wiley Periodicals, Inc.

  11. One-Photon Absorption Properties from a Hybrid Polarizable Density Embedding/Complex Polarization Propagator Approach for Polarizable Solutions

    DEFF Research Database (Denmark)

    Hršak, Dalibor; Nørby, Morten Steen; Coriani, Sonia

    2018-01-01

    We present a formulation of the polarizable density embedding (PDE) method in combination with the complex polarization propagator (CPP) method for the calculation of absorption spectra of molecules in solutions. The method is particularly useful for the calculation of near-edge X-ray absorption...... fine structure (NEXAFS) spectra. We compare the performance of PDE-CPP with the previously formulated polarizable embedding (PE)-CPP model for the calculation of the NEXAFS spectra of adenine, formamide, glycine, and adenosine triphosphate (ATP) in water at the carbon and nitrogen K-edges, as well...

  12. Binding of 5-phospho-D-arabinonohydroxamate and 5-phospho-D-arabinonate inhibitors to zinc phosphomannose isomerase from Candida albicans studied by polarizable molecular mechanics and quantum mechanics.

    Science.gov (United States)

    Roux, Celine; Gresh, Nohad; Perera, Lalith E; Piquemal, Jean-Philip; Salmon, Laurent

    2007-04-15

    Type I phosphomannose isomerase (PMI) is a Zn-dependent metalloenzyme involved in the isomerization of D-fructose 6-phosphate to D-mannose 6-phosphate. One of our laboratories has recently designed and synthesized 5-phospho-D-arabinonohydroxamate (5PAH), an inhibitor endowed with a nanomolar affinity for PMI (Roux et al., Biochemistry 2004, 43, 2926). By contrast, the 5-phospho-D-arabinonate (5PAA), in which the hydroxamate moiety is replaced by a carboxylate one, is devoid of inhibitory potency. Subsequent biochemical studies showed that in its PMI complex, 5PAH binds Zn(II) through its hydroxamate moiety rather than through its phosphate. These results have stimulated the present theoretical investigation in which we resort to the SIBFA polarizable molecular mechanics procedure to unravel the structural and energetical aspects of 5PAH and 5PAA binding to a 164-residue model of PMI. Consistent with the experimental results, our theoretical studies indicate that the complexation of PMI by 5PAH is much more favorable than by 5PAA, and that in the 5PAH complex, Zn(II) ligation by hydroxamate is much more favorable than by phosphate. Validations by parallel quantum-chemical computations on model of the recognition site extracted from the PMI-inhibitor complexes, and totaling up to 140 atoms, showed the values of the SIBFA intermolecular interaction energies in such models to be able to reproduce the quantum-chemistry ones with relative errors < 3%. On the basis of the PMI-5PAH SIBFA energy-minimized structure, we report the first hypothesis of a detailed view of the active site of the zinc PMI complexed to the high-energy intermediate analogue inhibitor, which allows us to identify active site residues likely involved in the proton transfer between the two adjacent carbons of the substrates. (c) 2007 Wiley Periodicals, Inc.

  13. Substituent effects of the alkyl groups: Polarity vs. polarizability

    Czech Academy of Sciences Publication Activity Database

    Exner, Otto; Böhm, S.

    -, č. 17 (2007), s. 2870-2876 ISSN 1434-193X Institutional research plan: CEZ:AV0Z40550506 Keywords : density functional calculations * hyperconjugation * inductive effect * polarizability Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.914, year: 2007

  14. Neutron polarizability. Possibilities of its determination in neutron experiments

    CERN Document Server

    Aleksandrov, Y A

    2001-01-01

    The history of question of neutron polarizability is discussed. Most of the neutron physical experiments conducted at neutron energies below 14 MeV to discover the electric polarizability of the neutron are reviewed.The existence of additional scattering after all known long range-related phenomena are taken into account are emphasized. In the keV neutron energy region, the effect of neutron polarizability on the angular distribution of scattering (over a wide range of angles) and the energy behavior of the total cross section of neutron interaction is studied. Finally, in the region of low energies (below 1 keV) the focus is on the influence of polarizability on the energy dependence of total neutron cross sections. It is emphasized that measurements at energies below several hundreds keV have not given any positive results yet due to the smallness of the experimental effect. Possible existence of an additional potential of neutron scattering on nuclei with a longer range than that of the usual nuclear poten...

  15. Polarizability effects on the structure and dynamics of ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br [Institute of Chemistry, University of Campinas – UNICAMP, Cx. P. 6154, Campinas, SP 13084-862 (Brazil); Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM (Brazil); Ribeiro, Mauro C. C. [Laboratório de Espectroscopia Molecular, Instituto de Química, Universidade de São Paulo, São Paulo, SP C.P. 26077, 05513 970 São Paulo, SP (Brazil); Skaf, Munir S. [Institute of Chemistry, University of Campinas – UNICAMP, Cx. P. 6154, Campinas, SP 13084-862 (Brazil)

    2014-04-14

    Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibrium structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.

  16. Theory and applications of atomic and ionic polarizabilities

    International Nuclear Information System (INIS)

    Mitroy, J; Safronova, M S; Clark, Charles W

    2010-01-01

    Atomic polarization phenomena impinge upon a number of areas and processes in physics. The dielectric constant and refractive index of any gas are examples of macroscopic properties that are largely determined by the dipole polarizability. When it comes to microscopic phenomena, the existence of alkaline-earth anions and the recently discovered ability of positrons to bind to many atoms are predominantly due to the polarization interaction. An imperfect knowledge of atomic polarizabilities is presently looming as the largest source of uncertainty in the new generation of optical frequency standards. Accurate polarizabilities for the group I and II atoms and ions of the periodic table have recently become available by a variety of techniques. These include refined many-body perturbation theory and coupled-cluster calculations sometimes combined with precise experimental data for selected transitions, microwave spectroscopy of Rydberg atoms and ions, refractive index measurements in microwave cavities, ab initio calculations of atomic structures using explicitly correlated wavefunctions, interferometry with atom beams and velocity changes of laser cooled atoms induced by an electric field. This review examines existing theoretical methods of determining atomic and ionic polarizabilities, and discusses their relevance to various applications with particular emphasis on cold-atom physics and the metrology of atomic frequency standards. (topical review)

  17. Partial Molar Volume of Methanol in Water: Effect of Polarizability

    Czech Academy of Sciences Publication Activity Database

    Moučka, F.; Nezbeda, Ivo

    2009-01-01

    Roč. 74, č. 4 (2009), s. 559-563 ISSN 0010-0765 R&D Projects: GA AV ČR IAA400720802 Institutional research plan: CEZ:AV0Z40720504 Keywords : water–methanol mixtures * partial molar volume * polarizability Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.856, year: 2009

  18. Theory and applications of atomic and ionic polarizabilities

    Energy Technology Data Exchange (ETDEWEB)

    Mitroy, J [School of Engineering, Charles Darwin University, Darwin NT 0909 (Australia); Safronova, M S [Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 (United States); Clark, Charles W, E-mail: jxm107@rsphysse.anu.edu.a, E-mail: msafrono@udel.ed, E-mail: charles.clark@nist.go [Joint Quantum Institute, National Institute of Standards and Technology and the University of Maryland, Gaithersburg, MD 20899-8410 (United States)

    2010-10-28

    Atomic polarization phenomena impinge upon a number of areas and processes in physics. The dielectric constant and refractive index of any gas are examples of macroscopic properties that are largely determined by the dipole polarizability. When it comes to microscopic phenomena, the existence of alkaline-earth anions and the recently discovered ability of positrons to bind to many atoms are predominantly due to the polarization interaction. An imperfect knowledge of atomic polarizabilities is presently looming as the largest source of uncertainty in the new generation of optical frequency standards. Accurate polarizabilities for the group I and II atoms and ions of the periodic table have recently become available by a variety of techniques. These include refined many-body perturbation theory and coupled-cluster calculations sometimes combined with precise experimental data for selected transitions, microwave spectroscopy of Rydberg atoms and ions, refractive index measurements in microwave cavities, ab initio calculations of atomic structures using explicitly correlated wavefunctions, interferometry with atom beams and velocity changes of laser cooled atoms induced by an electric field. This review examines existing theoretical methods of determining atomic and ionic polarizabilities, and discusses their relevance to various applications with particular emphasis on cold-atom physics and the metrology of atomic frequency standards. (topical review)

  19. Accounting for electronic polarization in non-polarizable force fields.

    Science.gov (United States)

    Leontyev, Igor; Stuchebrukhov, Alexei

    2011-02-21

    The issues of electronic polarizability in molecular dynamics simulations are discussed. We argue that the charges of ionized groups in proteins, and charges of ions in conventional non-polarizable force fields such as CHARMM, AMBER, GROMOS, etc should be scaled by a factor about 0.7. Our model explains why a neglect of electronic solvation energy, which typically amounts to about a half of total solvation energy, in non-polarizable simulations with un-scaled charges can produce a correct result; however, the correct solvation energy of ions does not guarantee the correctness of ion-ion pair interactions in many non-polarizable simulations. The inclusion of electronic screening for charged moieties is shown to result in significant changes in protein dynamics and can give rise to new qualitative results compared with the traditional non-polarizable force field simulations. The model also explains the striking difference between the value of water dipole μ∼ 3D reported in recent ab initio and experimental studies with the value μ(eff)∼ 2.3D typically used in the empirical potentials, such as TIP3P or SPC/E. It is shown that the effective dipole of water can be understood as a scaled value μ(eff) = μ/√ε(el), where ε(el) = 1.78 is the electronic (high-frequency) dielectric constant of water. This simple theoretical framework provides important insights into the nature of the effective parameters, which is crucial when the computational models of liquid water are used for simulations in different environments, such as proteins, or for interaction with solutes.

  20. Intermolecular dissociation energies of dispersively bound 1-naphtholṡcycloalkane complexes

    Science.gov (United States)

    Maity, Surajit; Ottiger, Philipp; Balmer, Franziska A.; Knochenmuss, Richard; Leutwyler, Samuel

    2016-12-01

    Intermolecular dissociation energies D0(S0) of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with cyclopentane, cyclohexane, and cycloheptane were determined to within theory (DFT) methods predict that the cycloalkane moieties are dispersively bound to the naphthol face via London-type interactions, similar to the "face" isomer of the 1-naphtholṡcyclopropane complex [S. Maity et al., J. Chem. Phys. 145, 164304 (2016)]. The experimental and calculated D0(S0) values of the cyclohexane and cyclopentane complexes are practically identical, although the polarizability of cyclohexane is ˜20 % larger than that of cyclopentane. Investigation of the calculated pairwise atomic contributions to the D2 dispersion energy reveals that this is due to subtle details of the binding geometries of the cycloalkanes relative to the 1-naphthol ring. The B97-D3 DFT method predicts dissociation energies within about ±1 % of experiment, including the cyclopropane face complex. The B3LYP-D3 and ωB97X-D calculated dissociation energies are 7-9 and 13-20% higher than the experimental D0(S0) values. Without dispersion correction, all the complexes are calculated to be unbound.

  1. Isotopic effects on non-linearity, molecular radius and intermolecular ...

    Indian Academy of Sciences (India)

    study the isotopic effects on the non-linearity parameter and the physicochemical proper- ties of the liquids, which in turn has been used to study their effect on the intermolecular interactions produced thereof. Keywords. Non-linearity parameter; molecular radius; free length; intermolecular inter- actions. PACS Nos 43.25.

  2. AUTOMATED FORCE FIELD PARAMETERIZATION FOR NON-POLARIZABLE AND POLARIZABLE ATOMIC MODELS BASED ONAB INITIOTARGET DATA.

    Science.gov (United States)

    Huang, Lei; Roux, Benoît

    2013-08-13

    Classical molecular dynamics (MD) simulations based on atomistic models are increasingly used to study a wide range of biological systems. A prerequisite for meaningful results from such simulations is an accurate molecular mechanical force field. Most biomolecular simulations are currently based on the widely used AMBER and CHARMM force fields, which were parameterized and optimized to cover a small set of basic compounds corresponding to the natural amino acids and nucleic acid bases. Atomic models of additional compounds are commonly generated by analogy to the parameter set of a given force field. While this procedure yields models that are internally consistent, the accuracy of the resulting models can be limited. In this work, we propose a method, General Automated Atomic Model Parameterization (GAAMP), for generating automatically the parameters of atomic models of small molecules using the results from ab initio quantum mechanical (QM) calculations as target data. Force fields that were previously developed for a wide range of model compounds serve as initial guess, although any of the final parameter can be optimized. The electrostatic parameters (partial charges, polarizabilities and shielding) are optimized on the basis of QM electrostatic potential (ESP) and, if applicable, the interaction energies between the compound and water molecules. The soft dihedrals are automatically identified and parameterized by targeting QM dihedral scans as well as the energies of stable conformers. To validate the approach, the solvation free energy is calculated for more than 200 small molecules and MD simulations of 3 different proteins are carried out.

  3. Interpolation of intermolecular potentials using Gaussian processes

    Science.gov (United States)

    Uteva, Elena; Graham, Richard S.; Wilkinson, Richard D.; Wheatley, Richard J.

    2017-10-01

    A procedure is proposed to produce intermolecular potential energy surfaces from limited data. The procedure involves generation of geometrical configurations using a Latin hypercube design, with a maximin criterion, based on inverse internuclear distances. Gaussian processes are used to interpolate the data, using over-specified inverse molecular distances as covariates, greatly improving the interpolation. Symmetric covariance functions are specified so that the interpolation surface obeys all relevant symmetries, reducing prediction errors. The interpolation scheme can be applied to many important molecular interactions with trivial modifications. Results are presented for three systems involving CO2, a system with a deep energy minimum (HF-HF), and a system with 48 symmetries (CH4-N2). In each case, the procedure accurately predicts an independent test set. Training this method with high-precision ab initio evaluations of the CO2-CO interaction enables a parameter-free, first-principles prediction of the CO2-CO cross virial coefficient that agrees very well with experiments.

  4. Intermolecular Structural Change for Thermoswitchable Polymeric Photosensitizer

    Energy Technology Data Exchange (ETDEWEB)

    Park, Wooram; Park, Sin-Jung [Center; Cho, Soojeong; Shin, Heejun [Center; Jung, Young-Seok [Center; Lee, Byeongdu [X-ray; Na, Kun [Center; Kim, Dong-Hyun

    2016-08-17

    A switchable photosensitizer (PS), which can be activated at a spe-cific condition beside light, has tremendous advantages for photo-dynamic therapy (PDT). Herein, we developed a thermo-switchable polymeric photosensitizer (T-PPS) by conjugating PS (Pheophor-bide-a, PPb-a) to a temperature-responsive polymer backbone of biocompatible hydroxypropyl cellulose (HPC). Self-quenched PS molecules linked in close proximity by pi-pi stacking in T-PPS were easily transited to an active monomeric state by the tempera-ture induced phase transition of polymer backbones. The tempera-ture responsive inter-molecular interaction changes of PS molecules in T-PPS were demonstrated in synchrotron small-angle X-ray scattering (SAXS) and UV-Vis spectrophotometer analysis. The T-PPS allowed switchable activation and synergistically enhanced cancer cell killing effect at the hyperthermia temperature (45 °C). Our developed T-PPS has the considerable potential not only as a new class of photomedicine in clinics but also as a biosensor based on temperature responsiveness.

  5. Intermolecular interaction studies of glyphosate with water

    Science.gov (United States)

    Manon, Priti; Juglan, K. C.; Kaur, Kirandeep; Sethi, Nidhi; Kaur, J. P.

    2017-07-01

    The density (ρ), viscosity (η) and ultrasonic velocity (U) of glyphosate with water have been measured on different ultrasonic frequency ranges from 1MHz, 2MHz, 3MHz & 5MHz by varying concentrations (0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, & 0.40%) at 30°C. The specific gravity bottle, Ostwald's viscometer and quartz crystal interferometer were used to determine density (ρ), viscosity (η) and ultrasonic velocity (U). These three factors contribute in evaluating the other parameters as acoustic impedance (Z), adiabatic compressibility (β), relaxation time (τ), intermolecular free length (Lf), free volume (Vf), ultrasonic attenuation (α/f2), Rao's constant (R), Wada's constant (W) and relative strength (R). Solute-solvent interaction is confirmed by ultrasonic velocity and viscosity values, which increases with increase in concentration indicates stronger association between solute and solvent molecules. With rise in ultrasonic frequency the interaction between the solute and solvent particles decreases. The linear variations in Rao's constant and Wada's constant suggest the absence of complex formation.

  6. Polarizability of deformed nuclei and energy shifts in muonic atoms

    International Nuclear Information System (INIS)

    Nali, P.F.; Quarati, P.

    1980-01-01

    The polarizability and nuclear-polarization energy shifts of nuclei composed of closed shells plus valence nucleons in muonic atoms have been calculated: the harmonic-oscillator results of the El polarizability and the energy shifts have been corrected by means of a perturbative approach, which takes into account the effects introduced by the deformation Nilsson potential. Furthermore, to take into account the core polarization effect, different harmonic-oscillator parameters for the core and the valence nucleons have been assumed. The energy shifts of a sequence of states occupied by the muon during its atomic electromagnetic cascade for the nuclei 17 O and 17 F, 41 Ca and 41 Sc have been calculated. (author)

  7. Dynamic polarizability of a complex atom in strong laser fields

    International Nuclear Information System (INIS)

    Rapoport, L.P.; Klinskikh, A.F.; Mordvinov, V.V.

    1997-01-01

    An asymptotic expansion of the dynamic polarizability of a complex atom in a strong circularly polarized light field is found for the case of high frequencies. The self-consistent approximation of the Hartree-Fock type for the ''atom+field'' system is developed, within the framework of which a numerical calculation of the dynamic polarizability of Ne, Kr, and Ar atoms in a strong radiation field is performed. The strong field effect is shown to manifest itself not only in a change of the energy spectrum and the character of behavior of the wave functions of atomic electrons, but also in a modification of the one-electron self-consistent potential for the atom in the field

  8. Variation of the electronic dipole polarizability on the reaction path.

    Science.gov (United States)

    Jędrzejewski, Mateusz; Ordon, Piotr; Komorowski, Ludwik

    2013-10-01

    The reaction force and the electronic flux, first proposed by Toro-Labbé et al. (J Phys Chem A 103:4398, 1999) have been expressed by the existing conceptual DFT apparatus. The critical points (extremes) of the chemical potential, global hardness and softness have been identified by means of the existing and computable energy derivatives: the Hellman-Feynman force, nuclear reactivity and nuclear stiffness. Specific role of atoms at the reaction center has been unveiled by indicating an alternative method of calculation of the reaction force and the reaction electronic flux. The electron dipole polarizability on the IRC has been analyzed for the model reaction HF + CO→HCOF. The electron polarizability determined on the IRC α e (ξ) was found to be reasonably parallel to the global softness curve S(ξ). The softest state on the IRC (not TS) coincides with zero electronic flux.

  9. Polarizability of π-mesons in the quark confinement model

    International Nuclear Information System (INIS)

    Avakyan, E.Z.; Avakyan, S.L.; Efimov, G.V.; Ivanov, M.A.

    1988-01-01

    The electric α π and magnetic β π polarizabilities are calculated in the Quark Confinement Model (QCM). The diagrams with vector, scalar and axial intermediate states are taken into account. It is found that intermediate scalar mesons give an essential contribution to electric and magnetic polarizabilities of pions. The following values for α π and β π are obtained: α π ± =4.06x10 -43 cm 3 ; β π ± =-3.84x10 -43 ; α π 0 =-0.18x10 -43 cm 3 ; β π 0 =1.92x10 -43 cm 3 . The widths of strong (α 0 (980) → πη, f 0 (975) → ππ, ε(730) → ππ) and radiative (α 0 (980), f 0 (980), ε(730) → γγ) decays are calculated. The results are obtained to be in satisfactory agreement with expermental data

  10. Detecting Stealth Dark Matter Directly through Electromagnetic Polarizability.

    Science.gov (United States)

    Appelquist, T; Berkowitz, E; Brower, R C; Buchoff, M I; Fleming, G T; Jin, X-Y; Kiskis, J; Kribs, G D; Neil, E T; Osborn, J C; Rebbi, C; Rinaldi, E; Schaich, D; Schroeder, C; Syritsyn, S; Vranas, P; Weinberg, E; Witzel, O

    2015-10-23

    We calculate the spin-independent scattering cross section for direct detection that results from the electromagnetic polarizability of a composite scalar "stealth baryon" dark matter candidate, arising from a dark SU(4) confining gauge theory-"stealth dark matter." In the nonrelativistic limit, electromagnetic polarizability proceeds through a dimension-7 interaction leading to a very small scattering cross section for dark matter with weak-scale masses. This represents a lower bound on the scattering cross section for composite dark matter theories with electromagnetically charged constituents. We carry out lattice calculations of the polarizability for the lightest "baryon" states in SU(3) and SU(4) gauge theories using the background field method on quenched configurations. We find the polarizabilities of SU(3) and SU(4) to be comparable (within about 50%) normalized to the stealth baryon mass, which is suggestive for extensions to larger SU(N) groups. The resulting scattering cross sections with a xenon target are shown to be potentially detectable in the dark matter mass range of about 200-700 GeV, where the lower bound is from the existing LUX constraint while the upper bound is the coherent neutrino background. Significant uncertainties in the cross section remain due to the more complicated interaction of the polarizablity operator with nuclear structure; however, the steep dependence on the dark matter mass, 1/m(B)(6), suggests the observable dark matter mass range is not appreciably modified. We briefly highlight collider searches for the mesons in the theory as well as the indirect astrophysical effects that may also provide excellent probes of stealth dark matter.

  11. Experimental Constraints on Polarizability Corrections to Hydrogen Hyperfine Structure

    International Nuclear Information System (INIS)

    Nazaryan, Vahagn; Carlson, Carl E.; Griffioen, Keith A.

    2006-01-01

    We present a state-of-the-art evaluation of the polarizability corrections--the inelastic nucleon corrections--to the hydrogen ground-state hyperfine splitting using analytic fits to the most recent data. We find a value Δ pol =1.3±0.3 ppm. This is 1-2 ppm smaller than the value of Δ pol deduced using hyperfine splitting data and elastic nucleon corrections obtained from modern form factor fits

  12. Modeling Electronic Circular Dichroism within the Polarizable Embedding Approach

    DEFF Research Database (Denmark)

    Nørby, Morten S; Olsen, Jógvan Magnus Haugaard; Steinmann, Casper

    2017-01-01

    We present a systematic investigation of the key components needed to model single chromophore electronic circular dichroism (ECD) within the polarizable embedding (PE) approach. By relying on accurate forms of the embedding potential, where especially the inclusion of local field effects...... are in focus, we show that qualitative agreement between rotatory strength parameters calculated by full quantum mechanical calculations and the more efficient embedding calculations can be obtained. An important aspect in the computation of reliable absorption parameters is the need for conformational...

  13. Time reversal violating nuclear polarizability and atomic electric dipole moment

    International Nuclear Information System (INIS)

    Ginges, J.S.M.; Flambaum, V.V.; Mititelu, G.

    2000-01-01

    Full text: We propose a nuclear mechanism which can induce an atomic electric dipole moment (EDM). The interaction of external electric E and magnetic H fields with nuclear electric and magnetic dipole moments, d and ,u, gives rise to an energy shift, U= -β ik E i H k , where β ik is the nuclear polarizability. Parity and time invariance violating (P,T-odd) nuclear forces generate a mixed P,T-odd nuclear polarizability, whereψ 0 and ψ n are P,T-odd perturbed ground and excited nuclear states, respectively. In the case of a heavy spherical nucleus with a single unpaired nucleon, the perturbed wavefunctions are U = -β ik E i H k , where ξis a constant proportional to the strength of the nuclear P,T-odd interaction, σ is the nuclear spin operator, and ψ n is an unperturbed wavefunction. There are both scalar and tensor contributions to the nuclear P,T-odd polarizability. An atomic EDM is induced by the interaction of the fields of an unpaired electron in an atom with the P,T-odd perturbed atomic nucleus. An estimate for the value of this EDM has been made. The measurements of atomic EDMs can provide information about P,T-odd nuclear forces and test models of CP-violation

  14. Density Functional Studies of Molecular Polarizabilities. 10. Fulvenes and Fulvalenes

    Directory of Open Access Journals (Sweden)

    Humberto J. Soscún Machado

    2000-09-01

    Full Text Available We report accurate Ab Initio Hartree Fock (HF and Density Functional Theory (DFT studies of the static dipole polarizabilities and first hyperpolarizabilities of the [n] fulvene and the [n,m] fulvalene series of molecules (with n, m = 3,5,7. Calculations are also reported for the parent cycloalkenes: cyclopropene, cyclopentadiene and cycloheptatriene (1-3 respectively. Geometries were optimized at the HF/6-311G(3d,2p level of theory. All the fulvenes (4-6 and the smaller fulvalenes (7, 9 and 10 are found to be planar. Pentaheptafulvalene (11 is slightly non-planar whilst heptafulvalene (12 has a folded C2h structure. Calculated C-C bond lengths are consistently smaller than the experimental values. Dipole polarizabilities and non-zero hyperpolarizabilities were calculated at the HF/6-311++G(3d,2p and BLYP/6-311++G(3d,2p levels of theory, using HF/6-311G(3d,2p geometries. Dipole polarizabilities correlate well with those given on the basis of atom additivity. Molecules (8, (9 and (11 show very large dipole hyperpolarizabilities.

  15. Theoretical study on the molecular structure, intermolecular ...

    Indian Academy of Sciences (India)

    It was revealed that S1 is formed by the edge(2-AP)-to-face(DDQ) linkage, which is stabilized by a moderate σ–π interaction and hydrogen binding interaction. ... the 2-AP(π)→DDQ(π*) charge transfer transitions in conformers S2 and S3 contribute to the two new charge transfer absorption bands which were experimentally ...

  16. Measurement of the Charged-Pion Polarizability

    CERN Document Server

    Adolph, C; Alexeev, M.G.; Alexeev, G.D.; Amoroso, A.; Andrieux, V.; Anosov, V.; Austregesilo, A.; Badelek, B.; Balestra, F.; Barth, J.; Baum, G.; Beck, R.; Bedfer, Y.; Berlin, A.; Bernhard, J.; Bicker, K.; Bieling, J.; Birsa, R.; Bisplinghoff, J.; Bodlak, M.; Boer, M.; Bordalo, P.; Bradamante, F.; Braun, C.; Bressan, A.; Buchele, M.; Burtin, E.; Capozza, L.; Chiosso, M.; Chung, S.U.; Cicuttin, A.; Colantoni, M.; Crespo, M.L.; Curiel, Q.; Dalla Torre, S.; Dasgupta, S.S.; Dasgupta, S.; Denisov, O.Yu.; Dinkelbach, A.M.; Donskov, S.V.; Doshita, N.; Duic, V.; Dunnweber, W.; Dziewiecki, M.; Efremov, A.; Elia, C.; Eversheim, P.D.; Eyrich, W.; Faessler, M.; Ferrero, A.; Filin, A.; Finger, M.; M. Finger jr; Fischer, H.; Franco, C.; von Hohenesche, N. du Fresne; Friedrich, J.M.; Frolov, V.; Gautheron, F.; Gavrichtchouk, O.P.; Gerassimov, S.; Geyer, R.; Gnesi, I.; Gobbo, B.; Goertz, S.; Gorzellik, M.; Grabmuller, S.; Grasso, A.; Grube, B.; Grussenmeyer, T.; Guskov, A.; Guthorl, T.; Haas, F.; von Harrach, D.; Hahne, D.; Hashimoto, R.; Heinsius, F.H.; Herrmann, F.; Hinterberger, F.; Hoppner, Ch.; Horikawa, N.; d'Hose, N.; Huber, S.; Ishimoto, S.; Ivanov, A.; Ivanshin, Yu.; Iwata, T.; Jahn, R.; Jary, V.; Jasinski, P.; Jorg, P.; Joosten, R.; Kabuss, E.; Ketzer, B.; Khaustov, G.V.; Khokhlov, Yu. A.; Kisselev, Yu.; Klein, F.; Klimaszewski, K.; Koivuniemi, J.H.; Kolosov, V.N.; Kondo, K.; Konigsmann, K.; Konorov, I.; Konstantinov, V.F.; Kotzinian, A.M.; Kouznetsov, O.; Kramer, M.; Kroumchtein, Z.V.; Kuchinski, N.; Kuhn, R.; Kunne, F.; Kurek, K.; Kurjata, R.P.; Lednev, A.A.; Lehmann, A.; Levillain, M.; Levorato, S.; Lichtenstadt, J.; Maggiora, A.; Magnon, A.; Makke, N.; Mallot, G.K.; Marchand, C.; Martin, A.; Marzec, J.; Matousek, J.; Matsuda, H.; Matsuda, T.; Meshcheryakov, G.; Meyer, W.; Michigami, T.; Mikhailov, Yu. V.; Miyachi, Y.; Moinester, M.A.; Nagaytsev, A.; Nagel, T.; Nerling, F.; Neubert, S.; Neyret, D.; Nikolaenko, V.I.; Novy, J.; Nowak, W.D.; Nunes, A.S.; Olshevsky, A.G.; Orlov, I.; Ostrick, M.; Panknin, R.; Panzieri, D.; Parsamyan, B.; Paul, S.; Peshekhonov, D.; Platchkov, S.; Pochodzalla, J.; Polyakov, V.A.; Pretz, J.; Quaresma, M.; Quintans, C.; Ramos, S.; Regali, C.; Reicherz, G.; Rocco, E.; Rossiyskaya, N.S.; Ryabchikov, D.I.; Rychter, A.; Samoylenko, V.D.; Sandacz, A.; Sarkar, S.; Savin, I.A.; Sbrizzai, G.; Schiavon, P.; Schill, C.; Schluter, T.; Schmidt, K.; Schmieden, H.; Schonning, K.; Schopferer, S.; Schott, M.; Shevchenko, O.Yu.; Silva, L.; Sinha, L.; Sirtl, S.; Slunecka, M.; Sosio, S.; Sozzi, F.; Srnka, A.; Steiger, L.; Stolarski, M.; Sulc, M.; Sulej, R.; Suzuki, H.; Szabelski, A.; Szameitat, T.; Sznajder, P.; Takekawa, S.; Wolbeek, J. ter; Tessaro, S.; Tessarotto, F.; Thibaud, F.; Uhl, S.; Uman, I.; Virius, M.; Wang, L.; Weisrock, T.; Wilfert, M.; Windmolders, R.; Wollny, H.; Zaremba, K.; Zavertyaev, M.; Zemlyanichkina, E.; Ziembicki, M.; Zink, A.

    2015-01-01

    The COMPASS collaboration at CERN has investigated pion Compton scattering, $\\pi^-\\gamma\\rightarrow \\pi^-\\gamma$, at centre-of-mass energy below 3.5 pion masses. The process is embedded in the reaction $\\pi^-\\mathrm{Ni}\\rightarrow\\pi^-\\gamma\\;\\mathrm{Ni}$, which is initiated by 190 GeV pions impinging on a nickel target. The exchange of quasi-real photons is selected by isolating the sharp Coulomb peak observed at smallest momentum transfers, $Q^2<0.0015$ (GeV/$c$)$^2$. From a sample of 63 000 events the pion electric polarisability is determined to be $\\alpha_\\pi = (2.0 \\pm 0.6_{\\mbox{stat}} \\pm 0.7_{\\mbox{syst}}) \\times 10^{-4} \\mbox{fm}^3$ under the assumption $\\alpha_\\pi=-\\beta_\\pi$, which relates the electric and magnetic dipole polarisabilities. It is the most precise measurement of this fundamental low-energy parameter of strong interaction, that has been addressed since long by various methods with conflicting outcomes. While this result is in tension with previous dedicated measurements, it is fou...

  17. Synthesis and intermolecular interactions of N-benzylidenetyramines

    Science.gov (United States)

    Maldonado, Mauricio; Pérez-Redondo, Adrián; Quevedo, Rodolfo

    2017-01-01

    In this paper, the synthesis and intermolecular interactions between N-benzylidenetyramine molecules were investigated. The crystal structure of N-(4-nitrobenzylidene)tyramine shows a molecular organization in zigzag chains with intermolecular O-H⋯N hydrogen bonds between the azomethine and phenolic hydroxyl groups. Those chains are held together by C-H⋯O hydrogen bonds to generate layers, which are connected by C-H⋯O, π⋯π and NO2⋯π interactions.

  18. Static electric dipole polarizabilities of An5+/6+ and AnO2+/2+ (An = U, Np, and Pu) ions

    International Nuclear Information System (INIS)

    Parmar, Payal; Peterson, Kirk A.; Clark, Aurora E.

    2014-01-01

    The parallel components of static electric dipole polarizabilities have been calculated for the lowest lying spin-orbit states of the penta- and hexavalent oxidation states of the actinides (An) U, Np, and Pu, in both their atomic and molecular diyl ion forms (An 5+/6+ and AnO 2 +/2+ ) using the numerical finite-field technique within a four-component relativistic framework. The four-component Dirac-Hartree-Fock method formed the reference for MP2 and CCSD(T) calculations, while multireference Fock space coupled-cluster (FSCC), intermediate Hamiltonian Fock space coupled-cluster (IH-FSCC) and Kramers restricted configuration interaction (KRCI) methods were used to incorporate additional electron correlation. It is observed that electron correlation has significant (∼5 a.u. 3 ) impact upon the parallel component of the polarizabilities of the diyls. To the best of our knowledge, these quantities have not been previously reported and they can serve as reference values in the determination of various electronic and response properties (for example intermolecular forces, optical properties, etc.) relevant to the nuclear fuel cycle and material science applications. The highest quality numbers for the parallel components (α zz ) of the polarizability for the lowest Ω levels corresponding to the ground electronic states are (in a.u. 3 ) 44.15 and 41.17 for UO 2 + and UO 2 2+ , respectively, 45.64 and 41.42 for NpO 2 + and NpO 2 2+ , respectively, and 47.15 for the PuO 2 + ion

  19. Physical Principles of Development of the State Standard of Biological Cell Polarizability

    Science.gov (United States)

    Shuvalov, G. V.; Generalov, K. V.; Generalov, V. M.; Kruchinina, M. V.; Koptev, E. S.; Minin, O. V.; Minin, I. V.

    2018-03-01

    A new state standard of biological cell polarizability based on micron-size latex particles has been developed. As a standard material, it is suggested to use polystyrene. Values of the polarizability calculated for erythrocytes and values of the polarizability of micron-size spherical latex particles measured with measuring-computing complexes agree within the limits of satisfactory relative error. The Standard allows one the unit of polarizability measurements [m3] to be assigned to cells and erythrocytes for the needs of medicine.

  20. Dynamic dipole polarizabilities of the Li atom and the Be+ ion

    International Nuclear Information System (INIS)

    Tang Liyan; Yan Zongchao; Shi Tingyun; Mitroy, J.

    2010-01-01

    The dynamic dipole polarizabilities for Li atoms and Be + ions in the 2 2 S and 2 2 P states are calculated using the variational method with a Hylleraas basis. The present polarizabilities represent the definitive values in the nonrelativistic limit. Corrections due to relativistic effects are also estimated. Analytic representations of the polarizabilities for frequency ranges encompassing the n=3 excitations are presented. The recommended polarizabilities for 7 Li and 9 Be + are 164.11±0.03 a 0 3 and 24.489±0.004 a 0 3 , respectively.

  1. Chiral model predictions for electromagnetic polarizabilities of the nucleon: A 'consumer report'

    International Nuclear Information System (INIS)

    Broniowski, W.

    1992-01-01

    This contribution has two parts: (1) The author critically discusses predictions for the electromagnetic polarizabilities of the nucleon obtained in two different approaches: (a) hedgehog models (HM), such as Skyrmions, chiral quark models, hybrid bags, NJL etc., and (b) chiral perturbation theory (χPT). (2) The author shows new results obtained in HM: N c -counting of polarizabilities, splitting of the neutron and proton polarizabilities (he argues that α n > α p in models with pionic clouds), relevance of dispersive terms in the magnetic polarizability β, important role of the Δ resonance in pionic loops, and the effects of non-minimal substitution terms in the effective lagrangian. 3 refs

  2. Energy transfer in oligothiophene inclusion compounds

    NARCIS (Netherlands)

    Loi, M.A.; Mura, A.; Bongiovanni, G.; Botta, C.; Silvestro, G. Di; Tubino, R.

    2001-01-01

    Energy transfer between terthiophene and quinquethiophene oligomers embedded in the nanochannels of perhydrotriphenylene crystals is investigated by fs-time-resolved photoluminescence spectroscopy. Excitonic effects in these compounds are suppressed due to the large intermolecular distances imposed

  3. Virtual Compton Scattering at MAMI and measurement of the proton generalized polarizabilities

    International Nuclear Information System (INIS)

    Roche, Julie

    1998-01-01

    We have measured the absolute unpolarized cross sections for photon electro-production of the proton with the Three-Spectrometer-Setup at MAMI at a momentum transfer q=600 MeV (or squared quadra-momentum of the virtual photon 0.33 GeV square) and a virtual photon polarization 0.62. The momentum for the outgoing real photon q' ranged from 33 to 111 MeV. We extracted two combinations of the generalized polarizabilities (GPs) of the proton. The reaction of interest is Virtual Compton Scattering off the proton. We can access to a measurement of the rigidity of the internal structure of the nucleon. Below pion production threshold but arbitrary squared quadra-momentum of the virtual photon, measured observables are the GPs. They generalize the concept of electric and magnetic polarizabilities already defined in Real Compton Scattering. Experimentally, the scattered electron was detected in coincidence with the recoiling proton in two high-resolution spectrometers. The photon emission process was selected by a cut on the missing mass squared distribution around zero. This PhD work describes the analysis work from raw data to absolute and precise cross sections (within a 3 pc statistical and 4 pc systematic accuracies). Our experiment at Mainz demonstrates that it is possible to measure two structure functions related to the GPs; extracted values are presented. These observables are compared with theoretical predictions and are very efficient to disentangle models of the non-perturbative structure of the nucleon. (author) [fr

  4. Quantifying intermolecular interactions of ionic liquids using cohesive energy densities

    Science.gov (United States)

    2017-01-01

    For ionic liquids (ILs), both the large number of possible cation + anion combinations and their ionic nature provide a unique challenge for understanding intermolecular interactions. Cohesive energy density, ced, is used to quantify the strength of intermolecular interactions for molecular liquids, and is determined using the enthalpy of vaporization. A critical analysis of the experimental challenges and data to obtain ced for ILs is provided. For ILs there are two methods to judge the strength of intermolecular interactions, due to the presence of multiple constituents in the vapour phase of ILs. Firstly, cedIP, where the ionic vapour constituent is neutral ion pairs, the major constituent of the IL vapour. Secondly, cedC+A, where the ionic vapour constituents are isolated ions. A cedIP dataset is presented for 64 ILs. For the first time an experimental cedC+A, a measure of the strength of the total intermolecular interaction for an IL, is presented. cedC+A is significantly larger for ILs than ced for most molecular liquids, reflecting the need to break all of the relatively strong electrostatic interactions present in ILs. However, the van der Waals interactions contribute significantly to IL volatility due to the very strong electrostatic interaction in the neutral ion pair ionic vapour. An excellent linear correlation is found between cedIP and the inverse of the molecular volume. A good linear correlation is found between IL cedIP and IL Gordon parameter (which are dependent primarily on surface tension). ced values obtained through indirect methods gave similar magnitude values to cedIP. These findings show that cedIP is very important for understanding IL intermolecular interactions, in spite of cedIP not being a measure of the total intermolecular interactions of an IL. In the outlook section, remaining challenges for understanding IL intermolecular interactions are outlined. PMID:29308254

  5. Quantifying intermolecular interactions of ionic liquids using cohesive energy densities.

    Science.gov (United States)

    Lovelock, Kevin R J

    2017-12-01

    For ionic liquids (ILs), both the large number of possible cation + anion combinations and their ionic nature provide a unique challenge for understanding intermolecular interactions. Cohesive energy density, ced , is used to quantify the strength of intermolecular interactions for molecular liquids, and is determined using the enthalpy of vaporization. A critical analysis of the experimental challenges and data to obtain ced for ILs is provided. For ILs there are two methods to judge the strength of intermolecular interactions, due to the presence of multiple constituents in the vapour phase of ILs. Firstly, ced IP , where the ionic vapour constituent is neutral ion pairs, the major constituent of the IL vapour. Secondly, ced C+A , where the ionic vapour constituents are isolated ions. A ced IP dataset is presented for 64 ILs. For the first time an experimental ced C+A , a measure of the strength of the total intermolecular interaction for an IL, is presented. ced C+A is significantly larger for ILs than ced for most molecular liquids, reflecting the need to break all of the relatively strong electrostatic interactions present in ILs. However, the van der Waals interactions contribute significantly to IL volatility due to the very strong electrostatic interaction in the neutral ion pair ionic vapour. An excellent linear correlation is found between ced IP and the inverse of the molecular volume. A good linear correlation is found between IL ced IP and IL Gordon parameter (which are dependent primarily on surface tension). ced values obtained through indirect methods gave similar magnitude values to ced IP . These findings show that ced IP is very important for understanding IL intermolecular interactions, in spite of ced IP not being a measure of the total intermolecular interactions of an IL. In the outlook section, remaining challenges for understanding IL intermolecular interactions are outlined.

  6. Intermolecular covalent pi-pi bonding interaction indicated by bond distances, energy bands, and magnetism in biphenalenyl biradicaloid molecular crystal.

    Science.gov (United States)

    Huang, Jingsong; Kertesz, Miklos

    2007-02-14

    Density-functional theory (DFT) calculations were performed for energy band structure and geometry optimizations on the stepped pi-chain, the isolated molecule and (di)cations of the chain, and various related molecules of a neutral biphenalenyl biradicaloid (BPBR) organic semiconductor 2. The dependence of the geometries on crystal packing provides indirect evidence for the intermolecular covalent pi-pi bonding interaction through space between neighboring pi-stacked phenalenyl units along the chain. The two phenalenyl electrons on each molecule, occupying the singly occupied molecular orbitals (SOMOs), are participating in the intermolecular covalent pi-pi bonding making them partially localized on the phenalenyl units and less available for intramolecular delocalization. The band structure shows a relatively large bandwidth and small band gap indicative of good pi-pi overlap and delocalization between neighboring pi-stacked phenalenyl units. A new interpretation is presented for the magnetism of the stepped pi-chain of 2 using an alternating Heisenberg chain model, which is consistent with DFT total energy calculations for 2 and prevails against the previous interpretation using a Bleaney-Bowers dimer model. The obtained transfer integrals and the magnetic exchange parameters fit well into the framework of a Hubbard model. All presented analyses on molecular geometries, energy bands, and magnetism provide a coherent picture for 2 pointing toward an alternating chain with significant intermolecular through-space covalent pi-pi bonding interactions in the molecular crystal. Surprisingly, both the intermolecular transfer integrals and exchange parameters are larger than the intramolecular through-bond values indicating the effectiveness of the intermolecular overlap of the phenalenyl SOMO electrons.

  7. Open-ended response theory with polarizable embedding

    DEFF Research Database (Denmark)

    Steindal, Arnfinn Hykkerud; Beerepoot, Maarten T P; Ringholm, Magnus

    2016-01-01

    We present the theory and implementation of an open-ended framework for electric response properties at the level of Hartree-Fock and Kohn-Sham density functional theory that includes effects from the molecular environment modeled by the polarizable embedding (PE) model. With this new state......) properties can be studied by evaluating single residues of the response functions. The PE approach includes mutual polarization effects between the quantum and classical parts of the system through induced dipoles that are determined self-consistently with respect to the electronic density. The applicability...

  8. Polarizability expressions for predicting resonances in plasmonic and Mie scatterers

    Science.gov (United States)

    Colom, Rémi; Devilez, Alexis; Enoch, Stefan; Stout, Brian; Bonod, Nicolas

    2017-06-01

    Polarizability expressions are commonly used in optics and photonics to model light scattering by small particles. Models based on Taylor series of the scattering coefficients of the particles fail to predict the morphologic resonances hosted by dielectric particles. Here we propose to use the factorization of the special functions appearing in the expression of the Mie scattering coefficients to derive pointlike models. These models can be applied to reproduce both Mie resonances of dielectric particles and plasmonic resonances of metallic particles. They provide simple but robust tools to predict accurately the electric and magnetic Mie resonances in dielectric particles.

  9. On the magnetic polarizability tensor of US coinage

    Science.gov (United States)

    Davidson, John L.; Abdel-Rehim, Omar A.; Hu, Peipei; Marsh, Liam A.; O’Toole, Michael D.; Peyton, Anthony J.

    2018-03-01

    The magnetic dipole polarizability tensor of a metallic object gives unique information about the size, shape and electromagnetic properties of the object. In this paper, we present a novel method of coin characterization based on the spectroscopic response of the absolute tensor. The experimental measurements are validated using a combination of tests with a small set of bespoke coin surrogates and simulated data. The method is applied to an uncirculated set of US coins. Measured and simulated spectroscopic tensor responses of the coins show significant differences between different coin denominations. The presented results are encouraging as they strongly demonstrate the ability to characterize coins using an absolute tensor approach.

  10. Calculations of polarizabilities and hyperpolarizabilities for the Be+ ion

    International Nuclear Information System (INIS)

    Tang Liyan; Zhang Junyi; Mitroy, J.; Yan Zongchao; Shi Tingyun; Babb, James F.

    2009-01-01

    The polarizabilities and hyperpolarizabilities of the Be + ion in the 2 2 S state and the 2 2 P state are determined. Calculations are performed using two independent methods: (i) variationally determined wave functions using Hylleraas basis set expansions and (ii) single electron calculations utilizing a frozen-core Hamiltonian. The first few parameters in the long-range interaction potential between a Be + ion and a H, He, or Li atom, and the leading parameters of the effective potential for the high-L Rydberg states of beryllium were also computed. All the values reported are the results of calculations close to convergence. Comparisons are made with published results where available.

  11. Pion and kaon polarizabilities in the quark confinement model

    International Nuclear Information System (INIS)

    Ivanov, M.A.; Mizutani, T.

    1992-01-01

    The quark confinement model (QCM) which is based on quark confinement and the composite nature of hadrons, is applied to the study of electromagnetic polarizabilities of the π and K mesons. The Compton scattering amplitude for pseudoscalar meson in the QCM obtains contributions from the following processes (or diagrams): (1) the photon scattering by a point charge, (2) diagrams which involve only one quark loop, (3) the scalar, vector, and axial meson exchanges. The presence of quark loops in QCM diagrams introduces nontrivial momentum dependences which do not exist in the effective Lagrangian scheme with only meson degrees of freedom

  12. 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.

  13. Weak-field Hall effect and static polarizability of Bloch electrons

    Czech Academy of Sciences Publication Activity Database

    Středa, Pavel; Jonckheere, T.

    2009-01-01

    Roč. 79, č. 11 (2009), 115115/1-115115/8 ISSN 1098-0121 R&D Projects: GA ČR GA202/08/0551 Institutional research plan: CEZ:AV0Z10100521 Keywords : Hall effect * magnetization * Bloch electrons electron polarizability * electron polarizability Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.475, year: 2009

  14. The electric double layer at high surface potentials: The influence of excess ion polarizability

    NARCIS (Netherlands)

    Hatlo, M. M.|info:eu-repo/dai/nl/412640678; van Roij, R.H.H.G.|info:eu-repo/dai/nl/152978984; Lue, L.

    2012-01-01

    By including the excess ion polarizability into the Poisson-Boltzmann theory, we show that the decrease in differential capacitance with voltage, observed for metal electrodes above a threshold potential, can be understood in terms of thickening of the double layer due to ion-induced polarizability

  15. Polarizability and alignment of dielectric nanoparticles in an external electric field: Bowls, dumbbells, and cuboids

    NARCIS (Netherlands)

    Kwaadgras, B.W.; Verdult, M.; Dijkstra, M.; van Roij, R.H.H.G.

    2011-01-01

    We employ the coupled dipole method to calculate the polarizability tensor of various anisotropic dielectric clusters of polarizable atoms, such as cuboid-, bowl-, and dumbbell-shaped nanoparticles. Starting from a Hamiltonian of a many-atom system, we investigate how this tensor depends on the size

  16. Statistical field theory description of inhomogeneous polarizable soft matter.

    Science.gov (United States)

    Martin, Jonathan M; Li, Wei; Delaney, Kris T; Fredrickson, Glenn H

    2016-10-21

    We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

  17. Enhancement of polarizabilities of cylinders with cylinder-slab resonances.

    Science.gov (United States)

    Xiao, Meng; Huang, Xueqin; Liu, H; Chan, C T

    2015-02-02

    If an object is very small in size compared with the wavelength of light, it does not scatter light efficiently. It is hence difficult to detect a very small object with light. We show using analytic theory as well as full wave numerical calculation that the effective polarizability of a small cylinder can be greatly enhanced by coupling it with a superlens type metamaterial slab. This kind of enhancement is not due to the individual resonance effect of the metamaterial slab, nor due to that of the object, but is caused by a collective resonant mode between the cylinder and the slab. We show that this type of particle-slab resonance which makes a small two-dimensional object much "brighter" is actually closely related to the reverse effect known in the literature as "cloaking by anomalous resonance" which can make a small cylinder undetectable. We also show that the enhancement of polarizability can lead to strongly enhanced electromagnetic forces that can be attractive or repulsive, depending on the material properties of the cylinder.

  18. Revised Parameters for the AMOEBA Polarizable Atomic Multipole Water Model.

    Science.gov (United States)

    Laury, Marie L; Wang, Lee-Ping; Pande, Vijay S; Head-Gordon, Teresa; Ponder, Jay W

    2015-07-23

    A set of improved parameters for the AMOEBA polarizable atomic multipole water model is developed. An automated procedure, ForceBalance, is used to adjust model parameters to enforce agreement with ab initio-derived results for water clusters and experimental data for a variety of liquid phase properties across a broad temperature range. The values reported here for the new AMOEBA14 water model represent a substantial improvement over the previous AMOEBA03 model. The AMOEBA14 model accurately predicts the temperature of maximum density and qualitatively matches the experimental density curve across temperatures from 249 to 373 K. Excellent agreement is observed for the AMOEBA14 model in comparison to experimental properties as a function of temperature, including the second virial coefficient, enthalpy of vaporization, isothermal compressibility, thermal expansion coefficient, and dielectric constant. The viscosity, self-diffusion constant, and surface tension are also well reproduced. In comparison to high-level ab initio results for clusters of 2-20 water molecules, the AMOEBA14 model yields results similar to AMOEBA03 and the direct polarization iAMOEBA models. With advances in computing power, calibration data, and optimization techniques, we recommend the use of the AMOEBA14 water model for future studies employing a polarizable water model.

  19. Lithium photoionization cross-section and dynamic polarizability using square integrable basis sets and correlated wave functions

    International Nuclear Information System (INIS)

    Hollauer, E.; Nascimento, M.A.C.

    1985-01-01

    The photoionization cross-section and dynamic polarizability for lithium atom are calculated using a discrete basis set to represent both the bound and the continuum-states of the atom, to construct an approximation to the dynamic polarizability. From the imaginary part of the complex dynamic polarizability one extracts the photoionization cross-section and from its real part the dynamic polarizability. The results are in good agreement with the experiments and other more elaborate calculations (Author) [pt

  20. Polarizability and alignment of dielectric nanoparticles in an external electric field: bowls, dumbbells, and cuboids.

    Science.gov (United States)

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

    2011-10-07

    We employ the coupled dipole method to calculate the polarizability tensor of various anisotropic dielectric clusters of polarizable atoms, such as cuboid-, bowl-, and dumbbell-shaped nanoparticles. Starting from a Hamiltonian of a many-atom system, we investigate how this tensor depends on the size and shape of the cluster. We use the polarizability tensor to calculate the energy difference associated with turning a nanocluster from its least to its most favorable orientation in a homogeneous static electric field, and we determine the cluster dimension for which this energy difference exceeds the thermal energy such that particle alignment by the field is possible. Finally, we study in detail the (local) polarizability of a cubic-shaped cluster and present results indicating that, when retardation is ignored, a bulk polarizability cannot be reached by scaling up the system. © 2011 American Institute of Physics

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Using the CCSD(T) model, we evaluated the intermolecular potential energy surfaces of the He-, Ne-, and Ar-phosgene complexes. We considered a representative number of intermolecular geometries for which we calculated the corresponding interaction energies with the augmented (He complex) and double......-phosgene surfaces were found to have absolute minima of -72.1, -140.4, and -326.6 cm -1 at distances between the rare-gas atom and the phosgene center of mass of 3.184, 3.254, and 3.516 Å, respectively. The potentials were further used in the evaluation of rovibrational states and the rotational constants...

  2. Quantitative analysis of intermolecular interactions in 2,2'-((4 ...

    Indian Academy of Sciences (India)

    SUBBIAH THAMOTHARAN

    2018-02-07

    Feb 7, 2018 ... REGULAR ARTICLE. Quantitative analysis of intermolecular interactions in ... The quantitative molecular electrostatic potential surface diagram depicts the potential binding sites which are in good agreement with the crystal ..... root mean squared deviation (rmsd: 0.19 Å) is observed for the compound I and ...

  3. 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…

  4. Phase transitions in liquids with directed intermolecular bonding

    OpenAIRE

    Son, L.; Ryltcev, R.

    2005-01-01

    Liquids with quasi - chemical bonding between molecules are described in terms of vertex model. It is shown that this bonding results in liquid - liquid phase transition, which occurs between phases with different mean density of intermolecular bonds. The transition may be suggested to be a universal phenomena for those liquids.

  5. All rights reserved Intermolecular Model Potentials and Virial ...

    African Journals Online (AJOL)

    ADOWIE PERE

    Key words: Equation of state, virial coefficients, speed of sound, intermolecular potentials. The virial equation of state (EOS) is based on ... general equation of state method that can predict volumetric and caloric thermodynamic ... standard cubic foot of gas per day and at the current price of $ 3.3 per 1000 cubic foot set by ...

  6. Intermolecular Interactions in Ternary Glycerol–Sample–H2O

    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 Gly–Gly enthalpic interaction, HGly-GlyEHEGly--Gly, in the presence of various samples (S). For S, tert...

  7. Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

    Directory of Open Access Journals (Sweden)

    Chen Zhang

    2013-05-01

    Full Text Available A co-catalyst of (PPh3AuCl/AgOTf for the intermolecular hydroamination of allenes with sulfonamides is shown. The reaction proceeded smoothly under mild conditions for differently substituted allenes giving N-allylic sulfonamides in good yields with high regioselectivity and E-selectivity.

  8. Connecting Protein Structure to Intermolecular Interactions: A Computer Modeling Laboratory

    Science.gov (United States)

    Abualia, Mohammed; Schroeder, Lianne; Garcia, Megan; Daubenmire, Patrick L.; Wink, Donald J.; Clark, Ginevra A.

    2016-01-01

    An understanding of protein folding relies on a solid foundation of a number of critical chemical concepts, such as molecular structure, intra-/intermolecular interactions, and relating structure to function. Recent reports show that students struggle on all levels to achieve these understandings and use them in meaningful ways. Further, several…

  9. The role of weak intermolecular CH… F interactions in ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 4. The role of weak intermolecular C-H…F interactions in supramolecular assembly: Structural investigations on 3,5- dibenzylidene-piperidin-4-one and database analysis. R S Rathore N S Karthikeyan Y Alekhya K Sathiyanarayanan P G Aravindan.

  10. Quantitative analysis of intermolecular interactions in 2, 2'-((4 ...

    Indian Academy of Sciences (India)

    The relative contributions of various intermolecular contacts in the title compound and its closely related analogs are evaluated using Hirshfeld surface analysis and the decomposed fingerprint plots. The common packing features exist between the title compound and its related analogs are identified.The quantitative ...

  11. 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…

  12. Effects of Intermolecular Coupling on Excimer Formation and Singlet Fission

    Science.gov (United States)

    Mauck, Catherine McKay

    compelling strategy for improving organic photovoltaic device efficiencies. The formation of triplet states through singlet fission can be characterized using femtosecond visible transient absorption spectroscopy (fsTA). However, in PDI, the triplet-triplet absorption spectrum is strongly overlapped with the ground state bleach absorption. Here, a dyad molecule where PDI is covalently attached to an apocarotene triplet acceptor is synthesized, and studied in solution aggregates and thin films with fsTA, to demonstrate that apocarotene can be used as a sensitive spectral tag for triplet formation in PDI due to triplet-triplet energy transfer from PDI to the carotenoid. The efficiency of singlet fission in DPP can be tuned by modulating the crystal packing in the solid state. By synthesizing 3,6-bis(thiophene) derivatives of DPP with a series of different sidechains, thin film DPP singlet fission is related to the crystal structure intermolecular geometries, to more precisely determine the relationship between interchromophore coupling and singlet fission rate, which will inform the design of more robust chromophores for singlet fission. Finally, the role of the dielectric environment and stabilization of charge transfer configurations and charge transfer states is explored in DPP singlet fission, through aqueous nanoparticles of 3,6-bis(phenylthiophene) with different surface area-to-volume ratios, and a covalently linked dimer of DPP in solvents of varying polarity which can undergo symmetry-breaking charge separation.

  13. Polarizability extraction of complementary metamaterial elements in waveguides for aperture modeling

    Science.gov (United States)

    Pulido-Mancera, Laura; Bowen, Patrick T.; Imani, Mohammadreza F.; Kundtz, Nathan; Smith, David

    2017-12-01

    We consider the design and modeling of metasurfaces that couple energy from guided waves to propagating wave fronts. To this purpose, we develop a comprehensive, multiscale dipolar interpretation for large arrays of complementary metamaterial elements embedded in a waveguide structure. Within this modeling technique, the detailed electromagnetic response of each metamaterial element is replaced by a polarizable dipole, described by means of an effective polarizability. In this paper, we present two methods to extract this effective polarizability. The first method invokes surface equivalence principles, averaging over the effective surface currents and charges induced in the element's surface in order to obtain the effective dipole moments, from which the effective polarizability can be inferred. The second method is based in the coupled-mode theory, from which a direct relationship between the effective polarizability and the amplitude coefficients of the scattered waves can be deduced. We demonstrate these methods on several variants of waveguide-fed metasurface elements (both one- and two-dimensional waveguides), finding excellent agreement between the two, as well as with the analytical expressions derived for circular and elliptical irises. With the effective polarizabilities of the metamaterial elements accurately determined, the radiated fields generated by a waveguide-fed metasurface can be found self-consistently by including the interactions between polarizable dipoles. The dipole description provides an effective perspective and computational framework for engineering metasurface structures such as holograms, lenses, and beam-forming arrays, among others.

  14. Multipolar Polarizabilities and Hyperpolarizabilities in the Sr Optical Lattice Clock

    Science.gov (United States)

    Porsev, S. G.; Safronova, M. S.; Safronova, U. I.; Kozlov, M. G.

    2018-02-01

    We address the problem of the lattice Stark shifts in the Sr clock caused by the multipolar M 1 and E 2 atom-field interactions and by the term nonlinear in lattice intensity and determined by the hyperpolarizability. We develop an approach to calculate hyperpolarizabilities for atoms and ions based on a solution of the inhomogeneous equation which allows us to effectively and accurately carry out complete summations over intermediate states. We apply our method to the calculation of the hyperpolarizabilities for the clock states in Sr. We also carry out an accurate calculation of the multipolar polarizabilities for these states at the magic frequency. Understanding these Stark shifts in optical lattice clocks is crucial for further improvement of the clock accuracy.

  15. Polarizable Force Field for DNA Based on the Classical Drude Oscillator: I. Refinement Using Quantum Mechanical Base Stacking and Conformational Energetics.

    Science.gov (United States)

    Lemkul, Justin A; MacKerell, Alexander D

    2017-05-09

    Empirical force fields seek to relate the configuration of a set of atoms to its energy, thus yielding the forces governing its dynamics, using classical physics rather than more expensive quantum mechanical calculations that are computationally intractable for large systems. Most force fields used to simulate biomolecular systems use fixed atomic partial charges, neglecting the influence of electronic polarization, instead making use of a mean-field approximation that may not be transferable across environments. Recent hardware and software developments make polarizable simulations feasible, and to this end, polarizable force fields represent the next generation of molecular dynamics simulation technology. In this work, we describe the refinement of a polarizable force field for DNA based on the classical Drude oscillator model by targeting quantum mechanical interaction energies and conformational energy profiles of model compounds necessary to build a complete DNA force field. The parametrization strategy employed in the present work seeks to correct weak base stacking in A- and B-DNA and the unwinding of Z-DNA observed in the previous version of the force field, called Drude-2013. Refinement of base nonbonded terms and reparametrization of dihedral terms in the glycosidic linkage, deoxyribofuranose rings, and important backbone torsions resulted in improved agreement with quantum mechanical potential energy surfaces. Notably, we expand on previous efforts by explicitly including Z-DNA conformational energetics in the refinement.

  16. Theoretical studies of the global minima and polarizabilities of small lithium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Hanshi; Zhao, Ya-Fan; Hammond, Jeffrey R.; Bylaska, Eric J.; Apra, Edoardo; van Dam, Hubertus JJ; Li, Jun; Govind, Niranjan; Kowalski, Karol

    2016-01-16

    Lithium clusters Lin (n=1-20) have been investigated with density functional theory (DFT) and coupled—cluster (CC) methods. The global-minimum structures are located via an improved basin---hopping algorithm and the lowest energy Lin isomers are confirmed with DFT geometry optimizations, CCSD(T) energy calculations, and by comparing simulated and experimental polarizabilities. The tetrahedral Li4 structure is found to be the basic building block of lithium clusters Lin (n=6-20). Simulated polarizabilities, including thermal effects at room temperature, are in good agreement with measured isotropic polarizabilities.

  17. Static and dynamic polarizabilities of Na- within a variationally stable coupled-channel hyperspherical method

    International Nuclear Information System (INIS)

    Masili, Mauro; Groote, J.J. de

    2004-01-01

    Using a model potential representation combined with a variationally stable method, we present a precise calculation of the electric dipole polarizabilities of the sodium negative ion (Na - ). The effective two-electron eigensolutions for Na - are obtained from a hyperspherical coupled-channel calculation. This approach allows efficient error control and insight into the system's properties through one-dimensional potential curves. Our result of 1018.3 a.u. for the static dipole polarizability is in agreement with previous calculations and supports our results for the dynamic polarizability, which has scarcely been investigated hitherto

  18. 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: 3.187, year: 2015

  19. Local Intermolecular Order Controls Photoinduced Charge Separation at Donor/Acceptor Interfaces in Organic Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Feier, Hilary M.; Reid, Obadiah G.; Pace, Natalie A.; Park, Jaehong; Bergkamp, Jesse J.; Sellinger, Alan; Gust, Devens; Rumbles, Garry

    2016-03-23

    How free charge is generated at organic donor-acceptor interfaces is an important question, as the binding energy of the lowest energy (localized) charge transfer states should be too high for the electron and hole to escape each other. Recently, it has been proposed that delocalization of the electronic states participating in charge transfer is crucial, and aggregated or otherwise locally ordered structures of the donor or the acceptor are the precondition for this electronic characteristic. The effect of intermolecular aggregation of both the polymer donor and fullerene acceptor on charge separation is studied. In the first case, the dilute electron acceptor triethylsilylhydroxy-1,4,8,11,15,18,22,25-octabutoxyphthalocyaninatosilicon(IV) (SiPc) is used to eliminate the influence of acceptor aggregation, and control polymer order through side-chain regioregularity, comparing charge generation in 96% regioregular (RR-) poly(3-hexylthiophene) (P3HT) with its regiorandom (RRa-) counterpart. In the second case, ordered phases in the polymer are eliminated by using RRa-P3HT, and phenyl-C61-butyric acid methyl ester (PC61BM) is used as the acceptor, varying its concentration to control aggregation. Time-resolved microwave conductivity, time-resolved photoluminescence, and transient absorption spectroscopy measurements show that while ultrafast charge transfer occurs in all samples, long-lived charge carriers are only produced in films with intermolecular aggregates of either RR-P3HT or PC61BM, and that polymer aggregates are just as effective in this regard as those of fullerenes.

  20. A general intermolecular force field based on tight-binding quantum chemical calculations

    Science.gov (United States)

    Grimme, Stefan; Bannwarth, Christoph; Caldeweyher, Eike; Pisarek, Jana; Hansen, Andreas

    2017-10-01

    A black-box type procedure is presented for the generation of a molecule-specific, intermolecular potential energy function. The method uses quantum chemical (QC) information from our recently published extended tight-binding semi-empirical scheme (GFN-xTB) and can treat non-covalently bound complexes and aggregates with almost arbitrary chemical structure. The necessary QC information consists of the equilibrium structure, Mulliken atomic charges, charge centers of localized molecular orbitals, and also of frontier orbitals and orbital energies. The molecular pair potential includes model density dependent Pauli repulsion, penetration, as well as point charge electrostatics, the newly developed D4 dispersion energy model, Drude oscillators for polarization, and a charge-transfer term. Only one element-specific and about 20 global empirical parameters are needed to cover systems with nuclear charges up to radon (Z = 86). The method is tested for standard small molecule interaction energy benchmark sets where it provides accurate intermolecular energies and equilibrium distances. Examples for structures with a few hundred atoms including charged systems demonstrate the versatility of the approach. The method is implemented in a stand-alone computer code which enables rigid-body, global minimum energy searches for molecular aggregation or alignment.

  1. The inclusion of electron correlation in intermolecular potentials: Applications to the formamide dimer and liquid formamide

    DEFF Research Database (Denmark)

    Brdarski, S.; Åstrand, P.-O.; Karlström, G.

    2000-01-01

    dipole moment is 11% lower at the MP2 level than at the Hartree-Fock (HF) level, whereas the isotropic part of the polarizability is increased by 36% by adding electron correlation and using a considerably larger basis set. The atomic charges, dipole moments and polarizabilities obtained at the HF level...

  2. Conduction of molecular electronic devices: Qualitative insights through atom-atom polarizabilities

    International Nuclear Information System (INIS)

    Stuyver, T.; Fias, S.; De Proft, F.; Geerlings, P.; Fowler, P. W.

    2015-01-01

    The atom-atom polarizability and the transmission probability at the Fermi level, as obtained through the source-and-sink-potential method for every possible configuration of contacts simultaneously, are compared for polycyclic aromatic compounds. This comparison leads to the conjecture that a positive atom-atom polarizability is a necessary condition for transmission to take place in alternant hydrocarbons without non-bonding orbitals and that the relative transmission probability for different configurations of the contacts can be predicted by analyzing the corresponding atom-atom polarizability. A theoretical link between the two considered properties is derived, leading to a mathematical explanation for the observed trends for transmission based on the atom-atom polarizability

  3. Conduction of molecular electronic devices: qualitative insights through atom-atom polarizabilities.

    Science.gov (United States)

    Stuyver, T; Fias, S; De Proft, F; Fowler, P W; Geerlings, P

    2015-03-07

    The atom-atom polarizability and the transmission probability at the Fermi level, as obtained through the source-and-sink-potential method for every possible configuration of contacts simultaneously, are compared for polycyclic aromatic compounds. This comparison leads to the conjecture that a positive atom-atom polarizability is a necessary condition for transmission to take place in alternant hydrocarbons without non-bonding orbitals and that the relative transmission probability for different configurations of the contacts can be predicted by analyzing the corresponding atom-atom polarizability. A theoretical link between the two considered properties is derived, leading to a mathematical explanation for the observed trends for transmission based on the atom-atom polarizability.

  4. Conduction of molecular electronic devices: Qualitative insights through atom-atom polarizabilities

    Energy Technology Data Exchange (ETDEWEB)

    Stuyver, T.; Fias, S., E-mail: sfias@vub.ac.be; De Proft, F.; Geerlings, P. [ALGC, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel (Belgium); Fowler, P. W. [Department of Chemistry, University of Sheffield, Sheffield S3 7HF (United Kingdom)

    2015-03-07

    The atom-atom polarizability and the transmission probability at the Fermi level, as obtained through the source-and-sink-potential method for every possible configuration of contacts simultaneously, are compared for polycyclic aromatic compounds. This comparison leads to the conjecture that a positive atom-atom polarizability is a necessary condition for transmission to take place in alternant hydrocarbons without non-bonding orbitals and that the relative transmission probability for different configurations of the contacts can be predicted by analyzing the corresponding atom-atom polarizability. A theoretical link between the two considered properties is derived, leading to a mathematical explanation for the observed trends for transmission based on the atom-atom polarizability.

  5. Metal-organic materials (MOMs) for adsorption of polarizable gases and methods of using MOMs

    Science.gov (United States)

    Zaworotko, Michael; Mohamed, Mona H.; Elsaidi, Sameh

    2017-06-14

    Embodiments of the present disclosure provide for multi-component metal-organic materials (MOMs), systems including the MOM, systems for separating components in a gas, methods of separating polarizable gases from a gas mixture, and the like.

  6. The electric polarizability of a particle bound by a one-dimensional ionic crystal

    International Nuclear Information System (INIS)

    Balderas, Daniel; González, Gabriel

    2013-01-01

    We consider the problem of a particle confined to a one-dimensional ionic crystal of finite length modeled by repulsive and attractive delta functions and subject to the application of an external constant electric field. Exact expressions for the electric polarizability of the system via the Dalgarno–Lewis technique are obtained in second order perturbation theory. The study uncovers the behavior of the electric polarizability as a function of the number of ions in the system. (paper)

  7. Influence of Gaussian white noise on the frequency-dependent linear polarizability of doped quantum dot

    Energy Technology Data Exchange (ETDEWEB)

    Ganguly, Jayanta [Department of Chemistry, Brahmankhanda Basapara High School, Basapara, Birbhum 731 215, West Bengal (India); Ghosh, Manas, E-mail: pcmg77@rediffmail.com [Department of Chemistry, Physical Chemistry Section, Visva Bharati University, Santiniketan, Birbhum 731 235, West Bengal (India)

    2014-06-25

    Highlights: • Linear polarizability of quantum dot has been studied. • Quantum dot is doped with a repulsive impurity. • The polarizabilities are frequency-dependent. • Influence of Gaussian white noise has been monitored. • Noise exploited is of additive and multiplicative nature. - Abstract: We investigate the profiles of diagonal components of frequency-dependent linear (α{sub xx} and α{sub yy}) optical response of repulsive impurity doped quantum dots. The dopant impurity potential chosen assumes Gaussian form. The study principally puts emphasis on investigating the role of noise on the polarizability components. In view of this we have exploited Gaussian white noise containing additive and multiplicative characteristics (in Stratonovich sense). The frequency-dependent polarizabilities are studied by exposing the doped dot to a periodically oscillating external electric field of given intensity. The oscillation frequency, confinement potentials, dopant location, and above all, the noise characteristics tune the linear polarizability components in a subtle manner. Whereas the additive noise fails to have any impact on the polarizabilities, the multiplicative noise influences them delicately and gives rise to additional interesting features.

  8. Analytical transition-matrix treatment of electric multipole polarizabilities of hydrogen-like atoms

    International Nuclear Information System (INIS)

    Kharchenko, V.F.

    2015-01-01

    The direct transition-matrix approach to the description of the electric polarization of the quantum bound system of particles is used to determine the electric multipole polarizabilities of the hydrogen-like atoms. It is shown that in the case of the bound system formed by the Coulomb interaction the corresponding inhomogeneous integral equation determining an off-shell scattering function, which consistently describes virtual multiple scattering, can be solved exactly analytically for all electric multipole polarizabilities. Our method allows to reproduce the known Dalgarno–Lewis formula for electric multipole polarizabilities of the hydrogen atom in the ground state and can also be applied to determine the polarizability of the atom in excited bound states. - Highlights: • A new description for electric polarization of hydrogen-like atoms. • Expression for multipole polarizabilities in terms of off-shell scattering functions. • Derivation of integral equation determining the off-shell scattering function. • Rigorous analytic solving the integral equations both for ground and excited states. • Study of contributions of virtual multiple scattering to electric polarizabilities

  9. Influence of Gaussian white noise on the frequency-dependent linear polarizability of doped quantum dot

    International Nuclear Information System (INIS)

    Ganguly, Jayanta; Ghosh, Manas

    2014-01-01

    Highlights: • Linear polarizability of quantum dot has been studied. • Quantum dot is doped with a repulsive impurity. • The polarizabilities are frequency-dependent. • Influence of Gaussian white noise has been monitored. • Noise exploited is of additive and multiplicative nature. - Abstract: We investigate the profiles of diagonal components of frequency-dependent linear (α xx and α yy ) optical response of repulsive impurity doped quantum dots. The dopant impurity potential chosen assumes Gaussian form. The study principally puts emphasis on investigating the role of noise on the polarizability components. In view of this we have exploited Gaussian white noise containing additive and multiplicative characteristics (in Stratonovich sense). The frequency-dependent polarizabilities are studied by exposing the doped dot to a periodically oscillating external electric field of given intensity. The oscillation frequency, confinement potentials, dopant location, and above all, the noise characteristics tune the linear polarizability components in a subtle manner. Whereas the additive noise fails to have any impact on the polarizabilities, the multiplicative noise influences them delicately and gives rise to additional interesting features

  10. Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model.

    Science.gov (United States)

    Ghosh, Soumya; Horvath, Samantha; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2014-05-13

    Electron transfer reactions at electrochemical interfaces play a critical role in a wide range of catalytic processes. A key parameter in the rate constant expressions for such processes is the reorganization energy, which reflects the energetic cost of the solute and solvent rearrangements upon electron transfer. In this paper, we present dielectric continuum methods for calculating the solvent reorganization energy for electrochemical processes. We develop a method for calculating the electrochemical solvent reorganization energies with molecular-shaped cavities within the framework of the polarizable continuum model (PCM). The electronic and inertial responses of the solvent are separated according to their respective time scales, and two limiting cases of the relation between the solute and solvent electrons are examined. The effects of the electrode are included with the integral equations formalism PCM (IEF-PCM), in which the molecule-solvent boundary is treated explicitly, but the effects of the electrode-solvent boundary are included through an external Green's function. This approach accounts for the effects of detailed molecular charge redistribution in a molecular-shaped cavity, as well as the electronic and inertial solvent responses and the effects of the electrode. The calculated total reorganization energies are in reasonable agreement with experimental measurements for a series of electrochemical systems. Inclusion of the effects of the electrode is found to be essential for obtaining even qualitatively accurate solvent reorganization energies. These approaches are applicable to a wide range of systems and can be extended to include other types of boundaries, such as a self-assembled monolayer or double layer separating the electrode and the molecule.

  11. Stark effect, polarizability, and electroabsorption in silicon nanocrystals

    Science.gov (United States)

    Bulutay, Ceyhun; Kulakci, Mustafa; Turan, Raşit

    2010-03-01

    Demonstrating the quantum-confined Stark effect (QCSE) in silicon nanocrystals (NCs) embedded in oxide has been rather elusive, unlike the other materials. Here, the recent experimental data from ion-implanted Si NCs is unambiguously explained within the context of QCSE using an atomistic pseudopotential theory. This further reveals that the majority of the Stark shift comes from the valence states which undergo a level crossing that leads to a nonmonotonic radiative recombination behavior with respect to the applied field. The polarizability of embedded Si NCs including the excitonic effects is extracted over a diameter range of 2.5-6.5 nm, which displays a cubic scaling, α=cDNC3 , with c=2.436×10-11C/(Vm) , where DNC is the NC diameter. Finally, based on intraband electroabsorption analysis, it is predicted that p -doped Si NCs will show substantial voltage tunability, whereas n -doped samples should be almost insensitive. Given the fact that bulk silicon lacks the linear electro-optic effect as being a centrosymmetric crystal, this may offer a viable alternative for electrical modulation using p -doped Si NCs.

  12. A NOVEL PROTON TRANSFER COMPOUND (A NEW ...

    African Journals Online (AJOL)

    Preferred Customer

    intermolecular proton transfer from (MoO4H2) to (OHRNH2) results in the formation of a new molybdate salt that ... KEY WORDS: Proton transfer, Molybdate salt, X-ray structure, MoO2(acac)2, 2-Amino-2-methyl-1-propanol ..... data can be obtained free of charge on application to The Director, CCDC, 12 Union Road,.

  13. Variational principles for the static electric and magnetic polarizabilities of anisotropic media with perfect electric conductor inclusions

    International Nuclear Information System (INIS)

    Sjoeberg, Daniel

    2009-01-01

    We present four variational principles for the electric and magnetic polarizabilities for a structure consisting of anisotropic media with perfect electric conductor (PEC) inclusions. From these principles, we derive monotonicity results and upper and lower bounds on the electric and magnetic polarizabilities. When computing the polarizabilities numerically, the bounds can be used as error bounds. The variational principles demonstrate important differences between electrostatics and magnetostatics when PEC bodies are present.

  14. Spin polarizabilities and characteristics of spin-one hadrons related to parity nonconservation in the Duffin-Kemmer-Petiau formalism

    International Nuclear Information System (INIS)

    Vakulina, E.V.; Maksimenko, N.V.

    2017-01-01

    Using the relativistic-invariant effective tensor representation of the Lagrangians of the two-photon interaction with hadrons within the Duffin-Kemmer-Petiau formalism, the spin polarizabilities of the spin 1 particles that are characteristic of spin 1/2 hadrons have been determined. Along with this, new spin polarizabilities of spin 1 particles have been determined, that are related to the presence of the tensor polarizabilities.

  15. Modeling Adsorption-Desorption Processes at the Intermolecular Interactions Level

    Science.gov (United States)

    Varfolomeeva, Vera V.; Terentev, Alexey V.

    2018-01-01

    Modeling of the surface adsorption and desorption processes, as well as the diffusion, are of considerable interest for the physical phenomenon under study in ground tests conditions. When imitating physical processes and phenomena, it is important to choose the correct parameters to describe the adsorption of gases and the formation of films on the structural materials surface. In the present research the adsorption-desorption processes on the gas-solid interface are modeled with allowance for diffusion. Approaches are proposed to describe the adsorbate distribution on the solid body surface at the intermolecular interactions level. The potentials of the intermolecular interaction of water-water, water-methane and methane-methane were used to adequately modeling the real physical and chemical processes. The energies calculated by the B3LYP/aug-cc-pVDZ method. Computational algorithms for determining the average molecule area in a dense monolayer, are considered here. Differences in modeling approaches are also given: that of the proposed in this work and the previously approved probabilistic cellular automaton (PCA) method. It has been shown that the main difference is due to certain limitations of the PCA method. The importance of accounting the intermolecular interactions via hydrogen bonding has been indicated. Further development of the adsorption-desorption processes modeling will allow to find the conditions for of surface processes regulation by means of quantity adsorbed molecules control. The proposed approach to representing the molecular system significantly shortens the calculation time in comparison with the use of atom-atom potentials. In the future, this will allow to modeling the multilayer adsorption at a reasonable computational cost.

  16. Combination Bands of the Nonpolar OCS Dimer Involving Intermolecular Modes

    Science.gov (United States)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.

    2012-06-01

    Spectra of the nonpolar carbonyl sulfide in the region of the OCS ν_1 fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Three bands centered at 2085.906, 2103.504, and 2114.979 cm-1 were observed and anlysed. The rotational assignment and fitting of the bands were made by fixing the lower state parameters to those for the ground state of nonpolar (OCS)_2, thus confirming that they were indeed combination bands of the of the most stable isomer of OCS dimer. The band centered at 2085.906 cm-1 is a combination of the forbidden A_g intramolecular mode plus the geared bend intermolecular mode and that centered at 2114.979 cm-1 is a combination of the allowed B_u intramolecular mode plus the intermolecular van der Waals stretch. The combination at 2103.504 cm-1 can be assigned as a band whose upper state involves four quanta of the intramolecular bend or the B_u intramolecular mode plus two quanta of the intermolecular torsional mode. Isotopic work is needed to conclusively identify the vibrational assignment of this band. Our experimental frequencies for the geared bend and van der Waals modes are in good agreement with a recent high level ab initio calculation by Brown et al. J. Brown, Xiao-Gang Wang, T. Carrington Jr. and Richard Dawes, Journal of Chemical Physics, submitted.

  17. An approach to the intermolecular energy in pure liquids

    Directory of Open Access Journals (Sweden)

    GAbriel Hernández de la Torre

    2010-07-01

    Full Text Available Se propone un método para: estimar la energía potencial de repulsión de cualquier molécula central como una función de las densidades ortobáricas en líquidos puros no auto asociados; estimar los parámetros necesarios para calcular la energía de dispersión de London; calcular los números de coordinación promedio, distancias intermoleculares de interacción, diámetros moleculares y de grupos; en moléculas globulares, moléculas planas y parafinas normales.

  18. High-precision measurements and theoretical calculations of indium excited-state polarizabilities

    Science.gov (United States)

    Vilas, N. B.; Wang, B.-Y.; Rupasinghe, P. M.; Maser, D. L.; Safronova, M. S.; Safronova, U. I.; Majumder, P. K.

    2018-02-01

    We report measurements of the scalar and tensor static polarizabilities of the 115In7 p1 /2 and 7 p3 /2 excited states using two-step diode laser spectroscopy in an atomic beam. These scalar polarizabilities are one to two orders of magnitude larger than for lower-lying indium states due to the close proximity of the 7 p and 6 d states. For the scalar polarizabilities, we find values (in atomic units) of 1.811 (4 ) ×105a03 and 2.876 (6 ) ×105a03 for the 7 p1 /2 and 7 p3 /2 states, respectively. We determine the tensor polarizability component of the 7 p3 /2 state to be -1.43 (18 ) ×104a03 . These measurements set high-precision benchmarks of the transition properties for highly excited states in trivalent atomic systems. We also present ab initio calculations of these quantities and other In polarizabilities using two high-precision relativistic methods to make a global comparison of the accuracies of the two approaches. The precision of the experiment is sufficient to differentiate between the two theoretical methods as well as to allow precise determination of the indium 7 p -6 d matrix elements. The results obtained in this paper are applicable to other heavier and more complicated systems, and provide much needed guidance for the development of even more precise theoretical approaches.

  19. Polarizable crystals in apocrine sweat gland tumors: A series of 3 cases.

    Science.gov (United States)

    Johnson, Gina; Gardner, Jerad M; Shalin, Sara C

    2017-08-01

    Polarizable calcium oxalate (CaOx) crystals have been well documented in breast biopsies, generally associated with benign apocrine metaplasia. In contrast, polarizable crystals are only rarely reported in skin adnexal neoplasms. We report 3 different cases of sweat gland tumors with polarizable crystals morphologically suggestive of CaOx: 1 apocrine hidrocystoma and 2 tubular apocrine adenomas. The histologic features were examined in 3 cases. Clinical presentation summary included 2 males and 1 female, ages 53 to 74 years, with lesions located on the left cheek, inferior vertex scalp and the left eyebrow. All 3 cases showed polarizable, geometric, plate-like and fractured, colorless crystals within the lumens of the neoplasm. Of note, these crystals were seen only on the toluidine blue-stained section of Case #1, but were not present on the corresponding permanent section. We hypothesize that polarizable crystals may be present in sweat gland neoplasms more often than previously documented, but that they may often dissolve with routine processing, accounting for their rare visibility. We highlight this rare finding, and suggest that it may be underreported. We only noted this finding in benign apocrine tumors; further investigation would be necessary to determine whether these crystals are also seen in other cutaneous adnexal neoplasms. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  20. 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

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

    International Nuclear Information System (INIS)

    Tsui, H.H.Y.

    2001-01-01

    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

  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.

  3. Some measurements of H/D polarizability isotope effects using differential refractometry

    International Nuclear Information System (INIS)

    Foster Smith, M.; Van Hook, W.A.

    1989-01-01

    Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.)

  4. Effect of substituents on polarizability and hyperpolarizability values of benzimidazole metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Praveen, P. A.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in [Crystal Growth and Thin films Laboratory, Department of Physics, Bharathidasan University, Tiruchirappalli - 620 024, Tamilnadu (India)

    2016-05-23

    In this report, the polarizability and first and second order hyperpolarizability values of bis benzimidazole Zn(II)-2R and bis benzimidazole Cd(II)-2R complexes, with different electron donating moieties R (R= Cl, Br, I, Acetate) were calculated using time dependent Hartree-Fock (TDHF) formalism embedded in MOPAC2012 package. Further the role of substituents on polarizability and hyperpolarizability values is investigated for the first time by analyzing the frontier molecular orbitals of the complexes with respect to the electronegativity of the substituents. It is found that the increase in electronegativity of the substituents correspondingly increases the energy gap of the molecules, which in turn reduces the polarizability values of both Zn and Cd benzimidazole complexes. Similarly, increase in electronegativity reduces the electric quadrupole moments of both the metal complexes, which in turn reduces the hyperpolarizability values.

  5. Geometry Optimization in Polarizable QM/MM Models: The Induced Dipole Formulation.

    Science.gov (United States)

    Caprasecca, Stefano; Jurinovich, Sandro; Viani, Lucas; Curutchet, Carles; Mennucci, Benedetta

    2014-04-08

    We present the mathematical derivation and the computational implementation of the analytical geometry derivatives for a polarizable QM/MM model (QM/MMPol). In the adopted QM/MMPol model, the focused part is treated at QM level of theory, while the remaining part (the environment) is described classically as a set of fixed charges and induced dipoles. The implementation is performed within the ONIOM procedure, resulting in a polarizable embedding scheme, which can be applied to solvated and embedded systems and combined with different polarizable force fields available in the literature. Two test cases characterized by strong hydrogen-bond and dipole-dipole interactions, respectively, are used to validate the method with respect to the nonpolarizable one. Finally, an application to geometry optimization of the chromophore of Rhodopsin is presented to investigate the impact of including mutual polarization between the QM and the classical parts in conjugated systems.

  6. Free energy simulations with the AMOEBA polarizable force field and metadynamics on GPU platform.

    Science.gov (United States)

    Peng, Xiangda; Zhang, Yuebin; Chu, Huiying; Li, Guohui

    2016-03-05

    The free energy calculation library PLUMED has been incorporated into the OpenMM simulation toolkit, with the purpose to perform enhanced sampling MD simulations using the AMOEBA polarizable force field on GPU platform. Two examples, (I) the free energy profile of water pair separation (II) alanine dipeptide dihedral angle free energy surface in explicit solvent, are provided here to demonstrate the accuracy and efficiency of our implementation. The converged free energy profiles could be obtained within an affordable MD simulation time when the AMOEBA polarizable force field is employed. Moreover, the free energy surfaces estimated using the AMOEBA polarizable force field are in agreement with those calculated from experimental data and ab initio methods. Hence, the implementation in this work is reliable and would be utilized to study more complicated biological phenomena in both an accurate and efficient way. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  7. Comparison of self-consistent calculations of the static polarizability of atoms and molecules

    International Nuclear Information System (INIS)

    Moullet, I.; Martins, J.L.

    1990-01-01

    The static dipole polarizabilities and other ground-state properties of H, H 2 , He, Na, and Na 2 are calculated using five different self-consistent schemes: Hartree--Fock, local spin density approximation, Hartree--Fock plus local density correlation, self-interaction-corrected local spin density approximation, and Hartree--Fock plus self-interaction-corrected local density correlation. The inclusion of the self-interaction corrected local spin density approximation in the Hartree--Fock method improves dramatically the calculated dissociation energies of molecules but has a small effect on the calculated polarizabilities. Correcting the local spin density calculations for self-interaction effects improves the calculated polarizability in the cases where the local spin density results are mediocre, and has only a small effect in the cases where the local spin density values are in reasonable agreement with experiment

  8. Parallelization of the polarizable embedding scheme for higher-order response functions

    Science.gov (United States)

    Hykkerud Steindal, Arnfinn; Magnus Haugaard Olsen, Jógvan; Frediani, Luca; Kongsted, Jacob; Ruud, Kenneth

    2012-10-01

    We present a parallel implementation of the Polarizable Embedding (PE) method, an advanced quantum mechanics/molecular mechanics (QM/MM) approach, for Hartree-Fock (PE-HF) and density functional theory (PE-DFT). The parallelization includes calculations of energies and linear, quadratic, and cubic response functions. The couplings to the QM system due to the polarizable embedding potential have been implemented using a master/slave approach. The implementation shows good scaling behaviour, demonstrated through calculations on a small (a water molecule in a bulk of water molecules) and a larger system (Green Fluorescent Protein (GFP)).

  9. A Fractionally Ionic Approach to Polarizability and van der Waals Many-Body Dispersion Calculations.

    Science.gov (United States)

    Gould, Tim; Lebègue, Sébastien; Ángyán, János G; Bučko, Tomáš

    2016-12-13

    By explicitly including fractionally ionic contributions to the polarizability of a many-component system, we are able to significantly improve on previous atom-wise many-body van der Waals approaches with essentially no extra numerical cost. For nonionic systems, our method is comparable in accuracy to existing approaches. However, it offers substantial improvements in ionic solids, e.g., producing better polarizabilities by over 65% in some cases. It has particular benefits for two-dimensional transition metal dichalcogenides and interactions of H 2 with modified coronenes, ionic systems of nanotechnological interest. It thus offers an efficient improvement on existing approaches, valid for a wide range of systems.

  10. 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

  11. Structural modeling and intermolecular correlation of liquid chlorine dioxide

    International Nuclear Information System (INIS)

    Ogata, Norio; Hironori, Shimakura; Kawakita, Yukinobu; Ohara, Yukoji; Kohara, Shinji; Takeda, Shinichi

    2009-01-01

    Chlorine dioxide (ClO 2 ) is water-soluble yellow gas at room temperature. It has long been used as a disinfectant of tap water and various commodities owing to its strong oxidizing activity against various microbial proteins. The oxidizing activity is believed to be due to the presence of unpaired electron in its molecular orbital. Despite wealth of physicochemical studies of gaseous ClO 2 , little is known about liquid ClO 2 , especially about fine molecular structure and intermolecular interactions of liquid ClO 2 . The purpose of this study is to elucidate the fine structure and intermolecular orientations of ClO 2 molecules in its liquid state using a high-energy X-ray diffraction technique. The measurements of liquid ClO 2 were carried out at -50 to 0 degree Celsius using a two-axis diffractometer installed at the BL04B2 beamline in the third-generation synchrotron radiation facility SPring-8 (Hyogo, Japan). The incident X-ray beamline was 113.4 keV in energy and 0.1093 Armstrong in wavelength from a Si(111) monochromator with the third harmonic reflection. Liquid ClO 2 held in a quartz capillary tube was placed in a temperature-controlled vacuum chamber. We obtained a structure factor S(Q) to a range of Q = 0.3-30 Amstrong -1 and a pair distribution function g(r) upon Fourier transform of the S(Q). The total g(r) showed peaks at 1.46, 2.08, 2.48, 3.16 and 4.24 Armstrong. From intramolecular bond lengths of 1.46 Armstrong for Cl-O and 2.48 Armstrong for O-O, O-Cl-O bond angle was estimated to be 116.1 degrees. Peaks at 3.16 and 4.24 Armstrong in the total g(r) strongly indicate presence of specific intermolecular orientations of ClO 2 molecules that are distinct from those observed as a dimer in the solid phase ClO 2 . This view was further supported by molecular simulation using a reverse Monte Carlo method (RMC). (author)

  12. Modulation of intermolecular interactions in single-molecule magnets

    Science.gov (United States)

    Heroux, Katie Jeanne

    Polynuclear manganese clusters exhibiting interesting magnetic and quantum properties have been an area of intense research since the discovery of the first single-molecule magnet (SMM) in 1993. These molecules, below their blocking temperature, function as single-domain magnetic particles which exhibit classical macroscale magnetic properties as well as quantum mechanical phenomena such as quantum tunnelling of magnetization (QTM) and quantum phase interference. The union of classical and quantum behavior in these nanomaterials makes SMMs ideal candidates for high-density information storage and quantum computing. However, environmental coupling factors (nuclear spins, phonons, neighboring molecules) must be minimized if such applications are ever to be fully realized. The focus of this work is making small structural changes in well-known manganese SMMs in order to drastically enhance the overall magnetic and quantum properties of the system. Well-isolated molecules of high crystalline quality should lead to well-defined energetic and spectral properties as well. An advantage of SMMs over bulk magnetic materials is that they can be chemically altered from a "bottom-up" approach providing a synthetic tool for tuning magnetic properties. This systematic approach is utilized in the work presented herein by incorporating bulky ligands and/or counterions to "isolate" the magnetic core of [Mn4] dicubane SMMs. Reducing intermolecular interactions in the crystal lattice (neighboring molecules, solvate molecules, dipolar interactions) is an important step toward developing viable quantum computing devices. Detailed bulk magnetic studies as well as single crystal magnetization hysteresis and high-frequency EPR studies on these sterically-isolated complexes show enhanced, and sometimes even unexpected, quantum dynamics. The importance of intra- and intermolecular interactions remains a common theme throughout this work, extending to other SMMs of various topology including

  13. Intermolecular potential energy surface for CS2 dimer.

    Science.gov (United States)

    Farrokhpour, Hossein; Mombeini, Zainab; Namazian, Mansoor; Coote, Michelle L

    2011-04-15

    A new four-dimensional intermolecular potential energy surface for CS(2) dimer is obtained by ab initio calculation of the interaction energies for a range of configurations and center-of-mass separation distances for the first time. The calculations were performed using the supermolecular approach at the Møller-Plesset second-order perturbation (MP2) level of theory with the augmented correlation consistent basis sets (aug-cc-pVxZ, x = D, T) and corrected for the basis-set superposition error using the full counterpoise correction method. A two-point extrapolation method was used to extrapolate the calculated energy points to the complete basis set limit. The effect of using the higher levels of theory, quadratic configuration interaction containing single, double, and perturbative triple excitations QCISD(T) and coupled cluster singles, doubles and perturbative triples excitations CCSD(T), on the shape of potential energy surface was investigated. It is shown that the MP2 level of theory apparently performs extremely poorly for describing the intermolecular potential energy surface, overestimating the total energy by a factor of nearly 1.73 in comparison with the QCISD(T) and CCSD(T) values. The value of isotropic dipole-dipole dispersion coefficient (C(6) ) of CS(2) fluid was obtained from the extrapolated MP2 potential energy surface. The MP2 extrapolated energy points were fitted to well-known analytical potential functions using two different methods to represent the potential energy surface analytically. The most stable configuration of the dimer was determined at R = 6.23 au, α = 90°, β = 90°, and γ = 90°, with a well depth of 3.980 kcal mol(-1) at the MP2 level of theory. Finally, the calculated second virial coefficients were compared with experimental values to test the quality of the presented potential energy surface. Copyright © 2010 Wiley Periodicals, Inc.

  14. Collision-induced spectroscopy with long-range intermolecular interactions: A diagrammatic representation and the invariant form of the induced properties

    International Nuclear Information System (INIS)

    Kouzov, A. P.; Chrysos, M.; Rachet, F.; Egorova, N. I.

    2006-01-01

    Collision-induced properties of two interacting molecules a and b are derived by means of a general diagrammatic method involving M molecule-molecule and N photon-molecule couplings. The method is an extension of previous graphical treatments of nonlinear optics because it exhaustively determines interaction-induced polarization mechanisms in a trustworthy and handy fashion. Here we focus on long-range intermolecular interactions. Retardation effects are neglected. A fully quantum-mechanical treatment of the molecules is made whereas second quantization for the electromagnetic field, in the nonrelativistic approximation, is implicitly applied. The collision-induced absorption, Raman, and hyper-Raman processes are viewed and studied, through guiding examples, as specific cases N=1, 2, and 3, respectively. In Raman (N=2), the standard first-order (M=1) dipole-induced dipole term of the incremental polarizability, Δα, is the result of a coupling of the two photons with distinct molecules, a and b, which perturb each other via a dipole-dipole mechanism. Rather, when the two photons interact with the same molecule, a or b, the (N=2, M=1) graphs predict the occurrence of a nonlinear polarization mechanism. The latter is expected to contribute substantially to the collision-induced Raman bands by certain molecular gases

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

    DEFF Research Database (Denmark)

    Cybulski, Hubert; Fernandez, Berta; Henriksen, Christian

    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 ...... Institute of Physics. [http://dx.doi.org/10.1063/1.4742153]...

  16. MDVRY: a polarizable classical molecular dynamics package for biomolecules

    Science.gov (United States)

    Souaille, M.; Loirat, H.; Borgis, D.; Gaigeot, M. P.

    2009-02-01

    The MDVRY classical molecular dynamics package is presented for the study of biomolecules in the gas and liquid phase. Electrostatic polarization has been implemented in the formalism of point induced dipoles following the model of Thole. Two schemes have been implemented for the calculation of induced dipoles, i.e. resolution of the self-consistent equations and a 'Car-Parrinello' dynamical approach. In this latter, the induced dipoles are calculated at each time step of the dynamics through the dynamics of additional degrees of freedom associated with the dipoles. This method saves computer time and allows to study polarized solvated proteins at a very low CPU cost. The program is written in C-language and runs on LINUX machines. A detailed manual of the code is given. The main features of the package are illustrated taking on examples of proteins in the gas phase or immersed in liquid water. Program summaryProgram title: MDVRY Catalogue identifier: AEBY_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEBY_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 39 156 No. of bytes in distributed program, including test data, etc.: 277 197 Distribution format: tar.bz2 Programming language: C Computer: Linux machines with FFTW Fourier Transform package installed Operating system: Linux machines, SUSE & RedHat distributions Classification: 3, 16.13, 23 External routines: FFTW ( http://www.fftw.org/) Nature of problem: Molecular Dynamics Software package. Solution method: Velocity Verlet algorithm. The implemented force field is composed of intra-molecular interactions and inter-molecular interactions (electrostatics, polarization, van der Waals). Polarization is accounted through induced point dipoles at each atomic site. Supplementary degrees of freedom are

  17. A model with charges and polarizability for CS₂ in an ionic liquid

    Indian Academy of Sciences (India)

    The environment of a solute molecule in an ionic liquid is likely to have large fluctuating electrostatic fields, and so the electrostatic properties of such a solute including its charge distribution and its polarizability may make a difference to both its static and dynamic properties. We have developed a new model forthe static ...

  18. Bulkiness versus anisotropy: The optimal shape of polarizable Brownian nanoparticles for alignment in electric fields

    NARCIS (Netherlands)

    Kwaadgras, B.W.; Dijkstra, M.; van Roij, R.H.H.G.

    2012-01-01

    Self-assembly and alignment of anisotropic colloidal particles are important processes that can be influenced by external electric fields. However, dielectric nanoparticles are generally hard to align this way because of their small size and low polarizability. In this work, we employ the coupled

  19. Polarizable Empirical Force Field for Halogen-Containing Compounds Based on the Classical Drude Oscillator.

    Science.gov (United States)

    Lin, Fang-Yu; MacKerell, Alexander D

    2018-02-13

    The quality of the force field is crucial to ensure the accuracy of simulations used in molecular modeling, including computer-aided drug design (CADD). To perform more accurate modeling and simulations of halogenated molecules, in this study the polarizable force field based on the classical Drude oscillator model was extended to both aliphatic and aromatic systems using halogenated ethane and benzene model compounds for the halogens F, Cl, Br, and I. The force field parameters were optimized targeting quantum mechanical dipole moments, water interactions, and molecular polarizabilities as well as experimental observables, including enthalpies of vaporization, molecular volumes, hydration free energies, and dielectric constants. The developed halogenated polarizable force field is capable of reproducing QM relative energies and geometries of both halogen bonds and halogen-hydrogen bond donor interactions at an unprecedented level due to the inclusion of a virtual particle and anisotropic atomic polarizability on the halogen and, notably, the inclusion of Lennard-Jones parameters on the halogen Drude particle. The model was validated on the basis of its ability to accurately reproduce pure solvent properties for halogenated naphthalenes and alkanes, including species analogous to those used as refrigerants. Accordingly, it is anticipated that the model will be applicable for the study of halogenated derivatives in CADD as well as in other chemical and biophysical studies.

  20. The Dynamic Electric Polarizability of a Particle Bound by a Double Delta Potential

    Science.gov (United States)

    Maize, M. A.; Smetanka, J. J.

    2008-01-01

    In this paper we derive an expression for the dynamic electric polarizability of a particle bound by a double delta potential for frequencies below and above the absolute value of the particle's ground state energy. The derived expression will be used to study some of the fundamental features of the system and its representation of real systems.…

  1. Optical basicity and electronic polarizability of zinc borotellurite glass doped La3+ ions

    Directory of Open Access Journals (Sweden)

    M.K. Halimah

    Full Text Available Zinc borotellurite glasses doped with lanthanum oxide were successfully prepared through melt-quenching technique. The amorphous nature of the glass system was validated by the presence of a broad hump in the XRD result. The refractive index of the prepared glass samples was calculated by using the equation proposed by Dimitrov and Sakka. The theoretical value of molar refraction, electronic polarizability, oxide ion polarizability and metallization criterion were calculated by using Lorentz-Lorenz equation. Meanwhile, expression proposed by Duffy and Ingram for the theoretical value of optical basicity of multi-component glasses were applied to obtain energy band gap based optical basicity and refractive index based optical basicity. The optical basicity of prepared glasses decreased with the increasing concentration of lanthanum oxide. Metallization criterion on the basis of refractive index showed an increasing trend while energy band gap based metallization criterion showed a decreasing trend. The small metallization criterion values of the glass samples represent that the width of the conduction band becomes larger which increase the tendency for metallization of the glasses. The results obtained indicates that the fabricated glasses have high potential to be applied on optical limiting devices in photonic field. Keywords: Borotellurite glasses, Refractive index, Electronic polarizability, Oxide ion polarizability, Optical basicity, Metallization criterion

  2. Polarizability of the Nitrate Anion and Its Solvation at the Air/Water Interface

    Czech Academy of Sciences Publication Activity Database

    Salvador, P.; Curtis, J. E.; Tobias, D. J.; Jungwirth, Pavel

    2003-01-01

    Roč. 5, - (2003), s. 3752-3757 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : polarizability * nitrate anion * air/water Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.959, year: 2003

  3. Electron polarizability of crystalline solids in quantizing magnetic fields and topological gap numbers

    Czech Academy of Sciences Publication Activity Database

    Středa, Pavel; Jonckheere, T.; Martin, T.

    2008-01-01

    Roč. 100, - (2008), 146804/1-146804/4 ISSN 0031-9007 R&D Projects: GA ČR GA202/05/0365 Institutional research plan: CEZ:AV0Z10100521 Keywords : electron polarizability * quantum Hall effect * topological numbers Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.180, year: 2008

  4. Transcendental-function representation of Stark-modified hydrogenic states and atomic dipole polarizability

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharya, A.; Talukdar, B. [Department of Physics, Visva-Bharati University, Santiniketan (India); Banerji, G. [Mathematics Department, BU, Burdwan (India); Roy, U. [Theoretical Physics Department, IACS, Calcutta (India)

    1998-01-30

    A differential equation approach to the perturbation theoretic correction for excited hydrogenic states is introduced. The radial equations for the problem are solved in terms of known transcendental functions and the method to determine the complete primitive is discussed. The constructed perturbative correction to the wavefunction is adapted to evaluate the dipole polarizability of hydrogenic atoms. (author)

  5. A model with charges and polarizability for CS2 in an ionic liquid

    Indian Academy of Sciences (India)

    RUTH M LYNDEN-BELL

    : CS2(C) and ring C1; red-dashed: CS2(S) and ring C1: .... The red curve shows the probability distribution of induced dipoles on the C site (which is purely axial as the polarizability is axial). The values of the C site dipole follow a Gaussian.

  6. Polarizable Embedded RI-CC2 Method for Two-Photon Absorption Calculations

    DEFF Research Database (Denmark)

    Hršak, Dalibor; Khah, Alireza Marefat; Christiansen, Ove

    2015-01-01

    We present a novel polarizable embedded resolution-of-identity coupled cluster singles and approximate doubles (PERI-CC2) method for calculation of two-photon absorption (TPA) spectra of large molecular systems. The method was benchmarked for three types of systems: a water-solvated molecule...

  7. Quadrupole polarizabilities of the pion in the Nambu-Jona-Lasinio model

    International Nuclear Information System (INIS)

    Hiller, B.; Broniowski, W.; Osipov, A.A.; Blin, A.H.

    2009-01-01

    The electromagnetic dipole and quadrupole polarizabilities of the neutral and charged pions are calculated in the Nambu-Jona-Lasinio model. Our results agree with the recent experimental analysis of these quantities based on dispersion sum rules. Comparison is made with the results from the chiral perturbation theory.

  8. Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates

    Science.gov (United States)

    Small, Meagan C.; Aytenfisu, Asaminew H.; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D.

    2017-04-01

    The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars ( d-allose and d-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars d-allose and d-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

  9. The static polarizability and second hyperpolarizability of fullerenes and carbon nanotubes

    NARCIS (Netherlands)

    Jensen, L; Astrand, PO; Mikkelsen, KV

    2004-01-01

    Utilizing a point-dipole interaction model, we present an investigation of the static polarizability and second hyperpolarizability of fullerenes and carbon nanotubes by varying their structure. The following effects are investigated: (1) the length dependence of the components of the static

  10. ''Atomic'' Bremsstrahlung or polarizational radiation in collision of many-electron ions

    International Nuclear Information System (INIS)

    Amusia, M.Ya.; Solov'yov, A.V.

    1991-01-01

    In this work the so-called ''Atomic'' bremsstrahlung (AB) or polarizational radiation, created in collisions of atoms or ions, is discussed. This kind of radiation arises due to the polarization of the electron shell of colliding particles. It is created by the structured projectiles and targets if the constituents are electrically charged. 6 refs, 2 figs

  11. Impact of graphene on the polarizability of a neighbour nanoparticle: A dyadic green's function study

    DEFF Research Database (Denmark)

    Amorim, B.; Dias Gonçalves, Paulo André; Vasilevskiy, M. I.

    2017-01-01

    produces a large enhancement of the real and imaginary parts of the renormalized polarizability. We show that the imaginary part can be changed by a factor of up to 100 relative to its value in the absence of graphene. We also show that the resonance in the case of the grating is narrower than...

  12. Electric dipole, polarizability and structure of cesium chloride clusters with one-excess electron

    International Nuclear Information System (INIS)

    Jraij, A.; Allouche, A.R.; Rabilloud, F.; Korek, M.; Aubert-Frecon, M.; Rayane, D.; Compagnon, I.; Antoine, R.; Broyer, M.; Dugourd, Ph.

    2006-01-01

    The measurement of the electric dipole of gas phase one-excess electron Cs n Cl n-1 clusters is reported together with a theoretical ab initio prediction of stable structures, dipole moments and electronic polarizabilities for these species in their ground state. Results are in agreement with NaCl cubic structures

  13. A quantum-mechanical perspective on linear response theory within polarizable embedding

    DEFF Research Database (Denmark)

    List, Nanna Holmgaard; Norman, Patrick; Kongsted, Jacob

    2017-01-01

    We present a derivation of linear response theory within polarizable embedding starting from a rigorous quantum-mechanical treatment of a composite system. To this aim, two different subsystem decompositions (symmetric and nonsymmetric) of the linear response function are introduced and the pole...

  14. Calculation of dipole polarizability derivatives of adamantane and their use in electron scattering computations

    DEFF Research Database (Denmark)

    Sauer, Stephan P. A.; Paidarová, Ivana; Čársky, Petr

    2016-01-01

    that the polarizability tensor is necessary to correct long-range behavior of DFT functionals used in electron-molecule scattering calculations. The impact of such a long-range correction is demonstrated on elastic and vibrationally inelastic electron collisions with adamantane, a molecule representing a large polyatomic...

  15. Scalable improvement of SPME multipolar electrostatics in anisotropic polarizable molecular mechanics using a general short-range penetration correction up to quadrupoles.

    Science.gov (United States)

    Narth, Christophe; Lagardère, Louis; Polack, Étienne; Gresh, Nohad; Wang, Qiantao; Bell, David R; Rackers, Joshua A; Ponder, Jay W; Ren, Pengyu Y; Piquemal, Jean-Philip

    2016-02-15

    We propose a general coupling of the Smooth Particle Mesh Ewald SPME approach for distributed multipoles to a short-range charge penetration correction modifying the charge-charge, charge-dipole and charge-quadrupole energies. Such an approach significantly improves electrostatics when compared to ab initio values and has been calibrated on Symmetry-Adapted Perturbation Theory reference data. Various neutral molecular dimers have been tested and results on the complexes of mono- and divalent cations with a water ligand are also provided. Transferability of the correction is adressed in the context of the implementation of the AMOEBA and SIBFA polarizable force fields in the TINKER-HP software. As the choices of the multipolar distribution are discussed, conclusions are drawn for the future penetration-corrected polarizable force fields highlighting the mandatory need of non-spurious procedures for the obtention of well balanced and physically meaningful distributed moments. Finally, scalability and parallelism of the short-range corrected SPME approach are addressed, demonstrating that the damping function is computationally affordable and accurate for molecular dynamics simulations of complex bio- or bioinorganic systems in periodic boundary conditions. Copyright © 2016 Wiley Periodicals, Inc.

  16. Polymorphism, Intermolecular Interactions, and Spectroscopic Properties in Crystal Structures of Sulfonamides.

    Science.gov (United States)

    Sainz-Díaz, C Ignacio; Francisco-Márquez, Misaela; Soriano-Correa, Catalina

    2018-01-01

    The antibiotics family of sulfonamides has been used worldwide intensively in human therapeutics and farm livestock during decades. Intermolecular interactions of these sulfamides are important to understand their bioactivity and biodegradation. These interactions are also responsible for their supramolecular structures. The intermolecular interactions in the crystal polymorphs of the sulfonamides, sulfamethoxypyridazine, and sulfamethoxydiazine, as models of sulfonamides, have been studied by using quantum mechanical calculations. Different conformations in the sulphonamide molecules have been detected in the crystal polymorphs. Several intermolecular patterns have been studied to understand the molecular packing behavior in these antibiotics. Strong intermolecular hydrogen bonds and π-π interactions are the main driving forces for crystal packing in these sulfonamides. Different stability between polymorphs can explain the experimental behavior of these crystal forms. The calculated infrared spectroscopy frequencies explain the main intermolecular interactions in these crystals. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  17. On the theory of electric double layer with explicit account of a polarizable co-solvent

    International Nuclear Information System (INIS)

    Budkov, Yu. A.; Kolesnikov, A. L.; Kiselev, M. G.

    2016-01-01

    We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to higher surface potentials. On

  18. On the theory of electric double layer with explicit account of a polarizable co-solvent.

    Science.gov (United States)

    Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

    2016-05-14

    We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to higher surface potentials. On

  19. Toward Peptide Nucleic Acid (PNA) Directed Peptide Translation Using Ester Based Aminoacyl Transfer

    DEFF Research Database (Denmark)

    Singhal, Abhishek; Bagnacani, Valentina; Corradini, Roberto

    2014-01-01

    intermolecular aminoacyl transfer using simple ester aminolysis chemistry primitively analogous to the ribosomal peptidyl transferase reaction in the absence of anchimeric assistance from ribose and ribosome catalysis. These results help define the minimum chemical boundary conditions for the translation process...

  20. Photoinduced electron transfer between the dendritic zinc phthalocyanines and anthraquinone

    Science.gov (United States)

    Chen, Kuizhi; Wen, Junri; Liu, Jiangsheng; Chen, Zhenzhen; Pan, Sujuan; Huang, Zheng; Peng, Yiru

    2015-03-01

    The intermolecular electron transfer between the novel dendritic zinc (II) phthalocyanines (G1-DPcB and G2-DPcB) and anthraquinone (AQ) was studied by steady-state fluorescence and UV/Vis absorption spectroscopic methods. The effect of dendron generation on intermolecular electron transfer was investigated. The results showed that the fluorescence emission of these dendritic phthalocyanines could be greatly quenched by AQ upon excitation at 610 nm. The Stern- Volmer constant (KSV) of electron transfer was decreased with increasing the dendron generations. Our study suggested that these novel dendritic phthalocyanines were effective new electron donors and transmission complexes and could be used as a potential artifical photosysthesis system.

  1. Effective oscillator strength distributions of spherically symmetric atoms for calculating polarizabilities and long-range atom–atom interactions

    International Nuclear Information System (INIS)

    Jiang, Jun; Mitroy, J.; Cheng, Yongjun; Bromley, M.W.J.

    2015-01-01

    Effective oscillator strength distributions are systematically generated and tabulated for the alkali atoms, the alkaline-earth atoms, the alkaline-earth ions, the rare gases and some miscellaneous atoms. These effective distributions are used to compute the dipole, quadrupole and octupole static polarizabilities, and are then applied to the calculation of the dynamic polarizabilities at imaginary frequencies. These polarizabilities can be used to determine the long-range C 6 , C 8 and C 10 atom–atom interactions for the dimers formed from any of these atoms and ions, and we present tables covering all of these combinations

  2. Effective oscillator strength distributions of spherically symmetric atoms for calculating polarizabilities and long-range atom–atom interactions

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Jun, E-mail: phyjiang@yeah.net [Key Laboratory of Atomic and Molecular Physics and Functional Materials of Gansu Province, College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070 (China); School of Engineering, Charles Darwin University, Darwin, Northern Territory, 0909 (Australia); Mitroy, J. [School of Engineering, Charles Darwin University, Darwin, Northern Territory, 0909 (Australia); Cheng, Yongjun, E-mail: cyj83mail@gmail.com [School of Engineering, Charles Darwin University, Darwin, Northern Territory, 0909 (Australia); Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin 150080 (China); Bromley, M.W.J., E-mail: brom@physics.uq.edu.au [School of Mathematics and Physics, The University of Queensland, Brisbane, Queensland 4075 (Australia)

    2015-01-15

    Effective oscillator strength distributions are systematically generated and tabulated for the alkali atoms, the alkaline-earth atoms, the alkaline-earth ions, the rare gases and some miscellaneous atoms. These effective distributions are used to compute the dipole, quadrupole and octupole static polarizabilities, and are then applied to the calculation of the dynamic polarizabilities at imaginary frequencies. These polarizabilities can be used to determine the long-range C{sub 6}, C{sub 8} and C{sub 10} atom–atom interactions for the dimers formed from any of these atoms and ions, and we present tables covering all of these combinations.

  3. Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

    Science.gov (United States)

    Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

    2011-03-01

    The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

  4. Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

    Science.gov (United States)

    Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

    2015-02-15

    The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported. © 2014 Wiley Periodicals, Inc.

  5. GROMOS polarizable charge-on-spring models for liquid urea: COS/U and COS/U2.

    Science.gov (United States)

    Lin, Zhixiong; Bachmann, Stephan J; van Gunsteren, Wilfred F

    2015-03-07

    Two one-site polarizable urea models, COS/U and COS/U2, based on the charge-on-spring model are proposed. The models are parametrized against thermodynamic properties of urea-water mixtures in combination with the polarizable COS/G2 and COS/D2 models for liquid water, respectively, and have the same functional form of the inter-atomic interaction function and are based on the same parameter calibration procedure and type of experimental data as used to develop the GROMOS biomolecular force field. Thermodynamic, dielectric, and dynamic properties of urea-water mixtures simulated using the polarizable models are closer to experimental data than using the non-polarizable models. The COS/U and COS/U2 models may be used in biomolecular simulations of protein denaturation.

  6. Tribenzylamine C-H activation and intermolecular hydrogen transfer promoted by WCl6.

    Science.gov (United States)

    Bortoluzzi, Marco; Marchetti, Fabio; Pampaloni, Guido; Zacchini, Stefano

    2014-04-07

    The 1:1 molar reaction of WCl6 with tribenzylamine (tba), in dichloromethane, selectively afforded the iminium salt [(PhCH2)2N═CHPh][WCl6], 1, and the ammonium one [tbaH][WCl6], 2, in equimolar amounts. The products were fully characterized by means of spectroscopic methods, analytical methods, and X-ray diffractometry. Density functional theory calculations were carried out with the aim of comprehending the mechanistic aspects.

  7. The effect of the intermolecular potential formulation on the state-selected energy exchange rate coefficients in N2-N2 collisions.

    Science.gov (United States)

    Kurnosov, Alexander; Cacciatore, Mario; Laganà, Antonio; Pirani, Fernando; Bartolomei, Massimiliano; Garcia, Ernesto

    2014-04-05

    The rate coefficients for N2-N2 collision-induced vibrational energy exchange (important for the enhancement of several modern innovative technologies) have been computed over a wide range of temperature. Potential energy surfaces based on different formulations of the intramolecular and intermolecular components of the interaction have been used to compute quasiclassically and semiclassically some vibrational to vibrational energy transfer rate coefficients. Related outcomes have been rationalized in terms of state-to-state probabilities and cross sections for quasi-resonant transitions and deexcitations from the first excited vibrational level (for which experimental information are available). On this ground, it has been possible to spot critical differences on the vibrational energy exchange mechanisms supported by the different surfaces (mainly by their intermolecular components) in the low collision energy regime, though still effective for temperatures as high as 10,000 K. It was found, in particular, that the most recently proposed intermolecular potential becomes the most effective in promoting vibrational energy exchange near threshold temperatures and has a behavior opposite to the previously proposed one when varying the coupling of vibration with the other degrees of freedom. Copyright © 2014 Wiley Periodicals, Inc.

  8. Exploring the Dipole Polarizability of $^{11}$Li at REX-ISOLDE

    CERN Multimedia

    2002-01-01

    Dipole polarizability refers to the effect of the excitation to negative parity states through the electric dipole interaction. In nuclear physics dipole polarizability has not yet played a major role. For nuclei close to the drip lines where the separation energies of neutrons (or protons) are small, a substantial part of the dipole strength function occurs at low excitation energies. We here propose to investigate this effect by measuring elastic scattering at energies close to the Coulomb barrier. REX-ISOLDE together with the new improved yields of $^{11}$Li provides the ideal setting for this experiment. We ask for a total of 24 shifts with proton beam plus 3 shifts of stable beam from a Ta-foil target.

  9. A polarizable embedding DFT study of one-photon absorption in fluorescent proteins

    DEFF Research Database (Denmark)

    Beerepoot, Maarten; Steindal, Arnfinn H.; Kongsted, Jacob

    2013-01-01

    A theoretical study of the one-photon absorption of five fluorescent proteins (FPs) is presented. The absorption properties are calculated using a polarizable embedding approach combined with density functional theory (PE-DFT) on the wild-type green fluorescent protein (wtGFP) and several of its...... shift from vacuum to protein. This is the first computational study of a range of fluorescent proteins using a polarizable embedding potential....... optimization of the chromophores within a frozen protein environment is needed in order to reproduce the experimental trends. Explicit account of polarization in the force field is not needed to yield the correct trend between the different FPs, but is necessary for reproducing the experimentally observed red...

  10. Induced-Charge Enhancement of the Diffusion Potential in Membranes with Polarizable Nanopores.

    Science.gov (United States)

    Ryzhkov, I I; Lebedev, D V; Solodovnichenko, V S; Shiverskiy, A V; Simunin, M M

    2017-12-01

    When a charged membrane separates two salt solutions of different concentrations, a potential difference appears due to interfacial Donnan equilibrium and the diffusion junction. Here, we report a new mechanism for the generation of a membrane potential in polarizable conductive membranes via an induced surface charge. It results from an electric field generated by the diffusion of ions with different mobilities. For uncharged membranes, this effect strongly enhances the diffusion potential and makes it highly sensitive to the ion mobilities ratio, electrolyte concentration, and pore size. Theoretical predictions on the basis of the space-charge model extended to polarizable nanopores fully agree with experimental measurements in KCl and NaCl aqueous solutions.

  11. Isotensor Axial Polarizability and Lattice QCD Input for Nuclear Double-β Decay Phenomenology

    Science.gov (United States)

    Shanahan, Phiala E.; Tiburzi, Brian C.; Wagman, Michael L.; Winter, Frank; Chang, Emmanuel; Davoudi, Zohreh; Detmold, William; Orginos, Kostas; Savage, Martin J.; Nplqcd Collaboration

    2017-08-01

    The potential importance of short-distance nuclear effects in double-β decay is assessed using a lattice QCD calculation of the n n →p p transition and effective field theory methods. At the unphysical quark masses used in the numerical computation, these effects, encoded in the isotensor axial polarizability, are found to be of similar magnitude to the nuclear modification of the single axial current, which phenomenologically is the quenching of the axial charge used in nuclear many-body calculations. This finding suggests that nuclear models for neutrinoful and neutrinoless double-β decays should incorporate this previously neglected contribution if they are to provide reliable guidance for next-generation neutrinoless double-β decay searches. The prospects of constraining the isotensor axial polarizabilities of nuclei using lattice QCD input into nuclear many-body calculations are discussed.

  12. Polarizability of Kr6+ from high-L Kr5+ fine-structure measurements

    International Nuclear Information System (INIS)

    Lundeen, S. R.; Fehrenbach, C. W.

    2007-01-01

    The transition between n=55 and n=109 Rydberg levels of Kr 5+ has been studied at high resolution using the resonant excitation stark ionization spectroscopy method. Resolved excitation of L=6, 7, 8, and 9 levels in n=55 lead to a determination of the fine-structure energies of these levels. Interpreted with the long-range polarization model, this leads to a measurement of the dipole polarizabilities of Zn-like Kr 6+ , α d =2.69(4)a 0 3 . Obtaining a value of the quadrupole polarizability from the data will require additional theoretical input. Factors contributing to the signal and noise levels in measurements of this type are discussed

  13. Analysis of intermolecular RNA-RNA recombination by rubella virus

    International Nuclear Information System (INIS)

    Adams, Sandra D.; Tzeng, W.-P.; Chen, M.-H.; Frey, Teryl K.

    2003-01-01

    To investigate whether rubella virus (RUB) undergoes intermolecular RNA-RNA recombination, cells were cotransfected with pairs of in vitro transcripts from genomic cDNA plasmid vectors engineered to contain nonoverlapping deletions: the replicative transcript maintained the 5'-proximal nonstructural (NS) ORF (which contained the replicase, making it RNA replication competent), had a deletion in the 3'-proximal structural protein (SP) ORF, and maintained the 3' end of the genome, including the putative 3' cis-acting elements (CSE), while the nonreplicative transcript consisted of the 3' half of the genome including the SP-ORF and 3' CSE. Cotransfection yielded plaque-forming virus that synthesized the standard genomic and subgenomic RNAs and thus was generated by RNA-RNA recombination. Using transcripts tagged with a 3'-terminal deletion, it was found that recombinants contained the 3' end derived from the replicative strand, indicating a cis-preference for initiation of negative-strand synthesis. In cotransfections in which the replicative transcript lacked the 3' CSE, recombination occurred, albeit at lower efficiency, indicating that initiation in trans from the NS-ORF can occur. The 3' CSE was sufficient as a nonreplicative transcript, showing that it can serve as a promoter for negative-strand RNA synthesis. While deletion mutagenesis showed that the presence of the junction untranslated region (J-UTR) between the ORFs appeared to be necessary on both transcripts for recombination in this region of the genome, analysis with transcripts tagged with restriction sites showed that the J-UTR was not a hot spot for recombination compared to neighboring regions in both ORFs. Sequence analysis of recombinants revealed that both precise (homologous) and imprecise recombination (aberrant, homologous resulting in duplications) occurred; however, imprecise recombination only involved the J-UTR or the 3' end of the NS-ORF and the J-UTR (maintaining the NS-ORF), indicating

  14. Measuring "Impossible" Intermolecular Cross-Peaks to Improve Selectivity and Specificity in Breast MRI

    National Research Council Canada - National Science Library

    Warren, Warren

    2000-01-01

    Work in my laboratory at the time of grant submission had shown that intermolecular cross-peaks could be generated in vivo, and that these peaks gave enhanced contrast in rat brain images, including tumor enhancement...

  15. 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.

  16. Calculation of dipole polarizability derivatives of adamantane and their use in electron scattering computations

    Czech Academy of Sciences Publication Activity Database

    Sauer, S. P. A.; Paidarová, Ivana; Čársky, Petr; Čurík, Roman

    2016-01-01

    Roč. 70, č. 5 (2016), č. článku 105. ISSN 1434-6060 R&D Projects: GA MŠk LD14088 Grant - others:COST(XE) CM1301 Institutional support: RVO:61388955 Keywords : DENSITY-FUNCTIONAL-THEORY * COUPLED-CLUSTER CALCULATIONS * FREQUENCY-DEPENDENT POLARIZABILITIES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.288, year: 2016

  17. Natural Fe3O4 nanoparticles embedded zinc–tellurite glasses: Polarizability and optical properties

    International Nuclear Information System (INIS)

    Widanarto, W.; Sahar, M.R.; Ghoshal, S.K.; Arifin, R.; Rohani, M.S.; Hamzah, K.; Jandra, M.

    2013-01-01

    Modifying the optical behavior of zinc–tellurite glass by embedding magnetic nanoparticles has implication in nanophotonics. A series of zinc–tellurite glasses containing natural Fe 3 O 4 nanoparticles with composition (80 − x)TeO 2 ·xFe 3 O 4 ·20ZnO (0 ≤ x ≤ 2) in mol% are synthesized by melt quenching method and their optical properties are investigated using FTIR and UV–vis–NIR spectroscopies. Lorentz–Lorenz relations are exploited to determine the refractive index, molar refraction and electronic polarizability. The sharp absorption peaks of FTIR spectra show a shift from 667 cm −1 to 671 cm −1 in the presence of nanoparticles that increase the non-bridging oxygen, confirmed by the intensity change of the TeO 3 peak at 752 cm −1 . A new peak around 461 cm −1 is also observed which is attributed to the band characteristic of covalent Fe–O linkages. A decrease in the Urbach energy as much as 0.122 eV and the optical energy band gap with the increase of Fe 3 O 4 concentration (0.5–1.0 mol%) is evidenced. Electronic polarizability of the glasses increases with increasing Fe 3 O 4 nanoparticles concentration up to 1 mol%. Interestingly, the polarizability tends to decrease with the further increase of Fe 3 O 4 concentration at 2 mol%. The role of magnetic nanoparticles in influencing the structural and optical behavior are examined and understood. - Highlights: ► Incorporation of natural Fe 3 O 4 nanoparticles into the zinc–tellurite glass. ► Influence of magnetic nanoparticles in modifying structure and optical properties. ► Enhancement of refraction index and change in electronic polarizability

  18. Polarizational stopping power of heavy-ion diclusters in two-dimensional electron liquids

    International Nuclear Information System (INIS)

    Ballester, D.; Fuentes, A. M.; Tkachenko, I. M.

    2007-01-01

    The in-plane polarizational stopping power of heavy-ion diclusters in a two-dimensional strongly coupled electron liquid is studied. Analytical expressions for the stopping power of both fast and slow projectiles are derived. To go beyond the random-phase approximation we make use of the inverse dielectric function obtained by means of the method of moments and some recent analytical expressions for the static local-field correction factor

  19. Solvation structure and dynamics of Ni{sup 2+}(aq) from a polarizable force field

    Energy Technology Data Exchange (ETDEWEB)

    Mareš, Jiří, E-mail: jiri.mares@oulu.fi; Vaara, Juha

    2014-10-31

    Highlights: • We parameterize the Ni{sup 2+} ion within the AMOEBA polarizable forcefield. • Besides vdW parameters, we fit also polarizability, Thole damping and charge. • We use an empirical adjustment to account for the transition into condensed phase. • Very good structural and dynamical properties of Ni{sup 2+}(aq) are demonstrated. - Abstract: An aqueous solution of Ni{sup 2+} has often been used as a prototypic transition-metal system for experimental and theoretical studies in nuclear and electron-spin magnetic resonance (NMR and ESR). Molecular dynamics (MD) simulation of Ni{sup 2+}(aq) has been a part of many of these studies. As a transition metal complex, its MD simulation is particularly difficult using common force fields. In this work, we parameterize the Ni{sup 2+} ion for a simulation of the aqueous solution within the modern polarizable force field AMOEBA. We show that a successful parameterization is possible for this specific case when releasing the physical interpretation of the electrostatic and polarization parameters of the force field. In doing so, particularly the Thole damping parameter and also the ion charge and polarizability were used as fitting parameters. The resulting parameterizations give in a MD simulation good structural and dynamical properties of the [Ni(H{sub 2}O){sub 6}]{sup 2+} complex, along with the expected excellent performance of AMOEBA for the water solvent. The presented parameterization is appropriate for high-accuracy simulations of both structural and dynamic properties of Ni{sup 2+}(aq). This work documents possible approaches of parameterization of a transition metal within the AMOEBA force field.

  20. Effect of Level Broadening on the Polarizability in a Two-Dimensional System

    Science.gov (United States)

    Ando, Tsuneya

    1982-10-01

    The Lindhard polarizability is calculated in a two-dimensional system in the self-consistent Born approximation by assuming short-range scatterers. The known singularity at q{=}2kF, where kF is the Fermi wave vector, is shown to be rounded off in the presence of impurities. The effect is similar to that of nonzero temperatures in contrast to the result of Nkoma [J. Phys. C 14 (1981) 1685].

  1. Frequency-dependent local field factors in dielectric liquids by a polarizable force field and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Davari, Nazanin; Haghdani, Shokouh; Åstrand, Per-Olof

    2015-01-01

    A force field model for calculating local field factors, i.e. the linear response of the local electric field for example at a nucleus in a molecule with respect to an applied electric field, is discussed. It is based on a combined charge-transfer and point-dipole interaction model for the polarizability, and thereby it includes two physically distinct terms for describing electronic polarization: changes in atomic charges arising from transfer of charge between the atoms and atomic induced dipole moments. A time dependence is included both for the atomic charges and the atomic dipole moments and if they are assumed to oscillate with the same frequency as the applied electric field, a model for frequency-dependent properties are obtained. Furthermore, if a life-time of excited states are included, a model for the complex frequency-dependent polariability is obtained including also information about excited states and the absorption spectrum. We thus present a model for the frequency-dependent local field factors through the first molecular excitation energy. It is combined with molecular dynamics simulations of liquids where a large set of configurations are sampled and for which local field factors are calculated. We are normally not interested in the average of the local field factor but rather in configurations where it is as high as possible. In electrical insulation, we would like to avoid high local field factors to reduce the risk for electrical breakdown, whereas for example in surface-enhanced Raman spectroscopy, high local field factors are desired to give dramatically increased intensities

  2. Bounds on complex polarizabilities and a new perspective on scattering by a lossy inclusion

    Science.gov (United States)

    Milton, Graeme W.

    2017-09-01

    Here, we obtain explicit formulas for bounds on the complex electrical polarizability at a given frequency of an inclusion with known volume that follow directly from the quasistatic bounds of Bergman and Milton on the effective complex dielectric constant of a two-phase medium. We also describe how analogous bounds on the orientationally averaged bulk and shear polarizabilities at a given frequency can be obtained from bounds on the effective complex bulk and shear moduli of a two-phase medium obtained by Milton, Gibiansky, and Berryman, using the quasistatic variational principles of Cherkaev and Gibiansky. We also show how the polarizability problem and the acoustic scattering problem can both be reformulated in an abstract setting as "Y problems." In the acoustic scattering context, to avoid explicit introduction of the Sommerfeld radiation condition, we introduce auxiliary fields at infinity and an appropriate "constitutive law" there, which forces the Sommerfeld radiation condition to hold. As a consequence, we obtain minimization variational principles for acoustic scattering that can be used to obtain bounds on the complex backwards scattering amplitude. Some explicit elementary bounds are given.

  3. Measurements of double-polarized compton scattering asymmetries and extraction of the proton spin polarizabilities.

    Science.gov (United States)

    Martel, P P; Miskimen, R; Aguar-Bartolome, P; Ahrens, J; Akondi, C S; Annand, J R M; Arends, H J; Barnes, W; Beck, R; Bernstein, A; Borisov, N; Braghieri, A; Briscoe, W J; Cherepnya, S; Collicott, C; Costanza, S; Denig, A; Dieterle, M; Downie, E J; Fil'kov, L V; Garni, S; Glazier, D I; Gradl, W; Gurevich, G; Hall Barrientos, P; Hamilton, D; Hornidge, D; Howdle, D; Huber, G M; Jude, T C; Kaeser, A; Kashevarov, V L; Keshelashvili, I; Kondratiev, R; Korolija, M; Krusche, B; Lazarev, A; Lisin, V; Livingston, K; MacGregor, I J D; Mancell, J; Manley, D M; Meyer, W; Middleton, D G; Mushkarenkov, A; Nefkens, B M K; Neganov, A; Nikolaev, A; Oberle, M; Ortega Spina, H; Ostrick, M; Ott, P; Otte, P B; Oussena, B; Pedroni, P; Polonski, A; Polyansky, V; Prakhov, S; Rajabi, A; Reicherz, G; Rostomyan, T; Sarty, A; Schrauf, S; Schumann, S; Sikora, M H; Starostin, A; Steffen, O; Strakovsky, I I; Strub, T; Supek, I; Thiel, M; Tiator, L; Thomas, A; Unverzagt, M; Usov, Y; Watts, D P; Witthauer, L; Werthmüller, D; Wolfes, M

    2015-03-20

    The spin polarizabilities of the nucleon describe how the spin of the nucleon responds to an incident polarized photon. The most model-independent way to extract the nucleon spin polarizabilities is through polarized Compton scattering. Double-polarized Compton scattering asymmetries on the proton were measured in the Δ(1232) region using circularly polarized incident photons and a transversely polarized proton target at the Mainz Microtron. Fits to asymmetry data were performed using a dispersion model calculation and a baryon chiral perturbation theory calculation, and a separation of all four proton spin polarizabilities in the multipole basis was achieved. The analysis based on a dispersion model calculation yields γ(E1E1)=-3.5±1.2, γ(M1M1)=3.16±0.85, γ(E1M2)=-0.7±1.2, and γ(M1E2)=1.99±0.29, in units of 10(-4)  fm(4).

  4. Relativistic many-body calculation of energies, lifetimes, hyperfine constants, and polarizabilities in 7Li

    International Nuclear Information System (INIS)

    Johnson, W. R.; Safronova, U. I.; Derevianko, A.; Safronova, M. S.

    2008-01-01

    The excitation energies of ns, np, nd, and nf (n≤6) states in neutral lithium are evaluated within the framework of relativistic many-body theory. First-, second-, third-, and all-order Coulomb energies and first- and second-order Breit corrections to energies are calculated. All-order calculations of reduced matrix elements, oscillator strengths, transition rates, and lifetimes are given for levels up to n=4. Electric-dipole (2s-np), electric-quadrupole (2s-nd), and electric-octupole (2s-nf), matrix elements are evaluated to obtain the corresponding ground-state multipole polarizabilities using the sum-over-states approach. Scalar and tensor polarizabilities for the 2p 1/2 and 2p 3/2 states are also calculated. Magnetic-dipole hyperfine constants A are determined for low-lying levels up to n=4. The quadratic Stark shift for the (F=2 M=0)↔(F=1 M=0) ground-state hyperfine transition is found to be -0.0582 Hz/(kV/cm) 2 , in slight disagreement with the experimental value -0.061±0.002 Hz/(kV/cm) 2 . Matrix elements used in evaluating polarizabilities, hyperfine constants, and the quadratic Stark shift are obtained using the all-order method

  5. Communication: Polarizable polymer chain under external electric field in a dilute polymer solution

    International Nuclear Information System (INIS)

    Budkov, Yu. A.; Kolesnikov, A. L.; Kiselev, M. G.

    2015-01-01

    We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such “field-induced” globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification

  6. The multi-configuration self-consistent field method within a polarizable embedded framework

    Science.gov (United States)

    Hedegârd, Erik Donovan; List, Nanna H.; Jensen, Hans Jørgen Aagaard; Kongsted, Jacob

    2013-07-01

    We present a detailed derivation of Multi-Configuration Self-Consistent Field (MCSCF) optimization and linear response equations within the polarizable embedding scheme: PE-MCSCF. The MCSCF model enables a proper description of multiconfigurational effects in reaction paths, spin systems, excited states, and other properties which cannot be described adequately with current implementations of polarizable embedding in density functional or coupled cluster theories. In the PE-MCSCF scheme the environment surrounding the central quantum mechanical system is represented by distributed multipole moments and anisotropic dipole-dipole polarizabilities. The PE-MCSCF model has been implemented in DALTON. As a preliminary application, the low lying valence states of acetone and uracil in water has been calculated using Complete Active Space Self-Consistent Field (CASSCF) wave functions. The dynamics of the water environment have been simulated using a series of snapshots generated from classical Molecular Dynamics. The calculated shifts from gas-phase to water display between good and excellent correlation with experiment and previous calculations. As an illustration of another area of potential applications we present calculations of electronic transitions in the transition metal complex, [Fe(NO)(CN)5]2 - in a micro-solvated environment. This system is highly multiconfigurational and the influence of solvation is significant.

  7. A Polarizable Atomic Multipole-Based Force Field for Molecular Dynamics Simulations of Anionic Lipids.

    Science.gov (United States)

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

    2017-12-31

    In all of the classical force fields, electrostatic interaction is simply treated and explicit electronic polarizability is neglected. The condensed-phase polarization, relative to the gas-phase charge distributions, is commonly accounted for in an average way by increasing the atomic charges, which remain fixed throughout simulations. Based on the lipid polarizable force field DMPC and following the same framework as Atomic Multipole Optimized Energetics for BiomoleculAr (AMOEBA) simulation, the present effort expands the force field to new anionic lipid models, in which the new lipids contain DMPG and POPS. The parameters are compatible with the AMOEBA force field, which includes water, ions, proteins, etc. The charge distribution of each atom is represented by the permanent atomic monopole, dipole and quadrupole moments, which are derived from the ab initio gas phase calculations. Many-body polarization including the inter- and intramolecular polarization is modeled in a consistent manner with distributed atomic polarizabilities. Molecular dynamics simulations of the two aqueous DMPG and POPS membrane bilayer systems, consisting of 72 lipids with water molecules, were then carried out to validate the force field parameters. Membrane width, area per lipid, volume per lipid, deuterium order parameters, electron density profile, electrostatic potential difference between the center of the bilayer and water are all calculated, and compared with limited experimental data.

  8. Measuring the dynamic polarizability of tungsten atom via electrical wire explosion in vacuum

    Science.gov (United States)

    Shi, Huantong; Zou, Xiaobing; Wang, Xinxin

    2018-02-01

    Electrical explosion of wire provides a practical approach to the experimental measurement of dynamic polarizability of metal atoms with high melting and boiling temperatures. With the help of insulation coating, a section of tungsten wire was transformed to the plasma state while the near electrode region was partially vaporized, which enabled us to locate the "neutral-region" (consisting of gaseous atoms) in the Mach-Zehnder interferogram. In this paper, the polarizability of the tungsten atom at 532 nm was reconstructed based on a technique previously used for the same purpose, and the basic preconditions of the measurement were verified in detail, including the existence of the neutral region, conservation of linear density of tungsten during wire expansion, and neglect of the vaporized insulation coating. The typical imaging time varied from 80 ns to as late as 200 ns and the reconstructed polarizability of the tungsten atom was 16 ± 1 Å3, which showed good statistical consistency and was also in good agreement with the previous results.

  9. Electroabsorption spectra of carotenoid isomers: Conformational modulation of polarizability vs. induced dipole moments

    International Nuclear Information System (INIS)

    Krawczyk, Stanislaw; Jazurek, Beata; Luchowski, Rafal; Wiacek, Dariusz

    2006-01-01

    Electroabsorption spectra of all-trans, 13-cis and 15-cis isomers of carotenoids violaxanthin and β-carotene frozen in organic solvents were analysed in terms of changes in permanent dipole moment, Δμ, and in the linear polarizability, Δα, on electronic excitation. The spectral range investigated covered the two carotenoid absorption bands in the VIS and UV, known to originate from differently oriented transition dipole moments. In contrast with the collinearity of the apparent Δμ with Δα in the lowest-energy allowed (VIS) transition 1A g - ->1B u + , the axis of the largest polarizability change in the UV transition 1A g - ->1A g + (''cis band'') was found to make a large angle with the transition moment, while the direction of Δμ appears to be much closer to it. These data support the view that Δμ's inferred from electrochromic spectra of carotenoids are apparent and are not induced by the local matrix field in the solvent cavity, but merely result from conformational modulation of molecular polarizability

  10. Intermolecular failure of L-type Ca2+ channel and ryanodine receptor signaling in hypertrophy.

    Directory of Open Access Journals (Sweden)

    Ming Xu

    2007-02-01

    Full Text Available Pressure overload-induced hypertrophy is a key step leading to heart failure. The Ca(2+-induced Ca(2+ release (CICR process that governs cardiac contractility is defective in hypertrophy/heart failure, but the molecular mechanisms remain elusive. To examine the intermolecular aspects of CICR during hypertrophy, we utilized loose-patch confocal imaging to visualize the signaling between a single L-type Ca(2+ channel (LCC and ryanodine receptors (RyRs in aortic stenosis rat models of compensated (CHT and decompensated (DHT hypertrophy. We found that the LCC-RyR intermolecular coupling showed a 49% prolongation in coupling latency, a 47% decrease in chance of hit, and a 72% increase in chance of miss in DHT, demonstrating a state of "intermolecular failure." Unexpectedly, these modifications also occurred robustly in CHT due at least partially to decreased expression of junctophilin, indicating that intermolecular failure occurs prior to cellular manifestations. As a result, cell-wide Ca(2+ release, visualized as "Ca(2+ spikes," became desynchronized, which contrasted sharply with unaltered spike integrals and whole-cell Ca(2+ transients in CHT. These data suggested that, within a certain limit, termed the "stability margin," mild intermolecular failure does not damage the cellular integrity of excitation-contraction coupling. Only when the modification steps beyond the stability margin does global failure occur. The discovery of "hidden" intermolecular failure in CHT has important clinical implications.

  11. Intermolecular Interactions and Electrostatic Properties of the [beta]-Hydroquinone Apohost: Implications for Supramolecular Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Clausen, Henrik F.; Chen, Yu-Sheng; Jayatilaka, Dylan; Overgaard, Jacob; Koutsantonis, George A.; Spackman, Mark A.; Iversen, Bo B. (Aarhus); (UWA); (UC)

    2012-02-07

    The crystal structure of the {beta}-polymorph of hydroquinone ({beta}-HQ), the apohost of a large family of clathrates, is reported with a specific focus on intermolecular interactions and the electrostatic nature of its cavity. Hirshfeld surface analysis reveals subtle close contacts between two interconnecting HQ networks, and the local packing and related close contacts were examined by breakdown of the fingerprint plot. An experimental multipole model containing anisotropic thermal parameters for hydrogen atoms has been successfully refined against 15(2) K single microcrystal synchrotron X-ray diffraction data. The experimental electron density model has been compared with a theoretical electron density calculated with the molecule embedded in its own crystal field. Hirshfeld charges, interaction energies and the electrostatic potential calculated for both models are qualitatively in good agreement, but small differences in the electrostatic potential persist due to charge transfer from all hydrogen atoms to the oxygen atoms in the theoretical model. The electrostatic potential in the center of the cavity is positive, very shallow and highly symmetric, suggesting that the inclusion of polar molecules in the void will involve a balance between opposing effects. The electric field is by symmetry zero in the center of the cavity, increasing to a value of 0.0185 e/{angstrom}{sup 2} (0.27 V/{angstrom}) 1 {angstrom} along the 3-fold axis and 0.0105 e/{angstrom}{sup 2} (0.15 V/{angstrom}) 1 {angstrom} along the perpendicular direction. While these values are substantial in a macroscopic context, they are quite small for a molecular cavity and are not expected to strongly polarize a guest molecule.

  12. Intermolecular hydrogen bonds: From temperature-driven proton ...

    Indian Academy of Sciences (India)

    Abstract. We have combined neutron scattering and a range of numerical simulations to study hydrogen bonds in condensed matter. Two examples from a recent thesis will be presented. The first concerns proton transfer with increasing temperature in short inter- molecular hydrogen bonds [1,2]. These bonds have unique ...

  13. Fabricating off-diagonal components of frequency-dependent linear and nonlinear polarizabilities of doped quantum dots by Gaussian white noise

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Surajit [Department of Chemistry, Bishnupur Ramananda College, Bishnupur, Bankura 722122, West Bengal (India); Ganguly, Jayanta [Department of Chemistry, Brahmankhanda Basapara High School, Basapara, Birbhum 731215, West Bengal (India); Ghosh, Manas, E-mail: pcmg77@rediffmail.com [Department of Chemistry, Physical Chemistry Section, Visva Bharati University, Santiniketan, Birbhum 731 235, West Bengal (India)

    2015-07-15

    We make a rigorous exploration of the profiles of off-diagonal components of frequency-dependent linear (α{sub xy}, α{sub yx}), first nonlinear (β{sub xyy}, β{sub yxx}), and second nonlinear (γ{sub xxyy}, γ{sub yyxx}) polarizabilities of quantum dots driven by Gaussian white noise. The quantum dot is doped with repulsive Gaussian impurity. Noise has been applied additively and multiplicatively to the system. An external oscillatory electric field has also been applied to the system. Gradual variations of external frequency, dopant location, and noise strength give rise to interesting features of polarizability components. The observations reveal intricate interplay between noise strength and dopant location which designs the polarizability profiles. Moreover, the mode of application of noise also modulates the polarizability components. Interestingly, in case of additive noise the noise strength has no role on polarizabilities whereas multiplicative noise invites greater delicacy in them. The said interplay provides a rather involved framework to attain stable, enhanced, and often maximized output of linear and nonlinear polarizabilities. - Highlights: • Linear and nonlinear polarizabilities of quantum dot are studied. • The polarizability components are off-diagonal and frequency-dependent. • Quantum dot is doped with a repulsive impurity. • Doped system is subject to Gaussian white noise. • Mode of noise application affects polarizabilities.

  14. Statistical theory of polarizable target compound impregnation into a polymer coil under the influence of an electric field.

    Science.gov (United States)

    Kolesnikov, A L; Budkov, Yu A; Basharova, E A; Kiselev, M G

    2017-06-21

    The paper presents a theoretical approach for describing the influence of an electric field on the conformation of an electrically neutral dielectric polymer chain dissolved in a dielectric solvent with an admixture of a target compound. Each monomer and each molecule of the target compound carries positive excess polarizability and the solvent is described as a continuous dielectric medium. The model is based on the Flory-type mean-field theory. We demonstrate non-monotonic dependences of the expansion factor and the concentration of the target compound on the strength of the electric field and molecular polarizability. Namely, the target compound concentration in the internal polymer volume as a function of electric field strength has pronounced maxima if the molecules are polarizable. In addition, the expansion factor of the non-polarizable polymer chain can be controlled by the electric field. The dependences of the expansion factor and target compound concentration on the monomer polarizability exhibit minima and intersection points. The intersection points correspond to the equality of dielectric permittivities in the bulk solution and in the internal polymer volume.

  15. Coupled influence of noise and damped propagation of impurity on linear and nonlinear polarizabilities of doped quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Ganguly, Jayanta [Department of Chemistry, Brahmankhanda Basapara High School, Basapara, Birbhum 731 215, West Bengal (India); Ghosh, Manas, E-mail: pcmg77@rediffmail.com [Department of Chemistry, Physical Chemistry Section, Visva Bharati University, Santiniketan, Birbhum 731 235, West Bengal (India)

    2015-02-02

    Highlights: • Linear and nonlinear polarizabilities of quantum dot are studied. • Quantum dot is doped with a repulsive impurity. • Doped system is subject to Gaussian white noise. • Dopant migrates under damped condition. • Noise-damping coupling affects polarizabilities. - Abstract: We investigate the profiles of diagonal components of static and frequency-dependent linear, first, and second nonlinear polarizabilities of repulsive impurity doped quantum dot. We have considered propagation of dopant within an environment that damps the motion. Simultaneous presence of noise inherent to the system has also been considered. The dopant has a Gaussian potential and noise considered is a Gaussian white noise. The doped system is exposed to an external electric field which could be static or time-dependent. Noise undergoes direct coupling with damping and the noise-damping coupling strength appears to be a crucial parameter that designs the profiles of polarizability components. This happens because the coupling strength modulates the dispersive and asymmetric character of the system. The frequency of external field brings about additional features in the profiles of polarizability components. The present investigation highlights some useful features in the optical properties of doped quantum dots.

  16. Atom interferometry experiments with lithium. Accurate measurement of the electric polarizability

    International Nuclear Information System (INIS)

    Miffre, A.

    2005-06-01

    Atom interferometers are very sensitive tools to make precise measurements of physical quantities. This study presents a measurement of the static electric polarizability of lithium by atom interferometry. Our result, α = (24.33 ± 0.16)*10 -30 m 3 , improves by a factor 3 the most accurate measurements of this quantity. This work describes the tuning and the operation of a Mach-Zehnder atom interferometer in detail. The two interfering arms are separated by the elastic diffraction of the atomic wave by a laser standing wave, almost resonant with the first resonance transition of lithium atom. A set of experimental techniques, often complicated to implement, is necessary to build the experimental set-up. After a detailed study of the atom source (a supersonic beam of lithium seeded in argon), we present our experimental atom signals which exhibit a very high fringe visibility, up to 84.5 % for first order diffraction. A wide variety of signals has been observed by diffraction of the bosonic isotope at higher diffraction orders and by diffraction of the fermionic less abundant isotope. The quality of these signals is then used to do very accurate phase measurements. A first experiment investigates how the atom interferometer signals are modified by a magnetic field gradient. An absolute measurement of lithium atom electric polarizability is then achieved by applying a static electric field on one of the two interfering arms, separated by only 90 micrometers. The construction of such a capacitor, its alignment in the experimental set-up and its operation are fully detailed.We obtain a very accurate phase measurement of the induced Lo Surdo - Stark phase shift (0.07 % precision). For this first measurement, the final uncertainty on the electric polarizability of lithium is only 0.66 %, and is dominated by the uncertainty on the atom beam mean velocity, so that a further reduction of the uncertainty can be expected. (author)

  17. Electromagnetic Scattering of Finite and Infinite 3D Lattices in Polarizable Backgrounds

    International Nuclear Information System (INIS)

    Gallinet, Benjamin; Martin, Olivier J. F.

    2009-01-01

    A novel method is elaborated for the electromagnetic scattering from periodical arrays of scatterers embedded in a polarizable background. A dyadic periodic Green's function is introduced to calculate the scattered electric field in a lattice of dielectric or metallic objects. The method exhibits strong advantages: discretization and computation of the field are restricted to the volume of the scatterers in the unit cell, open and periodic boundary conditions for the electric field are included in the Green's tensor, and finally both near and far-fields physics are directly revealed, without any additional computational effort. Promising applications include the design of periodic structures such as frequency-selective surfaces, photonic crystals and metamaterials.

  18. Polarizable Embedding Based on Multiconfigurational Methods: Current Developments and the Road Ahead

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Jensen, H. J. A.; Kongsted, J.

    2014-01-01

    This perspective gives a brief overview of recent developments within the polarizable embedding (PE) method - a multiscale approach developed over the last years. In particular, we are concerned with a recent coupling of the PE method to a multiconfiguration self-consistent field (MCSCF) code......-srDFT). A short discussion of CAS active spaces is also given. A few sample results using a retinal chromophore surrounded by a protein environment illustrate both the importance of the choice of active space and the importance of dynamical correlation. (C) 2014 Wiley Periodicals, Inc....

  19. Dynamical polarizability of graphene irradiated by circularly polarized ac electric fields

    DEFF Research Database (Denmark)

    Busl, Maria; Platero, Gloria; Jauho, Antti-Pekka

    2012-01-01

    We examine the low-energy physics of graphene in the presence of a circularly polarized electric field in the terahertz regime. Specifically, we derive a general expression for the dynamical polarizability of graphene irradiated by an ac electric field. Several approximations are developed...... that allow one to develop a semianalytical theory for the weak-field regime. The ac field changes qualitatively the single- and many-electron excitations of graphene: Undoped samples may exhibit collective excitations (in contrast to the equilibrium situation), and the properties of the excitations in doped...

  20. Effect of the deuteron anisotropy: longitudinal and transverse components of the electric dipole polarizability

    International Nuclear Information System (INIS)

    Kharchenko, A.V.

    1997-01-01

    The anisotropy effect of the electric polarization (stretching) of the deuteron in the Coulomb field, caused by the tensor character of the nuclear force, is investigated. The values of the longitudinal (with the major axis, or the spin of the deuteron, directed along the electric field), and transverse components of the deuteron electric dipole polarizability that correspond to the low-energy n-p data, are predicted to be α parallel =0.669 fm 3 and α perpendicular to =0.555 fm 3 (the potential YYm). The values of the major and minor semi-axes of the deuteron are calculated. (orig.)

  1. Molecular response functions for the polarizable continuum model physical basis and quantum mechanical formalism

    CERN Document Server

    Cammi, Roberto

    2013-01-01

    This Brief presents the main aspects of the response functions theory (RFT) for molecular solutes described within the framework of the Polarizable Continuum Model (PCM). PCM is a solvation model for a Quantum Mechanical molecular system in which the solvent is represented as a continuum distribution of matter. Particular attention is devoted to the description of the basic features of the PCM model, and to the problems characterizing the study of the response function theory for molecules in solution with respect to the analogous theory on isolated molecules.

  2. Blackbody radiation shift, multipole polarizabilities, oscillator strengths, lifetimes, hyperfine constants, and excitation energies in Ca+

    International Nuclear Information System (INIS)

    Safronova, M. S.; Safronova, U. I.

    2011-01-01

    A systematic study of Ca + atomic properties is carried out using a high-precision relativistic all-order method where all single, double, and partial triple excitations of the Dirac-Fock wave functions are included to all orders of perturbation theory. Reduced matrix elements, oscillator strengths, transition rates, and lifetimes are determined for the levels up to n=7. Recommended values and estimates of their uncertainties are provided for a large number of electric-dipole transitions. Electric-dipole scalar polarizabilities for the 5s, 6s, 7s, 8s, 4p j , 5p j , 3d j , and 4d j states and tensor polarizabilities for the 4p 3/2 , 5p 3/2 , 3d j , and 4d j states in Ca + are calculated. Methods are developed to accurately treat the contributions from highly excited states, resulting in significant (factor of 3) improvement in the accuracy of the 3d 5/2 static polarizability value, 31.8(3)a 0 3 , in comparison with the previous calculation [Arora et al., Phys. Rev. A 76, 064501 (2007).]. The blackbody radiation shift of the 4s-3d 5/2 clock transition in Ca + is calculated to be 0.381(4) Hz at room temperature, T=300 K. Electric-quadrupole 4s-nd and electric-octupole 4s-nf matrix elements are calculated to obtain the ground-state multipole E2 and E3 static polarizabilities. Excitation energies of the ns, np, nd, nf, and ng states with n≤ 7 in are evaluated and compared with experiment. Recommended values are provided for the 7p 1/2 , 7p 3/2 , 8p 1/2 , and 8p 3/2 removal energies for which experimental measurements are not available. The hyperfine constants A are determined for the low-lying levels up to n=7. The quadratic Stark effect on hyperfine structure levels of 43 Ca + ground state is investigated. These calculations provide recommended values critically evaluated for their accuracy for a number of Ca + atomic properties for use in planning and analysis of various experiments as well as theoretical modeling.

  3. Lanczos-driven coupled-cluster damped linear response theory for molecules in polarizable environments

    DEFF Research Database (Denmark)

    List, Nanna Holmgaard; Coriani, Sonia; Kongsted, Jacob

    2014-01-01

    We present an extension of a previously reported implementation of a Lanczos-driven coupled-cluster (CC) damped linear response approach to molecules in condensed phases, where the effects of a surrounding environment are incorporated by means of the polarizable embedding formalism. We...... by confirming numerically the validity of the routinely invoked neglect of the J matrix contribution as well as motivating future use of the approximation that offers a reduction of the dimensionality of the eigenvalue problem. Preliminary applications to K-edge absorption of liquid water and aqueous acrolein...

  4. Relativistic Quadrupole Polarizability for the Ground State of Hydrogen-Like Ions

    International Nuclear Information System (INIS)

    Zhang Yong-Hu; Zhang Xian-Zhou; Tang Li-Yan; Shi Ting-Yun; Mitroy Jim

    2012-01-01

    The static quadrupole polarizabilities for hydrogen-like ions from Z = 1 to Z = 100 in the 1S 1/2 ground state are calculated to high precision by solving the Dirac equation using the B-spline Galerkin method. The results are consistent with the expression of Kaneko [J. Phys. B 10 (1977) 3347] at low Z. The quadrupole oscillator strength sum Σ n f (2) gn is computed to be zero to a very high degree of precision. (atomic and molecular physics)

  5. Correlated, Static and Dynamic Polarizabilities of Small Molecules. Comparison of Four "Black Box" Methods

    DEFF Research Database (Denmark)

    Dalskov, Erik K.; Sauer, Stephan P. A.

    1998-01-01

    with coupled cluster singles and doubles amplitudes, SOPPA(CCSD), and the coupled cluster singles and doubles linear response function method, CCSDLR. The frequency dependence of the polarizabilities is given in terms of the dipole oscillator strength sum rules or Cauchy moments S(-4) and S(-6). Two basis sets...... were employed, Sadlej's medium size polarized basis set and Dunning's correlation consistent basis set of triple- quality augmented by two diffuse functions of each angular momentum (daug-cc-pVTZ). The results are compared to other theoretical results as well as to experimental values for the static...

  6. Self-consistent nonlinearly polarizable shell-model dynamics for ferroelectric materials

    International Nuclear Information System (INIS)

    Mkam Tchouobiap, S.E.; Kofane, T.C.; Ngabireng, C.M.

    2002-11-01

    We investigate the dynamical properties of the polarizable shellmodel with a symmetric double Morse-type electron-ion interaction in one ionic species. A variational calculation based on the Self-Consistent Einstein Model (SCEM) shows that a theoretical ferroelectric (FE) transition temperature can be derive which demonstrates the presence of a first-order phase transition for the potassium selenate (K 2 SeO 4 ) crystal around Tc 91.5 K. Comparison of the model calculation with the experimental critical temperature yields satisfactory agreement. (author)

  7. Domain nucleation in the contact layer at an interface of water and a polarizable substrate

    Science.gov (United States)

    Shevkunov, S. V.

    2013-10-01

    The growth of a molecular water film on the basic plane of a silver iodide monocrystal is studied through computer simulation. Decomposition into domains with spontaneous polarization is observed in the contact layer of the film at the interface with the substrate. The formation of domains is found to be sharply enhanced on a model substrate with the double polarizability of iodine ions; heteropolarization interactions caused by the formation of domain structures increase the film's coupling with the substrate. It is demonstrated that the vapor pressure needed for molecular film growth is reduced appreciably via heteropolarization interactions.

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

    Science.gov (United States)

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

    2018-03-01

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

  9. The iodine molecule insights into intra- and intermolecular perturbation in diatomic molecules

    CERN Document Server

    Lukashov, Sergey; Pravilov, Anatoly

    2018-01-01

    This book presents experimental and theoretical spectroscopic studies performed over the last 25 years on the iodine molecule’s excited states and their perturbations. It is going to be of interest to researchers who study intra- and intermolecular perturbations in diatomic molecules and more complex systems. The book offers a detailed treatment of the nonadiabatic perturbations of valence, ion pair and Rydberg states induced by intramolecular as well as intermolecular interactions in collisions or in weakly-bound complexes. It also provides an overview of current instrumentation and techniques as well as theoretical approaches describing intra- and intermolecular perturbations. The authors are experts in the use of spectroscopy for the study of intrinsic and collision-induced perturbations in diatomic iodine. They introduced new methods of two- and three-step optical population of the iodine ion-pair states. The iodine molecule has 23 valence states correlating with three dissociation limits, 20 so-called ...

  10. Influence of Gaussian white noise on the frequency-dependent first nonlinear polarizability of doped quantum dot

    Energy Technology Data Exchange (ETDEWEB)

    Ganguly, Jayanta [Department of Chemistry, Brahmankhanda Basapara High School, Basapara, Birbhum 731215, West Bengal (India); Ghosh, Manas, E-mail: pcmg77@rediffmail.com [Department of Chemistry, Physical Chemistry Section, Visva Bharati University, Santiniketan, Birbhum 731 235, West Bengal (India)

    2014-05-07

    We investigate the profiles of diagonal components of frequency-dependent first nonlinear (β{sub xxx} and β{sub yyy}) optical response of repulsive impurity doped quantum dots. We have assumed a Gaussian function to represent the dopant impurity potential. This study primarily addresses the role of noise on the polarizability components. We have invoked Gaussian white noise consisting of additive and multiplicative characteristics (in Stratonovich sense). The doped system has been subjected to an oscillating electric field of given intensity, and the frequency-dependent first nonlinear polarizabilities are computed. The noise characteristics are manifested in an interesting way in the nonlinear polarizability components. In case of additive noise, the noise strength remains practically ineffective in influencing the optical responses. The situation completely changes with the replacement of additive noise by its multiplicative analog. The replacement enhances the nonlinear optical response dramatically and also causes their maximization at some typical value of noise strength that depends on oscillation frequency.

  11. Evidence of low intermolecular coupling in rubrene single crystals by Raman scattering

    International Nuclear Information System (INIS)

    Weinberg-Wolf, J R; McNeil, L E; Liu Shubin; Kloc, Christian

    2007-01-01

    The observed Raman spectra for single crystals of rubrene and tetracene are compared with the calculated spectra for the isolated molecules. The Raman measurements presented are of the bulk properties of the material, and they confirmed that the vapour growth process yields very pure, unstrained rubrene crystals. Finally, Raman measurements indicate that rubrene, unlike many other oligoacenes, has very weak intermolecular coupling and no observable intermolecular Raman vibrational modes. We discuss the apparent conflict between the high mobility and the weak π-electron overlap in this material

  12. Influence of intramolecular and intermolecular hydrogen bonding on the fluorescence decay time of indigo derivatives

    International Nuclear Information System (INIS)

    Schneider, S.; Lill, E.; Hefferle, P.; Doerr, F.

    1981-01-01

    It is well known that both intramolecular and intermolecular hydrogen bonding can lead to drastic changes in the lifetime of the first excited singlet state. By employing a synchronously pumped, mode-locked dye-laser for excitation in connection with a continuously operated streak camera for detection, the solvent-dependent fluorescence decay times of several indigo derivatives were determined with high temporal resolution (approx. 5 ps with deconvolution). It is found that in indigo dyes intramolecular hydrogen bonding gives rise to a strong fluorescence quenching; intermolecular hydrogen bonding can also provide a channel for fast radiationless deactivation in those derivatives in which the former are not present. (author)

  13. Open-ended response theory with polarizable embedding: multiphoton absorption in biomolecular systems.

    Science.gov (United States)

    Steindal, Arnfinn Hykkerud; Beerepoot, Maarten T P; Ringholm, Magnus; List, Nanna Holmgaard; Ruud, Kenneth; Kongsted, Jacob; Olsen, Jógvan Magnus Haugaard

    2016-10-12

    We present the theory and implementation of an open-ended framework for electric response properties at the level of Hartree-Fock and Kohn-Sham density functional theory that includes effects from the molecular environment modeled by the polarizable embedding (PE) model. With this new state-of-the-art multiscale functionality, electric response properties to any order can be calculated for molecules embedded in polarizable atomistic molecular environments ranging from solvents to complex heterogeneous macromolecules such as proteins. In addition, environmental effects on multiphoton absorption (MPA) properties can be studied by evaluating single residues of the response functions. The PE approach includes mutual polarization effects between the quantum and classical parts of the system through induced dipoles that are determined self-consistently with respect to the electronic density. The applicability of our approach is demonstrated by calculating MPA strengths up to four-photon absorption for the green fluorescent protein. We show how the size of the quantum region, as well as the treatment of the border between the quantum and classical regions, is crucial in order to obtain reliable MPA predictions.

  14. Band gap and polarizability of boro-tellurite glass: Influence of erbium ions

    Science.gov (United States)

    Said Mahraz, Zahra Ashur; Sahar, M. R.; Ghoshal, S. K.

    2014-08-01

    Understanding the influence of rare earth ions in improving the structural and optical properties of inorganic glasses are the key issues. Er3+-doped zinc boro-tellurite glasses with composition 30B2O3-10ZnO-(60-x) TeO2-xEr2O3 are prepared (x = 0, 0.5, 1, 1.5 and 2 mol%) using melt quenching technique. The physical and optical characterizations are measured by density and UV-Vis-IR absorption spectroscopy. The color of the glass changed from light yellow to deep pink due to the introduction of Er3+ ions. The maximum density is found to be ∼4.73 g cm-3 for 1 mol% of Er3+ doping. The variations in the polarizability (6.7-6.8 cm3) and the molar volume (27.987-28.827 cm3 mol-1) with dopant concentration are ascribed to the formation of non-bridging oxygen. This observation is consistent with the alteration of number of bonds per unit volume. The direct and indirect optical band gaps are increased while the phonon cut-off wavelength and Urbach energy decreased with the increase of erbium content. A high density and wide transparency range in VIS-IR area are achieved. Our results on high refractive index (∼2.416) and polarizability suggest that these glasses are potential for photonics, solid state lasers and communications devices.

  15. The concept of apparent polarizability for calculating the extinction of electromagnetic radiation by porous aerosol particles

    Science.gov (United States)

    Haspel, C.; Adler, G.

    2017-04-01

    In the current study, the electromagnetic properties of porous aerosol particles are calculated in two ways. In the first, a porous target input file is generated by carving out voids in an otherwise homogeneous particle, and the discrete dipole approximation (DDA) is used to compute the extinction efficiency of the particle assuming that the voids are near vacuum dielectrics and assuming random particle orientation. In the second, an effective medium approximation (EMA) style approach is employed in which an apparent polarizability of the voids is defined based on the well-known solution to the problem in classical electrostatics of a spherical cavity within a dielectric. It is found that for porous particles with smaller overall diameter with respect to the wavelength of incident radiation, describing the voids as near vacuum dielectrics within the DDA sufficiently reproduces measured values of extinction efficiency, whereas for porous particles with moderate to larger overall diameters with respect to the wavelength of the radiation, the apparent polarizability EMA approach better reproduces the measured values of extinction efficiency.

  16. On a relationship between molecular polarizability and partial molar volume in water.

    Science.gov (United States)

    Ratkova, Ekaterina L; Fedorov, Maxim V

    2011-12-28

    We reveal a universal relationship between molecular polarizability (a single-molecule property) and partial molar volume in water that is an ensemble property characterizing solute-solvent systems. Since both of these quantities are of the key importance to describe solvation behavior of dissolved molecular species in aqueous solutions, the obtained relationship should have a high impact in chemistry, pharmaceutical, and life sciences as well as in environments. We demonstrated that the obtained relationship between the partial molar volume in water and the molecular polarizability has in general a non-homogeneous character. We performed a detailed analysis of this relationship on a set of ~200 organic molecules from various chemical classes and revealed its fine well-organized structure. We found that this structure strongly depends on the chemical nature of the solutes and can be rationalized in terms of specific solute-solvent interactions. Efficiency and universality of the proposed approach was demonstrated on an external test set containing several dozens of polyfunctional and druglike molecules.

  17. Enhancement of molecular polarizabilities by the push-pull mechanism: A DFT study of substituted hexatriene

    Energy Technology Data Exchange (ETDEWEB)

    Labidi, N.S., E-mail: labidi2006@univ-usto.d [Department of chemistry, Faculty of sciences, University of the Sciences and Technology of Oran (U.S.T.O.MB), BP-1505 Oran El-M' naouer, 31000 (Algeria); Djebaili, A. [Faculte des Sciences, Universite de Batna, 05000 (Algeria)

    2010-05-25

    The static polarizabilities {alpha} for a series of substituted hexatriene molecules of the NO{sub 2}-(CH=CH){sub 3}-D and NO{sub 2}-(CH=CH){sub 3}-A types (D, A = N(Me){sub 2}, Br, OCH{sub 3},CH{sub 3}, NH{sub 2}, Cl, OH, F, COCN, C{sub 2}H, COF, NO, CHO, CN, CF{sub 3}) have been computed using DFT method at B3LYP/6-311 G(d,p) level of theory. Our results allowed to sort out the considered {Pi}-donor and {Pi}-acceptor substituents by decreasing static isotropic {alpha} value. An excellent agreement between the DFT and PM6 results, they give a correlation coefficient of 0.97. Miller QSAR-quality polarizability calculations give a correlation coefficient of 0.99 when compared with B3LYP/6-311G(d,p) values. Empirical models based on molecular volumes give unrealistic values for <{alpha}> but these values correlate well 0.97 with B3LYP/6-311G(d,p) results.

  18. Electrochemical characteristics of ideal polarizable interfaces with limited number of charge carriers.

    Science.gov (United States)

    Přibyl, Michal; Slouka, Zdeněk

    2015-11-01

    Recent progress in material chemistry and surface engineering has led to emergence of new electrode materials with unique physical and electrochemical properties. Here, we introduce a physical model describing charging of ideal polarizable electrode-electrolyte interface where the electrode is characterized by a limited capacity to store charge. The analytical model treats the electrode and electrolyte phases as independent nonlinear capacitors that are eventually coupled through the condition of equality of the total stored electrical charge opposite in sign. Gouy-Chapman and condensed layer theories applied to a general 1:n valent electrolyte are used to predict dependencies of differential capacitance of the electrolyte phase and surface concentration of the electrical charge on the applied potential. The model of the nonlinear capacitor for the electrode phase is described by a theory of electron donors and acceptors present in conductive solids as a result of thermal fluctuations. Both the differential capacitance and the surface concentration of the electrical charge in the electrode are evaluated as functions of the applied potential and related to the capacity of the electrode phase to accumulate charge and its ability to form electron donors and acceptors. The knowledge of capacitive properties of both phases allows to predict electrochemical characteristics of ideal polarizable interfaces, e.g., current responses in linear sweep voltammetry. The coupled model also shows significant potential drops in the electrode comparable to those in the electrolyte phase for materials with low charge carrier concentrations.

  19. Calculations of the thermal conductivities of ionic materials by simulation with polarizable interaction potentials.

    Science.gov (United States)

    Ohtori, Norikazu; Salanne, Mathieu; Madden, Paul A

    2009-03-14

    Expressions for the energy current of a system of charged, polarizable ions in periodic boundary conditions are developed in order to allow the thermal conductivity in such a system to be calculated by computer simulation using the Green-Kubo method. Dipole polarizable potentials for LiCl, NaCl, and KCl are obtained on a first-principles basis by "force matching" to the results of ab initio calculations on suitable condensed-phase ionic configurations. Simulation results for the thermal conductivity, and also other transport coefficients, for the melts are compared with experimental data and with results obtained with other interaction potentials. The agreement with experiment is almost quantitative, especially for NaCl and KCl, indicating that these methodologies, perhaps with more sophisticated forms for the potential, can be used to predict thermal conductivities for melts for which experimental determination is very difficult. It is demonstrated that the polarization effects have an important effect on the energy current and are crucial to a predictive scheme for the thermal conductivity.

  20. Intermolecular thermoelectric-like effects in molecular nano electronic systems

    International Nuclear Information System (INIS)

    Sabzyan, H.; Safari, R.

    2012-01-01

    Intramolecular thermoelectric-like coefficients are introduced and computed of a single molecule nano electronic system. Values of the electronic Intramolecular thermoelectric-like coefficients are calculated based on the density and energy transfers between different parts of the molecule using quantum theory of atoms in molecule. Since, Joule and Peltier heating are even (symmetrical) and odd (antisymmetric) functions of the external bias, it is possible to divide Intramolecular thermoelectric-like coefficients into two components, symmetrical and antisymmetrical Intramolecular thermoelectric-like coefficients, which describe the intramolecular Joule-like and Peltier-like effects, respectively. In addition, a semiclassical temperature model is presented to describe intramolecular temperature mapping (intramolecular energy distributions) in molecular nano electronic systems.

  1. Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroaniline

    DEFF Research Database (Denmark)

    Eriksen, Janus J.; Sauer, Stephan P. A.; Mikkelsen, Kurt Valentin

    2013-01-01

    We investigate the failure of Time{Dependent Density Functional Theory (TDDFT) with the CAM{B3LYP exchange{correlation (xc) functional coupled to the Polarizable Embedding (PE) scheme (PE-CAM-B3LYP) in reproducing the solvatochromic shift of the lowest intense charge{transfer excitation in para{n...

  2. A NOVEL PROTON TRANSFER COMPOUND (A NEW ...

    African Journals Online (AJOL)

    Preferred Customer

    2-amino-2-methyl-1-propanol and MoO2(acac)2, synthesized and characterized by 1H NMR, X-ray diffraction analysis, UV-Vis and FT-IR spectroscopy. The single crystal X-ray diffraction analysis revealed that intra- and intermolecular proton transfer from (MoO4H2) to (OHRNH2) results in the formation of a new molybdate ...

  3. Ru(II)-catalyzed intermolecular ortho-C-H amidation of aromatic ketones with sulfonyl azides.

    Science.gov (United States)

    Bhanuchandra, M; Yadav, M Ramu; Rit, Raja K; Rao Kuram, Malleswara; Sahoo, Akhila K

    2013-06-07

    Ru(II)-catalyzed intermolecular ortho-C-H amidation of weakly coordinating aromatic ketones with sulfonyl azides is reported. The developed reaction protocol can be extended to various substituted aromatic ketones to afford a wide range of desired C-N bond formation products in good yields.

  4. Conformation and intermolecular interactions of SA2 peptides self-assembled into vesicles.

    NARCIS (Netherlands)

    van Hell, A.J.; Klymchenko, A.; Burgers, P.P.; Moret, E.E.; Jiskoot, W.; Hennink, W.E.; Crommelin, D.J.A.; Mastrobattista, E.

    2010-01-01

    Previously we have shown that the recombinantly produced SA2 amphiphilic oligopeptide (Ac-Ala-Ala-Val-Val-Leu-Leu-Leu-Trp-Glu-Glu-COOH) self-assembles into nanovesicles (van Hell et al. 2007). In this study, the intermolecular interactions that contribute to the formation of such peptide vesicles

  5. Ab initio and Gordon--Kim intermolecular potentials for two nitrogen molecules

    International Nuclear Information System (INIS)

    Ree, F.H.; Winter, N.W.

    1980-01-01

    Both ab initio MO--LCAO--SCF and the electron-gas (or Gordon--Kim) methods have been used to compute the intermolecular potential (Phi) of N 2 molecules for seven different N 2 --N 2 orientations. The ab initio calculations were carried out using a [4s3p] contracted Gaussian basis set with and without 3d polarization functions. The larger basis set provides adequate results for Phi>0.002 hartree or intermolecular separations less than 6.5--7 bohr. We use a convenient analytic expression to represent the ab initio data in terms of the intermolecular distance and three angles defining the orientations of the two N 2 molecules. The Gordon--Kim method with Rae's self-exchange correction yields Phi, which agrees reasonably well over a large repulsive range. However, a detailed comparison of the electron kinetic energy contributions shows a large difference between the ab initio and the Gordon--Kim calculations. Using the ab initio data we derive an atom--atom potential of the two N 2 molecules. Although this expression does not accurately fit the data at some orientations, its spherical average agrees with the corresponding average of the ab initio Phi remarkably well. The spherically averaged ab initio Phi is also compared with the corresponding quantities derived from experimental considerations. The approach of the ab initio Phi to the classical quadrupole--quadrupole interaction at large intermolecular separation is also discussed

  6. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun

    2017-02-15

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

  7. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view

    Science.gov (United States)

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-01

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  8. Ultrasonic and IR study of intermolecular association through hydrogen bonding in ternary liquid mixtures.

    Science.gov (United States)

    Awasthi, Aashees; Shukla, J P

    2003-08-01

    Complex formation in ternary liquid mixtures of dimethylsulfoxide (DMSO) with phenol and o-cresol in carbontetrachloride has been studied by measuring ultrasonic velocity at 2 MHz, in the concentration range of 0.019-0.162 (in mole fraction of DMSO) at varying temperatures of 20, 30 and 40 degrees C. Using measured values of ultrasonic velocity, other parameters such as adiabatic compressibility, intermolecular free length, molar sound velocity, molar compressibility, specific acoustic impedance and molar volume have been evaluated. These parameters have been utilized to study the solute-solute interactions in these systems. The ultrasonic velocity shows a maxima and adiabatic compressibility a corresponding minima as a function of concentration for these mixtures. The results indicate the occurrence of complex formation between unlike molecules through intermolecular hydrogen bonding between oxygen atom of DMSO molecule and hydrogen atom of phenol and o-cresol molecules. The excess values of adiabatic compressibility and intermolecular free length have also been evaluated. The variation of both these parameters with concentration also indicates the possibility of the complex formation in these systems. Further, to investigate the presence of O-HO bond complexes and the strength of molecular association with concentrations, the infrared spectra of both the systems, DMSO-phenol and DMSO-o-cresol, have been recorded for various concentrations at room temperature (20 degrees C). The results obtained using infrared spectroscopy for both the systems also support the occurrence of complex formation through intermolecular hydrogen bonding in these ternary liquid mixtures.

  9. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view.

    Science.gov (United States)

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-28

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  10. Transient process spectroscopy for the direct observation of inter-molecular photo-dissociation

    Directory of Open Access Journals (Sweden)

    Sena Hashimoto

    2017-09-01

    Full Text Available Transient process spectroscopy has previously been thought to be applicable only to the analysis of intra-molecular processes. Two metal ion bridges used in the present work have allowed us to visualize real-time variations of the molecular vibration frequencies during photo-disproportionation inside bimolecule aggregates, which directly shows transient inter-molecular reactions.

  11. Studying Intermolecular Forces with a Dual Gas Chromatography and Boiling Point Investigation

    Science.gov (United States)

    Cunningham, William Patrick; Xia, Ian; Wickline, Kaitlyn; Huitron, Eric Ivan Garcia; Heo, Jun

    2018-01-01

    A procedure for the study of structural differences and intermolecular attraction between ethanol and 1-butanol based in laboratory work is described. This study provides comparisons of data retrieved from both a determination of boiling point and gas chromatography traces for the mixture. The methodology reported here should provide instructors…

  12. Effect of structural changes in sesquifulvalene on the intramolecular charge transfer and nonlinear polarizations a theoretical study

    Science.gov (United States)

    Nandi, P. K.; Mandal, K.; Kar, T.

    2003-11-01

    Ab initio HF calculations of the ground state structural parameters, and the time dependent HF (TDHF) calculations of static nonlinear polarizabilities have been performed for a number of sesquifulvalene derivatives. The calculated NLO parameters show a good correlation with the hardness parameters. The nature of hetero-atoms and their positions can strongly influence the intramolecular charge transfer (ICT) interactions and the nonlinear polarizations of sesquifulvalene. Nonlinear polarizabilities in the twisted structures have been found to depend both on the energy barrier to twist and the transition energy corresponding to the twisted ICT (TICT) state characterized by the HOMO → LUMO transition.

  13. Integral-functional representation of mass operator of quasiparticles interacting with polarizational phonons at T = 0 K

    International Nuclear Information System (INIS)

    Tkach, M.V.

    2002-01-01

    The integral-functional representation of mass operator of spinless quasiparticles interacting with polarizational phonons at T = 0 K is obtained for the first time. This representation is equivalent to the infinite branched integral fraction. It does not depend on the binding force and effectively takes into account the many phonon processes

  14. Ab initio determination of polarizabilities and van der Waals coefficients of Li atoms using the relativistic coupled-cluster method

    NARCIS (Netherlands)

    Wansbeek, L. W.; Sahoo, B. K.; Timmermans, R. G. E.; Das, B. P.; Mukherjee, D.

    We report on a technique to determine the van der Waals coefficients of lithium (Li) atoms based on relativistic coupled-cluster theory. These quantities are determined using the imaginary parts of the scalar dipole and quadrupole polarizabilities, which are evaluated using an approach that we have

  15. Polarizability of Six-Helix Bundle and Triangle DNA Origami and Their Escape Characteristics from a Dielectrophoretic Trap.

    Science.gov (United States)

    Gan, Lin; Camacho-Alanis, Fernanda; Ros, Alexandra

    2015-12-15

    DNA nanoassemblies, such as DNA origamis, hold promise in biosensing, drug delivery, nanoelectronic circuits, and biological computing, which require suitable methods for migration and precision positioning. Insulator-based dielectrophoresis (iDEP) has been demonstrated as a powerful migration and trapping tool for μm- and nm-sized colloids as well as DNA origamis. However, little is known about the polarizability of origami species, which is responsible for their dielectrophoretic migration. Here, we report the experimentally determined polarizabilities of the six-helix bundle origami (6HxB) and triangle origami by measuring the migration times through a potential landscape exhibiting dielectrophoretic barriers. The resulting migration times correlate to the depth of the dielectrophoretic potential barrier and the escape characteristics of the origami according to an adapted Kramer's rate model, allowing their polarizabilities to be determined. We found that the 6HxB polarizability is larger than that of the triangle origami, which correlates with the variations in charge density of both origamis. Further, we discuss the orientation of both origami species in the dielectrophoretic trap and discuss the influence of diffusion during the escape process. Our study provides detailed insight into the factors contributing to the migration through dielectrophoretic potential landscapes, which can be exploited for applications with DNA and other nanoassemblies based on dielectrophoresis.

  16. Supramolecular salts of 5,7-dimethyl-1,8-naphthyridine-2-amine and acids through classical H-Bonds and other intermolecular interactions

    Science.gov (United States)

    Dong, Lingfeng; Jin, Shouwen; Jin, Shide; Gao, Xingjun; Xie, Xinxin; Lin, Zhihao; Wang, Yining; Xu, Weiqiang; Wang, Daqi

    2018-02-01

    This article demonstrates 5,7-dimethyl-1,8-naphthyridine-2-amine based organic salts formation of crystalline solids 1-9, in which the acidic units have been integrated via a variety of non-covalent bonds. Addition of equivalents of the acidic units to the solution of 5,7-dimethyl-1,8-naphthyridine-2-amine generates the single protonated species which direct the anions. The nine compounds crystallize as their salts with the acidic H transferred to the aromatic N of the 5,7-dimethyl-1,8-naphthyridine-2-amine. In 2, 3, 4, and 7 the methyl substituted N-rings were protonated, while others were protonated at the NH2 substituted N-ring. All salts have been characterized via IR, mp, EA and XRD technique. The major driving force for the salt formation is attributed to the classical H-bonds from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids. Other extensive intermolecular interactions also play great functions in space association of the molecular assemblies in the relevant crystals. The common R22(8) graph set has been observed in all salts due to the H-bonds and other intermolecular interactions, except 2, 4, and 6. For the synergistic interactions of the various non-covalent bonds, all salts displayed 3D structures.

  17. Nuclear dipole polarizability from mean-field modeling constrained by chiral effective field theory

    Science.gov (United States)

    Zhang, Zhen; Lim, Yeunhwan; Holt, Jeremy W.; Ko, Che Ming

    2018-02-01

    We construct a new Skyrme interaction Skχm* by fitting the equation of state and nucleon effective masses in asymmetric nuclear matter from chiral two- and three-body forces as well as the binding energies of finite nuclei. Employing this interaction to study the electric dipole polarizabilities of 48Ca, 68Ni, 120Sn, and 208Pb in the random-phase approximation, we find that the theoretical predictions are in good agreement with experimentally measured values without additional fine tuning of the Skyrme interaction, thus confirming the usefulness of the new Skyrme interaction in studying the properties of nuclei. We further use this interaction to study the neutron skin thicknesses of 48Ca and 208Pb, and they are found to be consistent with the experimental data.

  18. Basis set convergence on static electric dipole polarizability calculations of alkali-metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Fabio A. L. de; Jorge, Francisco E., E-mail: jorge@cce.ufes.br [Departamento de Fisica, Universidade Federal do Espirito Santo, 29060-900 Vitoria-ES (Brazil)

    2013-07-15

    A hierarchical sequence of all-electron segmented contracted basis sets of double, triple and quadruple zeta valence qualities plus polarization functions augmented with diffuse functions for the atoms from H to Ar was constructed. A systematic study of basis sets required to obtain reliable and accurate values of static dipole polarizabilities of lithium and sodium clusters (n = 2, 4, 6 and 8) at their optimized equilibrium geometries is reported. Three methods are examined: Hartree-Fock (HF), second-order Moeller-Plesset perturbation theory (MP2), and density functional theory (DFT). By direct calculations or by fitting the directly calculated values through one extrapolation scheme, estimates of the HF, MP2 and DFT complete basis set limits were obtained. Comparison with experimental and theoretical data reported previously in the literature is done (author)

  19. New predictions for generalized spin polarizabilities from heavy baryon chiral perturbation theory

    International Nuclear Information System (INIS)

    Chung-Wen Kao; Barbara Pasquini; Marc Vanderhaeghen

    2004-01-01

    We extract the next-to-next-to-leading order results for spin-flip generalized polarizabilities (GPs) of the nucleon from the spin-dependent amplitudes for virtual Compton scattering (VCS) at Ο(p 4 ) in heavy baryon chiral perturbation theory. At this order, no unknown low energy constants enter the theory, allowing us to make absolute predictions for all spin-flip GPs. Furthermore, by using constraint equations between the GPs due to nucleon crossing combined with charge conjugation symmetry of the VCS amplitudes, we get a next-to-next-to-next-to-leading order prediction for one of the GPs. We provide estimates for forthcoming double polarization experiments which allow to access these spin-flip GPs of the nucleon

  20. The Second-Order Polarization Propagator Approximation (SOPPA) method coupled to the polarizable continuum model

    DEFF Research Database (Denmark)

    Eriksen, Janus Juul; Solanko, Lukasz Michal; Nåbo, Lina J.

    2014-01-01

    We present an implementation of the Polarizable Continuum Model (PCM) in combination with the Second–Order Polarization Propagator Approximation (SOPPA) electronic structure method. In analogy with the most common way of designing ground state calculations based on a Second–Order Møller-Plesset (MP......2) wave function coupled to PCM, we introduce dynamical PCM solvent effects only in the Random Phase Approximation (RPA) part of the SOPPA response equations while the static solvent contribution is kept in both the RPA terms as well as in the higher order correlation matrix components of the SOPPA...... response equations. By dynamic terms, we refer to contributions that describe a change in environmental polarization which, in turn, reflects a change in the core molecular charge distribution upon an electronic excitation. This new combination of methods is termed PCM-SOPPA/RPA. We apply this newly...

  1. The Electromagnetic Zero-Point Field and the Flat Polarizable Vacuum Representation

    CERN Document Server

    Desiato, J T

    2003-01-01

    There are several interpretations of the Polarizable Vacuum (PV). One is the variable speed of light (VSL) approach, that has been shown to be isomorphic to General Relativity (GR) within experimental limits. However, another interpretation is representative of flat geometry, in which intervals of time and distance are measured in local inertial reference frames where the speed of light remains constant. The Flat PV approach leads to variable impedance transformations, governed by the spectral energy content of the Quantum Vacuum’s Electromagnetic (EM) Zero-Point Field (ZPF). The EM ZPF consists of photons. An unlimited number of photons may occupy the same quantum state at an arbitrary set of coordinates. Therefore, the spectral energy of the ZPF may be varied smoothly, represented by a superposition of EM waves with a large number of photons per cubic wavelength. Utilizing the Flat PV representation, a family of frequency dependent solutions of Poisson’s equation are derived, that may be applied as tool...

  2. Dispersion-corrected energy decomposition analysis for intermolecular interactions based on the BLW and dDXDM methods.

    Science.gov (United States)

    Steinmann, Stephan N; Corminboeuf, Clemence; Wu, Wei; Mo, Yirong

    2011-06-02

    As the simplest variant of the valence bond (VB) theory, the block-localized wave function (BLW) method defines the intermediate electron-localized state self-consistently at the DFT level and can be used to explore the nature of intermolecular interactions in terms of several physically intuitive energy components. Yet, it is unclear how the dispersion interaction affects such a kind of energy decomposition analysis (EDA) as standard density functional approximations neglect the long-range dispersion attractive interactions. Three electron densities corresponding to the initial electron-localized state, optimal electron-localized state, and final electron-delocalized state are involved in the BLW-ED approach; a density-dependent dispersion correction, such as the recently proposed dDXDM approach, can thus uniquely probe the impact of the long-range dispersion effect on EDA results computed at the DFT level. In this paper, we incorporate the dDXDM dispersion corrections into the BLW-ED approach and investigate a range of representative systems such as hydrogen-bonding systems, acid-base pairs, and van der Waals complexes. Results show that both the polarization and charge-transfer energies are little affected by the inclusion of the long-range dispersion effect, which thus can be regarded as an independent energy component in EDA. © 2011 American Chemical Society

  3. Polarizable water model for the coarse-grained MARTINI force field.

    Directory of Open Access Journals (Sweden)

    Semen O Yesylevskyy

    2010-06-01

    Full Text Available Coarse-grained (CG simulations have become an essential tool to study a large variety of biomolecular processes, exploring temporal and spatial scales inaccessible to traditional models of atomistic resolution. One of the major simplifications of CG models is the representation of the solvent, which is either implicit or modeled explicitly as a van der Waals particle. The effect of polarization, and thus a proper screening of interactions depending on the local environment, is absent. Given the important role of water as a ubiquitous solvent in biological systems, its treatment is crucial to the properties derived from simulation studies. Here, we parameterize a polarizable coarse-grained water model to be used in combination with the CG MARTINI force field. Using a three-bead model to represent four water molecules, we show that the orientational polarizability of real water can be effectively accounted for. This has the consequence that the dielectric screening of bulk water is reproduced. At the same time, we parameterized our new water model such that bulk water density and oil/water partitioning data remain at the same level of accuracy as for the standard MARTINI force field. We apply the new model to two cases for which current CG force fields are inadequate. First, we address the transport of ions across a lipid membrane. The computed potential of mean force shows that the ions now naturally feel the change in dielectric medium when moving from the high dielectric aqueous phase toward the low dielectric membrane interior. In the second application we consider the electroporation process of both an oil slab and a lipid bilayer. The electrostatic field drives the formation of water filled pores in both cases, following a similar mechanism as seen with atomistically detailed models.

  4. A polarizable QM/MM approach to the molecular dynamics of amide groups solvated in water

    Energy Technology Data Exchange (ETDEWEB)

    Schwörer, Magnus; Wichmann, Christoph; Tavan, Paul, E-mail: tavan@physik.uni-muenchen.de [Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians Universität München, Oettingenstr. 67, 80538 München (Germany)

    2016-03-21

    The infrared (IR) spectra of polypeptides are dominated by the so-called amide bands. Because they originate from the strongly polar and polarizable amide groups (AGs) making up the backbone, their spectral positions sensitively depend on the local electric fields. Aiming at accurate computations of these IR spectra by molecular dynamics (MD) simulations, which derive atomic forces from a hybrid quantum and molecular mechanics (QM/MM) Hamiltonian, here we consider the effects of solvation in bulk liquid water on the amide bands of the AG model compound N-methyl-acetamide (NMA). As QM approach to NMA we choose grid-based density functional theory (DFT). For the surrounding MM water, we develop, largely based on computations, a polarizable molecular mechanics (PMM) model potential called GP6P, which features six Gaussian electrostatic sources (one induced dipole, five static partial charge distributions) and, therefore, avoids spurious distortions of the DFT electron density in hybrid DFT/PMM simulations. Bulk liquid GP6P is shown to have favorable properties at the thermodynamic conditions of the parameterization and beyond. Lennard-Jones (LJ) parameters of the DFT fragment NMA are optimized by comparing radial distribution functions in the surrounding GP6P liquid with reference data obtained from a “first-principles” DFT-MD simulation. Finally, IR spectra of NMA in GP6P water are calculated from extended DFT/PMM-MD trajectories, in which the NMA is treated by three different DFT functionals (BP, BLYP, B3LYP). Method-specific frequency scaling factors are derived from DFT-MD simulations of isolated NMA. The DFT/PMM-MD simulations with GP6P and with the optimized LJ parameters then excellently predict the effects of aqueous solvation and deuteration observed in the IR spectra of NMA. As a result, the methods required to accurately compute such spectra by DFT/PMM-MD also for larger peptides in aqueous solution are now at hand.

  5. A polarizable QM/MM approach to the molecular dynamics of amide groups solvated in water.

    Science.gov (United States)

    Schwörer, Magnus; Wichmann, Christoph; Tavan, Paul

    2016-03-21

    The infrared (IR) spectra of polypeptides are dominated by the so-called amide bands. Because they originate from the strongly polar and polarizable amide groups (AGs) making up the backbone, their spectral positions sensitively depend on the local electric fields. Aiming at accurate computations of these IR spectra by molecular dynamics (MD) simulations, which derive atomic forces from a hybrid quantum and molecular mechanics (QM/MM) Hamiltonian, here we consider the effects of solvation in bulk liquid water on the amide bands of the AG model compound N-methyl-acetamide (NMA). As QM approach to NMA we choose grid-based density functional theory (DFT). For the surrounding MM water, we develop, largely based on computations, a polarizable molecular mechanics (PMM) model potential called GP6P, which features six Gaussian electrostatic sources (one induced dipole, five static partial charge distributions) and, therefore, avoids spurious distortions of the DFT electron density in hybrid DFT/PMM simulations. Bulk liquid GP6P is shown to have favorable properties at the thermodynamic conditions of the parameterization and beyond. Lennard-Jones (LJ) parameters of the DFT fragment NMA are optimized by comparing radial distribution functions in the surrounding GP6P liquid with reference data obtained from a "first-principles" DFT-MD simulation. Finally, IR spectra of NMA in GP6P water are calculated from extended DFT/PMM-MD trajectories, in which the NMA is treated by three different DFT functionals (BP, BLYP, B3LYP). Method-specific frequency scaling factors are derived from DFT-MD simulations of isolated NMA. The DFT/PMM-MD simulations with GP6P and with the optimized LJ parameters then excellently predict the effects of aqueous solvation and deuteration observed in the IR spectra of NMA. As a result, the methods required to accurately compute such spectra by DFT/PMM-MD also for larger peptides in aqueous solution are now at hand.

  6. Intra- und intermolecular hydrogen bonds. Spectroscopic, quantum chemical and molecular dynamics studies

    International Nuclear Information System (INIS)

    Simperler, A.

    1999-03-01

    Intra- and intermolecular H-bonds have been investigated with spectroscopic, quantum chemical, and molecular dynamics methods. The work is divided into the following three parts: 1. Intramolecular interactions in ortho-substituted phenols. Theoretical and experimental data that characterizes the intramolecular hydrogen bonds in 48 different o-substituted phenols are discussed. The study covers various kinds of O-H ... Y -type interactions (Y= N, O, S, F, Cl, Br, I, C=C, C=-C, and C-=N). The bond strength sequences for several series of systematically related compounds as obtained from IR spectroscopy data (i.e., v(OH) stretching frequencies) are discussed and reproduced with several theoretical methods (B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3LYP/6-31++G(d,p), B3LYP/DZVP, MP2/6-31G(d,p), and MP2/6-31++G(d,p) levels of theory). The experimentally determined sequences are interpreted in terms of the intrinsic properties of the molecules: hydrogen bond distances, Mulliken partial charges, van der Waals radii, and electron densities of the Y-proton acceptors. 2. Competitive hydrogen bonds and conformational equilibria in 2,6-disubstituted phenols containing two different carbonyl substituents. The rotational isomers of ten unsymmetrical 2,6-disubstituted phenols as obtained by combinations of five different carbonyl substituents (COOH, COOCH 3 , CHO, COCH 3 , and CONH 2 ) have been theoretically investigated at the B3LYP/6-31G(d,p) level of theory. The relative stability of four to five conformers of each compound were determined by full geometry optimization for free molecules as well as for molecules in reaction fields with dielectric constants up to ε=37.5. A comparison with IR spectroscopic data of available compounds revealed excellent agreement with the theoretically predicted stability sequences and conformational equilibria. The stability of a conformer could be interpreted to be governed by the following two contributions: (i) an attractive hydrogen bond

  7. Polarizable molecular mechanics studies of Cu(I)/Zn(II) superoxide dismutase: bimetallic binding site and structured waters.

    Science.gov (United States)

    Gresh, Nohad; El Hage, Krystel; Perahia, David; Piquemal, Jean-Philip; Berthomieu, Catherine; Berthomieu, Dorothée

    2014-11-05

    The existence of a network of structured waters in the vicinity of the bimetallic site of Cu/Zn-superoxide dismutase (SOD) has been inferred from high-resolution X-ray crystallography. Long-duration molecular dynamics (MD) simulations could enable to quantify the lifetimes and possible interchanges of these waters between themselves as well as with a ligand diffusing toward the bimetallic site. The presence of several charged or polar ligands makes it necessary to resort to second-generation polarizable potentials. As a first step toward such simulations, we benchmark in this article the accuracy of one such potential, sum of interactions between fragments Ab initio computed (SIBFA), by comparisons with quantum mechanics (QM) computations. We first consider the bimetallic binding site of a Cu/Zn-SOD, in which three histidines and a water molecule are bound to Cu(I) and three histidines and one aspartate are bound to Zn(II). The comparisons are made for different His6 complexes with either one or both cations, and either with or without Asp and water. The total net charges vary from zero to three. We subsequently perform preliminary short-duration MD simulations of 296 waters solvating Cu/Zn-SOD. Six representative geometries are selected and energy-minimized. Single-point SIBFA and QM computations are then performed in parallel on model binding sites extracted from these six structures, each of which totals 301 atoms including the closest 28 waters from the Cu metal site. The ranking of their relative stabilities as given by SIBFA is identical to the QM one, and the relative energy differences by both approaches are fully consistent. In addition, the lowest-energy structure, from SIBFA and QM, has a close overlap with the crystallographic one. The SIBFA calculations enable to quantify the impact of polarization and charge transfer in the ranking of the six structures. Five structural waters, which connect Arg141 and Glu131, are endowed with very high dipole moments

  8. Structural study of Na2O-B2O3-SiO2 glasses from molecular simulations using a polarizable force field

    Science.gov (United States)

    Pacaud, Fabien; Delaye, Jean-Marc; Charpentier, Thibault; Cormier, Laurent; Salanne, Mathieu

    2017-10-01

    Sodium borosilicate glasses Na2O-B2O3-SiO2 (NBS) are complex systems from a structural point of view. Three main building units are present: tetrahedral SiO4 and BO4 (BIV) and triangular BO3 (BIII). One of the salient features of these compounds is the change of the BIII/BIV ratio with the alkali concentration, which is very difficult to capture in force fields-based molecular dynamics simulations. In this work, we develop a polarizable force field that is able to reproduce the boron coordination and more generally the structure of several NBS systems in the glass and in the melt. The parameters of the potential are fitted from density functional theory calculations only, in contrast with the existing empirical potentials for NBS systems. This ensures a strong improvement on the transferability of the parameters from one composition to another. Using this new force field, the structure of NBS systems is validated against neutron diffraction and nuclear magnetic resonance experiments. A special focus is given to the distribution of BIII/BIV with respect to the composition and the temperature.

  9. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    Science.gov (United States)

    Chavda, Bhavin R.; Gandhi, Sahaj A.; Dubey, Rahul P.; Patel, Urmila H.; Barot, Vijay M.

    2016-05-01

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb -London -Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  10. 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 8 days 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 8 days, the proportion of ionic bonds sharply decreased, and that of disulfide bonds increased over the first 24 days. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

    Science.gov (United States)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

    Benzene carboxylic acids and benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by 1H, 13C and 15N NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations.

  12. Greenhouse effect in planetary atmospheres caused by molecular symmetry breaking in intermolecular interactions

    Science.gov (United States)

    Vigasin, A. A.; Mokhov, I. I.

    2017-03-01

    It is believed that the greenhouse effect is related to the parameters of absorption spectra of polyatomic molecules, usually trace gases, in planetary atmospheres. The main components of all known atmospheres of celestial bodies are symmetrical molecules that do not possess the dipole-allowed purely rotational (and in the case of diatomic molecules, vibrational-rotational) absorption spectrum. Upon increased pressure, a weak absorption appears, induced by intermolecular interaction, which can lead to a greenhouse effect. The contribution of the induced absorption in radiative forcing of a dense atmosphere may amount to a few or even tens of W/m2. In conditions typical for the atmospheres of terrestrial planets (including paleoatmospheres), the collision-induced absorption and associated greenhouse effect may lead to an increase in surface temperature above the freezing point of water. There is a correlation between the temperature of an atmosphere and the intermolecular bonding energy of gases that dominate in planetary atmospheres of the Solar System.

  13. Rotational Energy Transfer in N2

    Science.gov (United States)

    Huo, Winifred M.

    1994-01-01

    Using the N2-N2 intermolecular potential of van der Avoird et al. rotational energy transfer cross sections have been calculated using both the coupled state (CS) and infinite order sudden (IOS) approximations. The rotational energy transfer rate constants at 300 K, calculated in the CS approximation, are in reasonable agreement with the measurements of Sitz and Farrow. The IOS approximation qualitatively reproduces the dependence of the rate constants on the rotational quantum numbers, but consistently overestimates their magnitudes. The treatment of exchange symmetry will be discussed.

  14. Copper-catalyzed intermolecular trifluoromethylazidation of alkenes: convenient access to CF3 -containing alkyl azides.

    Science.gov (United States)

    Wang, Fei; Qi, Xiaoxu; Liang, Zhaoli; Chen, Pinhong; Liu, Guosheng

    2014-02-10

    A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3 -containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3 -containing amine derivatives. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 1H NMR study on the intermolecular interactions of macrocyclic and single α-amino acids

    Science.gov (United States)

    Quevedo, Rodolfo; Pabón, Laura; Quevedo-Acosta, Yovanny

    2013-06-01

    Through analysis of 1H NMR spectra, evidence was found for intermolecular interactions between macrocyclic amino acid derivatives from L-tyrosine and their importance in the formation of aggregates in solution. It was also shown that both macrocyclic and simple amino acids are capable of retaining alcohol molecules through hydrogen bonding, where the alcohol molecule acts as a proton donor and the amino group acts as an acceptor.

  16. Branched-Selective Intermolecular Ketone α-Alkylation with Unactivated Alkenes via an Enamide Directing Strategy.

    Science.gov (United States)

    Xing, Dong; Dong, Guangbin

    2017-10-04

    We describe a strategy for intermolecular branched-selective α-alkylation of ketones using simple alkenes as the alkylating agents. Enamides derived from isoindolin-1-one provide an excellent directing template for catalytic activation of ketone α-positions. High branched selectivity is obtained for both aliphatic and aromatic alkenes using a cationic iridium catalyst. Preliminary mechanistic study favors an Ir-C migratory insertion pathway.

  17. Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining

    Science.gov (United States)

    Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L.; Tomkinson, Alan E.; Tainer, John A.; Ellenberger, Tom

    2015-01-01

    Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. PMID:26130724

  18. VSCF calculations for the intra- and intermolecular vibrational modes of the water dimer and its isotopologs

    Energy Technology Data Exchange (ETDEWEB)

    Monteiro, João G.S.; Barbosa, André G.H., E-mail: andre@vm.uff.br

    2016-11-10

    In this work we show how the VSCF method may be successfully used to describe all fundamental vibrational transitions of several isotopologs of water dimer. By expressing the normal mode displacements in terms of appropriate delocalized internal coordinates we are able to minimize the mode-mode coupling in the PES and thus yield PT2-VSCF frequencies in good agreement with the experiment. The use of curvilinear normal modes is of paramount importance to describe vibrational transitions of the very soft intermolecular modes. Within our approach the maximum calculated error for the (H{sub 2}O){sub 2} intermolecular frequencies are reduced from 311 cm{sup −1} (Cartesian normal modes) to just 56 cm{sup −1} (curvilinear normal modes). Plots of the diagonal intermolecular potential and of the vibrational wave function illustrate the remarkable effect of different coordinate systems. In conclusion, our PT2-VSCF calculations provide a fair anharmonic description of the fundamental transitions of water dimers.

  19. Behavior of intermolecular interactions in α-glycine under high pressure

    Science.gov (United States)

    Shinozaki, Ayako; Komatsu, Kazuki; Kagi, Hiroyuki; Fujimoto, Chikako; Machida, Shinichi; Sano-Furukawa, Asami; Hattori, Takanori

    2018-01-01

    Pressure-response on the crystal structure of deuterated α-glycine was investigated at room temperature, using powder and single-crystal X-ray diffraction, and powder neutron diffraction measurements under high pressure. No phase change was observed up to 8.7 GPa, although anisotropy of the lattice compressibility was found. No significant changes in the compressibility and the intramolecular distance between non-deuterated α-glycine and deuterated α-glycine were observed. Neutron diffraction measurements indicated the distance of the intermolecular D⋯O bond along with the c-axis increased with compression up to 6.4 GPa. The distance of another D⋯O bond along with the a-axis decreased with increasing pressure and became the shortest intermolecular hydrogen bond above 3 GPa. In contrast, the lengths of the bifurcated N-D⋯O and C-D⋯O hydrogen bonds, which are formed between the layers of the α-glycine molecules along the b-axis, decreased significantly with increasing pressure. The decrease of the intermolecular distances resulted in the largest compressibility of the b-axis, compared to the other two axes. The Hirshfeld analysis suggested that the reduction of the void region size, rather than shrinkage of the strong N-D⋯O hydrogen bonds, occurred with compression.

  20. Influence of self-consistent screening and polarizability contractions on interlayer sliding behavior of hexagonal boron nitride

    Science.gov (United States)

    Gong, Wenbin; Zhang, Wei; Wang, Chengbin; Yao, Yagang; Lu, Weibang

    2017-11-01

    The interlayer sliding behaviors of hexagonal boron nitride (h -BN) were investigated via a density functional theory approach with dispersion interaction included. It was found that the self-consistent screening effect (SCS) and the polarizability contractions had significant influences on London dispersion forces, which are responsible for not only the stacking modes but also for the sliding behaviors of h -BN. In consideration of the ionic characteristics of h -BN, surprisingly, the calculated dispersion force was found to dominate the electrostatic interaction along a minimum-energy sliding pathway and make a pronounced contribution (˜35 %) to the barrier during the constrained sliding. This study demonstrates that the SCS and polarizability contractions play important roles in the sliding behaviors of h -BN and that the long-range dispersion interaction should be carefully treated, even in systems with ionic characteristics.

  1. 4fn-15d centroid shift in lanthanides and relation with anion polarizability, covalency, and cation electronegativity

    International Nuclear Information System (INIS)

    Dorenbos, P.; Andriessen, J.; Eijk, C.W.E. van

    2003-01-01

    Data collected on the centroid shift of the 5d-configuration of Ce 3+ in oxide and fluoride compounds were recently analyzed with a model involving the correlated motion between 5d-electron and ligand electrons. The correlation effects are proportional to the polarizability of the anion ligands and it leads, like covalency, to lowering of the 5d-orbital energies. By means of ab initio Hartree-Fock-LCAO calculations including configuration interaction the contribution from covalency and correlated motion to the centroid shift are determined separately for Ce 3+ in various compounds. It will be shown that in fluoride compounds, covalency provides an insignificant contribution. In oxides, polarizability appears to be of comparable importance as covalency

  2. Electric birefringence and streaming-electric birefringence of synthesized imogolite: the anisotropy of electric polarizability.

    Science.gov (United States)

    Matsumoto, Mitsuhiro; Koibuchi, Sae; Hayashi, Naoki

    2007-04-15

    Imogolite synthesized from sodium orthosilicate and aluminum trichloride was fractionated into four fractions by centrifuging at 12,000 x g (1h). The supernatant, which did not deposit by three times centrifugations, was used for all measurements. The signal of birefringence under a reversing electric pulse showed that the permanent dipole moment is negligibly small at low fields. The electric birefringence under a rectangular electric pulse is positive. The saturated value is proportional to the concentration of imogolite in the range of 0-0.1mg/ml and decreases rapidly with an increase of added salt concentration for NaCl and AgNO(3). It slightly depends on the pH of solution and is biggest in pure water. Then we have determined the anisotropy of electric polarizability (Deltaalpha) for imogolite in pure water at 0.05 mg/ml. Deltaalpha we obtained from the method decreases rapidly at low fields and slowly at high fields as shown in references [M. Matsumoto, Colloids Surf. A 148 (1999) 75, M. Matsumoto, Biophys. Chem. 58 (1996) 173]. It is approximately shown by the following expression, Deltaalpha=Deltaalpha(infinity)+(Deltaalpha(0)-Deltaalpha(infinity))/(1+KE), (Deltaalpha(0):Deltaalpha at E=0, Deltaalpha(infinity):Deltaalpha at E=infinity). Using this relation we can draw the curve of electric birefringence as a function of electric field and compare it with experimental values. The results, when Deltaalpha(0)=1.17x10(-28)Fm(2), Deltaalpha(infinity)=0.005x10(-28)Fm(2) and K=0.00031 m/V, are in good agreement with each other. In order to explain the reason why the anisotropy of electric polarizability rapidly decreases with an increase of electric field we propose that the difference of electrophoretic mobility between parts of colloidal particle causes the orientation of a rod like particle. The theoretical electric birefringence as a function of electric field we obtained is considerably in good agreement with the experimental values.

  3. Tunability of RF-Responses by Plasmonic Dielectric Amplification Using Branched e- -Polarizable C60-Adducts on Magnetic (Postprint)

    Science.gov (United States)

    2016-07-18

    energy can lead to the formation of polarizations at the surface region. Polarizability of this particular type of NPs, as a function of the size...Soumekh, M. Synthetic Aperture Radar Signal Processing with MATLAB Algorithms ; John Wiley & Sons: New York, 1999. (16) Kong, J. A. Electromagnetic Wave...FeOx NP core, was effectively released at the light-off stage to induce the intramolecular polarization of C60-DPAF adducts. Resulting charged

  4. Electric dipole strength and dipole polarizability in 48Ca within a fully self-consistent second random–phase approximation

    Directory of Open Access Journals (Sweden)

    D. Gambacurta

    2018-02-01

    Full Text Available The second random–phase–approximation model corrected by a subtraction procedure designed to cure double counting, instabilities, and ultraviolet divergences, is employed for the first time to analyze the dipole strength and polarizability in 48Ca. All the terms of the residual interaction are included, leading to a fully self-consistent scheme. Results are illustrated with two Skyrme parametrizations, SGII and SLy4. Those obtained with the SGII interaction are particularly satisfactory. In this case, the low-lying strength below the neutron threshold is well reproduced and the giant dipole resonance is described in a very satisfactory way especially in its spreading and fragmentation. Spreading and fragmentation are produced in a natural way within such a theoretical model by the coupling of 1 particle-1 hole and 2 particle-2 hole configurations. Owing to this feature, we may provide for the electric polarizability as a function of the excitation energy a curve with a similar slope around the centroid energy of the giant resonance compared to the corresponding experimental results. This represents a considerable improvement with respect to previous theoretical predictions obtained with the random–phase approximation or with several ab-initio models. In such cases, the spreading width of the excitation cannot be reproduced and the polarizability as a function of the excitation energy displays a stiff increase around the predicted centroid energy of the giant resonance.

  5. Dipole polarizability of alkali-metal (Na, K, Rb)-alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Science.gov (United States)

    Gopakumar, Geetha; Abe, Minori; Hada, Masahiko; Kajita, Masatoshi

    2014-06-01

    Electronic open-shell ground-state properties of selected alkali-metal-alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the 2Σ+ ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes (23Na, 39K, 85Rb)-(40Ca, 88Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  6. Electric dipole strength and dipole polarizability in 48Ca within a fully self-consistent second random-phase approximation

    Science.gov (United States)

    Gambacurta, D.; Grasso, M.; Vasseur, O.

    2018-02-01

    The second random-phase-approximation model corrected by a subtraction procedure designed to cure double counting, instabilities, and ultraviolet divergences, is employed for the first time to analyze the dipole strength and polarizability in 48Ca. All the terms of the residual interaction are included, leading to a fully self-consistent scheme. Results are illustrated with two Skyrme parametrizations, SGII and SLy4. Those obtained with the SGII interaction are particularly satisfactory. In this case, the low-lying strength below the neutron threshold is well reproduced and the giant dipole resonance is described in a very satisfactory way especially in its spreading and fragmentation. Spreading and fragmentation are produced in a natural way within such a theoretical model by the coupling of 1 particle-1 hole and 2 particle-2 hole configurations. Owing to this feature, we may provide for the electric polarizability as a function of the excitation energy a curve with a similar slope around the centroid energy of the giant resonance compared to the corresponding experimental results. This represents a considerable improvement with respect to previous theoretical predictions obtained with the random-phase approximation or with several ab-initio models. In such cases, the spreading width of the excitation cannot be reproduced and the polarizability as a function of the excitation energy displays a stiff increase around the predicted centroid energy of the giant resonance.

  7. The memory effect of a pentacene field-effect transistor with a polarizable gate dielectric

    Science.gov (United States)

    Unni, K. N. N.; de Bettignies, Remi; Dabos-Seignon, Sylvie; Nunzi, Jean-Michel

    2004-06-01

    The nonvolatile transistor memory element is an interesting topic in organic electronics. In this case a memory cell consists of only one device where the stored information is written as a gate insulator polarization by a gate voltage pulse and read by the channel conductance control with channel voltage pulse without destruction of the stored information. Therefore such transistor could be the base of non-volatile non-destructively readable computer memory of extremely high density. Also devices with polarizable gate dielectrics can function more effectively in certain circuits. The effective threshold voltage Vt can be brought very close to zero, for applications where the available gate voltage is limited. Resonant and adaptive circuits can be tuned insitu by polarizing the gates. Poly(vinylidene fluoride), PVDF and its copolymer with trifluoroethylene P(VDF-TrFE) are among the best known and most widely used ferroelectric polymers. In this manuscript, we report new results of an organic FET, fabricated with pentacene as the active material and P(VDF-TrFE) as the gate insulator. Application of a writing voltage of -50 V for short duration results in significant change in the threshold voltage and remarkable increase in the drain current. The memory effect is retained over a period of 20 hours.

  8. Tailored long range forces on polarizable particles by collective scattering of broadband radiation

    International Nuclear Information System (INIS)

    Holzmann, D; Ritsch, H

    2016-01-01

    Collective coherent light scattering by polarizable particles creates surprisingly strong, long range inter-particle forces originating from interference of the light scattered by different particles. While for monochromatic laser beams this interaction decays with the inverse distance, we show here that in general the effective interaction range and geometry can be controlled by the illumination bandwidth and geometry. As generic example we study the modifications inter-particle forces within a 1D chain of atoms trapped in the field of a confined optical nanofiber mode. For two particles we find short range attraction as well as optical binding at multiple distances. The range of stable distances shrinks with increasing light bandwidth and for a very large bandwidth field as e.g. blackbody radiation. We find a strongly attractive potential up to a critical distance beyond which the force gets repulsive. Including multiple scattering can even lead to the appearance of a stable configuration at a large distance. Such broadband scattering forces should be observable contributions in ultra-cold atom interferometers or atomic clocks setups. They could be studied in detail in 1D geometries with ultra-cold atoms trapped along or within an optical nanofiber. Broadband radiation force interactions might also contribute in astrophysical scenarios as illuminated cold dust clouds. (paper)

  9. Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

    International Nuclear Information System (INIS)

    Hedegård, Erik Donovan; Olsen, Jógvan Magnus Haugaard; Knecht, Stefan; Kongsted, Jacob; Jensen, Hans Jørgen Aagaard

    2015-01-01

    We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory, molecular properties such as excitation energies and oscillator strengths can be obtained. The PE-MC-srDFT method and the additional terms required for linear response have been implemented in a development version of DALTON. To benchmark the PE-MC-srDFT approach against the literature data, we have investigated the low-lying electronic excitations of acetone and uracil, both immersed in water solution. The PE-MC-srDFT results are consistent and accurate, both in terms of the calculated solvent shift and, unlike regular PE-MCSCF, also with respect to the individual absolute excitation energies. To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality to CASSCF/CASPT2 benchmarks

  10. Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

    Science.gov (United States)

    Hedegârd, Erik Donovan; Olsen, Jógvan Magnus Haugaard; Knecht, Stefan; Kongsted, Jacob; Jensen, Hans Jørgen Aagaard

    2015-03-01

    We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory, molecular properties such as excitation energies and oscillator strengths can be obtained. The PE-MC-srDFT method and the additional terms required for linear response have been implemented in a development version of Dalton. To benchmark the PE-MC-srDFT approach against the literature data, we have investigated the low-lying electronic excitations of acetone and uracil, both immersed in water solution. The PE-MC-srDFT results are consistent and accurate, both in terms of the calculated solvent shift and, unlike regular PE-MCSCF, also with respect to the individual absolute excitation energies. To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality to CASSCF/CASPT2 benchmarks.

  11. Exploration of dynamic dipole polarizability of impurity doped quantum dots in presence of noise

    Science.gov (United States)

    Ghosh, Anuja; Bera, Aindrila; Saha, Surajit; Arif, Sk. Md.; Ghosh, Manas

    2018-02-01

    Present study strives to perform a rigorous exploration of dynamic dipole polarizability (DDP) of GaAs quantum dot (QD) containing dopant with special reference to influence of Gaussian white noise. Several physical quantities have been varied over a range to observe the modulations of the DDP profiles. Aforesaid physical quantities include magnetic field, confinement potential, dopant location, dopant potential, noise strength, aluminium concentration (only for Alx Ga1 - x As alloy QD), position-dependent effective mass (PDEM), position-dependent dielectric screening function (PDDSF), anisotropy, hydrostatic pressure (HP) and temperature. The DDP profiles reveal noticeable characteristics governed by the particular physical quantity involved, presence/absence of noise, the manner (additive/multiplicative) noise is applied to the system and the incoming photon frequency. As a general observation we have found that additive noise causing greater deviation of the DDP profile from noise-free state than its multiplicative neighbor. The study highlights viable means of harnessing DDP of doped QD under the governance of noise by appropriate adjustment of several relevant factors. The study merits importance in the light of technological applications of QD-based devices where noise appears as an integral component.

  12. Two studies of colloidal interactions: electric polarizability and protein crystallization. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fraden, Seth; Hu, Yue

    2001-08-06

    (I)Electric polarizability. During this grant period, the focus was on five topics concerning electric field effects on colloids. The first topic focuses on electric interactions between charged colloids in the absence of external fields, and the remaining four deal with colloids in the presence of external fields. The topics are (1) calculation of the effect of confinement on the pair-potential between like-charged colloids, (2) experimental determination of the interparticle potential under the conditions of dielectric polarization, (3) measurement of the evolution of structure of ER fluids, (4) synthesis of novel colloids designed for ER studies, and (5) computer modeling of polarization of surface charge. (II) Protein crystallization. Studies of the phase behavior of mixtures of proteins and polymers were initiated. The motivation was to test recent theories that suggested that optimal conditions for protein crystallization could be obtained using such mixtures. Combined light scattering measurements of the virial coefficients and determination of the phase diagram of protein/polymer mixtures revealed that the theoretical picture needs to be substantially modified.

  13. Effect of dipole polarizability on positron binding by strongly polar molecules

    International Nuclear Information System (INIS)

    Gribakin, G F; Swann, A R

    2015-01-01

    A model for positron binding to polar molecules is considered by combining the dipole potential outside the molecule with a strongly repulsive core of a given radius. Using existing experimental data on binding energies leads to unphysically small core radii for all of the molecules studied. This suggests that electron–positron correlations neglected in the simple model play a large role in determining the binding energy. We account for these by including the polarization potential via perturbation theory and non-perturbatively. The perturbative model makes reliable predictions of binding energies for a range of polar organic molecules and hydrogen cyanide. The model also agrees with the linear dependence of the binding energies on the polarizability inferred from the experimental data (Danielson et al 2009 J. Phys. B: At. Mol. Opt. Phys. 42 235203). The effective core radii, however, remain unphysically small for most molecules. Treating molecular polarization non-perturbatively leads to physically meaningful core radii for all of the molecules studied and enables even more accurate predictions of binding energies to be made for nearly all of the molecules considered. (paper)

  14. The cavity electromagnetic field within the polarizable continuum model of solvation

    Energy Technology Data Exchange (ETDEWEB)

    Pipolo, Silvio, E-mail: silvio.pipolo@nano.cnr.it [Center S3, CNR Institute of Nanoscience, Modena (Italy); Department of Physics, University of Modena and Reggio Emilia, Modena (Italy); Corni, Stefano, E-mail: stefano.corni@nano.cnr.it [Center S3, CNR Institute of Nanoscience, Modena (Italy); Cammi, Roberto, E-mail: roberto.cammi@unipr.it [Department of Chemistry, Università degli studi di Parma, Parma (Italy)

    2014-04-28

    Cavity field effects can be defined as the consequences of the solvent polarization induced by the probing electromagnetic field upon spectroscopies of molecules in solution, and enter in the definitions of solute response properties. The polarizable continuum model of solvation (PCM) has been extended in the past years to address the cavity-field issue through the definition of an effective dipole moment that couples to the external electromagnetic field. We present here a rigorous derivation of such cavity-field treatment within the PCM starting from the general radiation-matter Hamiltonian within inhomogeneous dielectrics and recasting the interaction term to a dipolar form within the long wavelength approximation. To this aim we generalize the Göppert-Mayer and Power-Zienau-Woolley gauge transformations, usually applied in vacuo, to the case of a cavity vector potential. Our derivation also allows extending the cavity-field correction in the long-wavelength limit to the velocity gauge through the definition of an effective linear momentum operator. Furthermore, this work sets the basis for the general PCM treatment of the electromagnetic cavity field, capable to describe the radiation-matter interaction in dielectric media beyond the long-wavelength limit, providing also a tool to investigate spectroscopic properties of more complex systems such as molecules close to large nanoparticles.

  15. Electronic polarizability of light crude oil from optical and dielectric studies

    Science.gov (United States)

    George, A. K.; Singh, R. N.

    2017-07-01

    In the present paper we report the temperature dependence of density, refractive indices and dielectric constant of three samples of crude oils. The API gravity number estimated from the temperature dependent density studies revealed that the three samples fall in the category of light oil. The measured data of refractive index and the density are used to evaluate the polarizability of these fluids. Molar refractive index and the molar volume are evaluated through Lorentz-Lorenz equation. The function of the refractive index, FRI , divided by the mass density ρ, is a constant approximately equal to one-third and is invariant with temperature for all the samples. The measured values of the dielectric constant decrease linearly with increasing temperature for all the samples. The dielectric constant estimated from the refractive index measurements using Lorentz-Lorentz equation agrees well with the measured values. The results are promising since all the three measured properties complement each other and offer a simple and reliable method for estimating crude oil properties, in the absence of sufficient data.

  16. Physics-based scoring of protein-ligand interactions: explicit polarizability, quantum mechanics and free energies.

    Science.gov (United States)

    Bryce, Richard A

    2011-04-01

    The ability to accurately predict the interaction of a ligand with its receptor is a key limitation in computer-aided drug design approaches such as virtual screening and de novo design. In this article, we examine current strategies for a physics-based approach to scoring of protein-ligand affinity, as well as outlining recent developments in force fields and quantum chemical techniques. We also consider advances in the development and application of simulation-based free energy methods to study protein-ligand interactions. Fuelled by recent advances in computational algorithms and hardware, there is the opportunity for increased integration of physics-based scoring approaches at earlier stages in computationally guided drug discovery. Specifically, we envisage increased use of implicit solvent models and simulation-based scoring methods as tools for computing the affinities of large virtual ligand libraries. Approaches based on end point simulations and reference potentials allow the application of more advanced potential energy functions to prediction of protein-ligand binding affinities. Comprehensive evaluation of polarizable force fields and quantum mechanical (QM)/molecular mechanical and QM methods in scoring of protein-ligand interactions is required, particularly in their ability to address challenging targets such as metalloproteins and other proteins that make highly polar interactions. Finally, we anticipate increasingly quantitative free energy perturbation and thermodynamic integration methods that are practical for optimization of hits obtained from screened ligand libraries.

  17. Electrophoresis of a polarizable charged colloid with hydrophobic surface: A numerical study

    Science.gov (United States)

    Bhattacharyya, Somnath; Majee, Partha Sarathi

    2017-04-01

    We consider the electrophoresis of a charged colloid for a generalized situation in which the particle is considered to be polarizable and the surface exhibits hydrophobicity. The dielectric polarization of the particle creates a nonlinear dependence of the electrophoretic velocity on the applied electric field, and the core hydrophobicity amplifies the fluid convection in the Debye layer. Thus, a linear analysis is no longer applicable for this situation. The present analysis is based on the numerical solution of the nonlinear electrokinetic equations based on the Navier-Stokes-Nernst-Planck-Poisson equations coupled with the Laplace equation for the electric field within the dielectric particle. The hydrophobicity of the particle may influence its electric polarization by enhancing the convective transport of ions. The nonlinear effects, such as double-layer polarization and relaxation, are also influenced by the hydrophobicity of the particle surface. The present results compare well for a lower range of the applied electric field and surface charge density with the existing results for a perfectly dielectric particle with a hydrophobic surface based on the first-order perturbation analysis due to Khair and Squires [Phys. Fluids 21, 042001 (2009), 10.1063/1.3116664]. Dielectric polarization creates a reduction in particle electrophoretic velocity, and its impact is strong for a moderate range of Debye length. A quantitative measure of the nonlinear effects is demonstrated by comparing the electrophoretic velocity with an existing linear model.

  18. Using corresponding state theory to obtain intermolecular potentials to calculate pure liquid shock Hugoniots

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, M.L.

    1997-12-01

    Determination of product species, equations-of-state (EOS) and thermochemical properties of high explosives and pyrotechnics remains a major unsolved problem. Although, empirical EOS models may be calibrated to replicate detonation conditions within experimental variability (5--10%), different states, e.g. expansion, may produce significant discrepancy with data if the basic form of the EOS model is incorrect. A more physically realistic EOS model based on intermolecular potentials, such as the Jacobs Cowperthwaite Zwisler (JCZ3) EOS, is needed to predict detonation states as well as expanded states. Predictive capability for any EOS requires a large species data base composed of a wide variety of elements. Unfortunately, only 20 species have known JCZ3 molecular force constants. Of these 20 species, only 10 have been adequately compared to experimental data such as molecular scattering or shock Hugoniot data. Since data in the strongly repulsive region of the molecular potential is limited, alternative methods must be found to deduce force constants for a larger number of species. The objective of the present study is to determine JCZ3 product species force constants by using a corresponding states theory. Intermolecular potential parameters were obtained for a variety of gas species using a simple corresponding states technique with critical volume and critical temperature. A more complex, four parameter corresponding state method with shape and polarity corrections was also used to obtain intermolecular potential parameters. Both corresponding state methods were used to predict shock Hugoniot data obtained from pure liquids. The simple corresponding state method is shown to give adequate agreement with shock Hugoniot data.

  19. 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.

  20. Catalytic Asymmetric Synthesis of 8-Oxabicyclooctanes by Intermolecular [5+2] Pyrylium Cycloadditions**

    Science.gov (United States)

    Witten, Michael R.

    2014-01-01

    Highly enantioselective intermolecular [5+2] cycloadditions of pyrylium ion intermediates with electron-rich alkenes are promoted by a dual catalyst system composed of an achiral thiourea and a chiral primary aminothiourea. The observed enantioselectivity is highly dependent on the substitution pattern of the 5π component, and the basis for this effect is analyzed using experimental and computational evidence. The resultant 8-oxabicyclo[3.2.1]octane derivatives possess a scaffold common in natural products and medicinally active compounds and are also versatile chiral building blocks for further manipulations. Several stereoselective complexity-generating transformations of the 8-oxabicyclooctane products are presented. PMID:24782332

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

    DEFF Research Database (Denmark)

    Kristensen, Kasper; Ettenhuber, Patrick; Eriksen, Janus Juul

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

    DEFF Research Database (Denmark)

    Hanni, Matti; Lantto, Perttu; Ilias, Miroslav

    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...... in Xe gas. Our best results, obtained with the piecewise approximation for the binary chemical shift combined with the previously published state of the art theoretical potential energy curve for Xe2, are in excellent agreement with the experiment for the first time. © 2007 American Institute of Physics...

  3. Intermolecular interactions in binary system of 1-methylimidazole with methanol: A volumetric and theoretical investigation

    Science.gov (United States)

    Guo, Chang; Fang, Hui; Huang, Rong-Yi; Xu, Heng; Wu, Gen-Hua; Ye, Shi-Yong

    2013-11-01

    The Letter demonstrates an experimental and computational investigation of intermolecular interactions in binary system of 1-methylimidazole (MeIm) with methanol. The densities of binary system were measured at T = 288.15-323.15 K, and the values of excess molar volumes were obtained as a function of composition at each temperature. The experimental results indicate the formation of strong cross-associated complex in the binary system. Meanwhile, the nature of hydrogen bond of the associated complexes was explored based on theoretical calculations. In addition, the changes of thermodynamic properties from the monomers to cross-associated complex were also investigated.

  4. Intra- and inter-molecular energy transfer studies. Progress report, 1 June 1974--31 May 1975

    International Nuclear Information System (INIS)

    Nicol, M.F.

    1975-01-01

    The analysis of pressure-induced effects on the intersystem crossing in anthracene; determination of the influence of hydrogen-bonding on the intersystem crossing rate and phosphorescence of azines; experimental studies of the kinetics of high-pressure structural transitions in Teflon; testing of liquid helium temperature high-pressure optical cells; excimer production in compound crystalline aromatic hydrocarbons; and studies of the structure and chemistry of dianthracene at high pressures are described. (6 figs.) (GHT)

  5. Driving Unidirectional Molecular Rotary Motors with Visible Light by Intra- And Intermolecular Energy Transfer from Palladium Porphyrin

    NARCIS (Netherlands)

    Cnossen, Arjen; Hou, Lili; Pollard, Michael M.; Wesenhagen, Philana V.; Browne, Wesley R.; Feringa, Ben L.

    2012-01-01

    Driving molecular rotary motors using visible light (530-550 nm) instead of UV light was achieved using palladium tetraphenylporphyrin as a triplet sensitizer. Visible light driven rotation was confirmed by UV/vis absorption, circular dichroism and H-1 NMR spectroscopy and the rotation was confirmed

  6. Blackbody radiation shift, multipole polarizabilities, oscillator strengths, lifetimes, hyperfine constants, and excitation energies in Hg+

    International Nuclear Information System (INIS)

    Simmons, M.; Safronova, M. S.; Safronova, U. I.

    2011-01-01

    Excitation energies of the [Xe]4f 14 5d 10 ns, [Xe]4f 14 5d 10 np j , [Xe]4f 14 5d 10 nd j , [Xe]4f 14 5d 10 n ' f j , and [Xe]4f 14 5d 10 n ' g j states in Hg + are evaluated (n≤10, n ' ≤9, and [Xe]=1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 4d 10 5s 2 5p 6 ). First-, second-, third-, and all-order Coulomb energies and first- and second-order Coulomb-Breit energies are calculated. Reduced matrix elements, oscillator strengths, and transition rates are determined for electric-dipole transitions, including the ns (n=6-11), np (n=6-10), nd (n=6-10), nf (n=5-9), and ng (n=5-9) states. Lifetime values are determined for all above-mentioned states. The ground state E1, E2, and E3 polarizabilities are evaluated. The hyperfine structure in 199 Hg + and 201 Hg + ions is investigated. The hyperfine A and B values are determined for the first low-lying levels up to n = 7. The quadratic Stark effect on hyperfine structure levels of 199 Hg + and 201 Hg + ground states is investigated. The calculated shift for the 199 Hg + (F = 1, M = 0) ↔ (F = 0, M = 0) transition is -0.0597(2) Hz/(kV/cm) 2 , in agreement with previous theoretical result -0.060(3) Hz/(kV/cm) 2 . These calculations provide a theoretical benchmark for comparison with experiment and theory and provide values of blackbody radiation shifts for microwave frequency standards with 199 Hg + and 201 Hg + ions.

  7. Simulating the physicochemical properties of borosilicate and lanthanum borosilicate glasses using a polarizable force field

    International Nuclear Information System (INIS)

    Pacaud, Fabien

    2016-01-01

    as result of the nuclear waste vitrification, the knowledge and understanding of the dynamic and structural properties of glasses, including the behavior of radionuclides, is important (in liquid and solid phases). It can influence the glass waste properties, the lifetime of the vitrification process and the amount of radionuclides introduced in the glass matrix. Molecular dynamic simulations have been done to study the influence of the glass matrix composition into the structural and dynamic properties of the glass. a simplified glass, with 3 major oxides of the R7T7 glass such as SiO 2 , B 2 O 3 and Na 2 O, have been used to simulate the R7T7 industrial nuclear glass (a 30 oxides glass). The inclusion of La 2 O 3 allows us to simulate the impact of fission products and minor actinides into the properties of the glass matrix. Both systems, the SiO 2 -B 2 O 3 -Na 2 O and SiO 2 -B 2 O 3 -Na 2 O-La 2 O 3 , allow us to study the sodium and lanthanum effect on the properties of the glass. During this work, a polarizable force field has been developed to do these simulations. The results obtained at room temperature let us reproduce the experimental results of the structure, the distribution of BIII/BIV and the density. a study has been done on the viscosity and electrical conductivity of the liquid. The distribution BIV/BIII and the influence of the structural changes on the density along with the temperature have also been observed with thermal quenching. The current limits of this approach are also described. (author) [fr

  8. Binding Cellulose and Chitosan via Intermolecular Inclusion Interaction: Synthesis and Characterisation of Gel

    Directory of Open Access Journals (Sweden)

    Jiufang Duan

    2015-01-01

    Full Text Available A novel cellulose-chitosan gel was successfully prepared in three steps: (1 ferrocene- (Fc- cellulose with degrees of substitution (DS of 0.5 wt% was synthesised by ferrocenecarboxylic acid and cellulose within dimethylacetamide/lithium chloride (DMAc/LiCl; (2 the β-cyclodextrin (β-CD groups were introduced onto the chitosan chains by reacting chitosan with epichlorohydrin in dimethyl sulphoxide and a DS of 0.35 wt%; (3 thus, the cellulose-chitosan gel was obtained via an intermolecular inclusion interaction of Fc-cellulose and β-CD-chitosan in DMA/LiCl, that is, by an intermolecular inclusion interaction, between the Fc groups of cellulose and the β-CD groups on the chitosan backbone at room temperature. The successful synthesis of Fc-cellulose and β-CD-chitosan was characterised by 13C-NMR spectroscopy. The gel based on β-CD-chitosan and Fc-cellulose was formed under mild conditions which can engender autonomous healing between cut surfaces after 24 hours: the gel cannot self-heal while the cut surfaces were coated with a solution of a competitive guest (adamantane acid. The cellulose-chitosan complex made by this method underwent self-healing. Therefore, this study provided a novel method of expanding the application of chitosan by binding it with another polymer.

  9. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Chavda, Bhavin R., E-mail: chavdabhavin9@gmail.com; Dubey, Rahul P.; Patel, Urmila H. [Department of Physics, Sardar Patel University, Vallabh Vidyanagar-388120, Gujarat (India); Gandhi, Sahaj A. [Bhavan’s Shri I.L. Pandya Arts-Science and Smt. J.M. shah Commerce College, Dakar, Anand -388001, Gujarat, Indian (India); Barot, Vijay M. [P. G. Center in Chemistry, Smt. S. M. Panchal Science College, Talod, Gujarat 383 215 (India)

    2016-05-06

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb –London –Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  10. DFT-SAPT intermolecular interaction energies employing exact-exchange Kohn-Sham response methods.

    Science.gov (United States)

    Hesselmann, Andreas

    2018-03-22

    Intermolecular interaction energies have been calculated by symmetry-adapted perturbation theory based on density-functional theory monomer properties (DFT-SAPT) employing response functions from time-dependent exact-exchange (TDEXX) kernels. Combined with a new asymptotic correction scheme for the xc potentials of the monomers, it is shown that this DFT-SAPT[TDEXX] method delivers highly accurate intermolecular interaction energies for the S22, S66 and IonHB benchmark data bases by Hobza et al.. A corresponding DFT-SAPT approach employing the adiabatic TDEXX kernel in the response calculations has also been tested. While exhibiting a similar performance than DFT-SAPT[TDEXX] for dispersion-dominated dimer systems, it was found found that the accuracies of the interaction energies for hydrogen-bonded dimers deteriorate with this DFT-SAPT[ATDEXX] method. Compared to this, the DFT-SAPT[TDEXX] yields a balanced description of the interaction energies for various interaction-type motifs, similar to the standard DFT-SAPT method that utilises the ALDA xc kernel to compute the response functions.

  11. Noncovalent Intermolecular Interactions in Organic Electronic Materials: Implications for the Molecular Packing vs Electronic Properties of Acenes

    KAUST Repository

    Sutton, Christopher

    2015-10-30

    Noncovalent intermolecular interactions, which can be tuned through the toolbox of synthetic chemistry, determine not only the molecular packing but also the resulting electronic, optical, and mechanical properties of materials derived from π-conjugated molecules, oligomers, and polymers. Here, we provide an overview of the theoretical underpinnings of noncovalent intermolecular interactions and briefly discuss the computational chemistry approaches used to understand the magnitude of these interactions. These methodologies are then exploited to illustrate how noncovalent intermolecular interactions impact important electronic properties-such as the electronic coupling between adjacent molecules, a key parameter for charge-carrier transport-through a comparison between the prototype organic semiconductor pentacene with a series of N-substituted heteropentacenes. Incorporating an understanding of these interactions into the design of organic semiconductors can assist in developing novel materials systems from this fascinating molecular class. © 2015 American Chemical Society.

  12. Automated property optimization via ab initio O(N) elongation method: Application to (hyper-)polarizability in DNA

    International Nuclear Information System (INIS)

    Orimoto, Yuuichi; Aoki, Yuriko

    2016-01-01

    An automated property optimization method was developed based on the ab initio O(N) elongation (ELG) method and applied to the optimization of nonlinear optical (NLO) properties in DNA as a first test. The ELG method mimics a polymerization reaction on a computer, and the reaction terminal of a starting cluster is attacked by monomers sequentially to elongate the electronic structure of the system by solving in each step a limited space including the terminal (localized molecular orbitals at the terminal) and monomer. The ELG-finite field (ELG-FF) method for calculating (hyper-)polarizabilities was used as the engine program of the optimization method, and it was found to show linear scaling efficiency while maintaining high computational accuracy for a random sequenced DNA model. Furthermore, the self-consistent field convergence was significantly improved by using the ELG-FF method compared with a conventional method, and it can lead to more feasible NLO property values in the FF treatment. The automated optimization method successfully chose an appropriate base pair from four base pairs (A, T, G, and C) for each elongation step according to an evaluation function. From test optimizations for the first order hyper-polarizability (β) in DNA, a substantial difference was observed depending on optimization conditions between “choose-maximum” (choose a base pair giving the maximum β for each step) and “choose-minimum” (choose a base pair giving the minimum β). In contrast, there was an ambiguous difference between these conditions for optimizing the second order hyper-polarizability (γ) because of the small absolute value of γ and the limitation of numerical differential calculations in the FF method. It can be concluded that the ab initio level property optimization method introduced here can be an effective step towards an advanced computer aided material design method as long as the numerical limitation of the FF method is taken into account.

  13. Natural Fe{sub 3}O{sub 4} nanoparticles embedded zinc–tellurite glasses: Polarizability and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Widanarto, W. [Physics Study Program, Jenderal Soedirman University, Jl. Dr. Soeparno 61, Purwokerto 53123 (Indonesia); Sahar, M.R., E-mail: rahimsahar@utm.my [Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, Johor Bahru, Skudai 81310 (Malaysia); Ghoshal, S.K.; Arifin, R.; Rohani, M.S.; Hamzah, K. [Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, Johor Bahru, Skudai 81310 (Malaysia); Jandra, M. [FTI, University Teknologi Malaysia, Johor Bahru, Skudai 81310 (Malaysia)

    2013-02-15

    Modifying the optical behavior of zinc–tellurite glass by embedding magnetic nanoparticles has implication in nanophotonics. A series of zinc–tellurite glasses containing natural Fe{sub 3}O{sub 4} nanoparticles with composition (80 − x)TeO{sub 2}·xFe{sub 3}O{sub 4}·20ZnO (0 ≤ x ≤ 2) in mol% are synthesized by melt quenching method and their optical properties are investigated using FTIR and UV–vis–NIR spectroscopies. Lorentz–Lorenz relations are exploited to determine the refractive index, molar refraction and electronic polarizability. The sharp absorption peaks of FTIR spectra show a shift from 667 cm{sup −1} to 671 cm{sup −1} in the presence of nanoparticles that increase the non-bridging oxygen, confirmed by the intensity change of the TeO{sub 3} peak at 752 cm{sup −1}. A new peak around 461 cm{sup −1} is also observed which is attributed to the band characteristic of covalent Fe–O linkages. A decrease in the Urbach energy as much as 0.122 eV and the optical energy band gap with the increase of Fe{sub 3}O{sub 4} concentration (0.5–1.0 mol%) is evidenced. Electronic polarizability of the glasses increases with increasing Fe{sub 3}O{sub 4} nanoparticles concentration up to 1 mol%. Interestingly, the polarizability tends to decrease with the further increase of Fe{sub 3}O{sub 4} concentration at 2 mol%. The role of magnetic nanoparticles in influencing the structural and optical behavior are examined and understood. - Highlights: ► Incorporation of natural Fe{sub 3}O{sub 4} nanoparticles into the zinc–tellurite glass. ► Influence of magnetic nanoparticles in modifying structure and optical properties. ► Enhancement of refraction index and change in electronic polarizability.

  14. Molecular dynamics of polarizable point dipole models for molten NaI. Comparison with first principles simulations

    Directory of Open Access Journals (Sweden)

    Trullàs J.

    2011-05-01

    Full Text Available Molecular dynamics simulations of molten NaI at 995 K have been carried out using polarizable ion models based on rigid ion pair potentials to which the anion induced dipole polarization is added. The polarization is added in such a way that point dipoles are induced on the anions by both local electric field and deformation short-range damping interactions that oppose the electrically induced dipole moments. The structure and self-diffusion results are compared with those obtained by Galamba and Costa Cabral using first principles Hellmann-Feynman molecular dynamics simulations and using classical molecular dynamics of a shell model which allows only the iodide polarization

  15. Plane-Wave Density Functional Theory Meets Molecular Crystals: Thermal Ellipsoids and Intermolecular Interactions.

    Science.gov (United States)

    Deringer, Volker L; George, Janine; Dronskowski, Richard; Englert, Ulli

    2017-05-16

    Molecular compounds, organic and inorganic, crystallize in diverse and complex structures. They continue to inspire synthetic efforts and "crystal engineering", with implications ranging from fundamental questions to pharmaceutical research. The structural complexity of molecular solids is linked with diverse intermolecular interactions: hydrogen bonding with all its facets, halogen bonding, and other secondary bonding mechanisms of recent interest (and debate). Today, high-resolution diffraction experiments allow unprecedented insight into the structures of molecular crystals. Despite their usefulness, however, these experiments also face problems: hydrogen atoms are challenging to locate, and thermal effects may complicate matters. Moreover, even if the structure of a crystal is precisely known, this does not yet reveal the nature and strength of the intermolecular forces that hold it together. In this Account, we show that periodic plane-wave-based density functional theory (DFT) can be a useful, and sometimes unexpected, complement to molecular crystallography. Initially developed in the solid-state physics communities to treat inorganic solids, periodic DFT can be applied to molecular crystals just as well: theoretical structural optimizations "help out" by accurately localizing the elusive hydrogen atoms, reaching neutron-diffraction quality with much less expensive measurement equipment. In addition, phonon computations, again developed by physicists, can quantify the thermal motion of atoms and thus predict anisotropic displacement parameters and ORTEP ellipsoids "from scratch". But the synergy between experiment and theory goes much further than that. Once a structure has been accurately determined, computations give new and detailed insights into the aforementioned intermolecular interactions. For example, it has been debated whether short hydrogen bonds in solids have covalent character, and we have added a new twist to this discussion using an orbital

  16. Collision-induced Raman scattering by rare-gas atoms: The isotropic spectrum of Ne–Ne and its mean polarizability

    Energy Technology Data Exchange (ETDEWEB)

    Rachet, Florent; Chrysos, Michael, E-mail: michel.chrysos@univ-angers.fr [LUNAM Université, Université d’Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 Bd Lavoisier, 49045 Angers (France); Dixneuf, Sophie [Forschungszentrum Jülich GmbH IEK-8, Troposphere, 52425 Jülich (Germany)

    2015-05-07

    We report the room-temperature isotropic collision-induced light scattering spectrum of Ne–Ne over a wide interval of Raman shifts, and we compare it with the only available experimental spectrum for that system as well as with spectra calculated quantum-mechanically with the employ of advanced ab initio-computed data for the incremental mean polarizability. The spectral range previously limited to 170 cm{sup −1} is now extended to 485 cm{sup −1} allowing us to successfully solve the inverse-scattering problem toward an analytic model for the mean polarizability that perfectly matches our measurements. We also report the depolarization ratio of the scattering process, lingering over the usefulness of this property for more stringent checks between the various polarizability models.

  17. Collision-induced Raman scattering by rare-gas atoms: The isotropic spectrum of Ne-Ne and its mean polarizability.

    Science.gov (United States)

    Rachet, Florent; Dixneuf, Sophie; Chrysos, Michael

    2015-05-07

    We report the room-temperature isotropic collision-induced light scattering spectrum of Ne-Ne over a wide interval of Raman shifts, and we compare it with the only available experimental spectrum for that system as well as with spectra calculated quantum-mechanically with the employ of advanced ab initio-computed data for the incremental mean polarizability. The spectral range previously limited to 170 cm(-1) is now extended to 485 cm(-1) allowing us to successfully solve the inverse-scattering problem toward an analytic model for the mean polarizability that perfectly matches our measurements. We also report the depolarization ratio of the scattering process, lingering over the usefulness of this property for more stringent checks between the various polarizability models.

  18. Molecular dynamics study of response of liquid N,N-dimethylformamide to externally applied electric field using a polarizable force field

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Weimin; Niu, Haitao; Lin, Tong; Wang, Xungai; Kong, Lingxue [Institute for Frontier Materials, Deakin University, Waurn Ponds VIC 3216 (Australia)

    2014-01-28

    The behavior of Liquid N,N-dimethylformamide subjected to a wide range of externally applied electric fields (from 0.001 V/nm to 1 V/nm) has been investigated through molecular dynamics simulation. To approach the objective the AMOEBA polarizable force field was extended to include the interaction of the external electric field with atomic partial charges and the contribution to the atomic polarization. The simulation results were evaluated with quantum mechanical calculations. The results from the present force field for the liquid at normal conditions were compared with the experimental and molecular dynamics results with non-polarizable and other polarizable force fields. The uniform external electric fields of higher than 0.01 V/nm have a significant effect on the structure of the liquid, which exhibits a variation in numerous properties, including molecular polarization, local cluster structure, rotation, alignment, energetics, and bulk thermodynamic and structural properties.

  19. Identification of intra- and intermolecular disulfide bridges in the multidrug resistance transporter ABCG2

    DEFF Research Database (Denmark)

    Henriksen, Ulla Birk; Fog, Jacob U; Litman, Thomas

    2005-01-01

    cysteines predicted to be on the extracellular face of ABCG2. Upon mutation of Cys-592 or Cys-608 to alanine (C592A and C608A), ABCG2 migrated as a dimer in SDS-PAGE under non-reducing conditions; however, mutation of Cys-603 to Ala (C603A) caused the transporter to migrate as a single monomeric band....... Despite this change, C603A displayed efficient membrane targeting and preserved transport function. Because the transporter migrated as a dimer in SDS-PAGE, when only Cys-603 was present (C592A-C608A), the data suggest that Cys-603 forms a symmetrical intermolecular disulfide bridge in the ABCG2 homodimer...

  20. INS study of intermolecular interaction at the silicone-fumed silica interface

    International Nuclear Information System (INIS)

    Sheka, E.F.; Natkaniec, I.

    1999-01-01

    Complete text of publication follows. The paper presents results related to the interface formed between finned silica particles and polydimethylsiloxane polymers, presented in the study by a five-member cyclic oligomer SiS. The substrate surface is terminated by either hydroxyl units or by trimethylsiloxy ones. When the interface is formed, methyl units are the main constituents providing neutron scattering. Protium/deuterium exchange has been used to distinguish the latter belonging to either adsorbate or substrate. A detailed analysis of the intermolecular interaction impact on both adsorbed molecule and substrate has been performed. The observed features are supported by the vibrational spectra calculations performed on the basis of a modem quantum-chemical approach and supplemented by the solution of the inverse spectral problem. (author)

  1. A structural study of the intermolecular interactions of tyramine in the solid state and in solution

    Science.gov (United States)

    Quevedo, Rodolfo; Nuñez-Dallos, Nelson; Wurst, Klaus; Duarte-Ruiz, Álvaro

    2012-12-01

    The nature of the interactions between tyramine units was investigated in the solid state and in solution. Crystals of tyramine in its free base form were analyzed by Fourier transform infrared (FT-IR) spectroscopy and single-crystal X-ray diffraction (XRD). The crystal structure shows a linear molecular organization held together by "head-to-tail" intermolecular hydrogen bonds between the amino groups and the phenolic hydroxyl groups. These chains are arranged in double layers that can geometrically favor the formation of templates in solution, which may facilitate macrocyclization reactions to form azacyclophane-type compounds. Computational calculations using the PM6-DH+ method and electrospray ionization mass spectrometry (ESI-HRMS) reveal that the formation of a hydrogen-bonded tyramine dimer is favored in solution.

  2. Chain-length-dependent intermolecular packing in polyphenylenes: a high pressure study

    CERN Document Server

    Heimel, G; Oehzelt, M; Hummer, K; Koppelhuber-Bitschnau, B; Porsch, F; Ambrosch-Draxl, C; Resel, R

    2003-01-01

    We report on pressure-induced structural changes in crystalline oligo(para-phenylenes) containing two to six phenyl rings. The results are discussed with particular emphasis put on the implications these changes in intermolecular distances and molecular arrangement have on important bulk properties of this class of materials, such as optical response and charge transport. We performed energy dispersive x-ray diffraction in a systematic study on polycrystalline powders of biphenyl, para-terphenyl, p-quaterphenyl, p-quinquephenyl and p-sexiphenyl under hydrostatic pressure up to 60 kbar. Revisiting the crystal structures at ambient conditions reveals details in the packing principle. A linear relationship between the density at ambient conditions and the number of phenyl rings is found. High pressure data not only yields pressure-dependent lattice parameters and hints towards pressure-induced changes in the molecular arrangement but also allows for an analysis of the equations of state of these substances as a ...

  3. Asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent

    Science.gov (United States)

    Guo, Shuo; Cong, Fei; Guo, Rui; Wang, Liang; Tang, Pingping

    2017-06-01

    Fluorinated organic compounds are becoming increasingly important in pharmaceuticals, agrochemicals and materials science. The introduction of trifluoromethoxy groups into new drugs and agrochemicals has attracted much attention due to their strongly electron-withdrawing nature and high lipophilicity. However, synthesis of trifluoromethoxylated organic molecules is difficult owing to the decomposition of trifluoromethoxide anion and β-fluoride elimination from transition-metal-trifluoromethoxide complexes, and no catalytic enantioselective trifluoromethoxylation reaction has been reported until now. Here, we present an example of an asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with trifluoromethyl arylsulfonate (TFMS) as a new trifluoromethoxylation reagent. Compared to other trifluoromethoxylation reagents, TFMS is easily prepared and thermally stable with good reactivity. In addition, this reaction is operationally simple, scalable and proceeds under mild reaction conditions. Furthermore, broad scope and good functional group compatibility has been demonstrated by application of the method to the bromotrifluoromethoxylation of double bonds in natural products and natural product derivatives.

  4. An intermolecular binding mechanism involving multiple LysM domains mediates carbohydrate recognition by an endopeptidase

    DEFF Research Database (Denmark)

    Wong, Mei Mei Jaslyn Elizabeth; Midtgaard, Søren Roi; Gysel, Kira

    2015-01-01

    LysM domains, which are frequently present as repetitive entities in both bacterial and plant proteins, are known to interact with carbohydrates containing N-acetylglucosamine (GlcNAc) moieties, such as chitin and peptidoglycan. In bacteria, the functional significance of the involvement of multi......LysM domains, which are frequently present as repetitive entities in both bacterial and plant proteins, are known to interact with carbohydrates containing N-acetylglucosamine (GlcNAc) moieties, such as chitin and peptidoglycan. In bacteria, the functional significance of the involvement...... solution studies of this endopeptidase revealed the presence of a homodimer. The structure of the two LysM domains co-crystallized with N-acetyl-chitohexaose revealed a new intermolecular binding mode that may explain the differential interaction between LysM domains and short or long chitin oligomers...

  5. Intermolecular interactions of decamethoxinum and acetylsalicylic acid in systems of various complexity levels

    Directory of Open Access Journals (Sweden)

    O. V. Vashchenko

    2016-07-01

    Full Text Available Intermolecular interactions between decamethoxinum (DEC and acetylsalicylic acid (ASА have been studied in the phospholipid-containing systems of escalating complexity levels. The host media for these substances were solvents, L-α-dipalmitoylphosphatidylcholine (DPPC membranes, and samples of human erythrocytes. Peculiar effects caused by DEC-ASА interaction have been observed in each system using appropriate techniques: (a DEC-ASА non-covalent complexes formation in DPPC-containing systems were revealed by mass spectrometry with electrospray ionization; (b joint DEC-ASА action on DPPC model membranes led to increasing of membrane melting temperature Tm, whereas individual drugs caused pronounced Tm decreasing, which was demonstrated by differential scanning calorimetry; (c deceleration of DEC-induced haemolysis of erythrocytes under joint DEC-ASА application was observed by optical microscopy.

  6. 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.

  7. Molecular dynamics simulations of the d(CCAACGTTGG)2 decamer in crystal environment: comparison of atom-centered charge, extra-point and polarizable force fields.

    Science.gov (United States)

    Baucom, Jason; Transue, Thomas; Fuentes-Cabrera, Miguel; Krahn, Joseph; Darden, Thomas; Sagui, Celeste

    2004-03-01

    Molecular dynamics simulations of the DNA duplex d(CCAACGTTGG)2 were used to study the relationship between DNA sequence and structure. Three different force fields were used: a traditional description based on atomic point charges, a polarizable force field and an ``extra-point" force field (with additional charges on extra-nuclear sites). It is found that in crystal environment all the force fields reproduce fairly well the sequence-dependent features of the experimental structure. The polarizable force fields, however, outperforms the other two, pointing out to the need of the inclusion of polarization for accurate descriptions of DNA.

  8. To semi-centenary anniversary of discovering the Schwinger scattering and starting the first works on neutron polarizability

    International Nuclear Information System (INIS)

    Alexandrov, Yu.A.

    2006-01-01

    The theory of neutron Schwinger scattering was proposed and developed by Schwinger in 1948, but despite multiple efforts, the experimental discovery of this phenomenon was made eight years later. Currently, Schwinger scattering should be accounted for in many precise neutron experiments, for example, while studying the electromagnetic interaction of neutrons with nuclei. By means of Schwinger scattering it is possible to measure the degree of polarization of the initial beam even at particle energies of 1 GeV order. The concept of neutron polarizability was introduced as additional natural phenomenon indicating the nucleon space structure after the first Hofstadter's experiments (1953-1954). The neutron polarizability was detected in a small-angle neutron scattering experiment in 1957. However, the serious contradiction between the results obtained in megaelectronvolt and kiloelectronvolt neutron energy ranges was explained only in 2001. It is also shown that existent small-angle neutron experiments at megaelectronvolt energy by heavy nuclei do not confirm the idea of (n+3)-dimensional gravity

  9. Analytical gradients for MP2, double hybrid functionals, and TD‐DFT with polarizable embedding described by fluctuating charges

    Science.gov (United States)

    Carnimeo, Ivan; Cappelli, Chiara

    2015-01-01

    A polarizable quantum mechanics (QM)/ molecular mechanics (MM) approach recently developed for Hartree–Fock (HF) and Kohn–Sham (KS) methods has been extended to energies and analytical gradients for MP2, double hybrid functionals, and TD‐DFT models, thus allowing the computation of equilibrium structures for excited electronic states together with more accurate results for ground electronic states. After a detailed presentation of the theoretical background and of some implementation details, a number of test cases are analyzed to show that the polarizable embedding model based on fluctuating charges (FQ) is remarkably more accurate than the corresponding electronic embedding based on a fixed charge (FX) description. In particular, a set of electronegativities and hardnesses has been optimized for interactions between QM and FQ regions together with new repulsion–dispersion parameters. After validation of both the numerical implementation and of the new parameters, absorption electronic spectra have been computed for representative model systems including vibronic effects. The results show remarkable agreement with full QM computations and significant improvement with respect to the corresponding FX results. The last part of the article provides some hints about computation of solvatochromic effects on absorption spectra in aqueous solution as a function of the number of FQ water molecules and on the use of FX external shells to improve the convergence of the results. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:26399473

  10. Intermolecular Interactions and Cooperative Effects from Electronic Structure Calculations: An Effective Means for Developing Interaction Potentials for Condensed Phase Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Xantheas, Sotiris S.

    2004-05-01

    The modeling of the macroscopic properties of homogeneous and inhomogeneous systems via atomistic simulations such as molecular dynamics (MD) or Monte Carlo (MC) techniques is based on the accurate description of the relevant solvent-solute and solvent-solvent intermolecular interactions. The total energy (U) of an n-body molecular system can be formally written as [1,2,3

  11. Stereodynamics in the Collisional Autoionization of Water, Ammonia, and Hydrogen Sulfide with Metastable Rare Gas Atoms: Competition Between Intermolecular Halogen and Hydrogen Bonds.

    Science.gov (United States)

    Falcinelli, Stefano; Bartocci, Alessio; Cavalli, Simonetta; Pirani, Fernando; Vecchiocattivi, Franco

    2016-01-11

    Recent experiments on the title subject, performed with a high-resolution crossed-beam apparatus, have provided the total ionization cross sections as a function of the collision energy between noble gas atoms, electronically excited in their metastable states (Ng*), and H2 O, H2 S, and NH3 reagents, as well as the emitted electron energy spectra. This paper presents a rationalization of all the experimental findings in a unifying picture to cast light on the basic chemical properties of Ng* under conditions of great relevance both from a fundamental and from an applied point of view. The importance of this investigation is that it isolates the selective role of the intermolecular halogen and hydrogen bonds, to assess their anisotropic effects on the stereodynamics of the promoted ionization reactions, and to model energy transfer and reactivity in systems of applied interest, such as planetary atmospheres, plasmas, lasers, and flames. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Green synthesis, characterization and some physico-chemical studies on a novel intermolecular compound; 4-nitro-o-phenylenediamine-N, N-dimethylaminobenzaldehyde system

    Science.gov (United States)

    Rai, U. S.; Singh, Manjeet; Rai, R. N.

    2017-09-01

    An inter-molecular compound (IMC) L1 was synthesized by taking 1:1 molar ratio of p-nitro-o-phenylenediamine (NOPDA) and N, N-dimethylaminobenzaldehyde (DMAB) via thermally initiated solid state reaction. It was characterized by X-ray diffraction, spectral and optical studies. The single crystal of the (L1) was grown from saturated solution of ethanol using slow evaporation technique at 29 °C. From the single crystal X-ray diffraction analysis, it can be inferred that it crystallizes in triclinic unit cell with P-1 space group (CCDC No 1422765). Absorption spectrum of IMC (L1) shows a band at 318 nm attributed to the intra-molecular charge-transfer (ICT) excited state absorption and the other band at 376 nm is due to n→π* transition. The IMC (L1) shows a strong fluorescence at 418 nm with a Stokes shift (≈100 nm) and quantum efficiency (0.22) upon excitation in methyl alcohol at 318 nm.

  13. Aqueous solvation of As(OH)3: A Monte Carlo study with flexible polarizable classical interaction potentials

    Science.gov (United States)

    Hernández-Cobos, J.; Vargas, M. Cristina; Ramírez-Solís, A.; Ortega-Blake, I.

    2010-09-01

    A theoretical study of the hydration of arsenious acid is presented. This study included ab initio calculations and Monte Carlo simulations. The model potentials used for the simulations were ab initio derived and they include polarizability, nonadditivity, and molecular relaxation. It is shown that with these refined potentials it is possible to reproduce the available experimental evidence and therefore permit the study of clusters, as well as of the hydration process in solution. From the study of stepwise hydration and the Monte Carlo simulation of the condensed phase it is concluded that As(OH)3 presents a hydration scheme similar to an amphipathic molecule. This phenomenon is explained as due to the existence of both a positive electrostatic potential and a localized lone pair in the vicinity of As. These results are used to rationalize the known passage of As(OH)3 through aqua-glyceroporines.

  14. Water density and polarizability deduced from the refractive index determined by interferometric measurements up to 250 MPa.

    Science.gov (United States)

    Weiss, L; Tazibt, A; Tidu, A; Aillerie, M

    2012-03-28

    The refractive index of water is precisely determined in the visible light range as a function of the pressure until 250 MPa by means of a new measurement device that uses a special pipe tee included in an interferometer set. This technique allows revisiting the Bradley-Tait and Sellmeier equations to make them dependent on the wavelength and the pressure, respectively. The Bradley-Tait equation for the pressure dependence of the water refractive index is completed by a wavelength-dependent factor. Also, in the considered pressure and wavelength ranges, it is shown that the Sellmeier coefficients can be straightforwardly linked to the pressure, allowing the determination of the refractive index of water for either any wavelength or pressure. A new simple model allows the determination of the density of water as a function of the measured refractive index. Finally, the polarizability of water as function of pressure and wavelength is calculated by means of the Lorentz-Lorenz equation.

  15. Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

    DEFF Research Database (Denmark)

    List, Nanna Holmgaard; Beerepoot, Maarten; Olsen, Jógvan Magnus Haugaard

    2015-01-01

    We present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz...... for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C=O group of acetophenone in different solvents and derive its vibrational linear Stark...... and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger...

  16. Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

    Science.gov (United States)

    Duchemin, Ivan; Jacquemin, Denis; Blase, Xavier

    2016-04-01

    We have implemented the polarizable continuum model within the framework of the many-body Green's function GW formalism for the calculation of electron addition and removal energies in solution. The present formalism includes both ground-state and non-equilibrium polarization effects. In addition, the polarization energies are state-specific, allowing to obtain the bath-induced renormalisation energy of all occupied and virtual energy levels. Our implementation is validated by comparisons with ΔSCF calculations performed at both the density functional theory and coupled-cluster single and double levels for solvated nucleobases. The present study opens the way to GW and Bethe-Salpeter calculations in disordered condensed phases of interest in organic optoelectronics, wet chemistry, and biology.

  17. Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

    Energy Technology Data Exchange (ETDEWEB)

    Duchemin, Ivan, E-mail: ivan.duchemin@cea.fr [INAC, SP2M/L-Sim, CEA/UJF Cedex 09, 38054 Grenoble (France); Jacquemin, Denis [Laboratoire CEISAM - UMR CNR 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3 (France); Institut Universitaire de France, 1 rue Descartes, 75005 Paris Cedex 5 (France); Blase, Xavier [CNRS, Inst. NÉEL, F-38000 Grenoble (France); Univ. Grenoble Alpes, Inst. NÉEL, F-38000 Grenoble (France)

    2016-04-28

    We have implemented the polarizable continuum model within the framework of the many-body Green’s function GW formalism for the calculation of electron addition and removal energies in solution. The present formalism includes both ground-state and non-equilibrium polarization effects. In addition, the polarization energies are state-specific, allowing to obtain the bath-induced renormalisation energy of all occupied and virtual energy levels. Our implementation is validated by comparisons with ΔSCF calculations performed at both the density functional theory and coupled-cluster single and double levels for solvated nucleobases. The present study opens the way to GW and Bethe-Salpeter calculations in disordered condensed phases of interest in organic optoelectronics, wet chemistry, and biology.

  18. Intermolecular nuclear relaxation in paramagnetic solutions: from free radicals to rare earths

    Energy Technology Data Exchange (ETDEWEB)

    Belorizky, E. [Universite Joseph-Fourier, Lab. de Spectrometrie Physique, CNRS-UMR 5588, 38 - Saint Martin d' Heres (France); Fries, P.H.; Rast, S. [CEA Grenoble, Laboratoire de Reconnaissance ionique, Service de Chimie Inorganique et Biologique UMR 5046, Dept. de Recherche Fondamentale sur la Matiere Condensee, 38 (France)

    2001-11-01

    The principles of the intermolecular relaxation of a nuclear spin by its fluctuating magnetic dipolar interactions with the electronic spins of the paramagnetic surrounding species in solution are briefly recalled. It is shown that a very high dynamic nuclear polarization (DNP) of solvent protons is obtained by saturating allowed transitions of free radicals with a hyperfine structure, and that this effect can be used in efficient Earth field magnetometers. Recent work on trivalent lanthanide Ln{sup 3+} aqua complexes in heavy water solutions is discussed, including paramagnetic shift and relaxation rate measurements of the {sup 1}H NMR lines of probe solutes. This allows a determination of the effective electronic magnetic moments of the various Ln{sup 3+} ions in these complexes, and an estimation of their longitudinal and transverse electronic relaxation times T{sub 1e} and T{sub 2e}. Particular attention is given to Gd(III) hydrated chelates which can serve as contrast agents in magnetic resonance imaging (MRI). The full experimental electronic paramagnetic resonance (EPR) spectra of these complexes can be interpreted within the Redfield relaxation theory. Monte-Carlo simulations are used to explore situations beyond the validity of the Redfield approximation. For each Gd(III) complex, the EPR study leads to an accurate prediction of T{sub 1e}, which can be also derived from an independent relaxation dispersion study of the protons of the probe solutes. (authors)

  19. Characterization of the glass transition of water predicted by molecular dynamics simulations using nonpolarizable intermolecular potentials.

    Science.gov (United States)

    Kreck, Cara A; Mancera, Ricardo L

    2014-02-20

    Molecular dynamics simulations allow detailed study of the experimentally inaccessible liquid state of supercooled water below its homogeneous nucleation temperature and the characterization of the glass transition. Simple, nonpolarizable intermolecular potentials are commonly used in classical molecular dynamics simulations of water and aqueous systems due to their lower computational cost and their ability to reproduce a wide range of properties. Because the quality of these predictions varies between the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an extensive comparative investigation of various three-, four-, five-, and six-point water potentials in both the NPT and NVT ensembles. The T(g) predicted from NPT simulations is strongly correlated with the temperature of minimum density, whereas the maximum in the heat capacity plot corresponds to the minimum in the thermal expansion coefficient. In the NVT ensemble, these points are instead related to the maximum in the internal pressure and the minimum of its derivative, respectively. A detailed analysis of the hydrogen-bonding properties at the glass transition reveals that the extent of hydrogen-bonds lost upon the melting of the glassy state is related to the height of the heat capacity peak and varies between water potentials.

  20. A heuristic approach to evaluate peri interactions versus intermolecular interactions in an overcrowded naphthalene

    Science.gov (United States)

    Row, Tayur N. Guru

    2017-01-01

    Octachloronaphthalene (OCN), a serious environmental pollutant, has been investigated by charge density analysis to unravel several unexplored factors responsible for steric overcrowding. The topological features of the enigmatic peri interactions contributing to steric overcrowding are qualified and quantified from experimental and theoretical charge-density studies. A new facet in the fundamental understanding of peri interactions is revealed by NCI (non-covalent interaction) analysis. The potential role of these interactions in deforming the molecular geometry and subsequent effect on aromaticity are substantiated from NICS (Nuclear Independent Chemical Shift) and QTAIM (Quantum Theory of Atoms in Molecules) calculations. The eye-catching dissimilarity in the out-of-plane twisting of OCN renders the molecule in an asymmetric geometry in the crystalline phase compared with symmetric geometry in the optimized solvated phase. This is uniquely characterized by their molecular electrostatic potential (MESP), respectively, and is explained in terms of conflict between two opposing forces – peri interactions, and symbiotic intermolecular Cl⋯Cl and Cl⋯π contacts. PMID:28250940

  1. 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.

  2. Argon intermolecular potential from a measurement of the total scattering cross-section

    International Nuclear Information System (INIS)

    Wong, Y.W.

    1975-01-01

    An inversion method to obtain accurate intermolecular potentials from experimental total cross section measurements is presented. This method is based on the high energy Massey--Smith approximation. The attractive portion of the potential is represented by a multi-parameter spline function and the repulsive part by a Morse function. The best fit potential is obtained by a least squares minimization based on comparison of experimental cross sections with those obtained by a Fourier transform of the reduced Massey--Smith phase shift curve. An experimental method was developed to obtain the total cross sections needed for the above inversion procedure. In this technique, integral cross sections are measured at various resolutions and the total cross section is obtained by extrapolating to infinite resolution. Experimental results obtained for the Ar--Ar system are in excellent agreement with total cross sections calculated using the Barker-Fisher-Watts potential. Inversion of the data to obtain a potential distinguishable from the BFW-potential requires an extension of the method based on the Massey--Smith approximation to permit use of JWKB phase shifts and was not attempted

  3. Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions.

    Science.gov (United States)

    Zhu, Wuming; Toulouse, Julien; Savin, Andreas; Angyán, János G

    2010-06-28

    Range-separated methods combining a short-range density functional with long-range random phase approximations (RPAs) with or without exchange response kernel are tested on rare-gas dimers and the S22 benchmark set of weakly interacting complexes of Jurecka et al. [Phys. Chem. Chem. Phys. 8, 1985 (2006)]. The methods are also compared to full-range RPA approaches. Both range separation and inclusion of the Hartree-Fock exchange kernel largely improve the accuracy of intermolecular interaction energies. The best results are obtained with the method called RSH+RPAx, which yields interaction energies for the S22 set with an estimated mean absolute error of about 0.5-0.6 kcal/mol, corresponding to a mean absolute percentage error of about 7%-9% depending on the reference interaction energies used. In particular, the RSH+RPAx method is found to be overall more accurate than the range-separated method based on long-range second-order Moller-Plesset (MP2) perturbation theory (RSH+MP2).

  4. Arginine-phosphate salt bridges between histones and DNA: Intermolecular actuators that control nucleosome architecture

    Science.gov (United States)

    Yusufaly, Tahir I.; Li, Yun; Singh, Gautam; Olson, Wilma K.

    2014-10-01

    Structural bioinformatics and van der Waals density functional theory are combined to investigate the mechanochemical impact of a major class of histone-DNA interactions, namely, the formation of salt bridges between arginine residues in histones and phosphate groups on the DNA backbone. Principal component analysis reveals that the configurational fluctuations of the sugar-phosphate backbone display sequence-specific directionality and variability, and clustering of nucleosome crystal structures identifies two major salt-bridge configurations: a monodentate form in which the arginine end-group guanidinium only forms one hydrogen bond with the phosphate, and a bidentate form in which it forms two. Density functional theory calculations highlight that the combination of sequence, denticity, and salt-bridge positioning enables the histones to apply a tunable mechanochemical stress to the DNA via precise and specific activation of backbone deformations. The results suggest that selection for specific placements of van der Waals contacts, with high-precision control of the spatial distribution of intermolecular forces, may serve as an underlying evolutionary design principle for the structure and function of nucleosomes, a conjecture that is corroborated by previous experimental studies.

  5. MAu2GeS4-Chalcogel (M = Co, Ni): Heterogeneous Intra- and Intermolecular Hydroamination Catalysts

    KAUST Repository

    Davaasuren, Bambar

    2017-08-08

    High surface area macroporous chalcogenide aerogels (chalcogels) MAu2GeS4 (M = Co, Ni) were prepared from K2Au2GeS4 precursor and Co(OAc)2 or NiCl2 by one-pot sol-gel metathesis reactions in aqueous media. The MAu2GeS4-chalcogels were screened for catalytic intramolecular hydroamination of 4-pentyn-1-amine substrate at different temperatures. 87% and 58% conversion was achieved at 100 °C, using CoAu2GeS4- and NiAu2GeS4-chalcogels respectively, and the reaction kinetics follows the first order. It was established that the catalytic performance of the aerogels is associated with the M(2+) centers present in the structure. Intermolecular hydroamination of aniline with 1-R-4-ethynylbenzene (R = -H, -OCH3, -Br, -F) was carried out at 100 °C using CoAu2GeS4-chalcogel catalyst, due to its promising catalytic performance. The CoAu2GeS4-chalcogel regioselectively converted the pair of substrates to respective Markovnikov products, (E)-1-(4-R-phenyl)-N-phenylethan-1-imine, with 38% to 60% conversion.

  6. Intermolecular and very strong intramolecular C-SeO/N chalcogen bonds in nitrophenyl selenocyanate crystals.

    Science.gov (United States)

    Wang, Hui; Liu, Ju; Wang, Weizhou

    2018-02-14

    Single-crystal X-ray diffraction reveals that polymorphic ortho-nitrophenyl selenocyanate (o-NSC, crystals 1a and 1b) and monomorphic para-nitrophenyl selenocyanate (p-NSC, crystal 2) crystals are all stabilized mainly by intermolecular and very strong intramolecular C-SeO/N chalcogen bonds, as well as by other different interactions. Thermogravimetric (TG) and differential scanning calorimetry thermogram (DSC) analyses show that the starting decomposition temperatures and melting points of the three crystals are different, following the order 1b > 1a > 2, which is consistent with the structural characteristics of the crystals. In addition, atoms in molecules (AIM) and natural bond orbital (NBO) analyses indicate that the total strengths of the C-SeO and C-SeN chalcogen bonds decrease in the order 1b > 1a > 2. This study could be significant for engineering functional crystals based on robust C-SeO and C-SeN chalcogen bonds, and for designing drugs containing selenium as well as understanding their interaction in biosystems.

  7. Anti-plasticizing effect of amorphous indomethacin induced by specific intermolecular interactions with PVA copolymer.

    Science.gov (United States)

    Ueda, Hiroshi; Aikawa, Shohei; Kashima, Yousuke; Kikuchi, Junko; Ida, Yasuo; Tanino, Tadatsugu; Kadota, Kazunori; Tozuka, Yuichi

    2014-09-01

    The mechanism of how poly(vinyl alcohol-co-acrylic acid-co-methyl methacrylate) (PVA copolymer) stabilizes an amorphous drug was investigated. Solid dispersions of PVA copolymer, poly(vinyl pyrrolidone) (PVP), and poly(vinyl pyrrolidone-co-vinyl acetate) (PVPVA) with indomethacin (IMC) were prepared. The glass transition temperature (Tg)-proportion profiles were evaluated by differential scanning calorimetry (DSC). General Tg profiles decreasing with the IMC ratio were observed for IMC-PVP and IMC-PVPVA samples. An interesting antiplasticizing effect of IMC on PVA copolymer was observed; Tg increased up to 20% IMC ratio. Further addition of IMC caused moderate reduction with positive deviation from theoretical values. Specific hydrophilic and hydrophobic interactions between IMC and PVA copolymer were revealed by infrared spectra. The indole amide of IMC played an important role in hydrogen bonding with PVA copolymer, but not with PVP and PVPVA. X-ray diffraction findings and the endotherm on DSC profiles suggested that PVA copolymer could form a semicrystalline structure and a possibility of correlation of the crystallographic nature with its low hygroscopicity was suggested. PVA copolymer was able to prevent crystallization of amorphous IMC through both low hygroscopicity and the formation of a specific intermolecular interaction compared with that with PVP and PVPVA. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  8. An intermolecular binding mechanism involving multiple LysM domains mediates carbohydrate recognition by an endopeptidase

    Energy Technology Data Exchange (ETDEWEB)

    Wong, Jaslyn E. M. M. [Aarhus University, Gustav Wieds Vej 10C, 8000 Aarhus (Denmark); Midtgaard, Søren Roi [University of Copenhagen, Universitetsparken 5, 2100 Copenhagen (Denmark); Gysel, Kira [Aarhus University, Gustav Wieds Vej 10C, 8000 Aarhus (Denmark); Thygesen, Mikkel B.; Sørensen, Kasper K.; Jensen, Knud J. [University of Copenhagen, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Stougaard, Jens; Thirup, Søren; Blaise, Mickaël, E-mail: mickael.blaise@cpbs.cnrs.fr [Aarhus University, Gustav Wieds Vej 10C, 8000 Aarhus (Denmark)

    2015-03-01

    The crystal and solution structures of the T. thermophilus NlpC/P60 d, l-endopeptidase as well as the co-crystal structure of its N-terminal LysM domains bound to chitohexaose allow a proposal to be made regarding how the enzyme recognizes peptidoglycan. LysM domains, which are frequently present as repetitive entities in both bacterial and plant proteins, are known to interact with carbohydrates containing N-acetylglucosamine (GlcNAc) moieties, such as chitin and peptidoglycan. In bacteria, the functional significance of the involvement of multiple LysM domains in substrate binding has so far lacked support from high-resolution structures of ligand-bound complexes. Here, a structural study of the Thermus thermophilus NlpC/P60 endopeptidase containing two LysM domains is presented. The crystal structure and small-angle X-ray scattering solution studies of this endopeptidase revealed the presence of a homodimer. The structure of the two LysM domains co-crystallized with N-acetyl-chitohexaose revealed a new intermolecular binding mode that may explain the differential interaction between LysM domains and short or long chitin oligomers. By combining the structural information with the three-dimensional model of peptidoglycan, a model suggesting how protein dimerization enhances the recognition of peptidoglycan is proposed.

  9. Inter-molecular β-sheet structure facilitates lung-targeting siRNA delivery

    Science.gov (United States)

    Zhou, Jihan; Li, Dong; Wen, Hao; Zheng, Shuquan; Su, Cuicui; Yi, Fan; Wang, Jue; Liang, Zicai; Tang, Tao; Zhou, Demin; Zhang, Li-He; Liang, Dehai; Du, Quan

    2016-03-01

    Size-dependent passive targeting based on the characteristics of tissues is a basic mechanism of drug delivery. While the nanometer-sized particles are efficiently captured by the liver and spleen, the micron-sized particles are most likely entrapped within the lung owing to its unique capillary structure and physiological features. To exploit this property in lung-targeting siRNA delivery, we designed and studied a multi-domain peptide named K-β, which was able to form inter-molecular β-sheet structures. Results showed that K-β peptides and siRNAs formed stable complex particles of 60 nm when mixed together. A critical property of such particles was that, after being intravenously injected into mice, they further associated into loose and micron-sized aggregates, and thus effectively entrapped within the capillaries of the lung, leading to a passive accumulation and gene-silencing. The large size aggregates can dissociate or break down by the shear stress generated by blood flow, alleviating the pulmonary embolism. Besides the lung, siRNA enrichment and targeted gene silencing were also observed in the liver. This drug delivery strategy, together with the low toxicity, biodegradability, and programmability of peptide carriers, show great potentials in vivo applications.

  10. Competition between intermolecular interaction and configuration entropy as the structure-determining factor for inclusion compounds

    Energy Technology Data Exchange (ETDEWEB)

    Subbotin, O.; Belosludov, V.; Adamova, T. [Russian Academy of Science, Novosibirsk (Russian Federation). Nikolaev Inst. of Inorganic Chemistry; Belosludov, R.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research; Kudoh, J.I. [Tohoku Univ., Aoba-ku, Sendai (Japan). Center for Northeast Asia Studies

    2008-07-01

    This paper presented a newly developed method to accurately predict the thermodynamic properties of clathrate hydrates, particularly their structural phase transitions under pressure. The method is based on the theory of Van-der-Waals and Platteeuw with some modifications that include the influence of guest molecules on the host lattice. The model was used to explain the exception from the established rule that small guest molecules form structure s1 and large molecules form structure s2 hydrates. In this study, the thermodynamic properties of argon (Ar) hydrate and methane hydrate, each in both cubic structure s1 and s2 were modelled. The model showed that two competing factors play a role in the formation of inclusions, notably the intermolecular interaction of guest molecules with water molecules, and the configuration entropy. Competition of these 2 factors determines the structure of hydrate formed at different pressures. The model provides an accurate description of the thermodynamic properties of gas hydrates and how they behave under pressure. For the argon hydrates, the structural phase transition from structure s2 to s1 at high pressure was predicted, while methane hydrates were predicted to be metastable in the s2 structure. The model can be used for other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. 17 refs., 5 figs.

  11. Intermolecular interactions and aggregation of fac-tris(2-phenylpyridinato-C2,N)iridium(III) in nonpolar solvents.

    Science.gov (United States)

    Takayasu, Satoshi; Suzuki, Takayoshi; Shinozaki, Kazuteru

    2013-08-15

    The intermolecular interaction and aggregation of the neutral complex fac-tris(2-phenylpyridinato-C(2),N)iridium(III) (fac-Ir(ppy)3) in solution was investigated. Intermolecular interactions were found to effectively decrease the luminescence lifetime via self-quenching with increasing fac-Ir(ppy)3 concentrations. A Stern-Volmer plot for quenching in acetonitrile was linear, due to bimolecular self-quenching, but curved in toluene as the result of excimer formation. (1)H NMR spectra demonstrated a monomer-aggregate equilibrium which resulted in spectral shifts depending on solvent polarity. X-ray crystallography provided structural information concerning the aggregate, which is based on a tetramer consisting of two Δ-fac-Ir(ppy)3-Λ-fac-Ir(ppy)3 pairs. Offset π-π stacking of ppy ligands and electrostatic dipole-dipole interactions between complex molecules play an important role in the formation of these molecular pairs.

  12. Exciton dynamics reveal aggregates with intermolecular order at hidden interfaces in solution-cast organic semiconducting films.

    Science.gov (United States)

    Wong, Cathy Y; Cotts, Benjamin L; Wu, Hao; Ginsberg, Naomi S

    2015-01-12

    Large-scale organic electronics manufacturing requires solution processing. For small-molecule organic semiconductors, solution processing results in crystalline domains with high charge mobility, but the interfaces between these domains impede charge transport, degrading device performance. Although understanding these interfaces is essential to improve device performance, their intermolecular and electronic structure is unknown: they are smaller than the diffraction limit, are hidden from surface probe techniques, and their nanoscale heterogeneity is not typically resolved using X-ray methods. Here we use transient absorption microscopy to isolate a unique signature of a hidden interface in a TIPS-pentacene thin film, exposing its exciton dynamics and intermolecular structure. Surprisingly, instead of finding an abrupt grain boundary, we reveal that the interface can be composed of nanoscale crystallites interleaved by a web of interfaces that compound decreases in charge mobility. Our novel approach provides critical missing information on interface morphology necessary to correlate solution-processing methods to optimal device performance.

  13. Intermolecular vibrations of the CO2-CS2 complex: Experiment and theory agree, but understanding remains challenging

    Science.gov (United States)

    Dehghany, M.; Rezaei, Mojtaba; Moazzen-Ahmadi, N.; McKellar, A. R. W.; Brown, James; Wang, Xiao-Gang; Carrington, Tucker

    2016-12-01

    The infrared spectrum of the cross-shaped van der Waals complex CO2-CS2 is observed in the region of the CO2 ν3 fundamental band (≈2350 cm-1) using a tuneable diode laser to probe a pulsed supersonic slit jet expansion. Two combination bands are assigned, corresponding to the intermolecular torsion and CO2 bend modes, and their positions and rotational structure agree extremely well (torsional band is well-behaved, but the a-type CO2 bending band is highly unusual, with large shifts between the subband origins for Ka = 0, 2, and 4. The shifts may be rationalized as due to tunnelling effects and Ka-dependent perturbations from other intermolecular modes. But even though they are well predicted by our calculations, there is no simple qualitative explanation. The predicted low-lying planar slipped parallel isomer of CO2-CS2 is not observed.

  14. 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.

  15. Communication: Symmetry-adapted perturbation theory with intermolecular induction and dispersion energies from the Bethe-Salpeter equation

    Science.gov (United States)

    Holzer, Christof; Klopper, Wim

    2017-11-01

    A method for calculating intermolecular induction and dispersion energies based on a GW description of the monomers and employing response functions from the Bethe-Salpeter equation is proposed. Calculations on a test set of 10 weakly bound complexes with GW-based symmetry-adapted perturbation theory (GW-SAPT) show an improved performance in comparison with symmetry-adapted perturbation theory based on density-functional theory (DFT-SAPT).

  16. Highly Convergent Total Synthesis of (+)-Lithospermic Acid via a Late-Stage Intermolecular C–H Olefination

    Science.gov (United States)

    Wang, Dong-Hui; Yu, Jin-Quan

    2011-01-01

    The total synthesis of (+)-lithospermic acid is reported, which exploits two successive C–H activation reactions as the key steps. Rh-catalyzed carbene C–H insertion reaction using Davies’ catalyst built the dihydrobenzofuran core, and a late-stage intermolecular C–H olefination coupled the olefin unit with the dihydrobenzofuran core to construct the molecule in a highly convergent manner. PMID:21443224

  17. Intermolecular sulfenoamination of alkenes with sulfonamides and N-sulfanylsuccinimides to access β-sulfonylamino sulfides and dihydrobenzothiazines.

    Science.gov (United States)

    Liu, Tao; Tian, Jun; Gao, Wen-Chao; Chang, Hong-Hong; Liu, Qiang; Li, Xing; Wei, Wen-Long

    2017-07-19

    An acid-catalyzed intermolecular sulfenoamination reaction of alkenes is developed with sulfonamides as the nitrogen source and N-sulfanylsuccinimides as the sulfur source. This methodology provides a straightforward and general way to synthesize various β-sulfonylamino sulfides with high regio- and diastereoselectivity. The developed method was coupled with intramolecular C-N coupling in a one-pot procedure to afford a series of dihydrobenzothiazine derivatives, a kind of important heterocycle used as biologically active compounds in medicinal chemistry.

  18. 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.

  19. Programmable display of DNA-protein chimeras for controlling cell-hydrogel interactions via reversible intermolecular hybridization.

    Science.gov (United States)

    Zhang, Zhaoyang; Li, Shihui; Chen, Niancao; Yang, Cheng; Wang, Yong

    2013-04-08

    Extensive studies have been recently carried out to achieve dynamic control of cell-material interactions primarily through physicochemical stimulation. The purpose of this study was to apply reversible intermolecular hybridization to program cell-hydrogel interactions in physiological conditions based on DNA-antibody chimeras and complementary oligonucleotides. The results showed that DNA oligonucleotides could be captured to and released from the immobilizing DNA-functionalized hydrogels with high specificity via DNA hybridization. Accordingly, DNA-antibody chimeras were captured to the hydrogels, successfully inducing specific cell attachment. The cell attachment to the hydrogels reached the plateau at approximately half an hour after the functionalized hydrogels and the cells were incubated together. The attached cells were rapidly released from the bound hydrogels when triggering complementary oligonucleotides were introduced to the system. However, the capability of the triggering complementary oligonucleotides in releasing cells was affected by the length of intermolecular hybridization. The length needed to be at least more than 20 base pairs in the current experimental setting. Notably, because the procedure of intermolecular hybridization did not involve any harsh condition, the released cells maintained the same viability as that of the cultured cells. The functionalized hydrogels also exhibited the potential to catch and release cells repeatedly. Therefore, this study demonstrates that it is promising to regulate cell-material interactions dynamically through the DNA-programmed display of DNA-protein chimeras.

  20. Intermolecular detergent-membrane protein noes for the characterization of the dynamics of membrane protein-detergent complexes.

    Science.gov (United States)

    Eichmann, Cédric; Orts, Julien; Tzitzilonis, Christos; Vögeli, Beat; Smrt, Sean; Lorieau, Justin; Riek, Roland

    2014-12-11

    The interaction between membrane proteins and lipids or lipid mimetics such as detergents is key for the three-dimensional structure and dynamics of membrane proteins. In NMR-based structural studies of membrane proteins, qualitative analysis of intermolecular nuclear Overhauser enhancements (NOEs) or paramagnetic resonance enhancement are used in general to identify the transmembrane segments of a membrane protein. Here, we employed a quantitative characterization of intermolecular NOEs between (1)H of the detergent and (1)H(N) of (2)H-perdeuterated, (15)N-labeled α-helical membrane protein-detergent complexes following the exact NOE (eNOE) approach. Structural considerations suggest that these intermolecular NOEs should show a helical-wheel-type behavior along a transmembrane helix or a membrane-attached helix within a membrane protein as experimentally demonstrated for the complete influenza hemagglutinin fusion domain HAfp23. The partial absence of such a NOE pattern along the amino acid sequence as shown for a truncated variant of HAfp23 and for the Escherichia coli inner membrane protein YidH indicates the presence of large tertiary structure fluctuations such as an opening between helices or the presence of large rotational dynamics of the helices. Detergent-protein NOEs thus appear to be a straightforward probe for a qualitative characterization of structural and dynamical properties of membrane proteins embedded in detergent micelles.

  1. Intermolecular RNA Recombination Occurs at Different Frequencies in Alternate Forms of Brome Mosaic Virus RNA Replication Compartments

    Directory of Open Access Journals (Sweden)

    Hernan Garcia-Ruiz

    2018-03-01

    Full Text Available Positive-strand RNA viruses replicate their genomes in membrane-bound replication compartments. Brome mosaic virus (BMV replicates in vesicular invaginations of the endoplasmic reticulum membrane. BMV has served as a productive model system to study processes like virus-host interactions, RNA replication and recombination. Here we present multiple lines of evidence showing that the structure of the viral RNA replication compartments plays a fundamental role and that recruitment of parental RNAs to a common replication compartment is a limiting step in intermolecular RNA recombination. We show that a previously defined requirement for an RNA recruitment element on both parental RNAs is not to function as a preferred crossover site, but in order for individual RNAs to be recruited into the replication compartments. Moreover, modulating the form of the replication compartments from spherular vesicles (spherules to more expansive membrane layers increased intermolecular RNA recombination frequency by 200- to 1000-fold. We propose that intermolecular RNA recombination requires parental RNAs to be recruited into replication compartments as monomers, and that recruitment of multiple RNAs into a contiguous space is much more common for layers than for spherules. These results could explain differences in recombination frequencies between viruses that replicate in association with smaller spherules versus larger double-membrane vesicles and convoluted membranes.

  2. Role of dbnd NOH intermolecular interactions in oxime derivatives via Crystal structure, Hirshfeld surface, PIXELC and DFT calculations

    Science.gov (United States)

    Purushothaman, Gayathri; Thiruvenkatam, Vijay

    2017-11-01

    Oximes are building block of organic synthesis and they have wide range applications in laboratories, industries, and pharmaceutical as antidotes. Herein we report the crystal structures of oxime derivative Beta-p-Dimethylaminodeoxybenzionoxime (I) and o-Chloro-p-dimethylaminodeoxybenzion (II) the precursor molecule of o-Chloro-p-dimethylaminodeoxybenzionoxime and their intermolecular interactions studies through Hirshfeld surface & 2D-fingerprint plot analysis along with PIXELC and DFT calculations. The packing arrangements in I and II are driven by Osbnd H⋯N and Osbnd H⋯C interactions respectively. The Osbnd H⋯N hydrogen bonding in I facilitates the formation of the dimer with the motif of R (22(6)), whereas in II absence of oxime moiety (dbnd NOH) restricts the dimer formation. The 2D-fingerprint plot shows the close contacts for the intermolecular interactions in I & II. The PIXELC calculation of II suggests Osbnd H⋯C contributes for intermolecular interaction that stabilizes the crystal packing with the total energy value of 60.4 kcal/mol. The DFT calculation using B3LYP with 6-311G (d, p) functional set for both the derivatives shows a small deviation in the benzene ring (I) and chlorobenzene ring (II) with the RMSD value of 0.5095 Å and 0.8472 Å respectively.

  3. Synthesis, crystal structure and theoretical analysis of intermolecular interactions in two biologically active derivatives of 1,2,4-triazoles

    Science.gov (United States)

    Shukla, Rahul; Mohan, T. P.; Vishalakshi, B.; Chopra, Deepak

    2017-04-01

    In the present study, we have synthesized and structurally characterized two biologically active derivatives of 1,2,4 triazoles, namely 3-(4-fluoro-3-phenoxyphenyl)-1-(piperidin-1-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione (TR) and 1-((3-(4-fluoro-3-phenoxyphenyl)-5-(methylthio)-1H-1,2,4-triazol-1-yl)methyl)piperidine (TR1) via single crystal X-ray diffraction. Both the structures show the presence of various intermolecular interactions in the crystalline solid such as Csbnd H…F, Csbnd H…S, Csbnd H…N, Csbnd H…O, Csbnd H … π, and π … π intermolecular interactions. The role of these interactions in molecular packing was analyzed, and the nature of these interactions was evaluated through computational procedures using PIXEL. Hirshfeld analysis further reveals that the contribution of H…F interactions was more prominent towards packing as compared to H…N/O intermolecular interactions.

  4. Molecular structure, spectroscopic (FTIR, FT-Raman, 13C and 1H NMR, UV), polarizability and first-order hyperpolarizability, HOMO-LUMO analysis of 2,4-difluoroacetophenone.

    Science.gov (United States)

    Jeyavijayan, S

    2015-02-05

    The FTIR and FT-Raman spectra of 2,4-difluoroacetophenone (DFAP) have been recorded in the regions 4000-400 cm(-1) and 3500-50 cm(-1), respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of DFAP is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The MEP map shows the negative potential sites are on oxygen atom as well as the positive potential sites are around the hydrogen atoms. The UV-Vis spectral analysis of DFAP has also been done which confirms the charge transfer of DFAP. The chemical shifts of H atoms and C atoms were calculated using NMR analysis. Furthermore, the polarizability, the first hyperpolarizability and total dipole moment of the molecule have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Transfer Pricing

    OpenAIRE

    Larsen, Mads Grenaa; Nørgaard, Mads Frid; Hansen, Manjarita

    2013-01-01

    This project seeks to highlight some of the criticisms given towards the OECD Transfer Pricing Guidelines and the challenges Danish companies experience by pricing their goods and the problems this causes for trade. The project is based on a series of interviews that represent the different agents who are operating in Transfer Pricing business. These interviews, combined with the Transfer Pricing Guidelines, gives us the basis to analyse the challenges we want to clarify based on the hypothes...

  6. Transfer Pricing

    DEFF Research Database (Denmark)

    Rohde, Carsten; Rossing, Christian Plesner

    trade internally as the units have to decide what prices should be paid for such inter-unit transfers. One important challenge is to uncover the consequences that different transfer prices have on the willingness in the organizational units to coordinate activities and trade internally. At the same time...... the determination of transfer price will affect the size of the profit or loss in the organizational units and thus have an impact on the evaluation of managers‟ performance. In some instances the determination of transfer prices may lead to a disagreement between coordination of the organizational units...

  7. Intermolecular potential and rovibrational states of the H2O–D2 complex

    International Nuclear Information System (INIS)

    Avoird, Ad van der; Scribano, Yohann; Faure, Alexandre; Weida, Miles J.; Fair, Joanna R.; Nesbitt, David J.

    2012-01-01

    Graphical abstract: H 2 O–D 2 potential surface and pH 2 O–oD 2 ground state wave function, for planar geometries. Highlights: ► The interaction between H 2 O and H 2 is of great astrophysical interest. ► The rovibrational states of H 2 O–D 2 were computed on an ab initio potential surface. ► Results are compared with the rovibrational states of H 2 O–H 2 computed recently. ► We measured the high-resolution infrared spectrum of H 2 O–D 2 in the H 2 O bend region. ► Comparison with the calculations provides information on H 2 O–H 2 potential surface. - Abstract: A five-dimensional intermolecular potential for H 2 O–D 2 was obtained from the full nine-dimensional ab initio potential surface of Valiron et al. [P. Valiron, M. Wernli, A. Faure, L. Wiesenfeld, C. Rist, S. Kedžuch, J. Noga, J. Chem. Phys. 129 (2008) 134306] by averaging over the ground state vibrational wave functions of H 2 O and D 2 . On this five-dimensional potential with a well depth D e of 232.12 cm −1 we calculated the bound rovibrational levels of H 2 O–D 2 for total angular momentum J = 0–3. The method used to compute the rovibrational levels is similar to a scattering approach—it involves a basis of coupled free rotor wave functions for the hindered internal rotations and the overall rotation of the dimer—while it uses a discrete variable representation of the intermolecular distance coordinate R. The basis was adapted to the permutation symmetry associated with the para/ortho (p/o) nature of both H 2 O and D 2 , as well as to inversion symmetry. As expected, the H 2 O–D 2 dimer is more strongly bound than its H 2 O–H 2 isotopologue [cf. A. van der Avoird, D.J. Nesbitt, J. Chem. Phys. 134 (2011) 044314], with dissociation energies D 0 of 46.10, 50.59, 67.43, and 73.53 cm −1 for pH 2 O–oD 2 , oH 2 O–oD 2 , pH 2 O–pD 2 , and oH 2 O–pD 2 . A rotationally resolved infrared spectrum of H 2 O–D 2 was measured in the frequency region of the H 2 O bend

  8. Towards interpretation of intermolecular paramagnetic relaxation enhancement outside the fast exchange limit

    Energy Technology Data Exchange (ETDEWEB)

    Ceccon, Alberto; Marius Clore, G., E-mail: mariusc@mail.nih.gov; Tugarinov, Vitali, E-mail: vitali.tugarinov@nih.gov [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

    2016-09-15

    In an exchanging system between major and minor species, the transverse paramagnetic relaxation enhancement rate observed on the resonances of the major species (Γ{sub 2}{sup app}) is dependent upon the exchange regime between the species. Quantitative analysis of PRE data in such systems typically assumes that the overall exchange rate k{sub ex} between the species is fast on the PRE time scale (k{sub ex} ≫ Γ{sub 2}). Recently, we have characterized the kinetics of binding of the model protein ubiquitin to large (LUV) and small (SUV) unilamellar lipid-based nanoparticles or liposomes (Ceccon A, Tugarinov V, Bax A, Clore GM (2016). J Am Chem Soc 138:5789–5792). Building upon these results and taking advantage of a strong paramagnetic agent with an isotropic g-tensor, Gd{sup 3+}, we were able to measure intermolecular methyl carbon and proton PREs between paramagnetically-tagged liposomes and ubiquitin. In the limit of fast exchange (k{sub ex} ≫ Γ{sub 2}) the ratio of the apparent proton to carbon methyl PREs, ({sup 1}H{sub m}–Γ{sub 2}{sup app})/({sup 13}C{sub m}–Γ{sub 2}{sup app}), is equal to the square of the ratio of the gyromagnetic ratios of the two nuclei, (γ{sub Η}/γ{sub C}){sup 2}. However, outside the fast exchange regime, under intermediate exchange conditions (e.g. when Γ{sub 2} is comparable in magnitude to k{sub ex}) the ({sup 1}H{sub m}–Γ{sub 2}{sup app})/({sup 13}C{sub m}–Γ{sub 2}{sup app}) ratio provides a reliable measure of the ‘true’ methyl PREs.

  9. A trans-Complementing Recombination Trap Demonstrates a Low Propensity of Flaviviruses for Intermolecular Recombination▿

    Science.gov (United States)

    Taucher, Christian; Berger, Angelika; Mandl, Christian W.

    2010-01-01

    Intermolecular recombination between the genomes of closely related RNA viruses can result in the emergence of novel strains with altered pathogenic potential and antigenicity. Although recombination between flavivirus genomes has never been demonstrated experimentally, the potential risk of generating undesirable recombinants has nevertheless been a matter of concern and controversy with respect to the development of live flavivirus vaccines. As an experimental system for investigating the ability of flavivirus genomes to recombine, we developed a “recombination trap,” which was designed to allow the products of rare recombination events to be selected and amplified. To do this, we established reciprocal packaging systems consisting of pairs of self-replicating subgenomic RNAs (replicons) derived from tick-borne encephalitis virus (TBEV), West Nile virus (WNV), and Japanese encephalitis virus (JEV) that could complement each other in trans and thus be propagated together in cell culture over multiple passages. Any infectious viruses with intact, full-length genomes that were generated by recombination of the two replicons would be selected and enriched by end point dilution passage, as was demonstrated in a spiking experiment in which a small amount of wild-type virus was mixed with the packaged replicons. Using the recombination trap and the JEV system, we detected two aberrant recombination events, both of which yielded unnatural genomes containing duplications. Infectious clones of both of these genomes yielded viruses with impaired growth properties. Despite the fact that the replicon pairs shared approximately 600 nucleotides of identical sequence where a precise homologous crossover event would have yielded a wild-type genome, this was not observed in any of these systems, and the TBEV and WNV systems did not yield any viable recombinant genomes at all. Our results show that intergenomic recombination can occur in the structural region of flaviviruses

  10. Effects of intermolecular interactions on the stability of carbon nanotube–gold nanoparticle conjugates in solution

    Directory of Open Access Journals (Sweden)

    Konczak L

    2016-11-01

    Full Text Available Lukasz Konczak,1 Jolanta Narkiewicz-Michalek,2 Giorgia Pastorin,3 Tomasz Panczyk1 1Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Cracow, 2Department of Chemistry, Maria Curie-Sklodowska University, Lublin, Poland; 3Department of Pharmacy, National University of Singapore, Singapore Abstract: This work deals with the role of intermolecular interactions in the stability of a carbon nanotube (CNT capped by functionalized gold nanoparticles (AuNPs. The importance of such a system is due to its potential application as a pH-controlled drug carrier. Our preliminary experimental studies showed that fabrication of such a nanobottle/nanocontainer is feasible and it is possible to encapsulate the anticancer drug cisplatin inside the inner space of a CNT and seal its ends by functionalized AuNPs. The expected behavior, that is, detachment of AuNPs at acidic pH and the release of cisplatin, was, however, not observed. On the other hand, our theoretical studies of chemically identical system led to the conclusion that the release of cisplatin at acidic pH should be observed. Therefore, in this work, a deeper theoretical analysis of various factors that could be responsible for the disagreement between experimental and theoretical results were performed. The study found that the major factor is a large dispersion interaction component acting between CNT and AuNP in solution in the case of the experimental system. This factor can be controlled to some extent by tuning the system size or the ratio between AuNP diameter and CNT diameter. Thus, such kind of a pH-sensitive drug carrier is still of great interest, but its structural parameters need to be properly adjusted. Keywords: hydrazone bond, drug delivery, dispersion interactions, cisplatin, acidic pH

  11. Impact of proline and aspartic acid residues on the dissociation of intermolecularly crosslinked peptides.

    Science.gov (United States)

    Gardner, Myles W; Brodbelt, Jennifer S

    2008-03-01

    The dissociation of intermolecularly crosslinked peptides was evaluated for a series of peptides with proline or aspartic acid residues positioned adjacent to the crosslinking sites (lysine residues). The peptides were crosslinked with either disuccinimidyl suberate (DSS) or disuccinimidyl L-tartrate (DST), and the influence of proline and aspartic acid residues on the fragmentation patterns were investigated for precursor ions with and without a mobile proton. Collisionally activated dissociation (CAD) spectra of aspartic acid-containing crosslinked peptide ions, doubly-charged with both protons sequestered, were dominated by cleavage C-terminal to the Asp residue, similar to that of unmodified peptides. The proline-containing crosslinked peptides exhibited a high degree of internal ion formation, with the resulting product ions having an N-terminal proline residue. Upon dissociation of the doubly-charged crosslinked peptides, twenty to fifty percent of the fragment ion abundance was accounted for by multiple cleavage products. Crosslinked peptides possessing a mobile proton yielded almost a full series of b- and y-type fragment ions, with only proline-directed fragments still observed at high abundances. Interestingly, the crosslinked peptides exhibited a tendency to dissociate at the amide bond C-terminal to the crosslinked lysine residue, relative to the N-terminal side. One could envision updating computer algorithms to include these crosslinker specific product ions--particularly for precursor ions with localized protons--that provide complementary and confirmatory information, to offer more confident identification of both the crosslinked peptides and the location of the crosslink, as well as affording predictive guidelines for interpretation of the product-ion spectra of crosslinked peptides.

  12. Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (DiaminocarbenePdII Complexes

    Directory of Open Access Journals (Sweden)

    Alexander S. Mikherdov

    2018-02-01

    Full Text Available The coupling of cis-[PdCl2(CNXyl2] (Xyl = 2,6-Me2C6H3 with 4-phenylthiazol-2-amine in molar ratio 2:3 at RT in CH2Cl2 leads to binuclear (diaminocarbenePdII complex 3c. The complex was characterized by HRESI+-MS, 1H NMR spectroscopy, and its structure was elucidated by single-crystal XRD. Inspection of the XRD data for 3c and for three relevant earlier obtained thiazole/thiadiazole derived binuclear diaminocarbene complexes (3a EYOVIZ; 3b: EYOWAS; 3d: EYOVOF suggests that the structures of all these species exhibit intra-/intermolecular bifurcated chalcogen bonding (BCB. The obtained data indicate the presence of intramolecular S•••Cl chalcogen bonds in all of the structures, whereas varying of substituent in the 4th and 5th positions of the thiazaheterocyclic fragment leads to changes of the intermolecular chalcogen bonding type, viz. S•••π in 3a,b, S•••S in 3c, and S•••O in 3d. At the same time, the change of heterocyclic system (from 1,3-thiazole to 1,3,4-thiadiazole does not affect the pattern of non-covalent interactions. Presence of such intermolecular chalcogen bonding leads to the formation of one-dimensional (1D polymeric chains (for 3a,b, dimeric associates (for 3c, or the fixation of an acetone molecule in the hollow between two diaminocarbene complexes (for 3d in the solid state. The Hirshfeld surface analysis for the studied X-ray structures estimated the contributions of intermolecular chalcogen bonds in crystal packing of 3a–d: S•••π (3a: 2.4%; 3b: 2.4%, S•••S (3c: less 1%, S•••O (3d: less 1%. The additionally performed DFT calculations, followed by the topological analysis of the electron density distribution within the framework of Bader’s theory (AIM method, confirm the presence of intra-/intermolecular BCB S•••Cl/S•••S in dimer of 3c taken as a model system (solid state geometry. The AIM analysis demonstrates the presence of appropriate bond critical points for these

  13. Transfer Pricing

    DEFF Research Database (Denmark)

    Rohde, Carsten; Rossing, Christian Plesner

    trade internally as the units have to decide what prices should be paid for such inter-unit transfers. One important challenge is to uncover the consequences that different transfer prices have on the willingness in the organizational units to coordinate activities and trade internally. At the same time...

  14. Transfer Pricing

    DEFF Research Database (Denmark)

    Nielsen, Søren Bo

    2014-01-01

    Against a background of rather mixed evidence about transfer pricing practices in multinational enterprises (MNEs) and varying attitudes on the part of tax authorities, this paper explores how multiple aims in transfer pricing can be pursued across four different transfer pricing regimes. A MNE has...... a production subsidiary in one country, from where it sells the produced good locally as well as to a sales subsidiary in a second country. The latter subsidiary is engaged in duopolistic competition with a local competitor. The MNE has two aims in setting the transfer price: strategic delegation and tax...... minimization. We examine the extent to which the four transfer pricing regimes we set up allow the MNE to pursue these aims. While neither strategic delegation nor tax minimization will be eliminated, trade-offs are inevitable, albeit to varying degree....

  15. Transfer Pricing

    DEFF Research Database (Denmark)

    Nielsen, Søren Bo

    2014-01-01

    a production subsidiary in one country, from where it sells the produced good locally as well as to a sales subsidiary in a second country. The latter subsidiary is engaged in duopolistic competition with a local competitor. The MNE has two aims in setting the transfer price: strategic delegation and tax......Against a background of rather mixed evidence about transfer pricing practices in multinational enterprises (MNEs) and varying attitudes on the part of tax authorities, this paper explores how multiple aims in transfer pricing can be pursued across four different transfer pricing regimes. A MNE has...... minimization. We examine the extent to which the four transfer pricing regimes we set up allow the MNE to pursue these aims. While neither strategic delegation nor tax minimization will be eliminated, trade-offs are inevitable, albeit to varying degree....

  16. Time-Dependent Coupled Perturbed Hartree-Fock and Density-Functional-Theory Approach for Calculating Frequency-Dependent (Hyper)Polarizabilities with Nonorthogonal Localized Molecular Orbitals.

    Science.gov (United States)

    Peng, Daoling; Li, Shaopeng; Peng, Liang; Gu, Feng Long; Yang, Weitao

    2017-09-12

    The time-dependent coupled perturbed Hartree-Fock/density-functional-theory (TDHF/TDDFT) approach has been reformulated based on nonorthogonal localized molecular orbitals (NOLMOs). Based on the NOLMO Fock equation, we have derived the corresponding NOLMO-TDHF/TDDFT equations up to the third order, and the formula for the frequency-dependent (hyper)polarizabilities has been given. Our approach has been applied to calculate both static and dynamic (hyper)polarizabilities of molecules varying from small molecules to large molecules. The NOLMO-TDHF/TDDFT approach can reproduce the reference canonical molecular orbital (CMO) results for all of our testing calculations. With the help of ongoing development of optimized local virtual molecular orbitals, the NOLMO-TDHF/TDDFT approach would be a very efficient method for large system calculations and tp achieve linear scaling.

  17. Application of discrete solvent reaction field model with self-consistent atomic charges and atomic polarizabilities to calculate the χ(1) and χ(2) of organic molecular crystals

    Science.gov (United States)

    Lu, Shih-I.

    2018-01-01

    We use the discrete solvent reaction field model to evaluate the linear and second-order nonlinear optical susceptibilities of 3-methyl-4-nitropyridine-1-oxyde crystal. In this approach, crystal environment is created by supercell architecture. A self-consistent procedure is used to obtain charges and polarizabilities for environmental atoms. Impact of atomic polarizabilities on the properties of interest is highlighted. This approach is shown to give the second-order nonlinear optical susceptibilities within error bar of experiment as well as the linear optical susceptibilities in the same order as experiment. Similar quality of calculations are also applied to both 4-N,N-dimethylamino-3-acetamidonitrobenzene and 2-methyl-4-nitroaniline crystals.

  18. Dipole moment and polarizability of impurity doped quantum dots under anisotropy, spatially-varying effective mass and dielectric screening function: Interplay with noise

    Science.gov (United States)

    Ghosh, Anuja; Ghosh, Manas

    2018-01-01

    Present work explores the profiles of polarizability (αp) and electric dipole moment (μ) of impurity doped GaAs quantum dot (QD) under the aegis of spatially-varying effective mass, spatially-varying dielectric constant and anisotropy of the system. Presence of noise has also been invoked to examine how its intervention further tunes αp and μ. Noise term maintains a Gaussian white feature and it has been incorporated to the system through two different roadways; additive and multiplicative. The various facets of influence of spatially-varying effective mass, spatially-varying dielectric constant and anisotropy on αp and μ depend quite delicately on presence/absence of noise and also on the mode through which noise has been administered. The outcomes of the study manifest viable routes to harness the dipole moment and polarizability of doped QD system through the interplay between noise, anisotropy and variable effective mass and dielectric constant of the system.

  19. The Ice-Vapor Interface and the Melting Point of Ice I-h for the Polarizable POL3 Water Model

    Czech Academy of Sciences Publication Activity Database

    Muchová, E.; Gladich, Ivan; Picaud, S.; Hoang, P. N. M.; Roeselová, Martina

    2011-01-01

    Roč. 115, č. 23 (2011), s. 5973-5982 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GAP208/10/1724; GA MŠk LC512; GA MŠk MEB020919; GA MŠk MEB020715 Institutional research plan: CEZ:AV0Z40550506 Keywords : polarizable water force field * ice surface * melting point * ice slab Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.946, year: 2011

  20. Calculations of dipole and quadrupole polarizability radial functions for LiH and HF: A comparison of different linear response methods

    Czech Academy of Sciences Publication Activity Database

    Paidarová, Ivana; Sauer, S. P. A.

    2005-01-01

    Roč. 48, - (2005), s. 185-208 ISSN 0065-3276 R&D Projects: GA ČR GA203/04/2146; GA AV ČR 1ET400400410 Institutional research plan: CEZ:AV0Z40400503 Keywords : polarization propagator calculations * frequency-dependent polarizabilities * consistent-field calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.877, year: 2005

  1. Spin rotation and oscillations for high energy particles in a crystal and possibility to measure the quadrupole moments and tensor polarizabilities of elementary particles and nuclei

    OpenAIRE

    Baryshevsky, V. G.; Gurinovich, A. A.

    2005-01-01

    It is shown that particle motion in a bent (straight) crystal is accompanied by particle spin rotation and oscillations that allows to measure the tensor electric and magnetic polarizabilities of nuclei and elementary particles. It is shown that channelling of particles in either straight or bent crystal with the polarized nuclei could be used both to analyze polarization of high energy particles and polarize them.

  2. Conformation-based signal transfer and processing at the single-molecule level.

    Science.gov (United States)

    Li, Chao; Wang, Zhongping; Lu, Yan; Liu, Xiaoqing; Wang, Li

    2017-11-01

    Building electronic components made of individual molecules is a promising strategy for the miniaturization and integration of electronic devices. However, the practical realization of molecular devices and circuits for signal transmission and processing at room temperature has proven challenging. Here, we present room-temperature intermolecular signal transfer and processing using SnCl 2 Pc molecules on a Cu(100) surface. The in-plane orientations of the molecules are effectively coupled via intermolecular interaction and serve as the information carrier. In the coupled molecular arrays, the signal can be transferred from one molecule to another in the in-plane direction along predesigned routes and processed to realize logical operations. These phenomena enable the use of molecules displaying intrinsic bistable states as complex molecular devices and circuits with novel functions.

  3. Conformation-based signal transfer and processing at the single-molecule level

    Science.gov (United States)

    Li, Chao; Wang, Zhongping; Lu, Yan; Liu, Xiaoqing; Wang, Li

    2017-11-01

    Building electronic components made of individual molecules is a promising strategy for the miniaturization and integration of electronic devices. However, the practical realization of molecular devices and circuits for signal transmission and processing at room temperature has proven challenging. Here, we present room-temperature intermolecular signal transfer and processing using SnCl2Pc molecules on a Cu(100) surface. The in-plane orientations of the molecules are effectively coupled via intermolecular interaction and serve as the information carrier. In the coupled molecular arrays, the signal can be transferred from one molecule to another in the in-plane direction along predesigned routes and processed to realize logical operations. These phenomena enable the use of molecules displaying intrinsic bistable states as complex molecular devices and circuits with novel functions.

  4. Study of energy transfer between molecules placed in the vicinity of a bimetal composite nanoparticle

    Energy Technology Data Exchange (ETDEWEB)

    Daneshfar, Nader, E-mail: ndaneshfar@gmail.com, E-mail: ndaneshfar@razi.ac.ir [Department of Physics, Razi University, Kermanshah (Iran, Islamic Republic of)

    2015-10-15

    In this study, the problem of energy transfer between two molecules near a bimetallic composite nanoparticle is investigated. The influence of the interaction between metal particles on the intermolecular energy is studied, because when two metal nanoparticles are placed close to each other, their plasmons coupling giving rise to new features. On the other hand, we discuss the transfer of resonance energy between donor and acceptor molecules (a single donor and a single acceptor) in the presence of a nanocomposite containing gold and silver nanoparticles based on the Maxwell-Garnett effective medium theory and within the quasistatic limit. We show that the interaction energy strongly depends on the particle size, the filling factor of metal particles, the intermolecular distance (the distance between the donor and acceptor molecules), and the dielectric constant of host matrix.

  5. Dipole polarizability of alkali-metal (Na, K, Rb)–alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Energy Technology Data Exchange (ETDEWEB)

    Gopakumar, Geetha, E-mail: geetha@tmu.ac.jp; Abe, Minori; Hada, Masahiko [Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan); JST, CREST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Kajita, Masatoshi [National Institute of Information and Communications Technology, Koganei, Tokyo 184-8795 (Japan)

    2014-06-14

    Electronic open-shell ground-state properties of selected alkali-metal–alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the {sup 2}Σ{sup +} ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes ({sup 23}Na, {sup 39}K, {sup 85}Rb)–({sup 40}Ca, {sup 88}Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  6. Solvent effects on the three-photon absorption of a symmetric charge-transfer molecule.

    Science.gov (United States)

    Lin, Na; Ferrighi, Lara; Zhao, Xian; Ruud, Kenneth; Rizzo, Antonio; Luo, Yi

    2008-04-17

    We present a theoretical study of the solvent-induced three-photon absorption cross section of a highly conjugated fluorene derivative, performed using density functional (DFT) cubic response theory in combination with the polarizable continuum model. The applicability of the often used two-state model is examined by comparison against the full DFT response theory results. It is found that the simplified model performs poorly for the three-photon absorption properties of our symmetric charge-transfer molecule. The dielectric medium enhances the three-photon absorption cross section remarkably. The effects of solvent polarity and geometrical distortions have been carefully examined. A detailed comparison with experiment is presented.

  7. Manipulation of Intermolecular Interactions for Active Layer Morphology Optimization in Organic Photovoltaics

    Science.gov (United States)

    Barreda, Leonel

    Organic photovoltaics (OPVs) are an attractive solar energy technology for low-current applications. Herein is described the supramolecular design and methodology to manipulate intermolecular interactions in order to create an active layer in OPVs devices composed of crystalline and amorphous donor-acceptor domains, which has been proposed as the ideal morphology for high performance. To this end, a series of symmetric and asymmetric diketopyrrolopyrrole (DPP) derivatives containing either an amide (capable of hydrogen-bonding) or ester endgroups were synthesized. The symmetric designs faced problems with solubility, strong segregation and low performance, so asymmetric donors having one amide/ester were used. Upon addressing initial stability problems, analysis of the ester films with X-ray diffraction displayed greater crystallinity and pi-pi stacking. The amide formed short aggregates with smaller, less ordered domains, resulting from competition between hydrogen bonding and pi-pi stacking, which interestingly endowed devices with higher current and 50% increase in device efficiency over the ester. To better match solar emission, the DPP core was substituted by benzodithiophene (BDT). Amides again outperformed esters, but introduction of a benzothiadiazole ?-spacer between the amide/ester endgroups led to electron traps and lowered performance; replacing it with phenyldithiophene reduced stacking ability. A recurring issue was the competition between noncovalent interactions, which motivated the use of barbituric acid endgroups, but solubility was compromised. After addressing each problem, a design having a BDT core with planar ?-spacers, connected by an alkyl linker to the hydrogen-bonding endgroups is predicted to display optimized optoelectronic properties and cooperative noncovalent interaction. Next, a series of BDT-core molecules with DPP endgroups and alkyl tails resembling solvent additives (which improve donor-acceptor interaction but increase

  8. Studies on the stability and intermolecular interactions of cellulose and polylactide systems using molecular modeling

    Science.gov (United States)

    Karst, David T.

    The stability and intermolecular interactions of cellulose and polylactide (PLA) systems were studied using molecular modeling. This work explains how grafting various groups onto cellulose increases hydrolysis of the glycosidic linkages of cellulose. A substituent increases hydrolysis of cellulose by serving as an anchor to the end of the cleaved cellulose to which it is bonded, making it less mobile, and allowing it to have stronger interactions than those in pure hydrolyzed cellulose. Hydrolysis increases with the size of the substituent. Molecules sorbed but not grafted to cellulose do not increase hydrolysis. Hydrolysis mainly occurs at glucoses bonded to the substituent. A substituent on the sixth carbon position of cellulose increases hydrolysis to a greater extent than does one on the second or third carbon position. The effect of blending poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) and the effect of various arrangements of L-lactide and D-lactide in poly(L-lactide-co-D-lactide) on the resistance of polylactide (PLA) to hydrolysis has been explained. Among the homopolymer blends, the 50/50 PLLA/PDLA blend has the greatest resistance to hydrolysis due to its having stronger hydrogen-bonding and van der Waals forces than pure PLLA or PDLA. The change in potential energy for hydrolysis decreases linearly with increasing % PLLA or % PDLA from 0 to 50%. Among the copolymers containing a given percentage of L-lactide and D-lactide, those containing longer blocks of L-lactide and D-lactide have greater resistance to hydrolysis compared to those with shorter blocks or random copolymers because copolymers with longer blocks are more stable before hydrolysis compared to the other copolymers. Among the copolymers with long blocks of L- and D-lactide, those containing 50% L-lactide have a greater resistance to hydrolysis compared to the copolymers with 26% or 74% L-lactide. Blends or copolymers that are mirror images of each other have the same resistance to

  9. Spiro-linked hyperbranched architecture in electrophosphorescent conjugated polymers for tailoring triplet energy back transfer.

    Science.gov (United States)

    Shao, Shiyang; Ma, Zhihua; Ding, Junqiao; Wang, Lixiang; Jing, Xiabin; Wang, Fosong

    2012-04-17

    A spiro-linked hyperbranched architecture has been incorporated into electrophosphorescent conjugated polymers for the first time, aiming at simultaneously tailoring the intra- and intermolecular triplet energy back transfer from the phosphorescent guest to the conjugated polymer host. Based on a prototype with this unique structure, slower decay of triplet excitons, and 5-8 fold enhancement of device efficiencies are obtained compared with the conventional blending counterpart. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Station Transfers

    Data.gov (United States)

    Department of Homeland Security — ixed rail transit external system transfers for systems within the Continental United States, Alaska, Hawaii, the District of Columbia, and Puerto Rico. The modes of...

  11. Dynamic polarizability of Rydberg atoms: Applicability of the near-free-electron approximation, gauge invariance, and the Dirac sea

    Science.gov (United States)

    Topcu, Turker; Derevianko, Andrei

    2013-10-01

    Ponderomotive energy shifts experienced by Rydberg atoms in optical fields are known to be well approximated by the classical quiver energy of a free electron. We examine such energy shifts quantum mechanically and elucidate how they relate to the ponderomotive shift of a free electron in off-resonant fields. We derive and evaluate corrections to the ponderomotive free-electron polarizability in the length and velocity (transverse or Coulomb) gauges, which agree exactly as mandated by the gauge invariance. We also show how the free electron value emerges from the Dirac equation through summation over the Dirac sea states. We find that the free-electron ac Stark shift comes as an expectation value of a term proportional to the square of the vector potential in the velocity gauge. On the other hand, the same dominant contribution can be obtained to first order via a series expansion of the exact energy shift from the second-order perturbation theory in the length gauge. Finally, we numerically examine the validity of the free-electron approximation. The correction to the free-electron value becomes smaller with increasing principal quantum number, and it is well below a percent for 60s states of Rb and Sr away from the resonances.

  12. The 2ν{sub 3} Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

    Energy Technology Data Exchange (ETDEWEB)

    Chrysos, M., E-mail: michel.chrysos@univ-angers.fr; Rachet, F.; Kremer, D. [LUNAM Université, Université d’Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 Bd Lavoisier, 49045 Angers (France)

    2014-03-28

    Of the six normal vibrations of SF{sub 6}, ν{sub 3} has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2ν{sub 3} allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels E{sub g} and F{sub 2g} hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF{sub 6} polarizability second derivative with respect to the ν{sub 3}-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ν{sub 3} mode cannot but generate a polarized Raman band.

  13. Response calculations based on an independent particle system with the exact one-particle density matrix: polarizabilities.

    Science.gov (United States)

    Giesbertz, K J H; Gritsenko, O V; Baerends, E J

    2014-05-14

    Recently, we have demonstrated that the problems finding a suitable adiabatic approximation in time-dependent one-body reduced density matrix functional theory can be remedied by introducing an additional degree of freedom to describe the system: the phase of the natural orbitals [K. J. H. Giesbertz, O. V. Gritsenko, and E. J. Baerends, Phys. Rev. Lett. 105, 013002 (2010); K. J. H. Giesbertz, O. V. Gritsenko, and E. J. Baerends, J. Chem. Phys. 133, 174119 (2010)]. In this article we will show in detail how the frequency-dependent response equations give the proper static limit (ω → 0), including the perturbation in the chemical potential, which is required in static response theory to ensure the correct number of particles. Additionally we show results for the polarizability for H2 and compare the performance of two different two-electron functionals: the phase-including Löwdin-Shull functional and the density matrix form of the Löwdin-Shull functional.

  14. Unified many-body approach to van der Waals interactions based on semi-local polarizability functional

    Science.gov (United States)

    Hermann, Jan; Scheffler, Matthias; Tkatchenko, Alexandre

    Electromagnetic coupling of charge fluctuations leads to van der Waals (vdW) attraction in systems ranging from metal nanoparticles to dielectric materials. In this regard, broadly applicable and accurate description of vdW interactions in complex materials is an elusive and unsolved puzzle. Many promising approaches model various subsets of this general problem, but are limited in scope by the underlying parametrization (atomic models), in accuracy due to missing many-body interactions (nonlocal density functionals), or in efficiency by working with virtual orbital space (e.g., random-phase approximation). Here, we present a unifying method that combines key elements from different theories and accurately describes vdW interactions in covalent, ionic, and metallic systems. In particular, we employ a semi-local polarizability functional of the electron density and its gradient to parametrize material response and its coupling within the many-body dispersion framework, and demonstrate the generality of the method on binding in molecular dimers and crystals, carbon-based nanomaterials, oxides, and salts, as well as on adsorption of molecules on metal surfaces. Our approach allows consistent modelling of a wide spectrum of materials as well as hybrid materials with mixed bond types.

  15. Electronic polarizability, optical basicity and interaction parameter for Nd2O3 doped lithium-zinc-phosphate glasses

    Science.gov (United States)

    Algradee, M. A.; Sultan, M.; Samir, O. M.; Alwany, A. Elwhab B.

    2017-08-01

    The Nd3+-doped lithium-zinc-phosphate glasses were prepared by means of conventional melt quenching method. X-ray diffraction results confirmed the glassy nature of the studied glasses. The physical parameters such as the density, molar volume, ion concentration, polaron radius, inter-ionic distance, field strength and oxygen packing density were calculated using different formulae. The transmittance and reflectance spectra of glasses were recorded in the wavelength range 190-1200 nm. The values of optical band gap and Urbach energy were determined based on Mott-Davis model. The refractive indices for the studied glasses were evaluated from optical band gap values using different methods. The average electronic polarizability of the oxide ions, optical basicity and an interaction parameter were investigated from the calculated values of the refractive index and the optical band gap for the studied glasses. The variations in the different physical and optical properties of glasses with Nd2O3 content were discussed in terms of different parameters such as non-bridging oxygen and different concentrations of Nd cation in glass system.

  16. Relativistic coupled-cluster-theory analysis of energies, hyperfine-structure constants, and dipole polarizabilities of Cd+

    Science.gov (United States)

    Li, Cheng-Bin; Yu, Yan-Mei; Sahoo, B. K.

    2018-02-01

    Roles of electron correlation effects in the determination of attachment energies, magnetic-dipole hyperfine-structure constants, and electric-dipole (E 1 ) matrix elements of the low-lying states in the singly charged cadmium ion (Cd+) have been analyzed. We employ the singles and doubles approximated relativistic coupled-cluster (RCC) method to calculate these properties. Intermediate results from the Dirac-Hartree-Fock approximation,the second-order many-body perturbation theory, and considering only the linear terms of the RCC method are given to demonstrate propagation of electron correlation effects in this ion. Contributions from important RCC terms are also given to highlight the importance of various correlation effects in the evaluation of these properties. At the end, we also determine E 1 polarizabilities (αE 1) of the ground and 5 p 2P1 /2 ;3 /2 states of Cd+ in the ab initio approach. We estimate them again by replacing some of the E 1 matrix elements and energies from the measurements to reduce their uncertainties so that they can be used in the high-precision experiments of this ion.

  17. Intensity-modulated polarizabilities and magic trapping of alkali-metal and divalent atoms in infrared optical lattices

    Science.gov (United States)

    Topcu, Turker; Derevianko, Andrei

    2014-05-01

    Long range interactions between neutral Rydberg atoms has emerged as a potential means for implementing quantum logical gates. These experiments utilize hyperfine manifold of ground state atoms to act as a qubit basis, while exploiting the Rydberg blockade mechanism to mediate conditional quantum logic. The necessity for overcoming several sources of decoherence makes magic wavelength trapping in optical lattices an indispensable tool for gate experiments. The common wisdom is that atoms in Rydberg states see trapping potentials that are essentially that of a free electron, and can only be trapped at laser intensity minima. We show that although the polarizability of a Rydberg state is always negative, the optical potential can be both attractive or repulsive at long wavelengths (up to ~104 nm). This opens up the possibility of magic trapping Rydberg states with ground state atoms in optical lattices, thereby eliminating the necessity to turn off trapping fields during gate operations. Because the wavelengths are near the CO2 laser band, the photon scattering and the ensuing motional heating is also reduced compared to conventional traps near low lying resonances, alleviating an important source of decoherence. This work was supported by the National Science Foundation (NSF) Grant No. PHY-1212482.

  18. Energy decomposition analysis of intermolecular interactions using a block-localized wave function approach

    Science.gov (United States)

    Mo, Yirong; Gao, Jiali; Peyerimhoff, Sigrid D.

    2000-04-01

    An energy decomposition scheme based on the block-localized wave function (BLW) method is proposed. The key of this scheme is the definition and the full optimization of the diabatic state wave function, where the charge transfer among interacting molecules is deactivated. The present energy decomposition (ED), BLW-ED, method is similar to the Morokuma decomposition scheme in definition of the energy terms, but differs in implementation and the computational algorithm. In addition, in the BLW-ED approach, the basis set superposition error is fully taken into account. The application of this scheme to the water dimer and the lithium cation-water clusters reveals that there is minimal charge transfer effect in hydrogen-bonded complexes. At the HF/aug-cc-PVTZ level, the electrostatic, polarization, and charge-transfer effects contribute 65%, 24%, and 11%, respectively, to the total bonding energy (-3.84 kcal/mol) in the water dimer. On the other hand, charge transfer effects are shown to be significant in Lewis acid-base complexes such as H3NSO3 and H3NBH3. In this work, the effect of basis sets used on the energy decomposition analysis is addressed and the results manifest that the present energy decomposition scheme is stable with a modest size of basis functions.

  19. Intra- and intermolecular effects on the Compton profile of the ionic liquid 1,3-dimethylimidazolium chloride

    Energy Technology Data Exchange (ETDEWEB)

    Koskelo, J., E-mail: jaakko.koskelo@helsinki.fi; Juurinen, I.; Ruotsalainen, K. O.; Lehtola, S.; Galambosi, S.; Hämäläinen, K.; Huotari, S.; Hakala, M., E-mail: mikko.o.hakala@helsinki.fi [Department of Physics, University of Helsinki, P.O. Box 64, FI-00014 Helsinki (Finland); McGrath, M. J. [Laboratoire des Sciences du Climat et de l’Environnement, CEA-Orme des Merisiers, F-91191 Gif-sur-Yvette CEDEX (France); Kuo, I-F. [Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, California 94550 (United States)

    2014-12-28

    We present a comprehensive simulation study on the solid-liquid phase transition of the ionic liquid 1,3-dimethylimidazolium chloride in terms of the changes in the atomic structure and their effect on the Compton profile. The structures were obtained by using ab initio molecular dynamics simulations. Chosen radial distribution functions of the liquid structure are presented and found generally to be in good agreement with previous ab initio molecular dynamics and neutron scattering studies. The main contributions to the predicted difference Compton profile are found to arise from intermolecular changes in the phase transition. This prediction can be used for interpreting future experiments.

  20. Intermolecular Interactions in Crystalline Theobromine as Reflected in Electron Deformation Density and (13)C NMR Chemical Shift Tensors.

    Science.gov (United States)

    Bouzková, Kateřina; Babinský, Martin; Novosadová, Lucie; Marek, Radek

    2013-06-11

    An understanding of the role of intermolecular interactions in crystal formation is essential to control the generation of diverse crystalline forms which is an important concern for pharmaceutical industry. Very recently, we reported a new approach to interpret the relationships between intermolecular hydrogen bonding, redistribution of electron density in the system, and NMR chemical shifts (Babinský et al. J. Phys. Chem. A, 2013, 117, 497). Here, we employ this approach to characterize a full set of crystal interactions in a sample of anhydrous theobromine as reflected in (13)C NMR chemical shift tensors (CSTs). The important intermolecular contacts are identified by comparing the DFT-calculated NMR CSTs for an isolated theobromine molecule and for clusters composed of several molecules as selected from the available X-ray diffraction data. Furthermore, electron deformation density (EDD) and shielding deformation density (SDD) in the proximity of the nuclei involved in the proposed interactions are calculated and visualized. In addition to the recently reported observations for hydrogen bonding, we focus here particularly on the stacking interactions. Although the principal relations between the EDD and CST for hydrogen bonding (HB) and stacking interactions are similar, the real-space consequences are rather different. Whereas the C-H···X hydrogen bonding influences predominantly and significantly the in-plane principal component of the (13)C CST perpendicular to the HB path and the C═O···H hydrogen bonding modulates both in-plane components of the carbonyl (13)C CST, the stacking modulates the out-of-plane electron density resulting in weak deshielding (2-8 ppm) of both in-plane principal components of the CST and weak shielding (∼ 5 ppm) of the out-of-plane component. The hydrogen-bonding and stacking interactions may add to or subtract from one another to produce total values observed experimentally. On the example of theobromine, we demonstrate

  1. Triplet-Triplet Energy Transfer Study in Hydrogen Bonding Systems.

    Science.gov (United States)

    Wang, Zhijia; Zhao, Jianzhang; Guo, Song

    2015-01-01

    The 2,6-diiodoBodipy-styrylBodipy hydrogen bonding system was prepared to study the effect of hydrogen bonding on the triplet-triplet-energy-transfer (TTET) process. 2,6-DiiodoBodipy linked with N-acetyl-2,6-diaminopyridine (D-2) was used as the triplet energy donor, and the styrylBodipy connected with thymine (A-1) was used as triplet energy acceptor, thus the TTET process was established upon photoexcitation. The photophysical processes of the hydrogen bonding system were studied with steady-state UV-vis absorption spectroscopy, fluorescence spectroscopy, fluorescence lifetime measurement and nanosecond time-resolved transient absorption spectroscopies. The TTET of the intramolecular/hydrogen bonding/intermolecular systems were compared through nanosecond transient absorption spectroscopy. The TTET process of the hydrogen bonding system is faster and more efficient (kTTET = 6.9 × 10(4) s(-1), ΦTTET = 94.0%) than intermolecular triplet energy transfer (kTTET = 6.0 × 10(4) s(-1), ΦTTET = 90.9%), but slower and less efficient than intramolecular triplet energy transfer (kTTET > 10(8) s(-1)). These results are valuable for designing self-assembly triplet photosensitizers and for the study of the TTET process of hydrogen bonding systems.

  2. 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.

  3. Quantum electrodynamics with nonrelativistic sources. V. Electromagnetic field correlations and intermolecular interactions between molecules in either ground or excited states

    International Nuclear Information System (INIS)

    Power, E.A.; Thirunamachandran, T.

    1993-01-01

    Spatial correlations between electromagnetic fields arising from neutral sources with electric-dipole transition moments are calculated using nonrelativistic quantum electrodynamics in the multipolar formalism. Expressions for electric-electric, magnetic-magnetic, and electric-magnetic correlation functions at two points r and r' are given for a source molecule in either a ground or an excited state. In contrast to the electric-electric and magnetic-magnetic cases there are no electric-magnetic correlations for a ground-state molecule. For an excited molecule the downward transitions contribute additional terms which have modulating factors depending on (r-r')/λ. From these correlation functions electric and magnetic energy densities are found by setting r=r'. These energy densities are then used in a response formalism to calculate intermolecular energy shifts. In the case of two ground-state molecules this leads to the Casimir-Polder potential. However, for a pair of molecules, one or both excited, there are additional terms arising from downward transitions. An important feature of these energies is that they exhibit an R -2 dependence for large intermolecular separations R. This dependence is interpreted in terms of the Poynting vector, which itself can be obtained by setting r=r' in the electric-magnetic correlation function

  4. Influence of intermolecular interactions on solid state luminescence of imidazopyridines: theoretical interpretations using FMO-TDDFT and ONIOM approaches.

    Science.gov (United States)

    Shigemitsu, Yasuhiro; Mutai, Toshiki; Houjou, Hirohiko; Araki, Koji

    2014-07-28

    6-Cyano-2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine (6CN-HPIP) shows polymorph-dependent luminescence with the three different crystal forms exhibiting the packing-controlled tuning of bright colors, orange, yellow, and red. The distinctive emission in aggregated states was treated with finite cluster models and analyzed by means of quantum chemistry calculations. The influence of structural displacements and intermolecular interactions in the crystalline state on solid state luminescence was examined in detail using the Fragment Molecular Orbital (FMO) scheme, suitable for studies of aggregated molecular systems. The FMO pair interaction analysis of the S1-S0 emission maxima indicated that the intermolecular side-to-side interactions cause hypsochromic shifts; facial interactions induce bathochromic shifts; and crystal packing effects in total induce hypsochromic shifts. The FMO predictions of the emission maxima offered qualitatively satisfactory agreements with the experiments. However, the small cluster models including up to 17 molecules did not reach quantitative convergence, i.e., the emission colour order among them was not well reproduced.

  5. A quantum chemical study of H2S2: Intramolecular torsional mode and intermolecular interactions with rare gases.

    Science.gov (United States)

    Maciel, Glauciete S; Barreto, Patricia R P; Palazzetti, Federico; Lombardi, Andrea; Aquilanti, Vincenzo

    2008-10-28

    The structural and energetic properties of the H(2)S(2) molecule have been studied using density functional theory, second-order Moller-Plesset method, and coupled cluster theory with several basis sets. In order to extend previous work on intra- and intermolecular dynamics of the chirality changing modes for H(2)O(2) and its derivatives, our focus has been on the torsion around the S-S bond, along with an extensive characterization of the intermolecular potentials of H(2)S(2) with the rare gases (He, Ne, Ar, and Kr). Use is made of previously defined coordinates and expansion formulas for the potentials which allow for a faithful representation of geometrical and symmetry properties of these systems that involve the interaction of an atom with a floppy molecule. The potential energy surfaces obtained in this work are useful for classical and quantum mechanical simulations of molecular collisions responsible for chirality changing processes of possible interest in the modeling of prebiotic phenomena.

  6. Technology Transfer

    Science.gov (United States)

    Smith, Nanette R.

    1995-01-01

    The objective of this summer's work was to attempt to enhance Technology Application Group (TAG) ability to measure the outcomes of its efforts to transfer NASA technology. By reviewing existing literature, by explaining the economic principles involved in evaluating the economic impact of technology transfer, and by investigating the LaRC processes our William & Mary team has been able to lead this important discussion. In reviewing the existing literature, we identified many of the metrics that are currently being used in the area of technology transfer. Learning about the LaRC technology transfer processes and the metrics currently used to track the transfer process enabled us to compare other R&D facilities to LaRC. We discuss and diagram impacts of technology transfer in the short run and the long run. Significantly, it serves as the basis for analysis and provides guidance in thinking about what the measurement objectives ought to be. By focusing on the SBIR Program, valuable information regarding the strengths and weaknesses of this LaRC program are to be gained. A survey was developed to ask probing questions regarding SBIR contractors' experience with the program. Specifically we are interested in finding out whether the SBIR Program is accomplishing its mission, if the SBIR companies are providing the needed innovations specified by NASA and to what extent those innovations have led to commercial success. We also developed a survey to ask COTR's, who are NASA employees acting as technical advisors to the SBIR contractors, the same type of questions, evaluating the successes and problems with the SBIR Program as they see it. This survey was developed to be implemented interactively on computer. It is our hope that the statistical and econometric studies that can be done on the data collected from all of these sources will provide insight regarding the direction to take in developing systematic evaluations of programs like the SBIR Program so that they can

  7. Open-ended formulation of self-consistent field response theory with the polarizable continuum model for solvation.

    Science.gov (United States)

    Di Remigio, Roberto; Beerepoot, Maarten T P; Cornaton, Yann; Ringholm, Magnus; Steindal, Arnfinn Hykkerud; Ruud, Kenneth; Frediani, Luca

    2016-12-21

    The study of high-order absorption properties of molecules is a field of growing importance. Quantum-chemical studies can help design chromophores with desirable characteristics. Given that most experiments are performed in solution, it is important to devise a cost-effective strategy to include solvation effects in quantum-chemical studies of these properties. We here present an open-ended formulation of self-consistent field (SCF) response theory for a molecular solute coupled to a polarizable continuum model (PCM) description of the solvent. Our formulation relies on the open-ended, density matrix-based quasienergy formulation of SCF response theory of Thorvaldsen, et al., [J. Chem. Phys., 2008, 129, 214108] and the variational formulation of the PCM, as presented by Lipparini et al., [J. Chem. Phys., 2010, 133, 014106]. Within the PCM approach to solvation, the mutual solute-solvent polarization is represented by means of an apparent surface charge (ASC) spread over the molecular cavity defining the solute-solvent boundary. In the variational formulation, the ASC is an independent, variational degree of freedom. This allows us to formulate response theory for molecular solutes in the fixed-cavity approximation up to arbitrary order and with arbitrary perturbation operators. For electric dipole perturbations, pole and residue analyses of the response functions naturally lead to the identification of excitation energies and transition moments. We document the implementation of this approach in the Dalton program package using a recently developed open-ended response code and the PCMSolver libraries and present results for one-, two-, three-, four- and five-photon absorption processes of three small molecules in solution.

  8. Technology transfer

    International Nuclear Information System (INIS)

    Boury, C.

    1986-01-01

    This paper emphasizes in the specific areas of design, engineering and component production. This paper presents what Framatome has to offer in these areas and its export oriented philosophy. Then, a typical example of this technology transfer philosophy is the collaboration with the South Korean firm, Korea Heavy Industries Corporation (KHIC) for the supply of KNU 9 and KNU 10 power stations

  9. Cyclohexane/benzene organic glasses and ethylene/styrene copolymers behaviour under ionizing radiations: energy and species transfers between aliphatic and aromatic moieties

    International Nuclear Information System (INIS)

    Ferry, M.

    2008-11-01

    The aim of this study is to understand how aliphatic and aromatic groups interact under ionizing radiations. Three research orientations were explored: the determination of the relative contribution of energy and radical transfers, the determination of the intermolecular and intra-chain relative contribution, and the influence of the repartition of the aliphatic and aromatic units inside the polymer chain. Three systems composed of aromatic and aliphatic units were studied: the cyclohexane/benzene organic glasses (intermolecular reactions), the ethylene/styrene random copolymers (inter-chain and intra-chain reactions) and ethylene/styrene di-blocs copolymers (influence of the repartition of the aliphatic and aromatic units in the material). Considering the results obtained, we have concluded that energy transfers are important in the radiation protection effect of the aliphatic moiety by the aromatic one, although radical transfers are also contributing. Intermolecular transfers are efficient in the solid state and their efficiency seems equivalent to that of the intra-chain ones. Thanks to the use of infrared spectroscopy, we have shown an important effect of radiation sensitization of the aromatic moiety, whatever the irradiation temperature and the system studied: energy transfers to the aromatic moiety are carried out at the detriment of its stability. Finally, the repartition of the aliphatic and aromatic units in the polymer chain is not an important factor in the effects induced by the energy transfers. (author)

  10. The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

    Directory of Open Access Journals (Sweden)

    GAO Shan

    2017-12-01

    Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

  11. Atom interferometry experiments with lithium. Accurate measurement of the electric polarizability; Experiences d'interferometrie atomique avec le lithium. Mesure de precision de la polarisabilite electrique

    Energy Technology Data Exchange (ETDEWEB)

    Miffre, A

    2005-06-15

    Atom interferometers are very sensitive tools to make precise measurements of physical quantities. This study presents a measurement of the static electric polarizability of lithium by atom interferometry. Our result, {alpha} = (24.33 {+-} 0.16)*10{sup -30} m{sup 3}, improves by a factor 3 the most accurate measurements of this quantity. This work describes the tuning and the operation of a Mach-Zehnder atom interferometer in detail. The two interfering arms are separated by the elastic diffraction of the atomic wave by a laser standing wave, almost resonant with the first resonance transition of lithium atom. A set of experimental techniques, often complicated to implement, is necessary to build the experimental set-up. After a detailed study of the atom source (a supersonic beam of lithium seeded in argon), we present our experimental atom signals which exhibit a very high fringe visibility, up to 84.5 % for first order diffraction. A wide variety of signals has been observed by diffraction of the bosonic isotope at higher diffraction orders and by diffraction of the fermionic less abundant isotope. The quality of these signals is then used to do very accurate phase measurements. A first experiment investigates how the atom interferometer signals are modified by a magnetic field gradient. An absolute measurement of lithium atom electric polarizability is then achieved by applying a static electric field on one of the two interfering arms, separated by only 90 micrometers. The construction of such a capacitor, its alignment in the experimental set-up and its operation are fully detailed.We obtain a very accurate phase measurement of the induced Lo Surdo - Stark phase shift (0.07 % precision). For this first measurement, the final uncertainty on the electric polarizability of lithium is only 0.66 %, and is dominated by the uncertainty on the atom beam mean velocity, so that a further reduction of the uncertainty can be expected. (author)

  12. Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

    Science.gov (United States)

    del Valle, J C; García Blanco, F; Catalán, J

    2015-04-02

    The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).

  13. 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

    2013-01-01

    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...... 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 state energies...

  14. Theoretical study of binding of hydrated Zn(II) and Mg(II) cations to 5'-guanosine monophosphate. Toward polarizable molecular mechanics for DNA and RNA

    Czech Academy of Sciences Publication Activity Database

    Gresh, N.; Šponer, Judit E.; Špačková, Naďa; Leszczynski, J.; Šponer, Jiří

    2003-01-01

    Roč. 107, č. 33 (2003), s. 8669-8681 ISSN 1520-6106 R&D Projects: GA MŠk LN00A016 Grant - others:National Science Foundation(US) CREST 9805465; National Institutes of Health(US) RCMI G1 2RR13459-21; Wellcome Trust(GB) GR067507MF Institutional research plan: CEZ:AV0Z5004920 Keywords : polarizable molecular mechanics * quantum-chemical computations * hydrated cations Subject RIV: BO - Biophysics Impact factor: 3.679, year: 2003

  15. Technology transfer

    International Nuclear Information System (INIS)

    Anon.

    1977-01-01

    Illustrated by the example of the FRG's nuclear energy exports, it is shown that the nuclear technology transfer leads to new dimensions of intergovernmental relations, which hold within themselves on account of multiple state-to-state, scientific, industrial and - last but not least - personal contacts the chance of far-reaching friendships between countries and people. If the chance is taken, this can also be seen as an important contribution towards maintaining the peace. (orig.) [de

  16. Anatomy Transfer

    OpenAIRE

    Dicko, Ali Hamadi; Liu, Tiantian; Gilles, Benjamin; Kavan, Ladislav; Faure, François; Palombi, Olivier; Cani, Marie-Paule

    2013-01-01

    International audience; Characters with precise internal anatomy are important in film and visual effects, as well as in medical applications. We propose the first semi-automatic method for creating anatomical structures, such as bones, muscles, viscera and fat tissues. This is done by transferring a reference anatomical model from an input template to an arbitrary target character, only defined by its boundary representation (skin). The fat distribution of the target character needs to be sp...

  17. Transfer Zymography.

    Science.gov (United States)

    Pan, Daniel; Wilson, Karl A; Tan-Wilson, Anna

    2017-01-01

    The technique described here, transfer zymography, was developed to overcome two limitations of conventional zymography. When proteolytic enzymes are resolved by nonreducing SDS-PAGE into a polyacrylamide gel with copolymerized protein substrate, the presence of the protein substrate can result in anomalous, often slower, migration of the protease and an estimated mass higher than its actual mass. A further drawback is that the presence of a high background of substrate protein interferes with proteomic analysis of the protease band by excision, tryptic digestion, and LC-MS/MS analysis. In transfer zymography, the proteolytic enzymes are resolved by conventional nonreducing SDS-PAGE, without protein substrate in the gel. The proteins in the resolving gel are then electrophoretically transferred to a receiving gel that contains the protein substrate, by a process similar to western blotting. The receiving gel is then processed in a manner similar to conventional zymography. SDS is removed by Triton X-100 and incubated in conditions suitable for the proteolytic activity. After protein staining, followed by destaining, bands representing regions with active protease are visualized as clear bands in a darkly stained background. For proteomic analysis, electrophoresis is carried out simultaneously on a second resolving gel, and the bands corresponding to the clear regions in the receiving gel after zymogram development are excised for proteomic analysis.

  18. Propagator formalism and computer simulation of restricted diffusion behaviors of inter-molecular multiple-quantum coherences

    International Nuclear Information System (INIS)

    Cai Congbo; Chen Zhong; Cai Shuhui; Zhong Jianhui

    2005-01-01

    In this paper, behaviors of single-quantum coherences and inter-molecular multiple-quantum coherences under restricted diffusion in nuclear magnetic resonance experiments were investigated. The propagator formalism based on the loss of spin phase memory during random motion was applied to describe the diffusion-induced signal attenuation. The exact expression of the signal attenuation under the short gradient pulse approximation for restricted diffusion between two parallel plates was obtained using this propagator method. For long gradient pulses, a modified formalism was proposed. The simulated signal attenuation under the effects of gradient pulses of different width based on the Monte Carlo method agrees with the theoretical predictions. The propagator formalism and computer simulation can provide convenient, intuitive and precise methods for the study of the diffusion behaviors

  19. Central-field intermolecular potentials from the differential elastic scattering of H2(D2) by other molecules

    International Nuclear Information System (INIS)

    Kuppermann, Aron; Gordon, R.J.; Coggiola, M.J.

    1974-01-01

    Differential elastic scattering cross sections for the systems H 2 +O 2 , SF 6 , NH 3 , CO, and CH 4 and for D 2 +O 2 , SF 6 , and NH 3 have been obtained from crossed beam studies. In all cases, rapid quantum oscillations have been resolved which permit the determination of intermolecular potentiel parameters if a central-field assumption is adopted. These potentials were found to be independent of both the isotopic form of the hydrogen molecule, and the relative collision energy. As a result of this, and the ability of these spherical potentials to quantitatively describe the measured scattering, it is concluded that anisotropy effects do not seem important in these H 2 (D 2 ) systems

  20. Investigation on intermolecular interaction between berberine and β-cyclodextrin by 2D UV-Vis asynchronous spectra

    Science.gov (United States)

    He, Anqi; Kang, Xiaoyan; Xu, Yizhuang; Noda, Isao; Ozaki, Yukihiro; Wu, Jinguang

    2017-10-01

    The interaction between berberine chloride and β-cyclodextrin (β-CyD) is investigated via 2D asynchronous UV-Vis spectrum. The occurrence of cross peaks around (420 nm, 420 nm) in 2D asynchronous spectrum reveals that specific intermolecular interaction indeed exists between berberine chloride and β-CyD. In spite of the difficulty caused by overlapping of cross peaks, we manage to confirm that the 420 nm band of berberine undergoes a red-shift, and its bandwidth decreases under the interaction with β-CyD. The red-shift of the 420 nm band that can be assigned to n-π* transition indicates the environment of berberine becomes more hydrophobic. The above spectral behavior is helpful in understanding why the solubility of berberine is enhanced by β-CyD.

  1. Rational design of viscosity reducing mutants of a monoclonal antibody: hydrophobic versus electrostatic inter-molecular interactions.

    Science.gov (United States)

    Nichols, Pilarin; Li, Li; Kumar, Sandeep; Buck, Patrick M; Singh, Satish K; Goswami, Sumit; Balthazor, Bryan; Conley, Tami R; Sek, David; Allen, Martin J

    2015-01-01

    High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption.

  2. Crossover from layering to island formation in Langmuir-Blodgett growth: role of long-range intermolecular forces.

    Science.gov (United States)

    Mukherjee, Smita; Datta, Alokmay

    2011-04-01

    Combined studies by atomic force microscopy, x-ray reflectivity, and Fourier transform infrared spectroscopy on transition-metal stearate (M-St, M = Mn, Co, Zn, and Cd) Langmuir-Blodgett films clearly indicate association of bidentate coordination of the metal-carboxylate head group to layer-by-layer growth as observed in MnSt and CoSt and partially in ZnSt. Crossover to islandlike growth, as observed in CdSt and ZnSt, is associated with the presence of unidentate coordination in the head group. Morphological evolutions as obtained from one, three, and nine monolayers (MLs) of M-St films are consistent with Frank van der Merwe, Stranski-Krastanov, and Volmer Weber growth modes for M=Mn/Co, Zn, and Cd, respectively, as previously assigned, and are found to vary with number (n) of metal atoms per head group, viz. n=1 (Mn/Co), n=0.75 (Zn), and n=0.5 (Cd). The parameter n is found to decide head-group coordination such that n=1.0 corresponds to bidentate and n=0.5 corresponds to unidentate coordination; the intermediate value in Zn corresponds to a mixture of both. The dependence of the growth mode on head-group structure is explained by the fact that in bidentate head groups, with the in-plane dipole moment being zero, intermolecular forces between adjacent molecules are absent and hence growth proceeds via layering. On the other hand, in unidentate head groups, the existence of a nonzero in-plane dipole moment results in the development of weak in-plane intermolecular forces between adjacent molecules causing in-plane clustering leading to islandlike growth. ©2011 American Physical Society

  3. Modelling decomposition, intermolecular protection and physical aggregation based on organic matter quality assessed by 13C-CPMAS-NMR

    Science.gov (United States)

    Incerti, Guido; Bonanomi, Giuliano; Sarker, Tushar Chandra; Giannino, Francesco; Cartenì, Fabrizio; Peressotti, Alessandro; Spaccini, Riccardo; Piccolo, Alessandro; Mazzoleni, Stefano

    2017-04-01

    Modelling organic matter decomposition is fundamental to predict biogeochemical cycling in terrestrial ecosystems. Current models use C/N or Lignin/N ratios to describe susceptibility to decomposition, or implement separate C pools decaying with different rates, disregarding biomolecular transformations and interactions and their effect on decomposition dynamics. We present a new process-based model of decomposition that includes a description of biomolecular dynamics obtained by 13C-CPMAS NMR spectroscopy. Baseline decay rates for relevant molecular classes and intermolecular protection were calibrated by best fitting of experimental data from leaves of 20 plant species decomposing for 180 days in controlled optimal conditions. The model was validated against field data from leaves of 32 plant species decomposing for 1-year at four sites in Mediterranean ecosystems. Our innovative approach accurately predicted decomposition of a wide range of litters across different climates. Simulations correctly reproduced mass loss data and variations of selected molecular classes both in controlled conditions and in the field, across different plant molecular compositions and environmental conditions. Prediction accuracy emerged from the species-specific partitioning of molecular types and from the representation of intermolecular interactions. The ongoing model implementation and calibration are oriented at representing organic matter dynamics in soil, including processes of interaction between mineral and organic soil fractions as a function of soil texture, physical aggregation of soil organic particles, and physical protection of soil organic matter as a function of aggregate size and abundance. Prospectively, our model shall satisfactorily reproduce C sequestration as resulting from experimental data of soil amended with a range of organic materials with different biomolecular quality, ranging from biochar to crop residues. Further application is also planned based on

  4. Energy-donor phosphorescence quenching study of triplet–triplet energy transfer between UV absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Kikuchi, Azusa; Nakabai, Yuya [Department of Chemistry, Graduate School of Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan); Oguchi-Fujiyama, Nozomi; Miyazawa, Kazuyuki [Shiseido Research Center, Hayabuchi, Tsuzuki-ku, Yokohama 224-8558 (Japan); Yagi, Mikio, E-mail: yagimiki@ynu.ac.jp [Department of Chemistry, Graduate School of Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan)

    2015-10-15

    The intermolecular triplet–triplet energy transfer from a photounstable UV-A absorber, 4-tert-butyl-4′-methoxydibenzoylmethane (BMDBM), to UV-B absorbers, 2-ethylhexyl 4-methoxycinnamate (octyl methoxycinnamate, OMC), octocrylene (OCR) and dioctyl 4-methoxybenzylidenemalonate (DOMBM) has been observed using a 355 nm laser excitation in rigid solutions at 77 K. The decay curves of the energy-donor phosphorescence in the presence of the UV-B absorbers deviate from the exponential decay at the initial stage of the decay. The Stern–Volmer formulation is not valid in rigid solutions because molecular diffusion is impossible. The experimental results indicate that the rate constant of triplet–triplet energy transfer from BMDBM to the UV-B absorbers, k{sub T–T}, decreases in the following order: k{sub T–T} (BMDBM–DOMBM)>k{sub T–T} (BMDBM–OMC)≥k{sub T–T} (BMDBM–OCR). The presence of DOMBM enhances the photostability of the widely used combination of UV-A and UV-B absorbers, BMDBM and OCR. The effects of the triplet–triplet energy transfer on the photostability of BMDBM are discussed. - Highlights: • The intermolecular triplet–triplet energy transfer between UV absorbers was observed. • The phosphorescence decay deviates from exponential at the initial stage of decay. • The effects of triplet–triplet energy transfer on the photostability are discussed.

  5. Virtual Compton scattering off the proton at Jefferson Lab (experiment E93050): preliminary results of the cross-sections of the reaction (ep{yields}ep{gamma}) in order to find out the generalized polarizabilities (GPs) of the proton at Q{sup 2} = 1.9 GeV{sup 2}; Diffusion compton virtuelle a jefferson lab (experience E93050): resultat preliminaire des sections efficaces (ep{yields}ep{gamma}) en vue d'extraire les polarisabilites generalisees du proton a Q{sup 2} = 1.9 GEV{sup 2}

    Energy Technology Data Exchange (ETDEWEB)

    Jaminion, St

    2000-12-01

    Virtual Compton Scattering off the proton ({gamma}{sup *}p {yields} {gamma}p) at low energy is accessible via the reaction (ep {yields} ep{gamma}), and contains 6 new observables: Generalized Polarizabilities (GPs). Their extraction needs the measurement of absolute five fold differential cross sections for photon electroproduction off the proton. The determination of GPs will put new constraints on models of nucleon structure in the non-perturbative Quantum Chromodynamics region. Following the Mainz experiment realized at four momentum transfer Q{sup 2} = 0.33 GeV{sup 2}, the E93050 experiment which was performed in the Hall A of Jefferson Lab during march-april 1998, will allow the measurement of combinations of generalized polarizabilities at Q{sup 2}=1 and 1.9 GeV{sup 2}. The final electron and proton were detected in coincidence in the Hall A high resolution spectrometers. The final photon is reconstructed like a missing particle, and all its variables can be determined. We had to optimize optics tensor of each spectrometer in order to have the best reconstruction at vertex point. We created an acceptance function, which is included in the software simulating solid angle. We determined different cuts to substract our background dominating (ep {yields} ep{gamma}) reaction. This work allows to carry out our first photon electro-production cross section measurement at Q{sup 2}=1.9 GeV{sup 2}. The results seem to indicate a measurable effect of generalized polarizabilities, which remains however to be confirmed. (author)

  6. A Closer Look at Trends in Boiling Points of Hydrides: Using an Inquiry-Based Approach to Teach Intermolecular Forces of Attraction

    Science.gov (United States)

    Glazier, Samantha; Marano, Nadia; Eisen, Laura

    2010-01-01

    We describe how we use boiling-point trends of group IV-VII hydrides to introduce intermolecular forces in our first-year general chemistry classes. Starting with the idea that molecules in the liquid state are held together by some kind of force that must be overcome for boiling to take place, students use data analysis and critical reasoning to…

  7. Comprehensive study of electronic polarizability and band gap of B2O3–Bi2O3–ZnO–SiO2 glass network

    Directory of Open Access Journals (Sweden)

    Iskandar Shahrim Mustafa

    2017-10-01

    Full Text Available Quaternary glasses were successfully fabricated using melt quenching technique based on the chemical compound composition (xBi2O3–(0.5−x ZnO–(0.2B2O3–(0.3SiO2, where (x=0.1, 0.2, 0.3, 0.4, 0.45 mole. The sources of SiO2 was produced from rice husk ash (RHA at 99.36% of SiO2. The Urbach energy was increased from 0.16eV to the 0.29eV as the mole of Bi2O3 increased in the glass structure. The indirect energy band gap is indicated in decrement pattern with 3.15eV towards 2.51eV. The results of Urbach energy and band gap energy that were obtained are due to the increment of Bi3+ ion in the glass network. The refractive indexes for the prepared glasses were evaluated at 2.36 to 2.54 based on the Lorentz–Lorentz formulation which correlated to the energy band gap. The calculated of molar polarizability, electronic polarizability and optical basicity exemplify fine complement to the Bi2O3 addition in the glass network. The glass sample was indicated in amorphous state.

  8. Size dependence of the polarizability and Haynes rule for an exciton bound to an ionized donor in a single spherical quantum dot

    Energy Technology Data Exchange (ETDEWEB)

    Feddi, E., E-mail: e.feddi@um5s.net.ma; Zouitine, A. [Université Mohamed V Souissi, Ecole Normale Supérieure de l' Enseignement Technique (ENSET), Rabat (Morocco); Oukerroum, A.; Zazoui, M. [Laboratory of Condensed Matter, Faculty of Sciences and Techniques, University of Hassan II-Mohammedia, B.P. 146, 20800 Mohammedia (Morocco); Dujardin, F. [LCP-A2MC, Université de Lorraine, ICPM, 1 Bd Arago, 57070 Metz (France); Assaid, E. [Laboratoire d' Électronique et Optique des Nanostructures de Semiconducteurs, Faculté des Sciences, B. P. 20, El Jadida (Morocco)

    2015-02-14

    We study the effect of an external electric field on an exciton bound to an ionized donor (D{sup +}, X) confined in a spherical quantum dot using a perturbative-variational method where the wave function and energy are developed in series of powers of the electric field strength. After testing this new approach in the determination of the band gap for some semiconductor materials, we generalize it to the case of (D{sup +}, X) in the presence of the electric field and for several materials ZnO, PbSe, and InAs, with significant values of the mass ratio. Three interesting results can be deduced: First, we show that the present method allows to determine the ground state energy in the presence of a weak electric field in a simple way (E = E{sub 0} − αf{sup 2}) using the energy without electric field E{sub 0} and the polarizability α. The second point is that our theoretical predictions show that the polarizability of (D{sup +}, X) varies proportionally to R{sup 3.5} and follows an ordering α{sub D{sup 0}}<α{sub X}<α{sub (D{sup +},X)}. The last point to highlight is that the Haynes rule remains valid even in the presence of a weak electric field.

  9. C6 Coefficients and Dipole Polarizabilities for All Atoms and Many Ions in Rows 1-6 of the Periodic Table.

    Science.gov (United States)

    Gould, Tim; Bučko, Tomáš

    2016-08-09

    Using time-dependent density functional theory (TDDFT) with exchange kernels, we calculate and test imaginary frequency-dependent dipole polarizabilities for all atoms and many ions in rows 1-6 of the periodic table. These are then integrated over frequency to produce C6 coefficients. Results are presented under different models: straight TDDFT calculations using two different kernels; "benchmark" TDDFT calculations corrected by more accurate quantum chemical and experimental data; and "benchmark" TDDFT with frozen orbital anions. Parametrizations are presented for 411+ atoms and ions, allowing results to be easily used by other researchers. A curious relationship, C6,XY ∝ [αX(0)αY(0)](0.73), is found between C6 coefficients and static polarizabilities α(0). The relationship C6,XY = 2C6,XC6,Y/[(αX/αY)C6,Y + (αY/αX)C6,X] is tested and found to work well (30% errors) in a small fraction of cases.

  10. Polarizable Density Embedding

    DEFF Research Database (Denmark)

    Reinholdt, Peter; Kongsted, Jacob; Olsen, Jógvan Magnus Haugaard

    2017-01-01

    and diffuse basis sets that are otherwise questionable-due to electron spill-out effects-in standard embedding models. Based on our analysis, we find the PDE model to be robust and much more systematic than less sophisticated focused embedding models, and thus outline the PDE model as a very efficient...

  11. Spin polarizability of hyperons

    Indian Academy of Sciences (India)

    2014-11-04

    Nov 4, 2014 ... baryon system will have three terms of order p, the loop contribution of order p2, p3 and also counterterms of order p2 and p3. Hence, complete one-loop diagram to order O(p3) involves one insertion from L(1). φN and tree-level diagrams. In HBChPT, the amplitude for. Pramana – J. Phys., Vol. 83, No. 5 ...

  12. Resonance energy transfer and interface forces: quantum electrodynamical analysis

    Science.gov (United States)

    Bradshaw, David S.; Leeder, Jamie M.; Rodríguez, Justo; Andrews, David L.

    2007-01-01

    On the propagation of radiation with a suitably resonant optical frequency through a dense chromophoric system - a doped solid for example - photon capture is commonly followed by one or more near-field transfers of the resulting optical excitation, usually to closely neighboring chromophores. Since the process results in a change to the local electronic environment, it can be expected to also shift the electromagnetic interactions between the participant optical units, producing modified inter-particle forces. Significantly, it emerges that energy transfer, when it occurs between chromophores or particles with electronically dissimilar properties (such as differing polarizabilities), engenders hitherto unreported changes in the local potential energy landscape. This paper reports the results of quantum electrodynamical calculations which cast a new light on the physical link between these features. The theory also elucidates a significant relationship with Casimir-Polder forces; it transpires that there are clear and fundamental links between dispersion forces and resonance energy transfer. Based on the results, we highlight specific effects that can be anticipated when laser light propagates through an interface between two absorbing media. Both steady-state and pulsed excitation conditions are modeled and the consequences for interface forces are subjected to detailed analysis.

  13. Genetic plasticity of the Shigella virulence plasmid is mediated by intra- and inter-molecular events between insertion sequences.

    Science.gov (United States)

    Pilla, Giulia; McVicker, Gareth; Tang, Christoph M

    2017-09-01

    Acquisition of a single copy, large virulence plasmid, pINV, led to the emergence of Shigella spp. from Escherichia coli. The plasmid encodes a Type III secretion system (T3SS) on a 30 kb pathogenicity island (PAI), and is maintained in a bacterial population through a series of toxin:antitoxin (TA) systems which mediate post-segregational killing (PSK). The T3SS imposes a significant cost on the bacterium, and strains which have lost the plasmid and/or genes encoding the T3SS grow faster than wild-type strains in the laboratory, and fail to bind the indicator dye Congo Red (CR). Our aim was to define the molecular events in Shigella flexneri that cause loss of Type III secretion (T3S), and to examine whether TA systems exert positional effects on pINV. During growth at 37°C, we found that deletions of regions of the plasmid including the PAI lead to the emergence of CR-negative colonies; deletions occur through intra-molecular recombination events between insertion sequences (ISs) flanking the PAI. Furthermore, by repositioning MvpAT (which belongs to the VapBC family of TA systems) near the PAI, we demonstrate that the location of this TA system alters the rearrangements that lead to loss of T3S, indicating that MvpAT acts both globally (by reducing loss of pINV through PSK) as well as locally (by preventing loss of adjacent sequences). During growth at environmental temperatures, we show for the first time that pINV spontaneously integrates into different sites in the chromosome, and this is mediated by inter-molecular events involving IS1294. Integration leads to reduced PAI gene expression and impaired secretion through the T3SS, while excision of pINV from the chromosome restores T3SS function. Therefore, pINV integration provides a reversible mechanism for Shigella to circumvent the metabolic burden imposed by pINV. Intra- and inter-molecular events between ISs, which are abundant in Shigella spp., mediate plasticity of S. flexneri pINV.

  14. Applications of free-electron lasers to measurements of energy transfer in biopolymers and materials

    Science.gov (United States)

    Edwards, Glenn S.; Johnson, J. B.; Kozub, John A.; Tribble, Jerri A.; Wagner, Katrina

    1992-08-01

    Free-electron lasers (FELs) provide tunable, pulsed radiation in the infrared. Using the FEL as a pump beam, we are investigating the mechanisms for energy transfer between localized vibrational modes and between vibrational modes and lattice or phonon modes. Either a laser-Raman system or a Fourier transform infrared (FTIR) spectrometer will serve as the probe beam, with the attribute of placing the burden of detection on two conventional spectroscopic techniques that circumvent the limited response of infrared detectors. More specifically, the Raman effect inelastically shifts an exciting laser line, typically a visible frequency, by the energy of the vibrational mode; however, the shifted Raman lines also lie in the visible, allowing for detection with highly efficient visible detectors. With regards to FTIR spectroscopy, the multiplex advantage yields a distinct benefit for infrared detector response. Our group is investigating intramolecular and intermolecular energy transfer processes in both biopolymers and more traditional materials. For example, alkali halides contain a number of defect types that effectively transfer energy in an intermolecular process. Similarly, the functioning of biopolymers depends on efficient intramolecular energy transfer. Understanding these mechanisms will enhance our ability to modify biopolymers and materials with applications to biology, medecine, and materials science.

  15. Technology Transfer

    Science.gov (United States)

    Bullock, Kimberly R.

    1995-01-01

    The development and application of new technologies in the United States has always been important to the economic well being of the country. The National Aeronautics and Space Administration (NASA) has been an important source of these new technologies for almost four decades. Recently, increasing global competition has emphasized the importance of fully utilizing federally funded technologies. Today NASA must meet its mission goals while at the same time, conduct research and development that contributes to securing US economic growth. NASA technologies must be quickly and effectively transferred into commercial products. In order to accomplish this task, NASA has formulated a new way of doing business with the private sector. Emphasis is placed on forming mutually beneficial partnerships between NASA and US industry. New standards have been set in response to the process that increase effectiveness, efficiency, and timely customer response. This summer I have identified potential markets for two NASA inventions: including the Radially Focused Eddy Current Sensor for Characterization of Flaws in Metallic Tubing and the Radiographic Moire. I have also worked to establish a cooperative program with TAG, private industry, and a university known as the TAG/Industry/Academia Program.

  16. Analysis and Ranking of Protein-Protein Docking Models Using Inter-Residue Contacts and Inter-Molecular Contact Maps

    KAUST Repository

    Oliva, Romina

    2015-07-01

    In view of the increasing interest both in inhibitors of protein-protein interactions and in protein drugs themselves, analysis of the three-dimensional structure of protein-protein complexes is assuming greater relevance in drug design. In the many cases where an experimental structure is not available, protein-protein docking becomes the method of choice for predicting the arrangement of the complex. However, reliably scoring protein-protein docking poses is still an unsolved problem. As a consequence, the screening of many docking models is usually required in the analysis step, to possibly single out the correct ones. Here, making use of exemplary cases, we review our recently introduced methods for the analysis of protein complex structures and for the scoring of protein docking poses, based on the use of inter-residue contacts and their visualization in inter-molecular contact maps. We also show that the ensemble of tools we developed can be used in the context of rational drug design targeting protein-protein interactions.

  17. Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces.

    Science.gov (United States)

    Goldmann, Claire; Ribot, François; Peiretti, Leonardo F; Quaino, Paola; Tielens, Frederik; Sanchez, Clément; Chanéac, Corinne; Portehault, David

    2017-05-01

    A basic understanding of the driving forces for the formation of multiligand coronas or self-assembled monolayers over metal nanoparticles is mandatory to control and predict the properties of ligand-protected nanoparticles. Herein, 1 H nuclear magnetic resonance experiments and advanced density functional theory (DFT) modeling are combined to highlight the key parameters defining the efficiency of ligand exchange on dispersed gold nanoparticles. The compositions of the surface and of the liquid reaction medium are quantitatively correlated for bifunctional gold nanoparticles protected by a range of competing thiols, including an alkylthiol, arylthiols of varying chain length, thiols functionalized by ethyleneglycol units, and amide groups. These partitions are used to build scales that quantify the ability of a ligand to exchange dodecanethiol. Such scales can be used to target a specific surface composition by choosing the right exchange conditions (ligand ratio, concentrations, and particle size). In the specific case of arylthiols, the exchange ability scale is exploited with the help of DFT modeling to unveil the roles of intermolecular forces and entropic effects in driving ligand exchange. It is finally suggested that similar considerations may apply to other ligands and to direct biligand synthesis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface

    Science.gov (United States)

    Li, Fabing; Li, Zhanlong; Wang, Ying; Wang, Shenghan; Wang, Xiaojun; Sun, Chenglin; Men, Zhiwei

    2018-05-01

    The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063 cm-1 (2438 cm-1) in the recorded Raman spectra are assigned here to the Osbnd H (Osbnd D) bond stretching vibrations and they are compared with the corresponding bands observed at 3124 cm-1 (2325 cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

  19. Mechanism and Regioselectivity of Rh(III)-Catalyzed Intermolecular Annulation of Aryl-Substituted Diazenecarboxylates and Alkenes: DFT Insights

    KAUST Repository

    Ajitha, Manjaly John

    2016-02-05

    The mechanism of Rh-catalyzed intermolecular annulation of aryl-substituted diazenecarboxylates and alkenes was investigated using density functional theory (DFT) (PCM-M062X/6-311+G(d,p)//M062X/6-31G(d)). The acetate ligand (OAc)-assisted C-H activation via the formation of a five-membered rhodacycle (I-TS1; ΔG‡ = 19.4 kcal/mol) is more favorable compared to that via a four-membered intermediate (II-TS1; ΔG‡ = 27.8 kcal/mol). Our results also revealed that the seven-membered intermediate (I-3, ΔGrel = -6.8 kcal/mol) formed after the alkene insertion could undergo a coordination switch with the adjacent nitrogen atom (via TScs; ΔG‡ = 16.5 kcal/mol) to produce a thermodynamically stable six-membered intermediate (II-3, ΔGrel = -10.4 kcal/mol), eventually leading to a cyclization process followed by a barrierless ligand-assisted protonation to yield the final product. The β-hydride elimination product was found to be kinetically and thermodynamically undesirable. The rate-determining step is identified as the initial C-H activation, consistent with the previous kinetic studies. Notably, DFT studies offered important insights on the ability of the substrate (diazene carboxylate) to promote the switchable coordination site selectivity during the reaction to achieve a lower energy pathway. © 2016 American Chemical Society.

  20. Correlation distance dependence of the resonance frequency of intermolecular zero quantum coherences and its implication for MR thermometry.

    Science.gov (United States)

    Zhang, Le; McCallister, Andrew; Koshlap, Karl M; Branca, Rosa Tamara

    2018-03-01

    Because the resonance frequency of water-fat intermolecular zero-quantum coherences (iZQCs) reflects the water-fat frequency separation at the microscopic scale, these frequencies have been proposed and used as a mean to obtain more accurate temperature information. The purpose of this work was to investigate the dependence of the water-fat iZQC resonance frequency on sample microstructure and on the specific choice of the correlation distance. The effect of water-fat susceptibility gradients on the water-methylene iZQC resonance frequency was first computed and then measured for different water-fat emulsions and for a mixture of porcine muscle and fat. Similar measurements were also performed for mixed heteronuclear spin systems. A strong dependence of the iZQC resonance frequency on the sample microstructure and on the specific choice of the correlation distance was found for spin systems like water and fat that do not mix, but not for spin systems that mix at the molecular level. Because water and fat spins do not mix at the molecular level, the water-fat iZQC resonance frequency and its temperature coefficient are not only affected by sample microstructure but also by the specific choice of the correlation distance. Magn Reson Med 79:1429-1438, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.